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20 Games Like Rayman Raving Rabbids: TV Party()
The threequel to the party game phenomenon features the deadly quiz show Trivia Murder Party, the say-anything sequel Quiplash 2, the surprising survey game Guesspionage, the t-shirt slugfest Tee K.O., and the sneaky trickster game Fakin’ It.
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The biggest and fourthiest addition to this storied party game franchise features the blanking fun sequel Fibbage 3 and its new game mode, Fibbage: Enough About You; the web-based frame game Survive the Internet; the spooky date-a-thon Monster Seeking Monster; the deranged debate match Bracketeering; and the one-up art game Civic Doodle. Use your phones or tablets as controllers and play with up to 16 players, plus an audience of up to 10,000!
For 3-8 Players and an Audience of thousands!
The team behind the hit party games YOU DON’T KNOW JACK, Fibbage, and Drawful presents Quiplash, the laugh-a-minute battle of wits and wittiness! Use your phone or tablet to answer simple prompts like “Something you’d be surprised to see a donkey do” or “The worst soup flavor: Cream of _____.”
No rules, no correct answers! Say whatever you want!
Your answer is pitted against another player’s answer in a head-to-head clash of cleverness and comedy (or just “Which answer is least stupid?”). Other players – and even an Audience of people waiting to get in the next game – then vote for their favorite answer.
Quiplash is a go-to party game that everyone can play and enjoy!
"Grab a few friends and get ready to laugh. Use Your Words is the party game for funny people and their unfunny friends!
Use Your Words is a game that invites players to respond to a variety of mini-games and prompts with the funniest answers they can think of! Players play using their phones and tablets as controllers, making game-play seamless and quick to pick up. Players who get stumped can use one of the hidden "House Answers" to lay a trap for their fellow players once it's time for everyone to vote for their favorite.
Whether you're a total novice or a world-famous comedian, we guarantee hours of non-stop hilarity. So, grab a few friends and get ready to laugh along with Use Your Words!"
The team behind the hit party games Fibbage, Quiplash, and YOU DON’T KNOW JACK presents Drawful 2, the game of terrible drawings and hilariously wrong answers!
You use your phone or tablet to draw weird and funny things like “pitcher of nachos” or “death by trombone.” The other players type in what they think the (probably terrible) drawing is and those become the multiple-choice wrong answers. Then everyone - even an audience of potentially thousands – tries to guess the REAL answer.
Drawful 2 is a go-to party game that everyone can play and enjoy!
"Bubsy the Woolies Strike Back! is an all new Bubsy adventure featuring Bubsy in a bevy of exotic locations as he travels the planet looking for the beloved Golden Fleece.
Bubsy must use all of his classic moves and a few new ones to dodge and out bobcat a battalion of Woolies, not mention the gnarliest UFO bosses to ever grace a Bubsy adventure.
The wisecracking lynx also adds over a 100 new one liners to his lexicon to keep fans guessing what he’ll say next."
The greatest “giant rocks rolling through historical/artistic ages” tower defense game is back with Rock of Ages II: Bigger and Boulder. Just like the title says, Bigger and Boulder cranks up the surrealism and gameplay with to be, well… BIGGER AND BOULDER. With an emphasis on the chaotic new 2-vs-2 multiplayer, new time periods, and improved graphics, physics, and destructibility powered by Unreal Engine 4, players will need to be ready for some intense rocking and rolling.
Marvel Super Heroes 2 is an all-new, original adventure and sequel to the smash hit, Lego Marvel Super Heroes. Bringing together iconic Marvel Super Heroes and Super Villains from different eras and realities, along with signature LEGO humor, the latest adventure transports players into a cosmic battle across a myriad of Marvel locations ripped from time and space into the incredible open hub world of Chronopolis.
Players will go head-to-head with the time-traveling Kang the Conqueror in an epic battle across Chronopolis, from Ancient Egypt and The Old West to Sakaar and New York City in 2099. Along the way, gamers will be able to take control of a host of iconic characters, from Cowboy Captain America from the past to Spider-Man 2099 from the future along with Thor, Hulk, the Guardians of the Galaxy, Black Panther, Captain Marvel, Doctor Strange, Green Goblin, and dozens of other Marvel Super Heroes and Super Villains.
The game follows Sonic the Hedgehog as a member of a resistance force against Doctor Eggman, who has taken over the world with the help of his robot army and a mysterious new villain known as Infinite. Gameplay is similar to Sonic Generations with players controlling "Classic" and "Modern" versions of the titular character; the former plays from a 2.5D side-scrolling view reminiscent of the original Sonic games on the Sega Genesis, while the latter uses three-dimensional gameplay similar to Sonic Unleashed and Sonic Colors. In addition to the two Sonics, Sonic Forces also introduces a third gameplay mode featuring the "Avatar", the player's own custom character.
Monster Hunter: World sees players take on the role of a hunter that completes various quests to hunt and slay monsters within a lively living and breathing eco-system full of predators…. and prey. In the video you can see some of the creatures you can expect to come across within the New World, the newly discovered continent where Monster Hunter: World is set, including the Great Jagras which has the ability to swallow its prey whole and one of the Monster Hunter series favourites, Rathalos.
Players are able to utilise survival tools such as the slinger and Scoutfly to aid them in their hunt. By using these skills to their advantage hunters can lure monsters into traps and even pit them against each other in an epic fierce battle. Can our hunter successfully survive the fight and slay the Anjanath? He’ll need to select his weapon choice carefully from 14 different weapon classes and think strategically about how to take the giant foe down. Don’t forget to pack the camouflaging ghillie suit!
They've invaded the world of Rayman, and now the insane Rabbids have a new objective: invade planet Earth! They have established their base at a shopping mall and begun training for their nastiest scheme yet. As part of this training, the Rabbids must carry out several missions around the globe to help them in an attempt to dominate the world. The Rabbids will also try to study human behavior by mimicking everything we do... but in the Rabbid sort of way, with no logic... of course.
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"SpellForce 3 - The perfect blend between RTS and RPG!
SpellForce 3 goes back to the roots of the SpellForce saga. The story takes place before the acclaimed SpellForce: The Order of Dawn and the players becomes a part of a rich high fantasy world named Eo.
- RTS/RPG Mix: Unique gameplay combining RTS and Top Down RPG genres
- Create & Customize: Create your own hero and develop his skillset as you prefer!
- Build to Fight: Build your own army and fight epic mass battles with it.
- Epic Storyline: Unravel a deep and epic story in the SpellForce universe that doesn't require having played any of the former SpellForce games. Fans will still find a lot of interesting connections.
- Rich universe & lore: Explore the world Eo and discover intrigues, secrets and a lot of loot for your hero.
- Apply some tactics: Use advance tactics with your RTS army to defeat your enemies
- Play on your own: Long Single Player Campaign of 30+ hours
- Multiplayer: Strong multiplayer component with various modes - Play cooperatively or compete against each other "
The Earthlings have joined the interstellar club. The galaxy will never be the same.
The year is 2086 and Earth has detected an alien distress call originating from the surface of Triton. In response, Star Control is formed with you as The Captain of Earth's first prototype starship.
An open-world survival game in the brutal lands of Conan the Barbarian. You are an exile, one of thousands cast out to fend for themselves in a barbaric wasteland swept by terrible sandstorms and besieged on every side by enemies. Here you must fight to survive, build and dominate.
Hungry, thirsty and alone, your very first battle is that against the harsh environment. Grow crops or hunt animals for food. Harvest resources to build weapons and tools. Build a shelter to survive. Ride across a vast world and explore alone, or band together with other players to build entire settlements and strongholds to withstand fierce invasions.
When strong enough, march forth into battle and wage war against your enemies as you fight to dominate the exiled lands. Sacrifice enemy players on the altars of the gods and shift the balance of power your way. Unleash your fury in savage, fast-paced combat and execute bloody and bone-crushing attacks that will see heads rolling and limbs flying.
A new Gintama game for the PlayStation 4 and PlayStation Vita in Japan.
No western version has been announced but a trailer released for a version from Southeast Asia has English subtitles, PlayStation 4 only. This version will be available in a physical and digital format.
Welcome to Zombie California! Slay and survive with style in this co-op playground. Explore the vast Golden State, from lush forests to sunny beaches. Wield a variety of over-the-top, hand-crafted weapons against human and undead enemies. Upgrade your vehicles, grab your friends, and take a permanent vacation to the zombie apocalypse. Paradise meets hell and you are the matchmaker!
"Citadel: Forged With Fire is a massive online sandbox RPG with elements of magic, spellcasting and inter-kingdom conflict. As a newly minted apprentice of the magic arts, you will set off to investigate the dangerous world of Ignus. Your goal: create a name for yourself and achieve notoriety and power among the land’s ruling Houses.
You have complete freedom to pursue your own destiny; hatch plots of trickery and deceit to ascend the ranks among allies and enemies, become an infamous hunter of other players, build massive and unique castles, tame mighty beasts to do your bidding, and visit uncharted territories to unravel their rich and intriguing history. The path to ultimate power and influence is yours to choose."
"This explosive adventure is filled with intense heist missions, high stakes car battles, epic cop pursuits and jaw dropping set pieces. It’s blockbuster gameplay never before seen from the series, fueled by a gripping story of betrayal and revenge. With Need for Speed: Payback, it’s no longer just about being the first to cross the finish line or racing to prove to be the best, it’s about building the perfect ride, getting behind the wheel and playing out an action driving fantasy.
Set in the underworld of Fortune Valley, players will drive as three distinct characters reunited by a quest for vengeance against The House, a nefarious cartel that rules the city’s casinos, criminals and cops. They will take on a variety of challenges and events as Tyler, the Racer; Mac, the Showman; and Jess, the Wheelman to earn the respect of the underground. Featuring the deepest customization from the series, players can truly craft a personalized and unique ride, or spend hours finding and tuning an abandoned derelict into a supercar. They can then push their cars to the limit and raise the stakes by betting on their own performance, where they can either multiply their winnings or risk losing it all."


