text:
Brooklyn-based property owner Rachel Ohana has filed applications for a four-story, two-unit residential building at 555 Maple Street, in northern East Flatbush. The structure will measure 5,395 square feet. There will be one unit on the ground floor, followed by a townhouse-style apartment across part of the ground floor and the upper three floors. Lewis E. Garfinkel’s Brooklyn-based architecture firm is the architect of record. The 20-foot-wide, 2,300-square-foot lot is currently vacant. The Sterling Street stop on the 2 and 5 trains is six blocks away.
Many of the vinyl-clad, wood frame houses typical in eastern Williamsburg are biting the dust for new development. Today, we have a look at a new project replacing a little two story house at 95 Ainslie Street, between Lorimer Street and Union Avenue.
Downtown Brooklyn is abuzz with new construction. YIMBY has covered this extensively and it’s been plain to see for those traveling around the city. Now, one of two new hotels on the same block in the neighborhood is inching closer to completion.
Last week, the Jersey City Planning Board approved plans for a five-story, 308-unit mixed-use project at 100 Monitor Street, located on the corner of Johnson Avenue in the city’s Communipaw section. The building will include 2,980 square feet of ground-floor retail space and 8,000 square feet of office space, the latter of which will be leased to the Jersey City Redevelopment Agency, Jersey Digs reported. The residential units will be rentals and amenities will include an 85-car parking garage, a fitness center, a pool, and a landscaped garden. Ironstate Development and Landmark Developers are developing the building. The site is an assemblage of six vacant lots and groundbreaking is scheduled for early 2017.
Construction is wrapping up on the 19-story, 15-unit residential building under development at 60 East 86th Street, on the Upper East Side. The latest photo was posted to Instagram by the project’s design architect, Thomas Juul-Hansen. Dubbed Sixty East Eighty Sixth, the 55,407-square-foot structure includes one triplex apartment spanning the cellar through second floors, followed by a single unit per floor on floors three through nine, a duplex apartment spanning the 10th and 11th floors, another duplex spanning the 12th and 13th floors, one apartment per floor on the 14th through 16th floors, and, finally, a triplex penthouse spanning the 17th through 19th floors. The condominiums should average 3,730 square feet apiece. Amenities include a library, a fitness center, a children’s playroom, a wine room, private storage space, and storage for eight bikes. Glenwood Management is the developer and Stephen B. Jacobs Group is the executive architect. Occupancy is probably imminent.

domain: geography


RECENT POSTS IN zoom lens
Optical Zoom VS Digital Zoom – What’s The Difference?
These days, almost every camera with a built-in lens has some sort of a “zoom” label on it. However, not…
Canon Announces 4 New Full-Frame Mirrorless Lenses, One Printer
Today Canon is also introducing four new RF lenses and two RF lens teleconverters: The Canon RF100-500mm F4.5-7.1 L IS…
Sigma Shakes Things Up With An Expansion Of Several New Mirrorless Lens Options
Sigma Unveils 100-400mm F5-6.3 DG DN OS Contemporary Telephoto Lens for Full-Frame Mirrorless Cameras; Mirrorless-Exclusive Teleconverters; USB Dock for Sigma Mirrorless Lenses; and F1.4 Mirrorless L-Mount Lens Trio.
Tamron Launches The Worlds First All-In-One Zoom Lens For Sony E-Mount – The 28-200mm F/2.8-5.6 Di III RXD
Tamron has just announced the launch of the 28-200mm F/2.8-5.6 Di III RXD (Model A071), an all-in-one zoom lens for Sony E-mount full-frame mirrorless cameras. The lens is scheduled to be available on June 25 at $729(USD). Due to the spread of COVID-19, the release date or the product supply schedule could be delayed.
Canon RF 70-135mm f/2L Rumor Surfaces | Is Canon Working on the Greatest Telephoto Zoom Lens Ever?
Is Canon working on the greatest telephoto zoom lens of all time? According to a new rumor, Canon is currently testing a 70-135mm f/2L lens.
Tamron Officially Announces the Launch of the 70-180mm f/2.8 Di III VXD (Model A056)
Tamron announces the launch date of the 70-180mm F/2.8 Di III VXD (Model A056), a large aperture telephoto zoom lens for Sony E-mount full-frame mirrorless cameras that is the lightest and most compact in its class. The lens will be available in the U.S. on May 14th at $1199. However, due to the spread of COVID-19, the release date or the product supply schedule could be delayed.
Fujifilm Announces New 45-100mm GFX Lens and GF Lens Roadmap
FUJIFILM Launches a new GFX lens, and announces the latest developments for G-Mount Interchangeable Lenses with a 2020 Roadmap – Exclusive 13-lens lineup, including 2 newly-announced lenses, provides comprehensive shooting coverage


This is the popular pressure sensor connector made by Delphi. It suits a lot of the popular fuel/oil/nitrous pressure sensors used by many EMS manufacturers including FuelTech.
Unlike other connectors of this type, it can be disassembled to remove the pins without damaging the plug.
This connector has a rear flange to use a rubber boot or heatshrink. Boot sold separately.
Kit includes the connector body, locking cap, seals and pins.


In the process of PCBA production, it depends on many machinery equipment to finish a board assembly. Therefore, the quality level of equipment in a factory directly determines the manufacturing ability. Here are mainly introduces the basic equipment of universal PCBA factory.
The basic equipment required for PCBA production is the solder paste printer, SMD machine, reflow soldering machine, AOI inspection, component lead cutting machine, Wave soldering, X-Ray test, ICT test fixture, FCT test fixture, HALT test fixture, etc. Different PCBA factories equipped with machinery equipment will be different.
The main PCBA production equipment in following.
PCB Washing machine
PCB board is not strictly cleaned when leaving the PCB production workshop, there is a lot of dust remain on PCB board surface, edge, through hole and other places.
PCB board is easy to generate static electricity in the process of manufacturing, which makes it easy to cause static electricity injury or dust adsorption in the (PCB assembly) SMT process.
Dust and other foreign matter can cause paste printing defects and soldering defects such as cold soldering, empty soldering, component warping, deviation and so on.
The PCB bare boards entering the washing machine before SMT process can prevent and reduce the generation of defective products, improve the quality, and achieve the purpose of enhancing product reliability.
Automatic Solder Paste Printer
Modern solder paste printer generally consists of loading, solder paste adding, solder paste printing, input SPI Inspection and other mechanisms.
It’s working principle is as follows: firstly, the PCB board is fixed on the printing positioning platform, and then the left and right scraper of the printing machine will leak the solder paste or red glue through the stencil to the corresponding solder pad, and then the PCB board which printed the solder paste will be transferred to SPI Inspection for detection.
SPI (Solder paste inspection)
SPI is for the solder paste printing quality inspection and printing process verification and control.
Its basic functions are as follows:
- Find out the quality defects of solder paste printing in time. SPI can directly tell the user which solder paste printing is good or bad, and provide a hint of the types of defects.
- Through a series of solder joint inspection, the quality trend is found to change. SPI detects quality trends through a series of solder paste inspection, and identifies the underlying factors that cause such trends before the quality is out of range, such as adjustable control parameters, human factors, solder paste variation factors, etc. Then timely adjustment, control the trend to continue to spread.
Finally, the detected PCB board with good solder paste printing are transported to the Pick& Placement machine.
Pick& Placement machine
Pick & Placement process also called Surface Mount System. In the PCB assembly process line, it is placed behind the solder paste printer and is an equipment for placing the SMD type components accurately on the PCB pad by moving the mounting head.
Divided into two types： manual and automatic ，automatic one including normal machine, low, medium, high speed SMD machine. Finally, the assembled PCB boards with the installed components will be transported to reflow soldering through the visual inspection transmission platform.
There is a heating circuit inside the reflow soldering, it can heat air or nitrogen to a high enough temperature and then blow to the PCB board that has been soldered with the components, so that the solder paste on both sides of the component will be melted and solidify to the PCB board.
The advantages of this process are that the temperature is easily controlled, oxidation is avoided during soldering, and manufacturing costs are more easily controlled.
Automated Optical Inspection (AOI)
Automatic Optic Inspection is based on optical principle to detect common defects encountered in PCB assembly production equipment. AOI is a new emerging testing technology, but developed rapidly, many PCB manufacturers have launched AOI testing equipment. When automatic detection, the machine will scan the PCB automatically through the camera, collect images, compare the tested solder joints with the qualified parameters in the database, check the defects on the PCB after image processing, and display/mark the defects through the display or automatic signs for maintenance personnel to repair.
Component lead cutting machine
It is used for cutting and deforming for the soldering pins of DIP components.
Component insertion machine
It is a mechanical device that automatically inserts some regular DIP components (also called “automatic insert machine”) into the through hole of PCB board.
Wave soldering is to make the soldering surface of the plug-in through holes directly contact with the high temperature liquid tin to achieve the purpose of soldering.
The high temperature liquid tin to maintain a bevel, and by a special device to form a similar wave of liquid tin phenomenon, so it is called “wave soldering”, the main material is the solder bar.
Post-Wave soldering Automated Optical Inspection (AOI)
Because of the characteristic of the wave soldering process, in this process is the most likely to produce defects, such as soldering pins shorting, faulty soldering, missing soldering, etc., and with the PCB assembly process is more and more miniaturization, high precision, the original manual visual inspection has been completely restricted the production capacity and quality of development, professional machine view is used to replace artificial has higher stability and reliability.
X-Ray BGA Inspection
This testing is commonly performed on Quad-flat No-lead (QFN) PCBs, and Ball Grid Arrays (BGAs) in PCBA process.
X -ray inspection has advantages of fast speed, high efficiency, low cost, no damage to the sample.
First Article Inspection
Import the BOM, coordinate, designator or scan picture into the application software to generate a test program. Cooperate with the sophisticated LCR measuring instrument to measure each component according to the BOM.
The software automatically sets the LCR tap position, automatically compares the actual value of the component, automatically marks the automatic voice prompt PASS, and automatically generates the first article inspection report.
PCBA Washing machine
PCBA Washing machine used for cleaning PCB assembled (PCBA) board, can remove the residue after soldering.
Sensitive Component Storage Cabinet
The sensitive component storage cabinet is used for keeping the sensitive components.
Such as thermosensitive, photosensitive, electric pressure sensitive, pressure sensitive, magnetic sensitive, gas sensitive, humidity sensitive components.
FCT test fixture
FCT test fixtures mainly perform functional tests on PCBA products, such as voltage, current, power and frequency.
FCT test fixtures can test semi-finished products or finished products. Nowadays, FCT test fixture control mode is mainly automatic, and this kind of control mode has a very fast fixture test speed and accurate test data.


text:
Can anything stand in Omnicare's way?
David Russell | [email protected]
optionMONSTER's Heat Seeker monitoring system detected the purchase of more than 2,700 September 60 calls, most of which priced for $0.30. These are all new positions, as there was no open interest at the strike before the trades appeared.
The long calls lock in the price where shares can be purchased in the health-care company, which is already up 53 percent so far this year. Investors use the contracts to obtain cheap upside exposure, preventing them from missing a rally while limiting potential losses in a pullback. (See our Education section for more on how options can be used to manage risk.)
OCR is up 2.04 percent to $55.40 in afternoon trading, down slightly from an all-time high of $55.85 reached earlier in the session. The stock has been riding a wave of strong earnings reports as business grows and generic drugs help contain costs.
Total option volume is more than 15 times greater than average so far today, according to the Heat Seeker. Calls outnumbered puts by a bullish 18-to-1 ratio.