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As the weather is changing and the warmer days are almost behind us, I thought it was a good time to style up my master bedroom, give it a freshen up, as its one of the rooms in my house that needs a little revamping.
I had left my master bedroom till last to style as I’m super picky to what would go in the bedroom, it had to be stylish yet comfortable and a place where both hubby and I would love to spend time and relax in. Another significant role to choosing accessories and color palette for the room was considering it’s a shared place, it had to be appealing to the both of us. So, for most people this is where you might compromise some or your styling choices to suit the both of you.
I have stuck to my signature grey’s and whites that work so well for me in our home along with the touches of natural wood and leather throughout this room to accomplish that neutral base that is easy to work with and update at any point with pops of color through accessories.
“Most important is to create a warm and cozy environment despite the cool and crisp color palette”
To achieve this I combined a mixture of textures and layers keeping to the neutral colors with adding just some touches of hues of blue and Blush, tying all this in with the artwork and floral arrangement.
As a stylist, I try to find the balance between luxury and inexpensive, yet on trend products. It is important to find the balance between the two, trends change per season and if you are like me then every few months you will want to change and restyle your home.
Below you can shop the look I have created, for example, these amazing Canningvale bed sheets and Donna cover are simple yet luxurious, this is the one piece you would want to invest more in, it provides you comfort without compromising on style.
SHOP THE LOOK
Vintage soft wash cotton quilt cover set in grey – Queen size $269.95 Canningvale.com.au
Vintage soft wash cotton sheets in white – Queen size $299.9 canningvale.com
I always loved having a gallery wall so as seen in my guest bedroom I have recreated a gallery wall that has a slight structure to it. A gallery wall is a great way to showcase all the prints you love (and we all know there are so many gorgeous ones around) So this is a combination of something sexy and feminine but not to overpowering for the bedroom.
“Don’t be afraid to mix and match styles and sizes to create your own gallery wall, choose your key dominant print and pair it with some softer ones”
SHOP THE LOOK
Backside print – Hello little birdie
Feather Print – Wool & Willow
Hydrangea print – Martin Moore
One of the most popular items that would instantly transform your space would be leather details, I choose the staple leather strap holder which is versatile and can be used in any room of your home, here it has purely decorative purposes but if you are one to read in bed then it would make a perfect book or magazine holder.
“Add a touch of luxury with leather detailing and layering”
Styling my master bedroom I used natural fibers such as cotton and wool to layer over the quilt to create depth and warmth to the room. My newest throw addition is this cream tassel one, from Sheridan. This one has a lovely fringe detail to finish off the look of the bed.
A styling tip I have when decorating a bed would be to only use 3 accent cushions to tie in the whole room together. Stick to texture, plain color and pattern. So many overdo it with cushions on the bed these days that just creates a cluttered look to the room.
SHOP THE LOOK
Leather strap holder in natural – Interior Motives
Fringe natural rectangular cushion – Sea tribe
Round natural avocado dye tassel cushion – Burnt Country
Fringe throw in creame – Sheridan
Pink Valentini throw – Canningvale
Linen european pillowcases in teal – Target
Velour cushion in grey beach – Target
I would love to know what you think of this new look and if you have any questions feel free to ask below.
Thanks for reading

domain: artistic


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Implementation of the NSW Carers (Recognition) Act 2010:
The Carers Program plays a key role in the implementation of the NSW Carers (Recognition) Act 2010 and the NSW Carers Charter.
Carer Consultancy Program:
Using the Carer Consultant Model, the Carers Program provides managers with access to a range of viewpoints on service development and quality activities. The Carers Program Coordinator manages a register of expert consultants from a diverse range of caring circumstances. The consultants provide important information on the impact of service activities on carers and consumers. This information helps managers to ensure the success of the services they manage.
Service Development Consultancy Program:
The Carers Program offers a consultancy service to managers and senior clinicians regarding the introduction of strategies to improve a service unit’s response to carers. Recent activity includes the Emergency Respite Pathways Project, Celebrating Aboriginal and Torres Strait Islander Carers Initiative and the Top5 Project.
Staff Education Program:
Through a range of activities the Carers Program seeks to improve the awareness of staff on the issues that are essential to working with carers as a part of the care team. The Carers Program provides in-services to Nursing Units and presentations at staff education days and Assistant in Nursing training days. These activities are often conducted in partnership with external organisations and carers representatives. The Carers Program also utilises electronic and print media opportunities to raise the profile of carers across the LHD.
NSW Health and Ageing Disability and Home Care (ADHC) Joint Guidelines:
The guidelines aim to ensure that staff in hospitals and disability accommodation support services, are aware of their respective roles and responsibilities for people with a disability before, during and after transfer of care from hospital. It is intended that staff will develop the capacity to identify areas of risk that could compromise a person with the disability’s capacity to; ) achieve the best health outcomes and their safety and/or dignity during a hospital stay, 2) agree on what additional supports are required to reduce identified risks and 3) negotiate responsibility and resources for the provision of agreed additional support.
NSW Carers Strategy Implementation:
The Carers Program will take a lead role with the LHD’s implementation of the key components of NSW Carers Strategy.
Disability Action Plan and the Implementation of the Disability (Inclusion) Act 2014:
The Carers Program is currently involved in discussions with peak organisations regarding Disability services on the North Coast and is preparing to play a key role in the implementation of the Disability (Inclusion) Act 2014.

domain: health


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How to Use Potato Flakes in Your Everyday Cooking: Tips and Tricks
Meta-Description: Are you looking for a versatile and easy-to-use ingredient to add to your pantry? Look no further than potato flakes! Learn how to use potato flakes in your everyday cooking with our tips and tricks.
Potatoes are a versatile ingredient used in many dishes around the world. However, they can be time-consuming to prepare, especially if you’re in a hurry. Enter potato flakes – a convenient and easy-to-use alternative that can be used in a variety of dishes. In this article, we’ll explore the many ways you can incorporate potato flakes into your everyday cooking, from simple mashed potatoes to more creative dishes.
Potato Flakes: What Are They?
Potato flakes are dehydrated potatoes that have been processed into small flakes. They are made by cooking, mashing, and dehydrating potatoes, resulting in a product that is easy to store and use. Potato flakes are widely available in grocery stores and can be found in the baking or dried goods section.
Why Use Potato Flakes?
Potato flakes are a convenient and versatile ingredient that can be used in many different dishes. They are easy to store and have a long shelf life, making them a great addition to any pantry. Here are some of the benefits of using potato flakes in your cooking:
- Convenience: Potato flakes can be used in a variety of dishes and are easy to prepare. They can be used as a quick alternative to mashed potatoes or as a thickener for soups and stews.
- Shelf life: Potato flakes have a long shelf life and can be stored for months without spoiling.
- Cost-effective: Potato flakes are often less expensive than fresh potatoes and can be used in smaller quantities.
- Versatility: Potato flakes can be used in a variety of dishes, from simple mashed potatoes to more creative recipes like potato pancakes and gnocchi.
How to Use Potato Flakes
Potato flakes can be used in many different dishes, from savory to sweet. Here are some tips and tricks for using potato flakes in your cooking:
Potato flakes can be used to make quick and easy mashed potatoes. Simply mix the flakes with hot water or milk and butter, and you’ll have a delicious and creamy side dish in no time.
Soups and Stews
Potato flakes can be used as a thickener for soups and stews. Simply add a few tablespoons of potato flakes to your soup or stew, and the flakes will absorb the liquid and thicken the dish.
Breading and Coating
Potato flakes can be used as a breading or coating for meat, fish, or vegetables. Simply mix the flakes with your favorite seasonings and coat your food before frying or baking.
Potato flakes can be used to make delicious and crispy potato pancakes. Simply mix the flakes with hot water, flour, and eggs, and fry until golden brown.
Potato flakes can be used to make homemade gnocchi. Simply mix the flakes with flour, eggs, and salt, and knead until a dough forms. Roll the dough into small balls, and boil until cooked through.
Potato flakes can be used in baked goods like bread and rolls to add moisture and texture. Simply substitute some of the flour with potato flakes in your favorite recipe.

domain: food


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Singer/Songwriter Lauren Hulbert’ Releases New Single-Video “Gone In One”
Lauren Hulbert’s new single “Gone In One” has a style that some might be quick to describe as similar to the retro Seattle sound a lot of singer/songwriters tried to salvage as their own in the late 1990s, but from my perspective, the track and its companion video are far too eclectic in construction to be so easily branded. Lending itself over to the surrealism of indie pop while also bearing certain aesthetical traits indebted to a dirty rock n’ roll balladry you don’t hear a lot of on the FM dial anymore, “Gone In One” is a touch of the past as filtered through a postmodern lens, and it’s got my full attention beyond debate this October.
Official Website: https://www.laurenhulbert.com/
The smoky pipes of our leading lady aside, there’s a lot of charisma to the harmonies that Hulbert builds from the ground-up in this single undisputedly as responsible for the chills-factor as any of the lyrics she sings are. There’s something really natural about the fluidity of both her verses and the beats that back them up in this piece, and as limited as the percussive element is, there’s never a moment in which the rhythm doesn’t feel present and persistently drawing us closer.
Hulbert’s style of lyricism here is cutting and personal, but I definitely wouldn’t say it’s self-indulgent in any respect. It’s absolutely possible to get intimate with the narrative you’re presenting to an audience or even a specific listener without getting so wrapped up in poeticisms that you start to translate as insular, and to some extent, her performance in “Gone In One” goes a long way towards supporting this statement. She’s able to open to us while staying focused on a relatable, open-ended vibe, and that’s something I wouldn’t mind some of her contemporaries trying to embrace themselves.
A singer/songwriter with immense spunk and creative abilities that are only just now starting to blossom in a provocative way, Lauren Hulbert has won my heart with this latest single/video combo, and if given the opportunity, I think she’ll do the same for scores of listeners and critics around the country this autumn. “Gone In One” isn’t reinventing the wheel compositionally, but from a tonal point of view, it’s one of the smoother numbers I’ve heard from an independent, rock-influenced player in this capacity all year long. Hulbert is one to watch, and if you didn’t believe that before, you’ll know how true it is after hearing “Gone In One.”


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Tucked into a sheltered, private corner of its own secluded paddock this unique, handcrafted shepherd's hut / tiny home crossover is dotted with details, from the stable door and the stained-glass windows to the miniature stove.
It enjoys a swathe of outdoor space, and comes complete with fire pit, hot outdoor shower, and sheltered sun trap, all framed by freshly-planted apple trees. Apple Wagon is lovingly fitted with everything you need - a mini-kitchen, double bed and bench area - but it is compact inside - ideal for a solo retreat or a close couple!
"A perfect oasis of calm and tranquility, designed for simplicity, offering cosy comfort inside and a private space to connect with nature outside. Absolutely perfect for a mini retreat" - Jemima
"The wagon has so much charm! We enjoyed hearing the birds, seeing the stars and the burner provided more than enough warmth for a cold and stormy October night." - Chloe

domain: design


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Greetings from our natural paradise that is the island of Maui,
Despite only being a 25-minute plane ride from Oahu, Maui feels like a different planet – and the trip members felt the difference almost immediately. Gone are the skyscrapers and highways. Gone is the metropolis known as Honolulu and the hustle and bustle of Waikiki. In to replace them are country roads, that run along rocky coasts, cut through lush, green mountains, and pass through small seaside towns. The pace is slow here. It is quiet. If you know where to look however, you will find that the forests and beaches here are just as alive as any city.
We began settling into our new home after and our hotel’s wonderful pool before heading off to the coastal town of Paia. It was there that the group got their first taste of local Mahi – the famous Paia Fish Market. The trip members loved their fish tacos, seafood pasta, fresh grilled fish, and even a few burgers.
“I really liked how small it was, and the way that they would simply call the order for you to pick up and bring to your table.” – Amelia
“The fish tacos were delicious!” – Jacob
Friday was a day that most members had been anxiously awaiting since Day 1: SURFING! We all had the opportunity to catch a wave and ride it to shore. The professional instructors helped us successfully stand on our surfboards. Taylor J. was off to a good start and managed to bounce up on the board on his first attempt. Many others succeeded despite it being their first experiences with the sport. A congrats goes to Hannah, Jen, and Taylor C for successfully standing on their boards. Toward the end of the lesson, a few confident members began to catch waves on their own. Congratulations to Remi, Marika, Jess K. and Jonathan for applying what they had learned and seeking waves independently.
That very same evening, the group had opportunity to take part in a very unique experience – attending their very first Luau. The food was abundant: poi, macadamia nut encrusted fish, teriyaki chicken, fresh veggies (including local purple potatoes!), salad with papaya dressing and the freshest and sweetest pineapple imaginable – not to mention all the yummy desserts. The show that followed the feast was both entertaining and educational. Every scene focused on a different Polynesian culture. The narrative, expressed in traditional dance, was accompanied by Polynesian myth and music.
The group spent the next few days with ECO Maui exploring the fertile valleys and lush forests with guides Nature Ray and Nature Jay. We had the chance to help clean up an area known as Twin Falls. In its dense forests, Samantha and Marika learned to weave by ripping very thin strips of tree bark. It is in this same area that Emily tried freshly picked passion fruit. The composting project with which we were tasked was made easier because the food we were helping to grow was also providing us the energy to carry on.
The work was fun but the highlight of the day was when Jay and Ray took us on a hike through the property to two different waterfalls. Alex quickly became acquainted with the falling water, standing under the natural shower for the majority of our swim. The water was cool and refreshing. The backdrop was a rock climber’s paradise, as rocks jutted from the wall in every direction, sculpted by erosion and falling water. Words can’t quite convey how beautiful this place was so check out the trip albums so you can try to understand.
Our trip might be close to being over but we still have a lot of work to do before we leave. In the past few days we’ve been volunteering at the local Boys and Girls Club running programming and acting as positive role models for the children there. It’s been an incredible experience to give back to the youth of Maui, the island that has given to us in abundance.
The Westcoast Blogger