domain: news


text:
Option Care is pleased to offer a one-stop resource for accessing the most up-to-date, quality continuing education content. These complementary, accredited courses are another example of our ongoing commitment to patient care and to providing the healthcare community with the highest level of support and education.
Click on a course title to begin. After reading the course material, click on the Post Test in the left-hand column. The test will be scored automatically upon completion. Follow the instructions on the screen to receive your certification.

domain: medical


text:
From the classic discussion of the psychology of interruption in discourse: a power-oriented interruption is an attempt to establish dominance over an interlocutor by non-rational, semi-coercive means. In a televised debate, the television audience is a sort of interlocutor, so interruptions can be interpreted as attempts to establish dominance over the audience.
In this context, the relevant question is not who won the debate, but whether the audience acquiesces in domination or resists. The outcome of the “debate” was irrelevant because it wasn’t one. The whole event was simply a bid for domination, full stop, and its success or failure as an attempt depends on how the audience responds to the bid. Does the audience play along with the bid, take its aims for granted, and make excuses for it? Or does it push back in wholehearted rejection? There’s not much room here for neutrality or agnosticism.
Each one of us knows the answer to that question in our own case, and has the power to figure out what it is, partly by bringing it about. Voting may not give you much power or control over the powerful. But that one act does.
I didn’t feel dominated. I did feel morally disgusted and saddened by the spectacle — and had the desire to remove the cause of it from the scene.
The second sentence, especially the part after the dash, explains the first.

domain: psychology


text:
El Dorado is a legend about a Muisca tribal chief of South America who covered himself in gold dust. Later, it became the name of a mythical lost city of gold hidden deep within the rainforests of South America, which many European explorers unsuccessfully attempted to find.
Related categories 1
The Legend of El Dorado
Large amount of information pertaining to the legend of El Dorado, its history, and development.
About.com: Ten Facts About El Dorado
Ten facts related to the historical search for El Dorado.
About.com: The Legend of El Dorado, the Mysterious City of Gold
About.com article discussing the development of the legend of El Dorado.
El Dorado Legend Snared Sir Walter Raleigh
National Geographic article concerning Sir Walter Raleigh's search for the mythical lost city of El Dorado in the 17th century.
Historic Mysteries: The Legend of El Dorado
Article discussing the inspirations, development, and history of the legend of El Dorado.
The Poetry Foundation: Eldorado by Edgar Allan Poe
Online transcription of Edgar Allen Poe's poem titled "El Dorado."
The Stories of El Dorado, by Frona Eunice Wait
Project Gutenberg e-book of a 1904 collection of legends connected to El Dorado.
Last update:February 28, 2014 at 8:07:28 UTC

domain: history


text:
Multi Vitamin 6 Packs
A multivitamin that includes essential vitamins and minerals to complement a woman’s diet.*
- Fills nutritional gaps
- Supports better health*
- Superior ingredients, developed with doctors
A hard-working multi-vitamin with 15 vitamins and minerals carefully chosen to help women fill the nutritional gaps missing from a typical diet.

domain: health


text:
mongolian sloppy joes
- 1 pound ground beef (90% lean)
- 1 medium onion, chopped
- 2 serrano chiles, seeded, chopped
- 3 tablespoons hoisin sauce
- 2 tablespoons oyster sauce
- 2 tablespoons soy sauce
- 1 tablespoon honey
- 6 sesame seed hamburger buns, split
1. Heat large nonstick skillet over medium heat until hot. Add Ground Beef, onion and chiles; cook 8 to 10 minutes, breaking beef up into 3/4-inch crumbles. Remove drippings.
2. Stir in hoisin sauce, oyster sauce, soy sauce and honey; bring to boil. Reduce heat; simmer 5 minutes, stirring often.
3. Divide beef mixture evenly on bottom half of each bun; close sandwiches.
Test Kitchen Tips: Cooking times are for fresh or thoroughly thawed Ground Beef. Ground Beef should be cooked to an internal temperature of 160ºF. Color is not a reliable indicator of Ground Beef doneness.
Nutrition information per serving: 328 calories; 10 g fat (4 g saturated fat; 3 g monounsaturated fat); 51 mg cholesterol; 912 mg sodium; 36 g carbohydrate; 1.5 g fiber; 22 g protein; 4.2 mg niacin; 0.3 mg vitamin B6; 1.6 mcg vitamin B12; 2.0 mg iron; 12.6 mcg selenium; 4.0 mg zinc; 55.1 mg choline.
This recipe is an excellent source of protein, niacin, vitamin B12 and zinc; and a good source of vitamin B6, iron, selenium and choline.

domain: food


text:
How do you describe a sofa
to someone who has
never seen a chair before?
Do you talk of its soft and exposed top
or how it provides support?
but so does a young woman’s décolleté
and an old woman’s brassiere.
Do you say its legs are four?
two at the back, two at the front
but so has a goat and a dog
(and humans at the sound of gunshots).
So how do you describe a sofa
to someone who in all their years
has never seen a chair?
You don’t, you don’t describe the sofa
to someone who in all their life
has only ever sat on rocks
she won’t believe it, that there exists
in this world, something else to sit upon
that would have her back
and not grate her behind.
So you must take her by the hand
and wherever it may be
you lead this woman to a velvet sofa
you let her see it, feel it, sit upon it
see what world of difference there is
between rocks and the comfort
that plushy seats give.
So you led her to it
made her see it, feel it, sit upon it
But she baths it with keen distrust
and nothing would make her believe it
that the sofa shrouds no hidden motive
to later unfurl on her a painful fate
like all the rocks she’d sat on before.
She took the sofa home anyway
(since everyone needs a thing to sit upon)
but wrapped it in daily suspicion
and handled it the way she did
with all the rocks she’s had before.
She cracked her oil nuts on it
she milled her pepper on it
she spread her wet clothes on it
let goats scratch their backs on it
she sharpened her knives on it
she left the sofa out in the rain
just like all the rocks she’s had before.

domain: literature


text:
The French stock market is down in negative territory on Tuesday, with a sell-off in global stock markets amid mounting worries about geopolitical tensions and trade war concerns prompting investors to.. Credit: RTTNews - Published
European equity markets remained under some intense selling pressure on Tuesday and fell to their lowest level in nearly two years.
Rising geopolitical tensions, following the US President Donald.. Credit: FXstreet.com - Published
According to a U.S. official familiar with the matter, the United States is requesting that a World Trade Organization dispute resolution panel get involved in a clash the country is embroiled in. The..
The US-China trade war and rising global borrowing costs have brought headwinds more formidable than those during the two financial crises that hit Asia in the past two decades, according to the head.. Credit: S.China Morning Post - Published
· *Global markets fall once again after brief two-day relief rally.*
· *A "poisonous brewing cauldron of geopolitical and economic issues" is to blame for the risk-off sentiment gripping.. Credit: Business Insider - Published
A global fund originally set up in 2010 under the aegis of the UNFCCC to assist developing countries fight global warming got back on track with a $1 billion splurge, but the US vetoed a project that.. Credit: EurActiv - Published
Chinese imports of grains such as sorghum plunged in September from the year before, customs data showed on Tuesday, hit by escalating trade tensions with the United States and high prices elsewhere. Credit: Reuters India - Published
Analysts at Danske Bank point out that equity markets have traded lower again in Asia, ending the strong rally in Chinese stocks yesterday.
“The rebound on Monday was probably.. Credit: FXstreet.com - Published
The Tipping Point by Malcolm Gladwell asserts that, “Little Things Can Make a Big Difference.” This year small, innocuous events are building towards possible big changes for the Chinese.. Credit: Eurasia Review - Published
US President Donald Trump threatned Russia and China that Washington intends to build up its nuclear arsenal until “people come to their senses.”
The president said his words were directed.. Credit: Eurasia Review - Published

domain: finance


text:
Awasome Little Italy Art Walk Map 2022. This is an opportunity to broaden your palette by trying new things from new restaurants including desserts, dinner, appetizers, and cocktails. A walking tour app of little italy.
Search for events by keyword. Thousands of attendees come to view and purchase artwork, enjoy music and dance performances, and participate in interactive art experiences. 6/24/2022 june 2022 select date.
On October 2 & 3, 2021, Artwork Will Fill The Little Italy Neighborhood.
This is probably the most popular and touristic area of san francisco, and for a good reason, there are so many things to do and places to see. Clevelandartsevents.com by cuyahoga arts & culture (cac) connects you to cuyahoga county’s vibrant arts and culture scene. Little italy holiday art walk + small business fest.
A Walking Tour App Of Little Italy.
Little italy cleveland, cleveland, ohio. In the late 19th century, cleveland’s little italy neighborhood was established by the many italian. There are two routes to choose.
However, The Locomotive Age Made Poughkeepsie’s Little Italy, Sprouting In The Shadow Of A Train Trestle, Truly Distinct.
With chinatown closing in from the east and soho gobbling up its southern real estate, only the section of mulberry street between broom and canal remain visibly italian. Now in its 38th year, the mission fed artwalk. Grab your headphones and head out for an awesome day in new york city.
Come Visit Us At The Little Italy Art Walk!
Cac is one of the largest public funders of arts and culture in the nation and has invested more than $170 million in over. The two day april event also includes art on display from over 400 participating artists, live music, food vendors, a kids art section and upwards of 120,000 visitors! Day 3 of the little italy art walk!
Events Search And Views Navigation Search Enter Keyword.
Little italy art walk 2022 event information: Please be sure to pick up an art walk map when arriving in the neighborhood and watch for balloons indicating participating merchants! Touch device users, explore by touch or with swipe gestures.

domain: artistic


text:
|Will The Sox Win The AL East?||Connelly’s Top Ten: Brady Being Poked, Pink Hats Strike Again, Stand Up!||Connelly’s Top Ten: Sox Managers Worse Than Farrell, Loaded 1966 All-Star Team, Brady-Belichick’s ‘Feud’||NBA Preview: 2016-2017 Boston Celtics|
Bruins owner Jeremy Jacobs expects the NHL’s third annual Winter Classic, played outdoors on Jan. 1, to be held at Fenway Park. Jacobs believes an official announcement from the league could come in July.
Sports of Boston reported back in April that the Bruins’ likely opponent would be the arch-rival Montreal Canadiens.
It may seem impossible to imagie, but it appears a hockey rink will be on the field at Fenway Park this coming January. Will the Monster Seats be open? Will there be any field seats? This should definitley be interesting.


text:
To ask Her Majesty's Government what discussions they have had with universities in England about the support they can provide to improve the employment prospects of graduates.
8 June 2021
The government understands that the COVID-19 pandemic has had an adverse impact on students graduating this year, and we recognise that a number of graduates face particular challenges gaining employment due to the ongoing impact of the pandemic on the UK labour market and economy.
The government is doing all it can to help people who are at the start of their career journey. As part of the government’s Skills Recovery Package Plan for Jobs, we are investing an additional £32 million in the National Careers Service up to March 2022. This investment will support delivery of individual careers advice for over 500,000 people whose jobs or learning have been affected by the pandemic (by the end of the 2021/22 financial year). This represents an increase of 22%.
To provide additional support, we have developed the Graduate Employment and Skills Guide, which was published on 10 May on the Office for Students (OfS) website. The guide directs graduates to public, private, and voluntary sector opportunities to help them build employability skills, gain work experience, or enter the labour market, as well as providing links to further study options and resources on graduate mental health and wellbeing. The guide will also help graduates to recognise the valuable skills they have developed at university.
We have also engaged with Higher Education providers to produce a collection of Graduate Employability Case Studies. These case studies are published on the OfS website and demonstrate the breadth of innovative work and range of new measures university and college careers services have introduced to support final-year students and recent graduates as they move from university to graduate life.
Content on the National Careers Service website to support graduates includes information on graduate schemes and internships, sector-specific work experience, virtual work experience, virtual recruitment fairs, volunteering, developing soft skills, finding job vacancies, writing a CV and application form, telephone and video interviews, psychometric testing, using LinkedIn, gap years, and considering further study. On 29 September 2020, we added additional courses to the Skills Toolkit covering digital, numeracy, and employability skills. The new content includes a range of courses to develop ‘work readiness’ skills that employers value in their new recruits.
Where securing work is challenging, graduates may be able to access financial support. Graduates can apply for Universal Credit immediately after finishing a degree and can check their eligibility at https://www.gov.uk/universal-credit/eligibility.
We have worked with a range of institutions across the sector to understand what more we can do to support graduates who are looking to secure employment at this challenging time and ensure students continue to leave university with qualifications that have real value and reflect their hard work.


text:
Hey, everyone. I’m not usually one for robot reveals but I think this year I have something that I’d like to share with the community. When I saw Change Up released I was certainly underwhelmed, but at least was hoping to see some unique robot designs. Since the meta was quickly established as a hoodbot, I was disappointed. Seeing the same type of robot over and over for yet another season seemed boring to me, and I had a feeling that a tray lift could still be a viable competitive option. Since I knew this would be a year not like any other, I decided to push a non meta option and strive to make it as competitive of a design as possible. I designed this robot to match many of the features of a hood that a standard tray could not accomplish. I have really enjoyed working on something different, and having a final working solution that is completely my own. I also hope my efforts may serve to show that off meta ideas can still be made to be viable. Sometimes it’s fun to be creative and unique, as well as take on a different challenge, as opposed to simply feeling boxed into one standard model. I hope you enjoy my reveal, and maybe even take inspiration for the future! There’s nothing I enjoy more than seeing unique robot designs! Good luck in tipping point!
Thanks to @94999E_Yokai for editing!


text: This shop is fantastic for stone ground products. They carry everything from hush puppy mix and pancake mix to regular whole wheat flour. All of it ground at the store and grown in the area. They have plenty of parking and are easy to get to. The employees are really helpful. In addition to their grains you can also pick up specialty syrups and jellies. They have stations for tasting regularly. After you pick up your merchandise, take a quarter out back and get some fish food to feed the trout in the stream behind the mill. Beautiful waterfall near the mill.


text:
Gold prices moved in a narrow range on Wednesday, anchored by a retreat in the dollar as investors squared positions in the run-up to US consumer prices data later in the week.
Spot gold was little changed at $1,784.72 per ounce by 1351 GMT, having retreated slightly from the session's peak at $1792.90 before moving back into a tight range.
US gold futures rose 0.5% to $1,793.20 per ounce.
With markets more optimistic as worries over the Omicron coronavirus variant ease, gold has joined the bandwagon in part because of its inverted correlation with the dollar, Ricardo Evangelista, senior analyst at ActivTrades, said.
But gold's upside may be limited and it was not likely to move above the $1,810 level, especially with the narrative shifting back to central banks' tightening policy, which was likely to drive further US dollar gains, Evangelista added.
Although a move higher in benchmark US Treasury yields dimmed gold's appeal, this was offset by a retreat in the dollar index as a softer US dollar decreases bullion's cost for overseas buyers.
"Gold at the moment is not an arrow, it is a feather, and the feather is literally book squaring; it's people selling a bit here and buying a bit there and in thin markets you can get big moves," independent analyst Ross Norman said.
The market remained focused on Friday's US Consumer Price Index (CPI) report that may influence the timeline of the Fed's tapering of economic support before its next policy meeting on Dec. 14-15. Reduced stimulus and interest rate hikes tend to push government bond yields higher, raising the opportunity cost of holding gold, which bears no interest.
Spot silver shed 0.3% to $22.41 per ounce, platinum dropped 0.3%% to $948.48 per ounce and palladium dipped 0.9% to $1,835.90.

domain: economics


text:
Close this message
Van Nuys, California
Sign up below to request a quote.
I'm a novice author who self published her first book in what I hope will be a long series of books in the fantasy/horror genre. I am attempting to build a world in which many stories can emerge that are all interconnected.
Experienced copyeditor and proofreader specialising in children's and YA fiction and non-fiction.
Woking, United Kingdom
Non-fiction editor and writer with eight years of experience working for a range of publishers and authors.
London, United Kingdom


text:
Earth Day is April 22! We’ve gathered some of our favorite Earth Day activities, and additional resources to make celebrating the 50th anniversary of Earth Day fun!
Books, crafts, and exploring seeds to target a variety of speech goals:
Download and print an Earth Day Hat! Practice following multi- step directions to create an Earth Day hat.
Read Secrets of the Apple Tree and plant your own seeds! Using sequential concepts to describe how an apple tree grows, making predictions of what will happen next in the book and with the seeds when you plant them, and describing what a seed looks and feels like..
Earth Day Snack:
Have fun following multi-step directions with visuals to create a yummy Earth Day snack.
What you’ll need:
Rice cake, or other round snack asEarth
Green grapes (halved) as land
Spread cream cheese over your snack, then create the Earth by placing blueberries as water and grapes as land. Use a printed photo of Earth, or a globe, to talk about the Earth and what it looks like.
6oz Elmer’s Glitter Glue (can use regular glue and add glitter too!)
Contact Lens Solution (containing boric acid and sodium borate)
Flare! Whatever beads, glitter, gemstones or other additions you want to use you make your unicorn slime EXTRA unicorn-worthy
Grab your bowl to mix your slime together
Pour your entire 6 oz Elmer’s Glitter Glue into the bowl
Add 1/2 teaspoon of baking soda and mix in thoroughly (You can add 2 TBSP or up to 1/4 cup water if you want stretchier slime!)
Add your glitter and continue to mix
Slowly add in your contact lens solution (Reminder: contact lens solution should contain boric acid and sodium borate or your slime will not form). Add it in slowly and mix if possible so that you can adjust and ensure you do not add too much
Mix until your slime forms and begins to harden.
Now it’s time to knead! If it’s not the consistency you’re looking for, keep kneading. If it’s too sticky, add a little bit of lotion or baby oil to your hands.
You can choose to add beads, gemstones or other unciron-friendly additions!
Once you’re done adding all unicorn-worthy additions it’s time to play!
Pin the Horn on the Unicorn
Practice turn-taking and using lcoation words to describe where the horn was placed with PIN THE HORN ON THE UNICORN!
For this activity we used a poster board to draw our unicorn, and construction paper for the horns.
If you’re not feeling artistic and up for drawing a unicorn, don’t worry, you can print an image of a unicorn and cut horns from construction paper to match!
After a game of Pin the Horn on the Unicorn we kept the unicorn-themed fun going by reading our favorite unicorn books to practice using fun describing words like sparkly, shiny, bright, colorful and silly.
Want to receive more activities like this? Join our monthly mailing list! Subscribe here.
This post written for you by the staff of Columbus Speech & Hearing Center

domain: hobby


text:
NATO chief adopts Erdogan’s new name for Turkey amid Sweden-Finland stalemate |
Stoltenberg is on a mission to shepherd Sweden and Finland into NATO, but Erdogan stunned allies by raising a series of objections to their membership in the security bloc just as lawmakers in each country voted to join the trans-Atlantic alliance. Then, Turkish Foreign Minister Mevlut Cavusoglu asked the United Nations to replace the name “Turkey,” as the country has been known in English, with “Turkiye” in publications — and Stoltenberg hastened to comply.
“As you mentioned, Turkey has raised some concerns, including Turkiye’s fight against PKK, a group described as a terrorist organization by NATO allies, the EU, and also by Sweden,” Stoltenberg said Monday during a joint press conference with Swedish Prime Minister Magdalena Andersson. “So I remain in close contact with you, Magdalena, and your colleagues, as well as with Finland and our ally Turkiye about the way ahead.”
Stoltenberg lapsed occasionally into the usage of the customary “Turkey,” but NATO’s transcript of the press event did not record that outmoded pronunciation.
“They’re trying to sort of humor and please [Erdogan] because it comes at no cost to them, either NATO as an organization or the member states, humoring Erdogan in that way, because it has no cost attached to it,” Marine Corps University professor Sinan Ciddi told the Washington Examiner. “The only negative is if they go against him, right, because not calling it Turkiye doesn’t have any added benefits for them as far as diplomatic ties go.”
The adoption of the new name put a deferential bow on Stoltenberg’s latest attempt to manage a breakthrough in the NATO expansion process. The NATO chief, a former prime minister of Norway, used his trip to Sweden and Finland as an occasion to persuade Erdogan that his complaints about the Scandinavian countries, which the Turkish leader has accused of giving shelter to separatist Kurdish terrorists hostile to the Turkish central government, are being taken seriously.
“I am glad that you, prime minister, confirmed the Swedish government’s readiness to address Turkiye’s concerns as part of assuming the obligations of future NATO membership,” Stoltenberg said. “I welcome that Sweden has already started to change its counterterrorism legislation and that Sweden will ensure that their legal framework for arms exports will reflect their future status as a NATO member with new commitments to allies. These are two important steps to address concerns Turkiye has raised.”
Erdogan’s stated demands go beyond such modest changes, as he has referred to Swedish elected officials of Kurdish heritage as “terrorists” and demanded their ouster as a precondition for dropping his blockade of Sweden’s application.
“Even in their own parliaments, there are terrorists,” he said last week. “As long as these terrorists are in their parliaments and as long as…


text:
Lately, it seems like Internet companies are tripping over each other in a rush to do good deeds.
Amazon.com has decided to use an AIDS benefit CD to test out its new micropayment collection system.
Yahoo! has started hosting an auction of celebrity items to benefit the Easter Seals charity. The portal giant has also joined Microsoft in pledging millions of dollars to fights AIDS around the world.
Even the otherwise ruthless F**ckedcompany.com, the rumor repository for dot-com layoffs and failures, has collected US$13,000 from its visitors to help the families of victims of a shooting at a Massachusetts high-tech company.
Of course, businesses of all sorts and stripes have long embraced charity as a way of giving back to the community and, to be more cynical about it than is probably necessary, to insulate themselves against complaints that they are only interested in maximizing profits.
But for e-commerce players, the upside to these good deeds can be even bigger than for established, traditional firms. If done right, doing good may help the dot-com industry gain a much different image in the eyes of the public. Image becomes all the more important when companies are announcing sweeping layoffs.
So does e-commerce need a little image makeover? In short, yes.
If nothing else, it needs a distraction from the constant news of layoffs and bankruptcies and unpaid debts. But that — we hope — is only a temporary condition, one that will go away, one way or the other.
More than that, though, e-commerce also suffers from a detachment from its customers that few firms have found an effective way of overcoming. And many have tried.
There’s personalized e-mail missives ‘signed’ by the CEO of e-tailer X, or the customized home page, replete with your very own recommendations. E-tailers have even tried slipping little goodies into your order shipment. But all the free pens and note pads in the world won’t make me view a dot-com the same way I do my local retailer.
Warm and Fuzzy
So how does charity help? It takes the cold, hard edge off the e-tailer. It rounds out that company’s corporate image. And maybe most importantly of all, it makes us realize they live in the same world we do.
Because up until recently, that wasn’t too clear. E-tailers seemed to have appeared out of nowhere and suddenly were dominating the spotlight, from TV commercials to media events, all of which suggested they existed in a special world where the regular rules — especially economic ones — don’t apply.
That was good for a while. We wanted to believe that such a never-never land existed. But we now know it didn’t, doesnt and probably never will.
So the e-tailers have come down to earth. It’s clear now the world is not going to change to suit them. They need to do the adapting. That means meeting us mere mortal customers on our own turf.
Really Like Them?
Think about it: As great an e-tailer as it is, does anyone feel any particular affinity for Amazon? Appreciation of its reach and ease-of-use, maybe, but actual affection is hard to imagine.
But if suddenly I see Amazon donating or helping to donate thousands of dollars to a charity that I happen to believe in as well, that changes things quite a bit.
A little good deed may not change things overnight, but every little bit helps. E-tailers have spent lots of time and effort appealing to my eyes and my brain. A little proof that they have hearts too may make a difference next time I decide where to spend my money.
What do you think? Let’s talk about it.
Note: The opinions expressed by our columnists are their own and do not necessarily reflect the views of the E-Commerce Times or its management.