domain: travel


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Recent Reactive and Functional Polymers Articles
Catherine Branger | Walid Meouche | André Margaillan
Abstract: Selective recognition of metal ions is a real challenge for a large range of applications in the analytical field (from extraction to detection and quantification). For that purpose, ion-imprinted polymers (IIPs) have been increasingly developed during the last 15years on the principle of molecularly imprinted polymers (MIPs). Those imprinted materials are designed to mimic the binding sites of biological entities and assure an improved recognition of the template species. The aim of this review is to give the current state of the art in the conception of IIPs from the components to the polymerization process. Some applications of those materials will be also discussed.
Effect of the mimic structure on the molecular recognition properties of molecularly imprinted polymers for ochratoxin A prepared by a fragmental approach
Claudio Baggiani | Flavia Biagioli | Laura Anfossi | Cristina Giovannoli | Cinzia Passini | Gianfranco Giraudi
Abstract: In this work the fragmental approach was used to prepare several molecularly imprinted ethylene dimethacrylate-co-methacrylic acid polymers with molecular recognition towards the mycotoxin ochratoxin A, with the aim of searching for simpler mimic templates than the well-known N-(4-chloro-1-hydroxy-2-naphthoylamido)-(l)-phenylalanine. The screening for binding of two different kinds of ochratoxin-related molecules was performed by HPLC analysis. Ochratoxin A and the mimic templates were eluted in acetonitrile–acetic acid (0.1%v/v) and the imprinting factor was measured for all the ligands on all the columns packed with the imprinted polymers. The experimental results show that changes to the amino acidic sub-structure or the presence/absence of a chlorine atom in position 4 on the naphthalene ring system does not affect the molecular recognition of ochratoxin A by the resulting imprinted polymer. On the contrary, the presence of the bulky naphthalene ring system in the mimic template seems to be necessary to preserve the molecular recognition of ochratoxin. This binding behavior was found to be compatible with in silico simulations of the complexation between some of the mimic templates and molecules of methacrylic acid. The use of the mimic template N-(1-hydroxy-2-naphthoylamido)-(L)-phenylalanine seems to represent a synthetically simple approach to the preparation of imprinted polymers with molecular recognition properties towards ochratoxin A.
Synthesis and adsorption studies of novel hybrid mesoporous copolymer functionalized with protoporphyrin for batch and on-line solid-phase extraction of Cd2+ ions
Kristiany Moreira Diniz | Mariana Gava Segatelli | César Ricardo Teixeira Tarley
Abstract: A hybrid copolymer [poly(ethylene glycol dimethacrylate-co-protoporphyrin)-silica], synthesized by free radical copolymerization and sol–gel process was evaluated as novel adsorbent for solid-phase extraction of Cd2+ ions. Characterization of hybrid polymer was performed by FTIR, SEM and surface area analyzes. Adsorption isotherms built at pH 8.9 were very well adjusted (R2=0.9982) to hybrid non-linear Langmuir–Freundlich model for two sites, indicating the existence of different affinity constants for binding sites, which was confirmed by Scatchard plot. The estimated maximum adsorption capacity was found to be 8.28mgg−1. The adsorption kinetics data also corroborated to the isotherm, where the Cd2+ ions adsorption followed the pseudo-second-order kinetic (R2=0.998). The on-line preconcentration procedure, optimized by means of factorial designs, was based on sample preconcentration (16mL) at pH 8.9 through 50.0mg of hybrid copolymer packed in mini-column at 8.0mLmin−1 flow rate. The on-line desorption of Cd2+ ions towards the FAAS detector was carried out in countercurrent at 5.0mLmin−1 flow rate using 0.8molL−1 HNO3. Using the on-line preconcentration procedure, the maximum adsorption capacity determined from breakthrough curve was found to be 2.25mgg−1. Analytical curve ranged from 0.0 up to 50.0μgL−1 (r=0.997), limit of detection of 0.27μgL−1, preconcentration factor of 38.4, sample throughput of 30h−1 and consumptive index of 0.41mL, were achieved. The preconcentration method, very tolerable to several foreign ions, was successfully applied to the Cd2+ ions determination in water samples and cigarette sample. The accuracy was checked from analysis of certified reference materials.
In situ growth of CdS nanocrystal arrays by self-assembling microporous templates from dendritic-linear PGMA-HPAM-r-PS copolymers
Chi-Yuan Hung | Shang-Ju Hsieh | Cheng-Chien Wang | Chuh-Yung Chen
Abstract: A novel in situ chemical precipitation method to directly synthesize CdS nanocrystal arrays in the presence of microporous templates of poly(glycidyl methacrylate-grafted-3,3′-dimethyl-(4-hydroxyphenylazanediyl) bis(2-methylpropanoate))-random-polystyrene (PGHS), which were formed by self-assembling dendritic-linear PGHS copolymers via the solvent-induced phase separation process, were investigated. The surface morphology of the PGHS template and the spatial positions of the CdS nanocrystals in the PGH-CdS could be easily and quickly controlled by altering the content of the dendritic GMA-HPAM segments. The diameters of the CdS nanocrystals on the PGHS-CdS template were uniform in the range of 3–4nm. Large-area, hexagonally ordered CdS nanocrystal-array domains were discovered in the PGHS2-CdS template used in this study.
Synthesis, characterization and third-order nonlinear optical properties of novel hyperbranched donor–acceptor polyfluorenes based on 1,3,6,8-tertsubstituted carbazole core
Shuangzhu Li | Chao Gao | Feng Liu | Wei Wei
Abstract: Two novel hyperbranched donor–acceptor polyfluorenes based on 1,3,6,8-tertsubstituted carbazole core (4BrCzP1 and 4BrCzP2) were synthesized and characterized. The third order nonlinear optical properties of the materials were studied using Z-scan technique with femtosecond Ti: sapphire laser with delivering pulses of 140fs at 800nm. The nonlinear optical refractive index was 9.29×10−8esu for 4BrCzP1 and 3.19×10−7esu for 4BrCzP2, respectively. While the third order nonlinear susceptibility was 1.29×10−9esu for 4BrCzP1 and 4.33×10−9esu for 4BrCzP2, respectively. The experimental results indicated that the hyperbranched polyfluorenes was a promising candidate in the application of third order nonlinear optical materials.
Pinar Camurlu | Nese Karagoren
Abstract: In this study a novel, clickable, azide containing conducting polymers based on 1-(2-azido-ethyl)-2,5-dithiophene-2-yl-1H-pyrrole (SNS-N3) were synthesized and characterized. Optical and electronic properties of homopolymer (PSNS-N3) were investigated and colorimetric studies were performed. The homopolymer has a band gap of 2.49eV and it displays yellow to blue coloration upon doping. Electrochemically prepared copolymers of SNS-N3 and 3,4-ethylenedioxythiophene (EDOT) formed multichromic, color tunable electrochromic materials with continuous color gradient from cinnamon, mustard, lime green, blue and dark blue. Spectroelectrochemical analyses revealed that the neutral copolymers possess two absorption maxima (∼320 and 450nm) where the relative intensity and position of the two depends on polymerization potential. Copolymer films could be fully switched between their neutral and oxidized forms in ∼1.2s with a percent transmittance of ∼65% at 950nm. Moreover, a PSNS-N3 coated ITO electrode was subjected to click reaction using ethynylferrocene. CV and FTIR studies revealed that ferrocene could easily be attached onto the electrode surface without loss of electroactivity of both ferrocene and PSNS backbone. Our results suggest that electrochemically prepared PSNS-N3 films offer a novel and multipurpose platform for simple, effective post-functionalization of poly(2,5-dithienylpyrrole)s under mild conditions.
Zn2+-imprinted porous polymer beads: Synthesis, structure, and selective adsorption behavior for template ion
Minji Kim | Yang Jiang | Dukjoon Kim
Abstract: Zn2+-imprinted polymer was synthesized in porous spherical forms via a self-assembled complex between 2,2′-bipyridyl/4-vinylpyridine complexant/functional monomer and Zn2+ template ion. Diameters of particles ranged from 250 to 550μm to enlarge the surface area and thus enhance the adsorption capacity. The presence/absence of the template ion in the preparation of the imprinted polymer was confirmed by EDX spectroscopy, and the physical structure of the particles was investigated using ESEM and BET analysis. The particle and the pore size were controlled by the cross-linker/monomer feed ratio. The adsorption capacity of the imprinted polymers was 210.61μmolg−1 for Zn2+, while those for Cu2+, Ni2+, and Pb2+, were 37.92μmolg−1, 33.02μmolg−1, and 9.70μmolg−1, respectively. This big discrepancy of the adsorption capacities illustrates the excellent separation selectivity of the imprinted polymers. The adsorption capacity decreased significantly at pH below 4.5, as the polymers are easily protonated. The imprinted particles lost only 10 % of their adsorption ability after 10 repeated uses.
A novel cross-linked polyzwitterion/anion having pH-responsive carboxylate and sulfonate groups for the removal of Sr2+ from aqueous solution at low concentrations
Shaikh A. Ali | Shamsuddeen A. Haladu
Abstract: A novel cross-linked polyzwitterion (CPZ) was synthesized via cycloterpolymerization of N,N-diallyl-N-sulfopropylammonioethanoic acid (92.5mol%), a cross-linker 1,1,4,4-tetraallylpiperazinium dichloride (7.5mol%), and sulfur dioxide (100mol%) in the presence of azoisobutyronitrile in dimethylsulfoxide at 60°C. CPZ, upon treatment with NaOH, was converted into a cross-linked polyzwitterion/anion (CPZA). The experimental data for the adsorption of Sr2+ on CPZA fitted the pseudo-second-order kinetic model and Freundlich as well as Temkin isotherm models. The adsorption process was spontaneous and exothermic in nature with negative values for both ΔG and ΔH. The low activation energy of 7.18kJ/mol indicated the adsorption as a favorable process. The removal for the initial concentrations of 200ppb and 1000ppb (i.e., 1ppm) of Sr2+ ions was observed to be 87% and 92%, respectively. An efficient synthetic access to the resin and excellent adsorption capacity and desorption would enable its use in the treatment of radioactive nuclear waste containing Sr2+ ions. The CPZA provided an opportunity to test the efficacy of a zwiiterionic/anionic group in the removal of Sr2+ ions in low concentrations.
Immunoglobulin G recognition with Fab fragments imprinted monolithic cryogels: Evaluation of the effects of metal-ion assisted-coordination of template molecule
Sevgi Asliyuce | Lokman Uzun | Ridvan Say | Adil Denizli
Abstract: In this study, we applied the epitope imprinting approach to prepare molecularly imprinted monolithic cryogels for immunoglobulin G (IgG) recognition. In this respect, we imprinted Fab fragments of IgG molecules instead of intact protein molecules via two different non-covalent interactions. In the first approach, we directly coordinated Fab fragments with N-methacryloyl-L-histidine (MAH), polymerizable derivative of L-histidine, but for the second, we used cupric ions [Cu(II)] as mediator between MAH and Fab fragments. The monolithic cryogels were characterized by Fourier transform infrared (FTIR) spectroscopy, swelling test, and scanning electron microscopy. Then, the monolithic cryogels were used for Fab fragment adsorption from aqueous solution while evaluating the factors such as pH and Fab fragment concentration affecting on adsorption process in continuous set-up. After that, monolithic cryogels were used for IgG adsorption by varying pH, IgG concentration, flowrate, and temperature in appropriate ranges. Maximum IgG adsorption capacities were determined as 32.4mg/g and 49.0mg/g for directly coordinated cryogel (MIPDirect) and Cu(II) assisted cryogel (MIPCu(II) assisted), respectively. Non-imprinted monolithic cryogels were also prepared for control purposes. In addition to Fab fragments and IgG molecules, albumin and Fc fragment of IgG molecules were used as competitor biomolecules in order to investigate the selectivity gained by imprinting process. Relative selectivity constants were calculated as 1.47, 2.64 and 3.89 for MIPDirect and 2.90, 8.98, and 11.51 for MIPCu(II) assisted for Fab/IgG, Fab/Fc, and Fab/albumin as biomolecule pairs, respectively. The desorption efficiency and reusability of MIPCu(II) assisted cryogel were better than that of MIPDirect. The results reported here showed that the metal ion assistance improved the selectivity features of the imprinted cryogels and allowed to study under milder conditions with enhanced adsorptive properties.