|Friday, November 04, 2005|
Troublemaker: When a cop gets shot.
11:51:25 AM permalink comment
Chewie went to see Desmond Tutu at Guilford. I urge you to read her report.
She opens with a quote from the Archbishop Emeritus: "It is a privilege to come to this city, the first in this country to have a Truth and Reconciliation Commission, embodying the theme of reconciling love. The world salutes Greensboro."
11:42:53 AM permalink comment
DarkTimes: Krugman ("Defending Imperial Nudity") retells The Emporer's New Clothes as a tale of WMD:
The talk-show host Bill O'Reilly yelled, "Shut up! Shut up! Shut up!" at the little boy. Calling the boy a nut, he threatened to go to the boy's house and "surprise" him.
Fox News repeatedly played up possible finds of imperial clothing, then buried reports discrediting these stories. Months after the naked procession, a poll found that many of those getting most of their news from Fox believed that the emperor had in fact been clothed.
Imperial officials eventually admitted that they couldn't find any evidence that the suit ever existed, or that there had even been an effort to produce a suit. They insisted, however, that they had found evidence of wardrobe-manufacturing-and-distribution-related program activities.
Kicker: "And they all lived happily ever after -- in the story. Here in reality, a large and growing number are being killed by roadside bombs."
Friedman ("From Gunpowder to the Next Big Bang") says China is moving toward a new phase in its economy: "China is focusing on how to transform its classrooms so students become more innovative." Cultural obstacles remain, but Microsoft is already finding talent there, and a flood of venture capital may follow.
11:36:06 AM permalink comment
Background links here.
11:26:18 AM permalink comment


text:
A prevailing scenario of the origin of life postulates thioesters as key intermediates in protometabolism, but there is no experimental support for the prebiotic CO2 fixation routes to thioesters. Here we demonstrate that, under a simulated geoelectrochemical condition in primordial ocean hydrothermal systems (–0.6 to –1.0 V versus the standard hydrogen electrode), nickel sulfide (NiS) gradually reduces to Ni0, while accumulating surface-bound carbon monoxide (CO) due to CO2 electroreduction. The resultant partially reduced NiS realizes thioester (S-methyl thioacetate) formation from CO and methanethiol even at room temperature and neutral pH with the yield up to 35% based on CO. This thioester formation is not inhibited, or even improved, by 50:50 coprecipitation of NiS with FeS or CoS (the maximum yields; 27 or 56%, respectively). Such a simple thioester synthesis likely occurred in Hadean deep-sea vent environments, setting a stage for the autotrophic origin of life.
Thioesters occupy the central position in cellular metabolism as exemplified by acetyl-CoA. This fact has suggested thioesters to be the crucial components of prebiotic precursor of metabolism since as early as 1960’s1,2,3. A key enzyme in thioester biosynthesis is carbon monoxide dehydrogenase/acetyl-CoA synthase (CODH/ACS), in which the Ni-based active centers reduce CO2 to CO, react CO with a methyl group to form acetyl, and acetylate CoA to form acetyl-CoA. This apparently simple process with pivotal Ni has evoked the idea that a prebiotic CO2 fixation on a (Fe,Ni)S mineral preceded the CODH/ACS-based reaction4,5.
However, experimental support of this scenario remains limited. The CO2-to-CO conversion is endergonic even with H2 as the reductant (Supplementary Fig. 1), so biological CO production uses either electron bifurcation or a chemiosmotic pH gradient across the cell membrane to overcome the energy shortage. In the ACS catalytic cycle, the active Ni site serves as both the electron donor and accepter through changing its oxidation states between +1 and +3, facilitating both the reduction and oxidation intermediate steps6. Such redox bifunctionality of Ni has never been observed in natural Ni-bearing minerals. Although Huber and Wächtershäuser demonstrated S-methyl thioacetate (MTA) synthesis from CO and methanethiol in the presence of NiS as a potential prebiotic precursor of the ACS reaction7, the yield was very low (0.2% based on the initial amount of CO) even under their optimum condition (pH 1.6 and 100 °C), which is not so common in nature. A recent work suggested a one-pot pyruvate synthesis from CO2 and H2 on magnetite (Fe3O4) and awaruite (Ni3Fe) as a protometabolic acetyl-CoA pathway8. The proposed reaction, however, provides no explanation for the origin and antiquity of thioester-dependent metabolism. Thioesters might have played central roles in protometabolism not only as carbon sources but also as energy currencies in a manner analogous to ATP1,2,9, serving as an entry point of phosphate into metabolism5,10.
How were CO2-to-CO reduction and CO conversion realized under primordially realistic conditions? A clue lies in an on-site observation by Yamamoto et al.11 of electricity generation in deep-sea hydrothermal vent chimneys and mineral deposits. The geoelectricity arises from the redox coupling between hydrothermal fluid chemicals and seawater-dissolved species via electrically conducting yet thermally insulating sulfide rocks (Supplementary Fig. 1)12,13. Considering cool (0–50 °C) and slightly acidic (pH 6–7) character of the ancient seawater14 together with pH and temperature dependences of the H+/H2 and CO2/CO redox potentials, H2-rich alkaline hydrothermal systems must have readily provided negative electric potentials favorable for the CO2-to-CO reduction at the chimney-ancient seawater interface. We previously demonstrated efficient CO2 electroreduction to CO on certain metal sulfide catalysts (for example, cadmium sulfide) under a simulated early ocean geoelectrochemical condition15. It was later found that FeS undergoes day-scale electroreduction to Fe0 16. The resultant FeS-Fe0 assemblage, named FeS_PERM (FeS partially electroreduced to metal), showed the exceptional capability of promoting various prebiotically important reactions owing to the synergy between surface Fe sites with different oxidation states (Fe2+ and Fe0)17,18.
In our previous works15,16, NiS exhibited neither CO evolution nor Ni0 formation detectable by X-ray diffraction (XRD) analysis. However, our further investigation presented below found non-crystalline growth of Ni0 under geochemically feasible potential conditions, with a substantial amount of CO bound on the resultant surface Ni0 sites. We will also report here that the partially reduced NiS, that is, NiS_PERM realizes efficient conversion of CO and methanethiol to MTA even at room temperature and neutral pH. Notice that the accumulation of surface-bound CO during CO2 electroreduction is generally recognized as poisoning of surface (electro)catalytic activity19,20, but our results suggest that the CO accumulation process on NiS_PERM was rather a crucial step for subsequent primordial thioester formation in early ocean hydrothermal systems. Thioesters are versatile compounds in organic chemical synthesis as well as in biosynthesis, enabling diverse coupling reactions, including C–C bond formation, esterification, and amide bond formation owing to the activated acyl unit21,22,23. To the best of our knowledge, our study provides the first experimental demonstration of thioester synthesis from CO and thiol under mild aqueous conditions. Thus, besides rendering a realistic support for autotrophic scenarios of the origin of life1,2,3,4,5, our demonstrated CO-thiol reaction on NiS_PERM could be a practical approach to CO utilization24. In the following and in Supplementary Information, we also present the results for FeS and CoS and their influences on the NiS’s capabilities for CO production and MTA synthesis.
Metal sulfide electroreduction
We prepared metal sulfides, including NiS by simply mixing an aqueous solution of the corresponding metal chloride and an aqueous solution of sodium sulfide. The obtained sulfides were exposed to a constant electric potential (–0.5 to –1.0 VSHE (volt versus the standard hydrogen electrode)) for 7 days in 100 mM NaCl at room temperature (25 ± 2 °C) (Supplementary Figs. 2 and 3). The solution pH was maintained at 6 ± 0.25 by continuous CO2 bubbling. The electrolyzed sulfides were then separated from the supernatant solution, dried under vacuum, and used for the subsequent experiments.
The NiS consists of aggregated nanoparticles with an average particle diameter of 15 ± 11 nm (Supplementary Fig. 6). Although no significant morphological change was discerned (Supplementary Fig. 6), exposure at –0.5 VSHE led to the desulfurization of NiS to heazlewoodite (Ni3S2) (Fig. 1a), consistent with thermodynamic calculation (Fig. 1b). Further reduction of Ni3S2 at lower electric potentials was indicated by energy-dispersive X-ray spectroscopy (EDS) mapping on the NiS particles electrolyzed at –1.0 VSHE (Fig. 1c), where a clear decrease in the sulfur signal intensity relative to nickel was observed in comparison with pure NiS, and with the NiS electrolyzed at –0.5 VSHE (Fig. 1d; all EDS data are scaled to have the same S signal intensities at 2.3 keV). In agreement with the EDS result, enhancement of the reducing potential from –0.5 to –1.0 VSHE led spectral changes in the nickel K-edge X-ray absorption near-edge structure (XANES) of NiS samples (Fig. 1e) attributable to the occurrence and growth of Ni0 in Ni3S2 up to the Ni0 percentage of 12% (Fig. 1f and Supplementary Fig. 11). Similarly, XANES analysis showed 18% conversion of CoS to Co0 at –1.0 VSHE (Supplementary Fig. 12). Thus, NiS_PERM and CoS_PERM are formed at –1.0 VSHE and at even less negative potentials (i.e., closer to 0 VSHE) near their sulfide/metal equilibria (Fig. 1b, f, Supplementary Figs. 11 and 12) just as in the FeS case. However, in contrast to FeS_PERM that exhibited broad but clear XRD signals for Fe0 even at –0.7 VSHE (Supplementary Fig. 8)16, NiS_PERM showed no XRD signal for Ni0 in the examined potential range (≤ –1.0 VSHE) (Fig. 1a). The Ni0 percentage up to 12% (Fig. 1f) should be well above the detection limit of XRD (Supplementary Fig. 10) if Ni0 formed a localized crystalline domain in the Ni3S2 structure. Thus, NiS_PERM would be with more finely dispersed zerovalent metal than FeS_PERM.
CO production and accumulation on the metal-sulfide PERMs
To explore the possibility of CO production and accumulation on the metal-sulfide PERMs formed under CO2 atmosphere, we dissolved the resultant metal-sulfide PERMs completely in 35% hydrogen chloride, and quantified the released CO by gas chromatography (Supplementary Fig. 18 and Supplementary Movie 1). Except for FeS, all the sulfides exposed to ≤ –0.6 VSHE were found to retain CO (Fig. 2a and Supplementary Table 2). The threshold potential is close to the sulfide/metal equilibrium potentials for Ni and Co (–0.57 VSHE for both; Fig. 1b and Supplementary Fig. 4), and is also near the thermodynamic CO2/CO redox potential at the condition for sulfide electrolysis (–0.50 VSHE; Supplementary Fig. 1). The amount of CO increased with decreasing the potential up to 180 ± 40 μmol g−1 for the case of NiS. Because sulfurized Ni binds CO considerably more weakly than pure Ni0,25 the observed CO should be mostly due to the CO bound on the surface Ni0 sites. In fact, the maximum adsorption (180 ± 40 μmol g−1) corresponds to the surface coverage of one CO molecule per 8 ± 3 surface Ni atoms (Supplementary Fig. 13), consistent with the percentage of Ni0 grown at –1.0 VSHE (Fig. 1f). The similar interpretation should be applicable to the adsorption behavior of CO on the CoS_PERM26. Coprecipitation with FeS led to decline of the amounts of CO on NiS and CoS (Fig. 2a) probably because the resultant surface Fe sites were not involved in the CO accumulation owing to the stable Ni0–CO and Co0–CO bindings, as indicated by no CO evolution during the NiS and CoS electrolysis15.
Nonenzymatic thioester synthesis
We mixed the metal-sulfide PERMs retaining the surface-bound CO (Fig. 2a) (50 mg for each) with an aqueous solution of sodium methanethiolate (75 μmol) in a serum bottle (13.8 ml), and agitated it at room temperature (25 ± 2 °C) for up to 7 days without externally imposing electric potential. pH was buffered at neutral (7.0 ± 0.5) by filling the gas space with CO2 (1 atm). Despite this very mild condition, gas chromatography–mass spectrometry analysis revealed efficient MTA formation in the presence of specific electrolyzed sulfides (Fig. 2b, c). Organosulfur compounds detected with the amount higher than 0.01 μmol were methanethiol, MTA, dimethyl sulfide, and dimethyl disulfide (Supplementary Figs. 19 and 20), among which MTA was the sole product built from CO and methanethiol:
Experiments with the NiS_PERM prepared at –1.0 VSHE exhibited the following product characteristics. The yield of MTA increased over one week, while the amounts of CO and methanethiol decreased from their maxima at the beginning (Supplementary Fig. 24). CO appeared in the gas-phase through competitive adsorption with methanethiol: in the absence of methanethiol under otherwise identical condition, only a small amount of CO gas was detected (0.03 μmol) and no MTA was observed (Supplementary Fig. 21a). As long as methanethiol was available, replacement of CO2 in the gas space with helium (He), and dissolution of 1 M phosphate (pH 7.0) into the sample solution had no significant influence on the yield of MTA (3.2 ± 0.6 μmol; Fig. 2b → 3.6 ± 0.7 μmol). It was also confirmed with 13C-labeled CO2 that the CO2 filled in the serum bottle did not serve as a component of MTA. The MTA formed under 13CO2 atmosphere showed the mass spectrum identical to that of the standard MTA with normal carbon isotopic composition.
In aqueous solutions, acetate (0.19 ± 0.04 μmol = 0.25 ± 0.05 mM in 0.75 ml H2O) and formate (0.03 ± 0.01 μmol = 0.035 ± 0.01 mM in 0.75 ml H2O) were observed (Supplementary Fig. 25). The acetate concentration increased to 2.0 ± 0.4 mM when the product solution was basified by 1 M sodium hydroxide due to MTA hydrolysis. Because MTA hydrolysis is accelerated at elevated temperatures27, a one-day experiment at 80 °C resulted in a higher yield of acetate (2.4 ± 0.5 μmol = 3.2 ± 0.6 mM in 0.75 ml H2O) and a lower yield of MTA (0.68 ± 0.14 μmol) (Supplementary Fig. 25). Other biologically relevant organic acids, such as pyruvate and lactate, were not detected in any product solutions with concentrations higher than 0.01 mM. We also treated solid samples with 8 M potassium hydroxide after the reaction, but neither pyruvate nor lactate was observed.
When CO and methanethiol were initially introduced with equal amounts (75 μmol, or 0.14 bar in the gas space) in the presence of NiS_PERM formed at –1.0 VSHE, the yield of MTA more than doubled, compared with the case with methanethiol alone in the initial gas-phase (3.2 ± 0.6 → 7.4 ± 1.5 μmol; Fig. 2d and Supplementary Fig. 21a). In contrast, under the same initial condition with CO, few or no detectable MTA was formed in the presence of pure NiS, the Ni3S2 prepared at –0.5 VSHE, or pure Ni0 (Supplementary Fig. 21 and Supplementary Table 4), indicating the necessity of the coexistence of zerovalent and non-zerovalent Ni surface sites for efficient MTA production. It is also notable that the MTA yield decreased steeply as the NiS electroreduction potential was changed from –1.0 to –0.8 VSHE (Fig. 2b, d) although –0.8 VSHE is still sufficient for the Ni0 generation (Fig. 1f). In light of reported chemical functions of Ni and other metals in organometallic analogues of ACS28,29, one possible interpretation is that the MTA synthesis involves at least two adjacent surface Ni0 sites (Fig. 2e): one Ni0 serves as an electron donor for the reductive cleavage of methanethiol C–S bond. Close location of another Ni0 (the closest Ni–Ni distance = 2.48 Å; Supplementary Fig. 13) allows transfer of the generated electrophilic methyl onto the nucleophilic carbon of adsorbed CO. After the formation of C–C bond to make the acetyl-Ni0, its oxidative thiolysis to form MTA occurs through coupling with the reduction of neighboring non-zelovalent Ni atoms. The cleavage of methanethiol C–S bond also accounts for the formations of CH4 and dimethyl sulfide (Supplementary Tables 3 and 4), where the resultant methyl converts to CH4 via protonation, while thiolysis of the methyl generates dimethyl sulfide. If a random Ni0 distribution is assumed, a 12% conversion of Ni2+ to Ni0 achieved at –1.0 VSHE (Fig. 1f) results in 1.4% occurrence of the adjacent Ni0–Ni0 surface pair, while this percentage drops to 0.16% with a 4% conversion achieved at –0.8 VSHE. Thus, our proposed process taking multiple Ni sites into account (Fig. 2e) explains the large potential dependence in MTA productivity of NiS_PERM (Fig. 2b, d) as well as the few or no MTA formation on Ni3S2 and pure Ni0. This nonenzymatic process is expected to be eventually deactivated due to cumulative surface sulfurization (Fig. 2e), but the surface activity may be restored by additional solid electrolysis.
Interestingly, even greater CO-to-MTA conversion ratios were obtained with the NiS coprecipitating with FeS or CoS (Fig. 2c). Up to 56 ± 10% of the surface-bound CO, produced by CO2 electroreduction, was converted to MTA on the electrolyzed (Co,Ni)S. Although the electrolyzed (Fe,Ni)S produced MTA with low yields (Fig. 2b) due to the low surface accumulation of CO during the electroreduction, the percentages of CO to form MTA were kept at high levels (~20%) even at ≥ –0.8 VSHE (Fig. 2c). In fact, (Fe,Ni)S produced a considerable amount of MTA (1.44 ± 0.29 μmol) from externally introduced CO even when –0.6 VSHE was applied to the electrolysis (Fig. 2d). Since the electrochemical reducibility of FeS is higher than that of NiS (Supplementary Figs. 7 and 8), it may well be the case that Fe in the electrolyzed (Fe,Ni)S assists the performance of Ni as an electron donor at an intermediate reduction step just as the supportive role of Fe in ferredoxin serving as the redox mediator in the ACS-reaction6. Co is also involved in the enzymatic process as a transporter of the methyl group6.