Suprarmolecular hydrogels driven by the dual host–guest interactions between α-cyclodextrin and ferrocene-modified poly(ethylene glycol) with low-molecular-weight
Cheng-Gong Guo | Liang Wang | Ya-Kun Li | Cai-Qi Wang
Abstract: In general, α-cyclodextrin (α-CD) and low-molecular weight poly(ethylene glycol) (low-MW PEG) (Mw=400–10,000) cannot construct supramolecular hydrogels but easily form crystalline precipitates. In this study, low-MW PEG (Mn=2000, PEG-2000) was functionalized by ferrocene as mono-end-group. The obtained ferrocene-modified PEG-2000 (FcPEG-2000) further self-assembled into supramolecular hydrogel with α-CD even at low concentration (CFcPEG-2000=17mg/ml), driven by dual host–guest interaction between α-CD and FcPEG-2000. Interestingly, the hydrogel was still observed even when hydrophobic Fc group was oxidized to hydrophilic ferrocenium (Fc+) or included into the cavity of β-CD. In the former case, the existence of Fc+ end groups is considered to decrease the probability of PEG de-penetration from α-CD cavity, so that α-CDs have more location and opportunities to aggregate into more channel-type crystalline domains as physical cross-linking points. While in the later case, the synergistic effect of host–guest interaction between β-CD and ferrocenyl groups and host–guest interaction between α-CD and PEG chains are considered to be the main reason. The resultant FcPEG-2000 based hydrogels showed the property of shear-thinning.
Preparation of UV-curable functionalized graphene/polyurethane acrylate nanocomposite with enhanced thermal and mechanical behaviors
Xin Wang | Weiyi Xing | Lei Song | Bin Yu | Yuan Hu | Guan Heng Yeoh
Abstract: Functionalized graphene nanosheets (f-GNSs) were synthesized by a simple covalent functionalization of graphene with 3-methacryloxypropyl trimethoxysilane (MPTES). The results from FTIR, XPS and XRD showed that MPTES was successfully attached onto the surface of graphene. Functionalized graphene/polyurethane acrylate (f-GNS/PUA) nanocomposites were prepared by UV radiation of PUA with f-GNS. The onset thermal degradation temperature of f-GNS/PUA nanocomposite was increased by 16°C, at an f-GNS content of 1wt%. Meanwhile, the storage modulus and glass transition temperature of the nanocomposites were enhanced by incorporating f-GNS into the PUA. This is believed to be attributed to that the covalent functionalization of graphene can improve both the dispersion of f-GNSs in the polymer matrix and the interfacial interactions between f-GNSs and PUA.
A Metal-Sensitive Organic-Inorganic Hybrid Surfactant: POSS-Capped Dipicolinic Acid-Functionalized Poly(ethylene glycol) Amphiphile
Available online 14 May 2013
Chen Lingnan | Zeng Birong | Xie Jianjie | Yu Shirong | Yuan Conghui | Pan Yinyin | Luo Weiang | Liu Xinyu | He Kaibin | Xu Yiting | Dai Lizong
Abstract: A novel metal responsive organic-inorganic hybrid amphiphile with a well-defined cage structure bearing a hydrophobic polyhedral oligomeric silsesquioxane (POSS) head and a hydrophilic poly(ethylene glycol) tail functionalized with a bidendate ligand was synthesized via amidation and esterification reactions. The structure of the novel amphiphilic surfactant, aminopropylisooctyl-POSS-maleic acid-poly-(ethylene glycol)-dipicolinic acid (POSS-MA-PEG-DPA), was characterized by NMR, and its self-assembly behavior was investigated by transmission electron microscopy, dynamic light scattering, and UV-visible spectrophotometry. The experimental results revealed that the micelle morphology could be controlled by the addition of zinc ions. The proposed modulation mechanism involves the combination of hydrophobicity, metal coordination and repulsive interactions. Furthermore, the coordination bonds provide the micelles with good dynamic and thermal stability. We also found that the tadpole-shaped amphiphile could form reverse micelles with an average diameter of approximately 30 nm.
LCST Phase Separation and Thermoreversible Gelation in Aqueous Solutions of Stereo-Controlled Poly(N-isopropylacrylamide)s
Available online 14 May 2013
Fumihiko Tanaka | Yukiteru Katsumoto | Shinya Nakano | Rio Kita
Abstract: Stereoregular poly(N-isopropylacrylamide)s with controlled content of isotactic dyads have recently been synthesized, and interesting interference phenomena between LCST phase separation and high-temperature reversible gelation have been observed in their aqueous solutions. We develop a model solution in which dehydrated stereo-regular isotactic segments on polymers are driven into intermolecular cross-links leading to gelation. We theoretically calculate the phase diagrams for the varied content isotactic dyads and compare with the experimental data.
Available online 10 May 2013
Mitsuhiro Shibata | Naozumi Tetramoto | Ayumi Imada | Makiyo Neda | Shimon Sugimoto
Abstract: 5,5’-Bieugenol (BEG) and eugenol novolac (EGN) were synthesized by the oxidative coupling reaction of eugenol (EG) and the addition-condensation reaction of EG with formaldehyde, respectively. The EG, BEG and EGN were prepolymerized with 4,4’-bismaleimidediphenylmethane (BMI) at 180 °C and then compression-molded at finally 250 °C for 6 h to produce cured EG/BMI (EB), BEG/BMI (BB) and EGN/BMI (NB) resins with eugenol/maleimide unit ratios of 1/1, 1/2 and 1/3. The FT-IR analysis of EBs and 13C-NMR analysis of the model reaction product of EG/N-phenylmaleimide (PMI) 1/3 at 200 °C for 12 h suggested that the ene reaction and subsequent Diels-Alder/ene reactions mainly occurred for EBs. The FT-IR analyses of BBs and NBs supported the occurrence of ene reaction and subsequent thermal addition copolymerization in a similar manner to the well-known curing reaction of 2,2’-diallybisphenol A and BMI. The glass transition temperature (Tg) and 5% weight loss temperature (T5) of the cured resin increased with increasing BMI content, and EB 1/3 showed the highest Tg 377 °C and T5 475 °C. The flexural strengths and moduli of EBs and NBs were higher than those of BBs, and EB 1/2 showed the most balanced flexural strength and modulus (84.5 MPa and 2.75 GPa). The FE-SEM analysis revealed that there is no phase separation for all the cured resins.
Silylated montmorillonite based molecularly imprinted polymer for the selective binding and controlled release of thiamine hydrochloride
Available online 9 May 2013
T.S. Anirudhan | P.L. Divya | J. Nima
Abstract: In the present study, specific binding and controlled release of thiamine hydrochloride (THC) to and from a novel molecularly imprinted polymer matrix namely, THC-templated-silylated montmorillonite-itaconic acid polymer (MIP) was investigated. The polymer matrix was characterized by means of XRD, FTIR and SEM analyses. Optimization of various imprinting components and binding characteristics of THC by the novel MIP were examined in detail. The binding affinity of THC for MIP was found to be greater than that for non-imprinted polymer (NIP). The maximum binding was found to be at solution pH of 4.5. The Sips isotherm model was found to describe well the equilibrium binding data with maximum binding capacity of 100 mg/g for MIP. The kinetic study revealed that the binding of THC onto MIP follows pseudo-second-order kinetic model with correlation coefficient 0.999. The swelling study of MIP in distilled water showed that the maximum swelling capacity is 329.0 g/g at about 8 h. In vitro release experiments showed that MIP releases drug in intestinal fluid with a controlled manner. The release kinetics of drug from MIP was analyzed using Ritger-Peppas model. The binding specificity of MIP for THC was tested using different substrates having structural analogue to the template, THC.
Available online 9 May 2013
Wei Wang | Wenjing Nan | Liang Sun | Wenguang Liu
Abstract: Good blood compatibility and long-term circulation are very important to polycationic systemic gene vectors. In this work, polysulfobetaine-modified low molecular weight polyethyleneimine (LMW PEI, 1.8k) was synthesized and investigated as a vector for gene delivery in vitro and in vivo. PHEAA-b-PMPDSAH was synthesized via atomic transfer radical polymerization method, and then LMW PEI was grafted to PHEAA-b-PMPDSAH by an amido-hydroxy reaction. Incorporation of PMPDSAH into PEI was shown to retain the uncompromised ability to condense DNA into nanocomplexes. MTT assays revealed that the cytotoxicity of LMW PEI-PHEAA-b-PMPDSAH/DNA complexes was lower than that of PEI (25k)/DNA and LMW PEI-PHEAA/DNA complexes. LMW PEI-PHEAA-b-PMPDSAH50 was much superior to PEI (25k) in mediating gene transfection in the presence of 10% serum. At higher serum contents, the transfection of LMW PEI-PHEAA and PEI (25k) was deteriorated, whereas LMW PEI-PHEAA-b-PMPDSAH50 still retained better transfection efficiency, 8-fold more effective than PEI (25k). The expression of red fluorescence protein (RFP) was evaluated by small animal in vivo fluorescence imaging system and the results showed that the expression of RFP was much higher in the mice injected with LMW PEI-PHEAA-b-PMPDSAH50/pDNA-RFP than with LMW PEI-HEAA/pDNA-RFP. Both in vitro and in vivo results suggested that LMW PEI-PHEAA-b-PMPDSAHX copolymer holds a great potential as a vector for systemic gene therapy.
Development of a new azido-oxazoline monomer for the preparation of amphiphilic graft copolymers by combination of cationic ring-opening polymerization and click chemistry
Available online 9 May 2013
Thanh-Xuan Lav | Pierre Lemechko | Estelle Renard | Catherine Amiel | Valérie Langlois | Gisèle Volet
Abstract: A new monomer (2-(5-azidopentyl)-2-oxazoline) bearing an azido group was synthesized. The cationic ring-opening copolymerization of this monomer with 2-methyl-2-oxazoline resulted in a well-defined linear polymer backbone with pendant azido groups. Alkynyl-poly(d,l-lactide) was grafted onto the azido groups of poly(oxazoline) via a Huisgen 1,3-dipolar cycloaddition reaction to give a novel amphiphilic graft copolymer [poly(2-methyl-2-oxazoline-co-2-pentyl-2-oxazoline)-g-poly(d,l-lactide)] (P[(MeOx-co-PentOx)-g-LA]). Different graft copolymers were prepared with PLA of different lengths. Preliminary results of the self-association of this copolymer in water indicated the formation of nanoparticles, which suggests this copolymer may have applications as vehicles for drug delivery.
Available online 9 May 2013
Umile Gianfranco Spizzirri | Giuseppe Cirillo | Manuela Curcio | Ilaria Altimari | Nevio Picci | Francesca Iemma
Abstract: This study has the goal to evaluate thestabilityof B complex vitamins, loaded into catechin-based crosslinked hydrogels, in aqueous medium at accelerated conditions of oxidative stress. The formulations were prepared by coupling polyacrylic acid with catechin in the presence of dicycloexylcarbodiimide. Folic acid (FA) and Thiamine (TH) were chosen within the B complex vitamins because of the well-known oxidative degradation characteristics. The protective role of the hydrogels against the oxidation damage was monitored inducing oxidative stress, by means of UV irradiation and t-butyl hydroperoxide treatment for FA and TH, respectively. The characterization of the hydrogels was obtained by morphological, calorimetric, FT-IR analyses, antioxidant assays and evaluation of the swelling behaviour in aqueous media at different pH. The experimental results confirmed the suitability of the hydrogels as pH-responsive devices, furthermore the presence of oxidative condition proved the protective effect of the hydrogels. Catechin-based polymers gave a pronounced improvement in the stability of vitamins compared to hydrogels prepared by the coupling reaction of polyacrylic acid in the presence of 1,6-hexandiol. Under oxidative conditions, FA and TH were preserved by 96 and 60% respectively.
Available online 7 May 2013
Hendrik Lützen | Thorsten M. Gesing | Andreas Hartwig
Abstract: Partially crystalline thermosetting epoxy polymers of defined heterogeneous morphology are herein presented. Crystalline poly(ε-caprolactone) (PCL) domains are covalently integrated into the cationically polymerized epoxy network. Although crystallinity is common in thermoplastic polymers, these new materials are among the first examples of partially crystalline thermosetting polymers. Nucleation is crucial and leads to a defined heterogeneous morphology. Homogeneous and heterogeneous polymers with identical composition can be prepared by initiation below or above the melting point of the PCL, respectively. While the homogeneous polymer showed the expected decrease in crosslinking density of the epoxy network and low glass transition temperature (Tg), the epoxy phase is not substantially influenced in the case of the heterogeneous morphology, showing two separated modulus changes at the melting point of PCL and the Tg of the epoxy matrix polymer.
Chelidamic acid functionalized stimuli-responsive hydrogel supported-palladium catalyst for copper-free Sonogashira reaction in aqueous media
Jianhua Yang | Xi Zhang | Wei Yu | Weijie Liu | Fengling Bian
Abstract: A thermo and pH-responsive hydrogel (PNIPAM-co-PPAP) was synthesized via free radical polymerization of N-isopropylacrylamide (NIPAM) and potassium 4-(acryloyloxy) pyridine-2, 6-dicarboxylate (PAP) in mixed solvents of water and tetrahydrofuran. SEM micrographs revealed that the hydrogel was macroporous and the pores within the matrixes were interconnected. The chelidamic acid functionalized PNIPAM-co-PPAP hydrogel exhibited excellent capacity to anchor palladium (II) and the resulting material showed well catalytic activity for copper-free Sonogashira reaction of aryl halides with phenylacetylene in aqueous media. The reactions proceeded well with 0.1mol% of Pd (II) catalyst, due to the good dispersion of Pd2+ in the macroporous structure as well as the enrichment of reactants within hydrogel under reaction conditions. Through the reversibly swelling/deswelling, the PNIPAM-co-PPAP hydrogel-immobilized Pd (II) catalyst could be easily recovered by simple method. Furthermore, the PNIPAM-co-PPAP /Pd catalyst exhibited good recyclability and could be recycled six times without remarkable loss in catalytic activity.
Rodolfo J. González-Paz | Ana M. Ferreira | Clara Mattu | Francesca Boccafoschi | Gerard Lligadas | Juan C. Ronda | Marina Galià | Virginia Cádiz | Gianluca Ciardelli
Abstract: Two different polyurethanes synthesized from two triols derived from undecenoic acid (PU1) and oleic acid (PU2) fatty acids were functionalised with Collagen type I via plasma treatment aimed at obtaining novel biomaterials with improved biological properties. Scanning Electron Microscopy, X-ray photoelectron spectroscopy, optical microscopy, colorimetric titration methods and contact angle measurements confirmed the surface changes at each stage of treatment, both in terms of morphology and chemical composition. The results for osteoblastic cells (MG63) cultured in vitro proved that PUs modified with collagen had better cytocompatibility that the control PUs. In particular, PU2 displays higher cytocompatibility.
Vladimir Soldatov | Sergej Pristavko | Vladimir Zelenkovskii | Eugeny Kosandrovich
Abstract: Comparative studies of the state of water molecules in carboxylic acid resins were carried out using classic thermodynamics and ab initio quantum chemical calculation of the structure of representative fragments of their polymeric matrix in the presence of different amounts of water molecules. Water sorption isotherms were obtained for H+, Li+, Na+, K+ Mg2+, Ca2+ and Ba2+ forms of the carboxylic acid ion exchanger Lewatit S8227 using the isopiestic method. Quantum chemistry calculations were performed by the Firefly QC package, which is partially based on the GAMESS (US) source code, on the theory level RHF/MINI. Atomic structures of fragments of the resin interior containing 1–6 monomeric residues and 0–10 water molecules per functional group were computed. It has been shown that the water sorption isotherms are well described by the previously derived equation on the assumption of the presence in the swollen ion exchanger of one or two formal hydrates. Quantum chemistry calculations allow independent evaluation of the number of water molecules in the hydrates and in so doing reduce the number of fitting parameters needed for quantitative description of the water sorption isotherms. They also allow classifying the water molecules in the resin according to the type of interaction with fixed ion–counter-ion ion pair.
Abstract: Sorption mechanism of copper for spherical hydrogel structures formed by the phase inversion method are determined. Based on equilibrium and the research of structural attempt was made to explain the mechanism of sorption. Equilibria was describe by Langmuir, Langmuir–Freundlich equation. The chemical character of sorption was confirmed by IR and WAXS and XPS spectra.
High molecular weight copolymers of vinylferrocene and 3-phenylferrocenophane-1,5-dimethylene with various N-substituted maleimides
Jamie Carberry | Jennifer A. Irvin | Daniel T. Glatzhofer | Kenneth M. Nicholas | Charles J. Neef
Abstract: Two series of ferrocene-containing polymers have been synthesized from various N-substituted maleimides with 3-phenylferrocenophane-1,5-dimethylene (3A–C) or vinylferrocene (4A–C). These copolymers exhibit high molecular weights and 4A–C formed free standing films. Electrochemical studies with copolymers 3A–C and 4A–C in dimethylacetamide show chemical reversibility for all of the materials but only copolymers 4A–C show electrochemical reversibility. These copolymers were also electrochemically deposited from methylene chloride onto a platinum electrode to form chemically modified electrodes (CMEs). The CMEs show desorption of the ferrocene polymers in acetonitrile solutions but exhibited good stability in aqueous solution. The thermal stabilities of the copolymers 4A–C are typical for a ferrocene containing polymer with 10% weight loss occurring at ca. 385°C. Copolymers 3A–C exhibit higher thermal stabilities with 10% weight loss at 438°C. Differential scanning calorimetry measurements of the copolymers showed melt transitions just before the onset of thermal decomposition.
Synthesis of polyguanamines from 2-N,N-dibutylamino-4,6-dichloro-1,3,5-triazine with aromatic diamines
Kyohei Saito | Naoya Nishimura | Shigeko Sasaki | Yoshiyuki Oishi | Yuji Shibasaki
Abstract: Solution polycondensation of 2-N,N-dibutylamino-4,6-dichloro-1,3,5-triazine (BDCT) with various aromatic diamines, including 4,4′-oxydianiline (ODA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), o-tolidine (oTD), 4,4′-(9-fluorenylidene)dianiline (BAFL), and 2,4-diamino-6-(N,N-dibutylamino)-1,3,5-triazine (DABT), was investigated. High molecular weight (>10,000) polyguanamines (PGs) were obtained via the polymerization of BDCT with ODA, pPDA, oTD, and BAFL at 150–180°C in N-methylpyrrolidone (NMP) for 6h. The polymerizability with BDCT was determined on the basis of the molecular weights of the polymers and the chemical shifts of the NMR data as follows: ODA>oTD>BAFL>pPDA>mPDA≫DABT. PGs were obtained from the reaction of BDCT with ODA and mPDA in only 55–77% yield, which may be attributed to the formation of cyclic oligomers. All of the polymers showed high thermostability (5% weight-loss temperature in N2 greater than 444°C), and the polymers generated from reaction of BDCT with ODA, mPDA, and BAFL exhibited good solubility in tetrahydrofuran and polar aprotic solvents such as NMP.
Environmentally friendly PBS-based copolyesters containing PEG-like subunit: Effect of block length on solid-state properties and enzymatic degradation
Matteo Gigli | Andrea Negroni | Giulio Zanaroli | Nadia Lotti | Fabio Fava | Andrea Munari
Abstract: The use of biodegradable polymers could contribute to mitigate the huge environmental problems caused by the massive use of conventional non-biodegradable plastics, especially in the case of time-limited applications. In this framework, in the present study we propose a new class of multiblock eco-friendly copolyesters containing butylene succinate (BS) and triethylene succinate (TES) sequences. In particular, four copolyesters with the same chemical composition but different block lengths – P(BS10TES10), P(BS5TES5), P(BS3TES3), and P(BS2TES2) – were synthesized by reactive blending. For sake of comparison, homopolymer PBS was also considered. Physicochemical characterization (DSC, WAXS, tensile tests, WCA) of the copolymers synthesized demonstrated that it is possible to control polymer crystallinity, thermal and mechanical properties and wettability of the final product by simply varying block length. As a matter of fact, melting point, crystallinity degree, elastic modulus and surface wettability decreased with the block length; on the contrary, elongation to break significantly increased. Enzymatic hydrolysis performed with lipase from Candida cylindracea ([E]=50U/mL, T=30°C and pH=7.0), showed that copolymers biodegradation is much higher than that of PBS homopolymer. Moreover, copolymers displayed a tunable range of degradation rates, related to their crystallinity degree and hydrophilic/hydrophobic ratio, which render them promising for different time-span applications, ranging from long-term (P(BS10TES10) to very short-term (P(BS2TES2)).
Impedimetric detection of dopamine on poly(3-aminophenylboronic acid) modified skeleton nickel electrodes
Nicoleta Plesu | Andrea Kellenberger | Ioan Taranu | Bogdan Ovidiu Taranu | Iuliana Popa
Abstract: Detection of biologic compounds in particular dopamine is usually based on the complexation between boronic acid groups and diols. For this reason the development of new sensors based on direct monitoring of boronic acid–diol complexation is attractive. A measurable electric response due to a change in the dopamine concentration can be achieved on electrodes modified with boronic groups. In this work a modified electrode has been obtained by electropolymerization of 3-aminophenylboronic acid in aqueous solutions on a preformed polyaniline layer electrochemically deposited on smooth and skeleton nickel electrodes. The modified electrodes have been tested as impedimetric sensors for the detection of dopamine in aqueous phosphate buffer at pH=7.4. Both sensors gave a linear response for dopamine concentrations between 10−5 and 10−10molL−1. Poly(3-aminophenylboronic acid) modified skeleton nickel electrode has the advantage of an increased specific surface area, that lead to a high density of boronic acid groups and hence to a better sensitivity.
Magdalena Hasik | Monika Wójcik-Bania | Anna Nyczyk | Teresa Gumuła
Abstract: In the work, two linear polysiloxanes (D2V and V3 polymers) containing vinyl (Vi) groups regularly distributed along their chains were cross-linked by hydrosilylation with SiH groups containing polyhedral oligomeric silsesquioxane (POSS) molecules, namely: dimethylsiloxy-substituted octahedral oligosilsesquioxane (Q8M8H). The reactions were carried out at equimolar SiVi: SiH groups ratios in methylene chloride, tetrahydrofuran and toluene in order find out the optimum solvent for achieving the highest possible polymer cross-linking levels. In toluene, cross-linking was also performed at lower reactive groups molar ratios. Investigation of the cross-linked systems allowed establishing that hydrosilylation in toluene was the most efficient. Independently of the SiVi: SiH groups molar ratio in the starting reaction medium, D2V polymer reacted with Q8M8H to a higher extent than the V3 one. In some systems, Q8M8H acted not only as a cross-linker, but also as filler. Pyrolysis of the cross-linked polymers conducted in Ar atmosphere led to formation of SiCO ceramics with high yields (63.4–85.1wt.%). Particularly advantageous effect of incorporation of POSS molecules on ceramic yield was observed for the D2V polymer. SiCO materials obtained are pore- and crack-free and can be applied as chemically and thermally stable protective layers on various substrates.