Our experiments revealed that partial electroreduction product of NiS, that is, NiS_PERM, promotes thioester synthesis from CO and methanethiol. NiS_PERM accumulates surface-bound CO during the formation under CO2 atmosphere, so NiS offers a two-step CO2 fixation route to thioester with the aid of electric energy. The electric potential required for these reactions (≤ –0.6 VSHE; Figs. 1 and 2) is more reducing than that observed in a present-day black smoker system (≥ –0.022 VSHE)11. However, the value of –0.6 VSHE and even lower potentials are available in H2-rich alkaline hydrothermal fields (Supplementary Fig. 1)30,31. Deep-sea systems are more advantageous than terrestrial ones because the elevated pressure increases the solubility of H2, which indeed serves as an electron source for the reduction of seawater CO2 in the presence of (Fe,Ni)S precipitates32. On the primordial ocean floor, widespread occurrence of elevated hydrothermal H2 fluxes has been suggested from the presence of awaruite in many fossilized serpentinization systems33,34.
In the Archean to Hadean eons, submarine hydrothermal environments may also have favored NiS precipitation owing to the huge supply of mantle-derived Ni into the ocean. The resultant massive Ni sulfide deposits are seen today in association with Archean komatiite with the Ni/Fe weight ratios occasionally exceeding one35. Given the estimated Ni2+ and Fe2+ concentrations in the early Archean seawater with their sulfide solubilities, selective NiS precipitation relative to FeS is expected in micro- to semimicro-molal level presence of hydrogen sulfide (H2S and HS–) (Supplementary Fig. 26), which is a likely concentration range at the outer surface of ancient alkaline hydrothermal chimneys36.
Within deep-sea vent chimneys, dynamic mixing of hydrothermal fluids with seawater through the pore systems is envisioned (Fig. 3)37. Occasional increase of hydrogen sulfide concentration would remove the surface-bound CO (see “Methods”, Supplementary Figs. 27 and 28). On the other hand, such H2S-rich condition is advantageous to thiol synthesis from CO or CO2.38,39 Once H2S recedes, methanethiol may react with restored CO to form MTA on Ni sulfide_PERMs (Fig. 2b–d). Thus, fluid-mediated material transport should have favored the occurrence and combination of multiple reactions through interlinked mineral pores (Fig. 3). It is conceivable, for example, that the CO formed on NiS_PERM and CoS_PERM is trapped on (Fe,Ni)S_PERM with thiols, thereby realizing the thioester formation with mild electric potentials (Fig. 2d). Thus, the thioester synthesis via the formation of Ni sulfide_PERMs should have been possible in primordial ocean alkaline hydrothermal systems. Just as Huber and Wächtershäuser7, however, we have not yet discussed seriously the source of methanethiol. To make a realistic estimate for the activity and robustness of abiotic thioester synthesis, further investigation for the geochemical availabilities of thiols and the other necessary reaction parameters (the electric potential and the Ni-sulfide composition) is desirable.
Nowadays, growing consensus for CO2 as the dominant carbon species on the Hadean Earth has stimulated exploration of geo- and astro-chemical events that could have transiently realized highly reducing early atmosphere40. Subsequent photochemical and aqueous-phase processes with reactive carbon sources, powerful oxidizing/reducing agents, and/or UV light might have realized abiotic thioester synthesis41,42. Although these reactions might have played a role in enriching prebiotic soup, their relevance to biosynthesis is ambiguous. Consequently, numerous questions remain unanswered by the transient scenario as to the gap between prebiotic chemistry and early biochemistry conserved in the metabolic and phylogenetic architectures of life.
The two key facts: CO2 fixation utilizing various states of Ni due to our experiments (Fig. 2) and the well-known central role of Ni at the active sites of CODH/ACS6 may lead to a plausible scenario for the emergence of protometabolism prior to the origin of life. Sustained occurrence of electrochemical energy adequate for the Ni sulfide_PERM formation, ≤ –0.6 VSHE in the ancient seawater condition (Figs. 1 and 2), is limited in nature except for deep-sea hydrothermal settings (Supplementary Fig. 1). This environmental specificity with the known necessity of Ni in both biological and chemical CO2 fixation suggest that the Ni sulfide_PERM-promoted thioester synthesis in early ocean hydrothermal systems (Fig. 3) is a primordial precursor of the CODH/ACS reaction. The CO production on metal-sulfide_PERMs (Fig. 2a) may also have served as crucial carbon and energy sources for the early chemolithotrophic ecosystem, thereby supporting, or even directing, the origin and early evolution of autotrophs as suggested from the autotrophic metabolism core43.
Preparation of metal sulfides
All metal sulfides were prepared by adding 100 mM sodium sulfide (Na2S) dropwisely into the corresponding 100 mM metal chlorides (NiCl2, FeCl2, or CoCl2) or their binary mixtures (for example, 50 mM NiCl2 plus 50 mM FeCl2) under vigorous stirring to a final volume ratio of 1:1. Solid precipitates were then separated from the supernatant solutions by centrifugation (8000 rpm, 10 min) and were dried under vacuum. To prevent oxidation by atmospheric O2, the sample preparation was conducted in a glove box filled with N2 gas (>99.99995% purity), with 4% H2 (>99.99999% purity) being added (the Coy system). All chemicals were purchased from FUJIFILM Wako Pure Chemical Corporation as reagent grade. Deaerated Milli-Q water (18.2 megohms) was used as the solvent.
Pure metals (Fe0, Co0, and Ni0) were obtained from EM Japan. Their reported characteristics and XRD patterns measured in this study are presented in Supplementary Table 1 and Supplementary Fig. 9, respectively.
Metal sulfide electrolysis was conducted under a simulated early ocean condition in accordance with the procedure reported previously16. Briefly, 400 mg of sulfide samples was deposited on a carbon working electrode (5.7 cm2) in a H-type cell (Supplementary Fig. 2), immersed in a deaerated 100 mM NaCl, and exposed to a flow (20 ml min−1) of CO2 (>99.995% purity) containing 4 ppm of H2S. The CO2 gas buffered the solution pH at slightly acidic (6.0 ± 0.25). The H2S partial pressure was determined by thermodynamic calculation to supply H2S and HS– into solution with the equilibrium total concentration of 0.5 μmol kg−1. Although the ionic strength and pressure conditions adopted in this experiment are different from the ancient deep-sea hydrothermal settings36,44, a thermodynamic calculation indicates that these differences have no significant influence on the redox potentials for the sulfide/metal and the CO2/CO systems (Supplementary Fig. 5)16.
While keeping the CO2 gas flow that was started at least 1 h before each experiment, a constant potential was applied on the carbon electrode for 7 days by using a multi-potentiostat (PS-08; Toho Technical Research). All potentials were measured against an Ag/AgCl reference electrode in saturated KCl and were converted to the SHE scale by the following equation:
After the electrolysis, the electrochemical cell was immediately transferred into a glove box filled with N2 and H2 gases (volume ratio, 96:4). The solid sample was then separated from the supernatant solution, dried under vacuum for 1 h, and stored inside the glove box. A dry vacuum pump (RDA-281H, ULVAC) with the reported ultimate pressure of 0.08 Pa was used for the dehydration. The surface-bound CO was expected to be intact at this vacuum condition25,45,46.
The prepared sulfide_PERMs were stable in the anaerobic glove box over weeks, but were oxidized rapidly in the air. Typically, a minute exposure to the air completely degraded their capabilities for promoting MTA synthesis. Their high susceptibilities to oxidation are not a severe problem in the geoelectrochemical scenario (Supplementary Fig. 1) because of the absence of O2 and other reactive oxidants (for example, H2O2) in primordial deep-sea environments.
Scanning electron microscopy (SEM) imaging was performed on a Helios G4 UX (Thermo Fisher Scientific) equipped with a PP-3010 cryo preparation system (Quorum) and an Octane Super C5 EDS detector (AMTEC). An acceleration voltage of 2 kV was applied for secondary electron imaging and 20 kV for EDS analysis under a reduced pressure of <1 × 10−4 Pa at room temperature (23 ± 2 °C). Samples were prepared as follows. First, sulfide sample sealed in a serum bottle was placed in a vacuum chamber of the cryo-preparation system, whose internal atmosphere was replaced with N2 gas from liquid N2 vaporization by three times of evacuation-purge cycles. Under flow of N2 gas, the serum bottle was opened, and the sulfide was rubbed onto a carbon tape (Nisshin EM) attached on a transfer shuttle by a plastic spatula. The shuttle was transferred into a transfer device under ~102 Pa, and then to the SEM chamber via a cryo-preparation chamber (<10−4 Pa).
Particle size distribution (Supplementary Fig. 6) was determined by manual segmentation on Affinity Photo for iPad 126.96.36.199 (Serif (Europe) Ltd.) followed by image analysis with Image-Pro 3D v9.3 (Media Cybernetics). Particle diameters were calculated from the segmented areas assuming spherical morphology.
X-ray diffraction (XRD) patterns of sulfide samples were measured by using an X-ray diffractometer with Cu Kα radiation (MiniFlex 600, Rigaku). All runs were conducted with 2θ ranging from 10° to 90° using 0.02° 2θ step with a scan rate of 0.1 or 1° min−1. To prevent oxidation by atmospheric O2 during the measurement, the solid samples were shielded in an air-sensitive sample holder (Rigaku). Peak identifications were made on the basis of the reference patterns reported in the Powder Diffraction File published by the International Centre for Diffraction Data. The reference patterns are presented in Fig. 1a and Supplementary Figs. 8–11 with the measured XRD data.
X-ray absorption near-edge structure (XANES) spectra at Ni and Co K-edges were measured at BL-12C (bending magnet beamline) in a synchrotron radiation facility (Photon Factory) in High Energy Accelerator Research Organization (KEK), Tsukuba, Japan. In the beamline, X-ray from a synchrotron operated at 2.5 GeV (current: 450 mA) was monochromatized with a Si(111) double-crystal monochromator, and focused to an area of 0.5 × 0.5 mm2 with a bent cylindrical mirror, which also reduced the higher order. XANES spectra were obtained in transmission mode using two ion chambers to measure intensities of incident (I0) and transmitted (I) X-rays. Energy step within the XANES region was 0.25 eV, and the absorbance by the sample (μt) was obtained as μt = ln(I/I0). Sulfide samples were diluted with boron nitride (BN, < 150 nm, 99% purity) to yield the metal/BN molar ratio of 1:25, and shielded by an O2-impermeable polyethylene film. Measurement was conducted for a part of the sample with uniform thickness within the area of the X-ray beam.
The percentages of zerovalent metal in the electrolyzed NiS and CoS were estimated by a least-squares fitting of the sample spectra after background-subtraction and normalization with an X-ray absorption spectroscopy data processing software ATHENA47. For the NiS samples, the linear combination of pure Ni0 and the NiS electrolyzed at –0.5 VSHE were used for the fitting between 8300 and 8440 eV. The NiS electrolyzed at –0.5 VSHE was used as a reference of Ni3S2 based on the thermodynamic calculation (Fig. 1b), XRD pattern (Fig. 1e), and the XANES spectral profile (Supplementary Fig. 11a) identical to that of pure Ni3S2.48 The energy region higher than 8440 eV was not analyzed because of lower signal-to-noise ratio and of greater influence from the local environment of Ni atom. The best fit was determined by calculating the lowest R factor, which was defined as:
In this equation, μexp and μcal are the experimental and the calculated absorbances at a given energy E, respectively. For the CoS samples, the energy range 7690–7830 eV were fitted with the linear combination of pure Co0 and the CoS electrolyzed at –0.5 VSHE in a manner similar as Ni described above.
Search for the surface-bound CO on electrolyzed sulfides
Each sulfide sample (50 mg for each) was sealed in a serum bottle (124.7 ml) with a Teflon-laminated butyl rubber cap and an aluminum stopper in a glove box filled with N2 and H2 gases (volume ratio, 96:4). The bottle was then filled with pure He gas (>99.99995%) by flowing the He through a stainless needle at a rate of 100 ml min−1 over 10 min. This was followed by the addition of 5 ml of 35% HCl (super special grade; FUJIFILM) under vigorous agitation. After the sulfide sample dissolved completely under 60 rpm rotation of the bottle at room temperature (25 ± 2 °C) (typically, within 30 min), the headspace gas was analyzed by gas chromatography (GC) (Fig. 2a, Supplementary Fig. 18 and Supplementary Table 2). To ensure reproducibility, we carried out multiple independent runs, using several sulfide samples for each metal. Differences among the data obtained at the identical condition were less than 20%. The same was true for the following two experiments “Nonenzymatic thioester synthesis” and “Competitive adsorption of CO with H2S”.
To verify the CO production and accumulation on the NiS_PERM, we conducted the following experiment with isotopically labeled sodium bicarbonate (NaH13CO3, 99% purity) provided by Cambridge Isotope Laboratories, Inc. First, 400 mg of NiS was electrolyzed at –1.0 VSHE for 7 days in 60 ml of 0.5 M phosphate buffer solution (pH 6.0) under pure N2 gas flow (>99.9998%). Then, the gas headspace of the electrochemical cell (~40 ml) was purged with 13CO2 gas that was provided by a dropwise addition of 0.1 M phosphoric acid (H3PO4) onto NaH13CO3 powder under vigorous stirring in a closed vial connected with the electrochemical cell with a polyvinyl chloride tube and stainless needles. After additional two-hour electrolysis with the gas inlet and outlet closed, the NiS_PERM on the carbon paper was collected, dried under vacuum, and dissolved completely in 35% HCl. GC-MS analysis of the released gas revealed the formation of 13CO with the m/z = 29 (Supplementary Fig. 18c). No 13CO was detected in the 13CO2 formed by the H3PO4 addition to NaH13CO3 (Supplementary Fig. 18).
In the normal CO2 gas bubbled during the sulfide electrolysis, we detected no CO with our GC’s maximum performance (detection limit; ~1 ppm). Even if a very slight amount of CO impurity is present in the CO2, its contribution to the surface-bound CO (Fig. 2a and Supplementary Table 2) must be negligible because the electrolyzed FeS released almost no CO despite the fact that Fe0 has an even stronger CO binding energy than Ni0 and Co0.49
Supplementary Movie 1 presents a demonstration of the surface-bound CO on the NiS electrolyzed at –1.0 VSHE. A weak acid (1 M H3PO4) was used here to make sure that the gas bubble formation is not due to NiS dissolution but from the purging of the electrolyzed surface.
Nonenzymatic thioester synthesis
Each sulfide sample (50 mg for each) was sealed in a serum bottle (13.8 ml) with a Teflon-laminated butyl rubber cap and an aluminum stopper in a glove box filled with N2 and H2 gases (volume ratio, 96:4). The bottle was then filled with pure CO2 gas (>99.995%) by flowing the CO2 through a stainless needle at a rate of 100 ml min−1 over 5 min. This was followed by the addition of 0.75 ml of 100 mM sodium methanethiolate (CH3SNa) with or without 1.86 ml of CO gas (1 atm, 99.9% purity). After rotating the bottle at 60 rpm for 7 days at room temperature (25 ± 2 °C), the headspace gas was analyzed by GC (Fig. 2b–d, Supplementary Figs. 19–23 and Supplementary Tables 3 and 4). The aqueous suspension was then centrifuged (10,000 rpm, 2 min) and measured for pH by a portable pH meter (Seven2Go Pro, Mettler Toledo).
We did not carry out “one-pot” organic synthesis in an electrochemical cell because H2 evolution during sulfide electrolysis15 prevented us from keeping methanethiol in the cell in the reaction period due to pressurization. As discussed in the main text, however, occurrence and combination of multiple reactions are likely to be more realistic than a single-pot reaction in natural hydrothermal vent environments.
Competitive adsorption of CO with H2S
Sulfide sample (50 mg for each) was sealed in a serum bottle (19.5 ml) with a Teflon-laminated butyl rubber cap and an aluminum stopper in a globe box filled with N2 and H2 gases (volume ratio, 96:4). The bottle was then filled with pure He gas (>99.99995%) by flowing the He through a stainless needle at a rate of 100 ml min−1 over 5 min. This was followed by the addition of 1 ml of 300 mM Na2S and the subsequent addition of 1 ml of 450 mM HCl. After rotating the bottle at 60 rpm for 1 day at room temperature (25 ± 2 °C), the headspace gas was analyzed by GC (Supplementary Figs. 26 and 27 and Supplementary Table 5). No carbon-sulfur compounds (for example, methanethiol, carbon disulfide, carbonyl sulfide) were detected.