Nidhal Okhay | Corinne Jegat | Nathalie Mignard | Mohamed Taha
Abstract: Reversibly crosslinked polymethylmethacrylate were prepared by Diels–Alder (DA) reaction using multi-furan and multi-imide precursors. Furan functionalized PMMA were obtained by reactive extrusion (transesterification) between a commercial PMMA and furfuryl alcohol using tin(II)2-ethylhexanoate (Sn(oct)2) or 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) catalysts. Maleimide based coupling agents were prepared by amine–anhydride reaction. Thermomechanical properties of the PMMA precursors and issued networks were analyzed. Two G′ and G″ cross-over temperatures were obtained during the heating and cooling cycles. The first one at 110°C can be assimilated to physical gel formation and the second one at 160°C to its breaking. When the network was formed, an increasing of these temperatures is observed. Also, the G′ between these temperatures increased with the network density. The obtained network had a shape memory behavior.
A novel electron beam-based method for the immobilization of trypsin on poly(ethersulfone) and poly(vinylidene fluoride) membranes
Sandra Starke | Marco Went | Andrea Prager | Agnes Schulze
Abstract: A novel technique for the covalent immobilization of trypsin in a one-step reaction using low-energy electron beam is described. The enzyme immobilization was applied on poly(ethersulfone) and poly(vinylidene fluoride) microfiltration membranes. For this purpose, the membranes were dipped in an aqueous solution of trypsin followed by electron beam treatment.The effect of irradiation conditions on the immobilization was investigated, as well as the resulting membrane properties with respect to enzymatic activity, immobilized enzyme concentration, pure water flux, scanning electron microscopy, and porosimetry. This technique shall provide a simple, inexpensive method for enzyme immobilization on various polymer membranes and offer a tool for the application in enzymatic membrane reactors.
Synthesis, characterization, and properties of novel hydrophobically associating fluorinated copolymers for DNA delivery
Wei Kuang | Xiaodong Zhao
Abstract: Novel fluorinated associative copolymers poly(ethylene glycol)-b-poly(2-(perfluorohexyl)ethyl methacrylate (PFHEMA)-co-3-[N-(2-methacroyloylethyl)-N,N-dimethylammonio]-propane sulfonate (DMAPS)) (PEG-b-PPFHEMA/PDMAPS) were prepared as a type of non-viral gene vector. The series of PEG-b-PFHEMA/DMAPS with different molecular weights and compositions were characterized by gel permeation chromatography–multi-angle light scattering, 1H NMR, 19F NMR, and elemental analysis. The interactions of the copolymers with calf thymus DNA and the morphologies of the resulting complexes were studied by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. In addition, the DNA–polymer interaction, as determined by the gel retardation assay, and the low cytotoxicity of PEG-b-PPFHEMA/PDMAPS demonstrated that these copolymers have good DNA binding capacity and potential for high performance in the practical application of DNA delivery.
Promoted cell proliferation and mechanical relaxation of nanocomposite hydrogels prepared in cell culture medium
Tao Wang | Weixiang Sun | Xinxing Liu | Chaoyang Wang | Shiyu Fu | Zhen Tong
Abstract: Nanocomposite hydrogels (NC gels) were synthesized through in situ polymerization of N-isopropylacrylamide (NIPAm) in the hectorite clay suspension made from cell culture medium Dulbecco’s modified Eagle medium (DMEM). Cell cultured on these NC gels (D-NC gels) surface proliferated faster compared with that on the NC gels synthesized in water due to the nutrients in the D-NC gels. Cells attached and proliferated faster on the D-NC gels with higher modulus. In addition, cell sheets with good viability spontaneously detached from the gel surface by lowering temperature. Their tensile elongation at break was higher than 7 and the true strength σtrue was up to 800kPa. The stress–strain curves of the D-NC gels were described quantitatively with the Mooney–Rivlin equation. A stretched exponential stress equation was adopted to express the stress relaxation of the D-NC gels with an average relaxation time τ (∼102s) estimated from data fitting, showing a broad distribution (polydispersity k∼0.4). The τ value, which was used in simulation for the tensile creep compliance of the D-NC gels, became shorter with increasing clay concentration due to the decrease in the network chain length. The relaxation process was similar to the natural articular cartilage. This work provides a facile way to produce hydrogels with improved cell compatibility and satisfactory mechanical properties for biomedical applications.
Preparation of quaternized poly(vinylidene fluoride) membranes by γ-ray irradiation induced graft polymerization and their antibacterial property
Available online 30 April 2013
Qingyang Gu | Zhiqian Jia
Abstract: PVDF microfiltration membranes were modified by γ-ray irradiation induced grafting polymerization of 4-vinyl pyridine (4-VP) and then quaternization by n-butyl chloride. The effects of grafting method (simultaneous irradiation, pre-irradiation/UV), grafting conditions (absorbed dose, UV irradiation time, and 4-VP concentration) and quaternization conditions (temperature, time, and concentration of n-butyl chloride) were investigated. It was found that, the grafting degree initially increases with the absorbed dose and then reaches a plateau. The optimal concentration of 4-VP is around 15 wt%. The ion exchange capacity increases with quaternization temperature, time, and concentration of n-butyl chloride. After modification, the pores size, permeation flux, as well as elongation at break, of quaternized membrane decreases, while the retention coefficient, tensile strength and Young’s modulus increase apparently. Upon contacting with the membranes, the E. coli concentration decreases gradually. It is the adsorption mechanism for the pristine membranes whereas contact-killing mechanism for the quaternized membranes. Simultaneous irradiation is more effective than pre-irradiation/UV in the improvement of antibacterial property of membranes.
Available online 30 April 2013
Nikolai B. Ferapontov | Mikhail G. Tokmachev | Aleksander N. Gagarin | Nadezda L. Strusovskaya | Svetlana N. Khudyakova
Abstract: The influence of water activity on swelling of cross-linked hydrophilic polymers in electrolyte solutions of various concentrations was studied. A heterophase model was proposed to explain the polymer swelling. It was shown that the change in polymer swelling deals with different water sorption, and is described by water vapour sorption isotherm. At the same time, the volume of external solution taken up by polymer at swelling is constant and independent of concentration of the solution. Three models describing the structure of polymer gels were suggested and discussed on the base of the obtained results.
Structure and biological evaluation of amino-functionalized PVP nanogels for fast cellular internalization
Available online 30 April 2013
C. Dispenza | S. Rigogliuso | N. Grimaldi | M.A. Sabatino | D. Bulone | M.L. Bondì | G. Ghersi
Abstract: Aminopropyl methacrylamide chloride-graft-poly(N-vinyl pyrrolidone) nanogels (NGs) were designed to exploit the favorable properties of poly(N-vinyl pyrrolidone) (PVP), such as its high affinity to water and complexation ability of ions, molecules and macromolecules, with the availability of primary amino groups for bioconjugation reactions. A thorough structural characterization of the nanoscalar networks was performed via 1H-NMR and solid state 13C-NMR spectroscopies, while solid state NMR relaxation time measurements completed the NGs description in terms of polymer network density. Information on the hydrodynamic size and surface charge densities were sought via dynamic light scattering (DLS) and ζ-potential measurements. These measurements, carried out both in water and in buffer and at the variance of pH, temperature and time, support the excellent colloidal stability of the amino-graft PVP nanogels and their redispersability from the dry physical form. The total absence of in-vitro toxicity and immunogenicity was ascertained first, and then cell localization studies in cell cultures of fluorescent variants were performed. Furthermore, the possibility of decorating the nanogels with bovine serum albumin (BSA) to obtain a stable bio-hybrid colloidal nanoconstruct was established. All the gathered evidences qualify these materials as potential candidates to be used as nanocarriers for intra-cellular delivery of protein and other biomolecular drugs.
Available online 30 April 2013
Rakesh Kumar | V.R. Sinha
Abstract: The major challenge for any drug delivery system is the attainment of effective bioavailability without affecting the protective physiological mechanisms within the body. Systems based on mucoadhesive polymers have been widely preferred as these polymers not only prolong the residence time of the system on mucosal surfaces, but also retarded drug elimination. Mucin is one of the prominent targets to improve drug retention by enhancing adhesion between polymer and mucus membrane. Thiomers are modified mucoadhesive polymers that possess thiol bearing side chains display enhanced mucoadhesion that could be attributed to the formation of disulfide bonds between thiolated polymers and cysteine-rich subdomains of mucus glycoproteins. This review proposes the potential of thiomer as a promising and effective carrier for delivery of therapeutics.
Examining structure property relationships in coatings based on substituted linear aromatic polycyanurates
Available online 30 April 2013
I. Hamerton | B.J. Howlin | D.A. Tilbrook
Abstract: Three series of halogenated and non-halogenated polycyanurates are prepared in good yield and purity, and fully characterised. Many of the resulting polymers, formed at room temperature using phase transfer catalysis, can be cast into films with good resilience and high thermal stability (some examples suffer no mass loss when held isothermally at 190°C and only display appreciable losses when held continuously at 300°C). Char yields of 35-65% are achieved in nitrogen depending on backbone structure. Some problems were encountered with solubility, particularly with heavily halogenated dichlorotriazines, which limited molecular weights (Mn = 2000-4000 g mol-1 depending on backbone structure) although when the phase volume ratio was altered to 0.25 higher molecular weights (Mn = 10000-30000 g mol-1) were possible. Best solubility was achieved by using aromatic diols with at least two equivalent phenylene units per dichlorotriazine unit. DSC reveals polymerisation exotherms with maxima at 190-260°C (ΔHp = 35-57 kJ/mol.) followed by embrittlement and shrinkage (when heated to 300°C). These phenomena may be due to the formation of poorly formed crystallites (activation energies span 155-380 kJ/mol) combined with thermal isomerisation.
Polymerization of β-cyclodextrin with 1,2,3,4-butanetetracarboxylic dianhydride: Synthesis, structural characterization, and bisphenol A adsorption capacity
Available online 26 April 2013
Hiroyuki Kono | Taichi Nakamura
Abstract: Water-soluble and water-insoluble β-cyclodextrin polymers (β-CDPs) were prepared from β-CD using 1,2,3,4-butanetetracarboxylic dianhydride (BTCA) as a cross-linker. The structures of the synthesized water-soluble and water-insoluble β-CDPs were characterized in detail using FT-IR, solution- and solid-state NMR, and 1H diffusion-ordered spectroscopic techniques. The water solubility of β-CDP was dependent on the reaction temperature as well as the initial feed ratio of β-CD and BTCA. The BTCA content and the ratio of BTCA molecules cross-linked and grafted to β-CD were also found to influence the water solubility of the polymers. Insoluble β-CDPs were effective in adsorbing bisphenol A (BPA) from aqueous media, with this absorption being highest in materials of low BTCA content, which corresponds to material of high β-CD content per unit mass of β-CDP.
Available online 26 April 2013
Guangren Yu | Ziwei Man | Qingzeng Li | Na Li | Xinying Wu | Charles Asumana | Xiaochun Chen
Abstract: A new porous polymeric microparticle, poly[4-vinylbenzyltriethylammonium chloride] (P[VBTEA][Cl]), is prepared from the crosslinking polymerization of 4-vinylbenzyltriethylammonium chloride with N,N-methylenebisacrylamide via inverse suspension polymerization using cyclohexane as continuous phase, Span 80-Tween 80 as dispersant, and PEG600 as porogen. Two other microparticles, P[VBTEA][BF4] and P[VBTEA][PF6] are further obtained through ion-exchange. FT-IR, TGA, SEM, and EDS analyzes indicate that these microparticles have good porosity (apparent porosities are 55.0, 69.7 and 64.3%, respectively), high thermal stability, and large specific surface area, which make them potentially applicable as adsorbent agents. Their CO2 adsorption-desorption performance is investigated. It is observed that such porous polymeric microparticles present high CO2 sorption capability; typically, the CO2 sorption of P[VBTEA][PF6] is 1.38wt% at 25°C and 1bar. Such porous polymeric microparticles are good candidates for CO2 adsorption.
Synthesis and characterization of molecularly imprinted polymers with metallic zinc center for enrofloxacin recognition
Available online 22 April 2013
JJ. Recillas Mota | MJ. Bernad Bernad | J.A. Mayoral-Murillo | J. Gracia Mora
Abstract: A molecularly imprinted polymer with a metallic center (MIPc) was prepared and characterized. The template molecule for MIPc was a complex [Zn(Aza-f)(Enr)]NO3·H2O, Com, based on the ligands: enrofloxacin (Enr) and azabis(oxazoline) functionalized with styrene. Com was characterized before preparing MIPc. Moreover, the polymer prepared via non-covalent (MIPe) was prepared using Enr as the template molecule while no template molecules were used to prepare the non-imprinted polymer (NIP).MIPc was characterized using different spectroscopic techniques. In addition, the polymer molecular recognition capacity was studied by using rebinding kinetic studies. The kinetics shows that MIPc reach the equilibrium before the MIPe and NIP and the amount of Enr adsorbed is approximately 5 times higher that MIPe and NIP.Scatchard plots analysis for NIP, MIPe and MIPc shows Kd= 0.4768, 0.020, 0.0067 (mmolL-1) respectively. In comparison with the MIPe the binding affinity is nearly 100 times higher taking into account the high affinity sites. The selectivity of MIPc for Enr was higher than that for ofloxacin or flumequin, isotherms were fit to the Langmuir-Freundlich model, and the Enr showed a value of Ko = 21.38 mM-1, while the ofloxacin had a value of 2.2 x10-8 mM-1 and the flumequin of 1.6 x10-5 mM-1.
Available online 20 April 2013
Arnaud Zenerino | Sonia Amigoni | Elisabeth Taffin de Givenchy | Denis Josse | Frédéric Guittard
Abstract: The main difficulty still encountered in the elaboration of polymer/silica nanocomposites is the control of the nanoparticles dispersion homogeneity and the stability of the nanoparticle dispersion in the surrounding substance. The innovative point of this work is the elaboration of hybrid networks in aqueous solution performed with ASE (alkali swellable emulsion) thickeners grafted with silica nanoparticles. The thickening ability of the polymer should favour silica nanoparticles dispersion in fluid matrices. Two ASE copolymers were realised by copolymerisation in emulsion of MA (methacrylic acid) and EA (ethyl acrylate) and/or TFEM (trifluoroethyl methacrylate). The substitution of a part of EA by TFEM gave fluorinated ASE copolymers. Their free acid functions were then coupled with different ratio of amine functionalized silica nanoparticles to afford nanocomposites. The amounts of silica nanoparticles in the copolymers were determined by thermogravimetric experiments. Depending on the silica nanoparticles/copolymer ratio in basic aqueous solutions we achieved stable translucent gel like aqueous suspensions of silica nanoparticles containing 1 wt.% of the polymer/SiO2 nanocomposite.
Coupling reaction with thiols as the efficient method of functionalization of ,,clickable’’ polylactide
Available online 20 April 2013
Abstract: The effectiveness of coupling reactions with thiols proceeding under different conditions is compared as the method of polylactide functionalization. Metal-free syntheses of polylactides (PLAs) fitted at one chain end with unsaturated (allyl, propargyl or acrylate) groups were performed by applying acid catalyzed activated monomer polymerization of lactide using allyl and propargyl alcohols or hydroxyethyl acrylate as initiators. Functional PLAs were used for thiol-ene and thiol-yne reactions proceeding according to radical as well as nucleophilic addition. The coupling efficiency for thiols containing carboxyl groups (in comparison with model benzyl thiol) was investigated by MALDI TOF method.
Available online 20 April 2013
Rong-Jay Lee | Rauno Temmer | Tarmo Tamm | Alvo Aabloo | Rudolf Kiefer
Abstract: Conductive polymers have the ability to capture radicals and have become in focus for antioxidant applications of food packaging or biomedical applications. Unfortunately, the conducting polymers such as polypyrrole are difficult to suspense in solution after chemical or electrochemical polymerization. Chitosan, as a natural polymer from chitin, can be dissolved in diluted acetic acid solutions. In the present study, composites suspensible in diluted acetic acid solutions have been produced by the chemical polymerization of pyrrole in chitosan solution using ammonium persulfate (APS) as the oxidant. FTIR and UV-Vis measurements did identify an attachment of polypyrrole to chitosan.In order to optimize the activity and stability of the composites, the ratios of APS: polypyrrole: chitosan were analyzed. The chitosan-polypyrrole composites were formed as membranes (coatings); impedance measurements indicated their conductivity to be in the range of 10-3-10-7Scm-1. The antioxidant (radical scavenger activity) properties were determined by the di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium (DPPH) assay. The radical scavenger activity of the composites was found renewable by means of electrochemical cycling.
Available online 2 April 2013
P. Basnett | K.Y. Ching | M. Stolz | J.C. Knowles | A.R. Boccaccini | C. Smith | I.C. Locke | T. Keshavarz | I. Roy
Abstract: Novel Poly(3-hydroxybutyrate)/Poly(3-hydroxyoctanoate) blends were developed with varying amounts of Poly(3-hydroxyoctanoate), P(3HO) and Poly(3-hydroxybutyrate), P(3HB) for their potential use in various medical applications. These blend films exhibited higher tensile strength and Young’s modulus values compared to neat P(3HO). The overall protein adsorption and % cell viability was also found to be significantly higher in the blend films than the neat P(3HO) film. Hydrolytic degradation was faster in the blend films and the degradation rate could potentially be tailored to achieve the optimum rate required for a particular medical application. Hence, these novel blends were found to be highly biocompatible with surface, mechanical and thermal properties suitable for a range of potential medical applications, a great step forward in the area of medical materials.
Available online 2 April 2013
Katrin Greimel | Annemarie Marold | Christian Sohar | Roland Feola | Armin Temel | Thomas Schoenbacher | Enrique Herrero Acero | Georg M. Guebitz
Abstract: The potential of two hydrolytic enzymes, namely a lipase from Thermomyces lanuginosus (TlL) and a cutinase from Humicola insolens (HiC) for hydrolysis of the phthalic acid backbone based polyester coatings was assessed. Two phthalic acid/trimethylolpropane based model substrates resembling the structure of the polyester backbone of coatings were synthesized. Out of both enzymes, only the cutinase was able to hydrolyze both model substrates while the larger substrate was hydrolyzed at a lower rate. The cutinase was also able to hydrolyze a coating (alkyd resin) both in suspension and as dried film. LC–MS analysis of the hydrolysis products released from the coating revealed the presence of oleic acid, its monoglyceride, phthalic acid and 2-((3-((2-((2,3-dihydroxypropoxy)carbonyl)benzoyl)oxy)-2-hydroxypropoxy)carbonyl)benzoic acid. These results indicate that the enzyme was able to hydrolyze the polyester backbone as well as to release fatty acid side chains. Consequently, enzymatic hydrolysis has a potential for the removal of coatings, their recycling or their functionalization.
Sibel Kacmaz | Kadriye Ertekin | Mustafa Gocmenturk | Aslihan Suslu | Yavuz Ergun | Erdal Celik
Abstract: In this work, a new procedure for the direct determination of picomolar levels of iron in water is presented. Ethyl cellulose (EC) based nano-fibers were fabricated by electrospinning technique. The limit of detection for Fe3+ is 0.07pM (based on 3s of the blank, n=4). A fluorescent chromoionophore and an ionic liquid were used together as sensing agent and signal stabilizer additives, respectively. The offered composite displayed a sensitive response for Fe3+ ions over a wide concentration range [1.0×10−12–1.0×10−6M]. The sensing design exhibited a response time of less than 30 s which is one of the shortest reported responses among similar solid state sensing agents. The sensor was fully reversible and regeneration time was shorter than 60s. Preliminary results show that sensitivity and selectivity of the nanofibrous membranes to detect Fe3+ ions are higher than those reported previously. Additionally, the exploited nanostructures provided faster sensor dynamics in applications.
Synthesis of sulfonated organic–inorganic hybrids through the radical copolymerization of vinyl sulfonate esters and vinyl trialkoxysilanes
Hideharu Mori | Yosuke Saito | Eri Takahashi | Kazuhiro Nakabayashi | Atsuhiko Onuma | Makoto Morishima
Abstract: Novel organic–inorganic hybrids with sulfonic acid groups were prepared using random copolymers composed of vinyl sulfonate esters and vinyl trialkoxysilanes. Five vinyl sulfonate esters with different substituent groups were employed as protecting monomers for the production of the poly(vinyl sulfonic acid) component, and three vinyl trialkoxysilanes were used as cross-linkable monomers. Free radical and reversible addition-fragmentation chain transfer (RAFT) copolymerizations were performed for the production of random copolymers with two different functional groups. The selective deprotection of the sulfonate esters of the copolymers proceeded smoothly and resulted in the formation of copolymers with lithium vinyl sulfonate units and cross-linkable trialkoxysilane units. The co-condensation of the trialkoxysilane moieties in the deprotected copolymers with cross-linkers yielded transparent hybrid films that contained lithium sulfonate groups without aromatic rings or ester linkages.
Research on curing mechanism and thermal property of bis-allyl benzoxazine and N,N′-(2,2,4-trimethylhexane-1,6-diyl) dimaleimide blend
Zhi Wang | Jiacheng Zhao | Qichao Ran | Rongqi Zhu | Yi Gu
Abstract: A blend of 2,2′-bis(8-allyl-3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) propane (Bz-allyl) and N,N′-(2,2,4-trimethylhexane-1,6-diyl) dimaleimide (TBMI) was prepared. The curing mechanism and thermal property of the cured blend were studied with Differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) and Dynamic mechanical analysis (DMA). It was found that in BzT11 the thermal polymerization reaction of TBMI, the reaction of TBMI catalyzed by Bz-allyl, Ene reaction between TBMI and allyl groups occurred at a low temperature (160°C) simultaneously. About 20% of TBMI was consumed by Ene reaction. Besides, seldom oxzine ring of Bz-allyl polymerized at a low temperature (160°C) and most oxzine ring of Bz-allyl reacted at a high temperature (over 160°C). The Tg of cured blends was increased with the increment of the proportion of TBMI in the blends.