From the pH values of aqueous suspensions (7.5–8.0; Supplementary Table 5), the initial dissolved H2S and HS– concentrations are predicted to be 90–120 mM in total, equilibrium H2S distribution being assumed in the gas and liquid phases without the surface adsorption.
Inorganic gases, including H2, CO, and CH4, were quantified by a Shimadzu GC system equipped with a BID-2010 Plus detector (Tracera). A MICROPACKED-ST column (Shinwa) was attached. He (>99.99995%) was used as the carrier gas at a column flow rate of 7 ml min−1. The column temperature was initially kept at 35 °C for 2.5 min, raised to 250 °C at a rate of 20 °C min−1, and then raised to 265 °C at a rate of 4 °C min−1. A chromatogram for a standard gas sample is shown in Supplementary Fig. 14 with obtained calibration curves.
Gas-phase sulfur compounds were analyzed by using a Shimadzu gas chromatograph-mass spectrometer (GCMS-QP2010 Ultra) equipped with a DB–SULFUR SCD column (60 m, 0.32 mm I.D, Agilent). He (>99.99995%) was used as the carrier gas at a column flow rate of 33.2 cm s−1. The column temperature was initially kept at 35 °C for 5 min, raised to 155 °C at a rate of 10 °C min−1, and then raised to 235 °C at a rate of 20 °C min−1. The scan range was set to m/z 5–200 Da. Compounds were identified by comparing the observed retention times and mass spectra with those of respective standards prepared from commercial reagents, and were quantified based on calibration curves (Supplementary Fig. 15). Several gas samples were also analyzed by the Tracera GC system with a DB–SULFUR SCD column at the measurement condition described in this paragraph (Supplementary Fig. 16).
Aqueous-phase products were characterized, after filtration with a polytetrafluoroethylene membrane filter (pore size, 0.2 μm), by using a Shimadzu HPLC system equipped with an electric conductivity detector and an anion exchange column (Shim-pack SCR-102H, Shimadzu) set at 40 °C. The p-toluenesulfonic acid aqueous solution (5 mM) was used as the eluent at a rate of 1.6 ml min−1. A chromatogram for several organic acids is shown in Supplementary Fig. 17 with the obtained calibration curves.
Note that basified aqueous samples stored in non-airtight containers over several days occasionally showed 1–10 μM of acetate and pyruvate signals (data not shown) because basification facilitates absorption of organic acids from ambient air. To avoid crucial contaminations such as pyruvate, we set our detection cutoff at 0.01 mM and analyzed all aqueous samples as soon as they were prepared.
Quantification of organosulfur products
The four organosulfur compounds observed in the present study (methanethiol, MTA, dimethyl sulfide, and dimethyl disulfide) distribute both the gas- and aqueous-phases with significant fractions. Thus, aqueous-phase concentrations of methanethiol, dimethyl sulfide, and dimethyl disulfide were calculated from the partial pressures of respective compounds quantified by GC with the Henry’s law constants reported in the literature (0.38, 0.56, and 0.58 mol l−1 atm−1, respectively)50. The constant for MTA was determined experimentally to be 5.8 ± 1.0 mol l−1 atm−1 from three independent measurements of the water-gas partitioning of MTA in a closed glass vial containing a certain volume of 100 mM phosphate buffer solution (pH 6.7). The constants for methanethiol, dimethyl sulfide, and dimethyl disulfide determined by this method were in agreement with the literature values with the percentage errors less than 15%.
The organosulfur compounds may also be present on the sulfide surfaces. Actually, when 1 M phosphoric acid (H3PO4) was added after the 7-day interaction of methanethiol with the NiS_PERM formed at –1.0 VSHE, the gas-phase concentrations of MTA and methanethiol increased by 30 and 70%, respectively, while that of dimethyl sulfide decreased by 50%. Nevertheless, because such chemical processes may cause undesirable reactions that consume MTA, we did not take account of the surface adsorption in the yield determination of organosulfur compounds. For the same reason, in the nonenzymatic thioester synthesis experiment, we report the amounts of inorganic gases (H2, CO, and CH4) quantified from the gas-phase analysis alone (Supplementary Figs. 19b, 22, and 23, Supplementary Tables 3 and 4).
Dimethyl disulfide was always observed in the presence of methanethiol with the amount typically less than a few percent of the initial amount of methanethiol (Supplementary Figs. 19a and 20). A probable cause of the dimethyl disulfide formation is methanethiol oxidation by atmospheric O2 (2 CH3SH + 0.5 O2 → CH3SSCH3 + H2O) at the timing of sample injections into the GC system owing to air intrusion (Supplementary Fig. 19b). Except for dimethyl disulfide, no oxidative organosulfur compound was detected (Supplementary Fig. 20). It was also confirmed that MTA, dimethyl sulfide, and dimethyl disulfide were stable in air.
Redox potentials (Eh) of the H+/H2 and the CO2/CO couples as functions of temperature and pH (Supplementary Fig. 1) were calculated with the following equations:
In these equations, T, R, and F stand for temperature in kelvins, the gas constant (8.3145 J mol‒1 K‒1), and the Faraday constant (96,485 J mol‒1 V‒1), respectively. αi represents the activity of the species i that was calculated either using the extended Debye-Hückel equation51 for aqueous ionic species (H+) or setting the activity coefficient to unity for aqueous neutral species (H2, CO2, and CO). ∆fG°(i) signifies the standard Gibbs energy of formation of the species i at the temperature and pressure of interest, which were calculated according to the revised HKF equations of state52 using the relevant thermodynamic data and the revised HKF parameters reported in the literature53,54. ∆fG° of H2O was taken from Helgeson and Kirkham55.
The Eh–pH diagrams of the sulfide–metal systems (Fig. 1b and Supplementary Fig. 4) were computed with the Act2 program in Geochemist’s Workbench version 10.0.5 by using the thermodynamic dataset for aqueous species calculated by the above procedures, those for sulfide minerals listed in Supplementary Table 3 presented by Kitadai et al.16, and those for pure metals compiled in Robie and Hemingway56.
All data needed to evaluate the conclusions of this study are presented in this article, the Supplementary Information and/or the Supplementary Movie. Additional data related to this study are available from the corresponding author on reasonable request.
de Duve, C. Blueprint For a Cell: The Nature and Origin of Life (Neil Patterson Publishers, 1991).
Hartman, H. Speculations on the origin and evolution of metabolism. J. Mol. Evol. 4, 359–370 (1975).
Wächtershäuser, G. Groundworks for an evolutionary biochemistry: The iron–sulphur world. Prog. Biophys. Molec. Biol. 58, 85–201 (1992).
Russell, M. J. & Martin, W. The rocky roots of the acetyl-CoA pathway. Trends Biochem. Sci. 29, 358–363 (2004).
Sousa, F. L. et al. Early bioenegetic evolution. Philos. Trans. R. Soc. B 368, 20130088 (2013).
Can, M., Giles, L. J., Ragsdale, S. W. & Sarangi, R. X-ray absorption spectroscopy reveals an organometallic Ni–C bond in the CO-treated form of acetyl-CoA synthase. Biochem. 56, 1248–1260 (2017).
Huber, C. & Wächtershäuser, G. Activated acetic acid by carbon fixation on (Fe,Ni)S under primordial conditions. Science 276, 245–247 (1997).
Preiner, M. et al. A hydrogen-dependent geochemical analogue of primordial carbon and energy metabolism. Nat. Eco. Evol. 4, 534–542 (2020).
Goldford, J. E., Hartman, H., Smith, T. F. & Segre, D. Remnants of an ancient metabolism without phosphate. Cell 168, 1126–1134 (2017).
Whicher, A., Camprubi, E., Pinna, S., Herschy, B. & Lane, N. Acetyl phosphate as a primordial energy currency at the origin of life. Orig. Life Evol. Biosph. 48, 159–179 (2018).
Yamamoto, M. et al. Spontaneous and widespread electricity generation in natural deep-sea hydrothermal fields. Angew. Chem. Int. Ed. 56, 5725–5728 (2017).
Nakamura, R. et al. Electrochemical current generation across a black smoker chimney. Angew. Chem. Int. Ed. 49, 7692–7694 (2010).
Ang, R. et al. Thermoelectricity generation and electron–magnon scattering in a natural chalcopyrite mineral from a deep-sea hydrothermal vent. Angew. Chem. Int. Ed. 54, 12909–12913 (2015).
Krissansen-Totton, J., Arney, G. N. & Catling, D. C. Constraining the climate and ocean pH of the early Earth with a geological carbon cycle model. Proc. Natl Acad. Sci. USA 115, 4105–4110 (2018).
Kitadai, N. et al. Geoelectrochemical CO production: Implications of the autotrophic origin of life. Sci. Adv. 4, eeao7265 (2018).
Kitadai, N. et al. Metals likely promoted protometabolism in early ocean alkaline hydrothermal systems. Sci. Adv. 5, eeav7848 (2019).
Zhu, W. et al. Nickel sulfide microsphere film on Ni foam as an efficient bifunctional electrocatalyst for overall water splitting. Chem. Commun. 52, 1486–1489 (2016).
Xiao, H., Goddard, W. A. III, Cheng, T. & Liu, Y. Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2. Proc. Natl Acad. Sci. USA 114, 6685–6688 (2017).
Hori, Y. & Murata, A. Electrochemical evidence of intermediate formation of adsorbed CO in cathodic reduction of CO2 at a nickel electrode. Electrochim. Acta 35, 1777–1780 (1990).
Hansen, H. A., Varley, J. B., Peterson, A. A. & Nørskov, J. K. Understanding trends in the electrocatalytic activity of metals and enzymes for CO2 reduction to CO. J. Phys. Chem. Lett. 4, 388–392 (2013).
Kondo, T. & Mitsudo, T. Metal-catalyzed carbon–sulfur bond formation. Chem. Rev. 100, 3205–3220 (2000).
Hirschbeck, V., Gehrtz, P. H. & Fleisher, I. Metal-catalyzed synthesis and use of thioesters: recent developments. Chem. Eur. J. 24, 7092–7107 (2018).
Pietrocola, F., Galluzzi, L., Pedro, J. M. B., Madeo, F. & Kroemer, G. Acetyl coenzyme A: a central metabolite and second messenger. Cell Metab. 21, 805–821 (2015).
Satanowski, A. & Bar-Even, A. A one-carbon path for fixing CO2. EMBO Rep. 21, e50273 (2020).
Erley, W. & Wagner, H. Sulfur poisoning of carbon monoxide adsorption on Ni(111). J. Catal. 53, 287–294 (1978).
Ma, S. H., Jiao, Z. Y., Wang, T. X. & Zu, X. T. Effect of preadsorbed S on the adsorption of CO on Co(0001). J. Phys. Chem. 113, 16210–16215 (2009).
Chandru, K., Gilbert, A., Butch, C., Aono, M. & Cleaves, H. J. II The abiotic chemistry of tholated acetate derivatives and the origin of life. Sci. Rep. 6, 29883 (2016).
Lindahl, P. A. Acetyl-coenzyme A synthase: the case for a Ni0p-based mechanism of catalysis. J. Biol. Inorg. Chem. 9, 516–524 (2004).
Horn, B., Limberg, C., Herwig, C. & Mebs, S. (2011) The conversion of nickel-bound CO into an acetyl thioester: organometallic chemistry relevant to the acetyl coenzyme A synthase active site. Angew. Chem. Int. Ed. 50, 12621–12625 (2011).
Morrill, P. L. et al. Geochemistry and geobiology of a present-day serpentinization site in California: the Cedars. Geochim. Cosmochim. Acta 109, 222–240 (2013).
Boyd, E. S., Amenabar, M. J., Poudel, S. & Templeton, A. S. Bioenergetic constraints on the origin of autotrophic metabolism. Philos. Trans. R. Soc. A 378, 20190151 (2019).
Hudson, R. et al. CO2 reduction driven by a pH gradient. Proc. Natl Acad. Sci. USA 117, 22873–22879 (2020).
Rajendran, S. & Nasir, S. Hydrothermal altered serpentinized zone and a study of Ni-magnesioferrite-magnetite-awaruite occurrences in Wadi Hibi, Northrn Oman Mountain: Discrimination through ASTER mapping. Ore Geol. Rev. 62, 211–226 (2014).
McCollom, T. M. Abiotic methane formation during experimental serpentinization of olivine. Proc. Natl Acad. Sci. USA 113, 13956–13970 (2016).
Bekker, A. et al. Atmospheric sulfur in Archean komatiite-hosted nickel deposits. Science 326, 1086–1089 (2009).
Shibuya, T., Russell, M. J. & Takai, K. Free energy distribution and hydrothermal mineral precipitation in Hadean submarine alkaline vent systems: Importance of iron redox reactions under anoxic conditions. Geochim. Cosmochim. Acta 175, 1–19 (2016).
Tivey, M. K. Generation of seafloor hydrothermal vent fluids and associated mineral deposits. Oceanography 20, 50–65 (2007).
Heinen, W. & Lauwers, A. M. Organic sulfur compounds resulting from the interaction of iron sulfide, hydrogen sulfide and carbon dioxide in an anaerobic aqueous environment. Orig. Life Evol. Biosph. 26, 131–150 (1996).
Schulte, M. D. & Rogers, K. L. Thiols in hydrothermal solution: standard partial molal properties and their role in the organic geochemistry of hydrothermal environments. Geochim. Cosmochim. Acta 68, 1087–1097 (2004).
Benner, S. A. et al. When did life likely emerge on Earth in an RNA-first process? ChemSystemsChem 1, e1900035 (2019).
Weber, A. L. Nonenzymatic formation of “energy-rich” lactoyl and glyceroyl thioesters from glyceraldehyde and a thiol. J. Mol. Evol. 20, 157–166 (1984).
Chevallot-Beroux, E., Gorges, J. & Moran, J. Energy conservation via thioesters in a non-enzymatic metabolism-like reaction network. ChemRxiv. Preprint at https://doi.org/10.26434/chemrxiv.8832425 (2019).
Ragsdale, S. W. Life with carbon monoxide. Crit. Rev. Biochem. Mol. Biol. 39, 165–195 (2004).
Amend, J. P. & McCollom, T. M. in Chemical Evolution II: From the Origins of Life to Modern Society, (eds. Zaikowski, L., Fredrich, J. M. & Seidel, S. R.) 63–94 (American Chemical Society, 2009).
Bridge, M. E., Comrie, C. M. & Lambert, R. M. Chemisorption studies on cobalt single crystal surfaces I. carbon monoxide on Co(0001). Surf. Sci. 67, 393–404 (1977).
Gonzalez, L., Miranda, R. & Ferrer, S. A thermal desorption study of the adsorption of CO on Fe(110); enhancement of dissociation by surface defects. Sur. Sci. 119, 61–70 (1982).
Ravel, B. & Newville, M. (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Rad. 12, 537–541 (2005).
Van Loon, L. L., Throssell, C. & Dutton, M. D. Comparison of nickel speciation in workplace aerosol samples using sequential extraction analysis and X-ray absorption near-edge structure spectroscopy. Environ. Sci. Process. Impacts 17, 922–931 (2015).
Abild-Pedersen, F. & Andersson, M. P. CO adsorption energies on metals with correction for high coordination adsorption sites—a density functional study. Surf. Sci. 601, 1747–1753 (2007).
Sander, R. Compilation of Henry’s law constants (version 4.0) for water as solvent. Atmos. Chem. Phys. 15, 4399–4981 (2015).
Helgeson, H. C., Kirkham, D. H. & Flowers, G. C. Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures: IV. Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600oC and 5 KB. Am. J. Sci. 281, 1249–1516 (1981).
Shock, E. L., Oelkers, E. H., Johnson, J. W., Sverjensky, D. A. & Helgeson, H. C. Calculation of the thermodynamic properties of aqueous species at high pressures and temperatures. J. Chem. Soc. Faraday Trans. 88, 803–826 (1992).
Shock, E. L., Helgeson, H. C. & Sverjensky, D. A. Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Standard partial molal properties of inorganic neutral species. Geochim. Cosmochim. Acta 53, 2157–2183 (1989).
Shock, E. L. & McKinnon, W. B. Hydrothermal processing of cometary volatiles–applications to triton. Icarus 106, 464–477 (1993).
Helgeson, H. C. & Kirkham, D. H. Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures: I. summary of the thermodynamic/electrostatic properties of the solvent. Am. J. Sci. 274, 1089–1198 (1974).
Robie, R. A. & Hemingway, B. S. “Thermodynamic Properties of Minerals and Related Substances at 298.15 K and 1 Bar (105 Pascals) Pressure and at Higher Temperatures” (U.S. Geological Survey Bulletin 2131, U.S. Geological Survey, 1995).
Aono, M., Kitadai, N. & Oono, Y. A principled approach to the origin problem. Orig. Life. Evol. Biopsh 45, 327–338 (2015).
Reeves, E. P., McDermott, J. M. & Seewald, J. S. The origin of methanethiol in midocean ridge hydrothermal fluids. Proc. Natl Acad. Sci. USA 111, 5474–5479 (2014).
We thank Reiko Nagano and Atsuko Fujishima for their help in laboratory experiments. This study was supported by JSPS KAKENHI (Grant Nos. 18H04456 and 20H00209) and the Astrobiology Center Program of NINS (Grant No. AB292004).
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Kitadai, N., Nakamura, R., Yamamoto, M. et al. Thioester synthesis through geoelectrochemical CO2 fixation on Ni sulfides. Commun Chem 4, 37 (2021). https://doi.org/10.1038/s42004-021-00475-5
This article is cited by
Nature Catalysis (2023)
Liquid and supercritical CO2 as an organic solvent in Hadean seafloor hydrothermal systems: implications for prebiotic chemical evolution
Progress in Earth and Planetary Science (2022)
Geoelectrochemistry-driven alteration of amino acids to derivative organics in carbonaceous chondrite parent bodies
Nature Communications (2022)