domain: chemistry


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(FixThisNation.com) – “Squad” House Democrats who are known for their previous criticisms of Israel have been slammed online following their statements after Hamas’ terrorist assaults on the Middle Eastern country. Many of the members of the “Squad” released statements on Saturday condemning the attacks that had occurred earlier that day.
On “Squad” member, Rashida Tlaib, D-Mich., has opted to not make a statement following the deadly terrorist attack. However, Rep. Alexandria Ocasio-Cortez, D-N.Y., who is considered the most important member of the “Squad” called for hostilities to de-escalate and for a “ceasefire.”
In her statement, she pointed out that the attack was “devastating” for those in Palestine and Israel who have been trying to secure a long-lasting peace. She also condemned the attack arguing that violence was not something that any family should need to endure. She then argued that this violence was not going to help bring a solution to the “ongoing oppression and occupation in the region” which was why a ceasefire was required to save lives.
South Carolina GOP Rep. Nancy Mace, was quick to slam Ocasio-Cortez for this statement pushing for a ceasefire and referred to her colleague as a “Hamas apologist.”
Rep. Ilhan Omar, D-Minn., who is known for having made several controversial statements against Israel referred to the attack as “horrific” and argued that this “senseless violence” that keeps repeating in a cycle should not be allowed to continue. She then stated that a ceasefire and de-escalation were necessary.
However, Rachel Campos-Duffy, the co-host of “FOX & Friends Weekend” criticized Omar arguing that she would never acknowledge that during the Trump administration, there was peace in both Europe and the Middle East.
Copyright 2023, FixThisNation.com

domain: news


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Saturday, Sept. 28, 11 a.m.-2 p.m.
For ages 3-8. A fun and exciting day for the whole family is right in your backyard! Come to this indoor-outdoor festival and enjoy live entertainment, crafts and activities. Children can buy their own pumpkins from the pumpkin patch (with the help of a parent/guardian) to decorate at the crafts station. Food will be available for purchase.

domain: entertainment


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Join us for this tour from August 10 to August 28, 2020!
Book Title: The Journey: A Traveling Companion Through the New Testament by Debbie Johnson
Category: Adult Non-fiction 18 yrs +, 293 pages
Genre: Memoir, Religious, Inspirational
Publisher: Convenant Books
Release date: 2019
Format available for review: print (USA & Canada) mobi (for Kindle)
Tour dates: August 10 to August 28, 2020
Content Rating: G. No obscenity, violence, sexual content
“With the New Testament in one hand and Debbie’s guidebook in the other, you will experience the Christian journey to be an exciting venture–though not one for the fainthearted.”
Dr. William W. Klein, Ph.D. Professor of New Testament, Denver Seminary
At a time of unprecedented crisis in our lives comes an inspirational book, THE JOURNEY: A Traveling Companion Through the New Testament by Debbie Johnson, who has spent decades as a mission worker, and is the founder DenverWorks, a nonprofit dedicated to helping the unemployed find work. Whether you are a Christian, religious, or irreligious, Johnson’s contemporary interpretation of The New Testament will inspire all who read her book.
Years ago, Debbie took a glorious six-week backpacking trip to Europe. Now she takes readers on a metaphorical trek through the New Testament, filling her backpack with a year’s worth of inspirational items. For Debbie, her destination is love, plus the sense of “mission accomplished” in her life’s work.
“Maybe this is a time for homebound people (all of us) to read through the NT,” says Debbie who begins her journey as Christ began his, when he met two sets of brothers and said, “Follow me” and eventually there were 12 friends, the 12 apostles. Jesus was no longer by himself,” says Johnson and got to experience the strength of friends. “My best friends and I remind each other that we are never alone, even though some of us live hundreds of miles apart.” Here are some of her many useful and inspiring key insights:
In trying times such as these, Debbie Johnson’s THE JOURNEY will brings readers daily inspiration and comfort for themselves and their families.
About the Author
Debbie Johnson is the author of two previous books, A Pocketful of Seeds and Lessons Learned from the Bottom of the Stairs: A Story of Faith and Resilience with Randy Milliken. She graduated from Ouachita Baptist University (BME, MME) and has done graduate work in social work at the University of Denver. In 1995, she founded DenverWorks to equip the unemployed in her community. She led the organization for ten years before engaging in international ministry, first as the vice president of Programs at the Dalit Freedom Network and then as executive director of India Transformed. She grew up in Little Rock, Arkansas. Today she and her husband live on a farm in Colorado with two dogs and a bunch of chickens.
Connect with the Author: website ~ twitter ~ facebook ~ instagram ~
Aug 10 – Splashes of Joy – book review / guest post / giveaway
Aug 10 – Cover Lover Book Review – book review / giveaway
Aug 11 –Over Coffee Conversations – book spotlight / giveaway
Aug 12 –My Journey Back – book review / giveaway
Aug 13 – Sefina Hawke's Books - book spotlight
Aug 14 – Rockin' Book Reviews – book review / guest post / giveaway
Aug 17 –Books for Books - book spotlight
Aug 18 –Books and Zebras – book review / giveaway
Aug 19 –Jazzy Book Reviews – book spotlight / guest post / giveaway
Aug 21 –Literary Flits – book spotlight / giveaway
Aug 24 – A Mama's Corner of the World – book review / giveaway
Aug 25 – Locks, Hooks and Books – book review / giveaway
Aug 26 – The Epistles Of Mark Paul – book review / giveaway
Aug 28 –Confessions of the Perfect Mom – book review
Enter the Giveaway:
* Acorn Book Services/iRead Book Tours is a participant in the Amazon Services LLC Associates Program, an affiliate advertising program designed to provide a means for sites to earn advertising fees by advertising and linking to Amazon.com.
Not only does Lauren do a fantastic job of organizing the tour and communicating with you at every step of the way, but I found the tour hosts that signed up for her tour to be of a higher caliber. The reviews that I got on this tour were thoughtful and well-written and I noticed an uptick in sales during this tour. I also appreciated the fact that many of her tour hosts that wrote reviews posted them on multiple sites, not just on their blog or Instagram account. This is invaluable to an author. I highly recommend Lauren and iReads Book Tours. - Allyson Rice, author of The Key to Circus-Mom Highway
Lauren Carr's iReads Book Tour is amazing! She gets real results. Not only did I get thousands of new eyes on my series, but I grew my following on all social media channels as well. Lauren has a dedicated group of reviewers and bloggers who are competent and reliable - no more wasted ARCs mailed out with no results.
- Michelle Cox, author of the Henrietta and Inspector Howard Novels
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domain: library


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Food sovereignty and traditional seeds
The Ecoruralis Association
“There is food security when someone throws you fish. There is food sovereignty when someone gives you a fishing rod.“ Szőcs-Boruss Miklós-Attila - EcoruralisVideo ▶
Ecoruralis comprises over 1000 Romanian peasants who practice traditional and ecological agriculture. The Association is affiliated to the International Peasant Movement (Via Campesina), an international organization which brings together Romanian Peasants, South African farmers threatened by genetically modified monocultures or African people lacking lands and means for producing foods, under the umbrella of the “food sovereignty” concept. As opposed to governmental agricultural policies, based on the food security and food safety concepts, which are synonym to over-production and stiff regulations, the food sovereignty concept “makes sure that the rights to use and manage lands, territories, water, seeds, livestock and biodiversity are in the hands of those who produce food and not of the corporate sector.” (Via Campesina)
The food sovereignty concept is also tested hands-on by all Romanian peasants, as well as by the staff of the Association. The latter, together with the University of Agricultural Sciences and Veterinary Medicine in Cluj and with the help of interns, cater for a garden of traditional seeds, intended for free distribution. The preservation of traditional varieties and their free circulation represent resilient practices supporting agricultural biodiversity and social sustainability, as well as food independence.
“There is food security when someone throws you fish. There is food sovereignty when someone gives you a fishing rod.“ (Szőcs-Boruss Miklós-Attila, Ecoruralis)