domain: chemistry


text:
Pop stars and movie stars pretty much get equal amounts of attention from both the media and the public, so of course, a few of them are going to go "Hey, I can do one of these things, so I must be able to do the other!"
While singers like Mark Wahlberg and David Bowie made some pretty successful transitions into Hollywood, these 10 pop stars made us all unanimously wonder what they were thinking.
Lance Bass - On The Line
While his *NSYNC bandmate Justin Timberlake has gone on to a reasonably successful acting career with movies like The Social Network and In Time, Lance Bass struck out immediately with this mess of a movie that pretty much everybody's already forgotten about.
Jessica Simpson - Dukes of Hazzard
People flocked to see her argue with her then-husband Nick Lachey on MTV, but when Jessica decided to flex her acting muscles as the iconic Daisy Duke, the result was a performance where the only thing people remember about it is her in tight jeans.
Britney Spears - Crossroads
During a time when Britney was the biggest thing on the charts and everybody was tripping over themselves to buy anything she was involved with, the singer starred in this musical road movie that pretty much has to be seen to be believed. I don't mean that in a positive way.
Prince - Under The Cherry Moon
To be fair, Prince did have a pretty big acting credit to his name for Purple Rain, but let's get real, that was basically a movie-length music video. The success of that led Warner Bros. to let him both direct and star in this infamous disaster, and he basically never acted again.
The movies just get worse from here, people...

domain: entertainment


text:
College of Science’s Patricia Hammer promoted to associate dean for faculty affairs and graduate studies
The Virginia Tech College of Science has promoted Patricia Hammer to the position of associate dean for faculty affairs and graduate studies.
In her new role, Hammer will lead all aspects of faculty affairs for the college, including recruitment, retention, and development.
“By consolidating responsibility of faculty affairs under one person, it will assure that we are doing everything we can to recruit the best people, develop faculty to be their best, and support faculty as they move throughout their careers,” said Sally C. Morton, dean of the College of Science.
“Dr. Hammer has a breadth of experience across a variety of functions,” Morton added, “including, undergraduate education, faculty education, and teaching. She will be able to see the big picture.”
Hammer joined Virginia Tech as assistant dean for administration and analytics in the College of Science in September 2019. She will now coordinate the college’s promotion and tenure processes, changes to appointments, recognition programs, and research leaves. Hammer will also be responsible for graduate student issues and advising, graduate student awards and program reviews, and graduate assistantships, scholarships, and fellowships.
Hammer’s new role recognizes the importance of graduate students to the College of Science, Morton said, and helps support them and their work. “Graduate students are the wind in the sails of our successful research program,” she said.
Associate Dean of Research Randy Heflin will now focus on that research program, which he has led to remarkable growth in the past several years. In the past year, the College of Science has increased its external research awards by 26 percent to $43.6 million ($51.8 million with Fralin Biomedical Research Institute at VTC faculty with a tenure home in the college included). This a 71 percent increase in the past four years.
Hammer previously was at Hollins University in Roanoke for nearly 30 years. Most recently, she served as vice president for academic affairs. At Hollins, she also served as dean of academic services from 2009 to 2013 and was a professor of mathematics. She also twice served as chair of the Department of Mathematics and Statistics, from 1997 to 2000 and 2004 to 2008, respectively.
Hammer is a three-time Hokie alumna, earning her bachelor’s degree in 1983, a master’s degree in 1984, and a Ph.D. in 1990, all from the Department of Mathematics, part of the College of Science.
“Dr. Hammer is a wonderful, incredibly talented colleague who has contributed to the College of Science in so many ways,” said Ron Fricker, senior associate dean in the college. “I very much look forward to continuing to work with and learn from Trish in her new role.”


Kerry Washington, who plays Olivia Pope on the ABC show “Scandal” steals every scene with her elegant yet classic style. Here’s how you can steal Olivia Pope’s style: How to dress like Olivia Pope [Infographic] by the team at kerry-washingtonfan.us
Bellamy Young, Kerry Washington and Tony Goldwyn #EWTGIT
scott foley - Google Search
Can't get enough 'Scandal'? Read these books next!