text:
|Numéro de publication||US5455673 A|
|Type de publication||Octroi|
|Numéro de demande||US 08/250,396|
|Date de publication||3 oct. 1995|
|Date de dépôt||27 mai 1994|
|Date de priorité||27 mai 1994|
|État de paiement des frais||Caduc|
|Autre référence de publication||CA2190627A1, CA2190627C, CN1079533C, CN1149334A, DE69513517D1, DE69513517T2, EP0760938A1, EP0760938B1, WO1995033189A1|
|Numéro de publication||08250396, 250396, US 5455673 A, US 5455673A, US-A-5455673, US5455673 A, US5455673A|
|Inventeurs||Daniel C. Alsmeyer, Brinda A. Gala, Vincent A. Nicely|
|Cessionnaire d'origine||Eastman Chemical Company|
|Exporter la citation||BiBTeX, EndNote, RefMan|
|Citations de brevets (11), Citations hors brevets (33), Référencé par (62), Classifications (8), Événements juridiques (8)|
|Liens externes: USPTO, Cession USPTO, Espacenet|
This invention relates generally to Raman spectrometry, and more particularly to a standardized Raman spectrometry apparatus capable of measuring and compensating for variabilities in the system.
The use of spectrometry in analytical laboratories for measuring physical and analytical properties of materials is a well established art. Raman spectrometry is one such technique that can provide qualitative and quantitative information about composition and/or molecular structure of chemical substances. When incident radiation interacts with matter it may undergo a process called scattering. Scattered radiation may be elastic, in which the incident wavelength is unchanged in the scattered radiation, or inelastic, in which the scattered radiation has different wavelengths than the incident radiation. In one form of inelastic radiation scatter, referred to as Raman scattering, incident photons are scattered with either a gain or loss of energy. The energy difference between the scattered and incident radiation is commonly referred to as the Raman shift. The resultant Raman shift spectrum provides the energy of various molecular vibrational motions and conveys chemical and molecular information regarding the matter studied.
The Raman scattering effect is extremely weak; typically a few Raman scattered photons exist among millions of elastically scattered photons. This small Raman signal amongst the large elastically scattered signal places severe demands on the instrumental design of any spectrometer used to collect useful Raman spectra.
Numerous radiation sources are capable of generating Raman scatter from a material. For analytical measurement, these sources need to emit monochromatic radiation of high intensity. In this regard, lasers are well suited radiation sources. U.S. Pat. No. 3,556,659, the disclosures of which are incorporated herein by reference, describes a Raman spectrometer in which a sample contained in a tube is irradiated by radiation from a laser along the axis of the tube.
There are various classes of laser radiation sources, including: gas lasers, such as helium-neon, nitrogen, argon ion and krypton ion; solid state lasers, such as ruby lasers and Nd:YAG (neodymium:yttrium-aluminum-garnet) lasers; dye lasers; chemical lasers; and solid state lasers, such as single mode and multi-mode diode lasers.
Of these, gas lasers are generally accepted as especially suitable for dispersive Raman spectrometry because of their high degree of wavelength stability. Unfortunately, they are either expensive and require extensive maintenance, or they have low output power. The use of semiconductor diode lasers in Raman spectrometry, which can provide large power output in a compact, rugged device but which may exhibit inherent instabilities in their output properties, are described in Wang and McCreery, Anal. Chem., 1990, Vol. 62, pp. 2647-2651, the disclosures of which are incorporated herein by reference.
Because the Raman scattering process relates to a shift from an incident wavelength, different lasers provide spectra in different wavelength regions. However, the Raman shift spectra in those regions are similar, and essentially the same structural information can be obtained through the use of different incident laser wavelengths.
Fluorescence is a process by which absorbed radiation induces broad emission, characteristic of the molecular structure. The induced fluorescence signal, if observed, is typically many orders of magnitude larger than the Raman signal and in some cases completely masks the Raman shift spectrum. Thus, it is desirable to select an incident wavelength that minimizes fluorescence emission processes.
A well known method to reduce fluorescence background problems is to use lasers which generate red or near infrared radiation, with wavelengths from about 660 nanometers to 1100 nanometers, as described in D. B. Chase, J. Am. Chem. Soc., 1986, Vol. 108, pp. 7485-7488, the disclosures of which are incorporated herein by reference. Such a method is useful because the fluorescence emission profile is independent of incident wavelength and the Raman process is a shift from the incident wavelength. Typical radiation sources operating in this region include krypton ion gas lasers, single mode diode lasers, multi-mode diode lasers, and Nd:YAG lasers.
The large ratio of elastically to Raman scattered photons requires an efficient method of photon separation. Traditionally, this has been accomplished with double or triple spectrograph systems, constructed with two or three dispersive elements, respectively. Other radiation filtering devices can sufficiently reject the elastically scattered photons to permit the use of smaller, more efficient single dispersive element spectrograph devices; for example, holographic Bragg diffraction filters are described in Carrabba et al., Appl. Spec., 1990, Vol. 44, pp. 1558-1561, the disclosures of which are incorporated herein by reference.
The detector element is critical to the performance of the Raman instrument and must be capable of discerning extremely low levels of radiation. Traditional scanning monochromator systems have used photomultiplier tubes that are capable of observing low photon signals. More recent instruments employ array detectors such as photodiode arrays (PDA) or charge coupled devices (CCD). Array detectors consist of multiple optical elements that can simultaneously observe a region of the spectrum up to the entire Raman spectrum. CCD detectors are multi-dimensional and able to observe multiple Raman spectra at more than one wavelength simultaneously.
The previously mentioned paper by Wang and McCreery describes the use of a charge coupled device together with a near-infrared diode laser in a Raman spectrometer of high sensitivity. Also, Newman et al., Appl. Spec., 1992, Vol. 46, pp. 262-265, the disclosures of which are incorporated herein by reference, describes the use of a CCD and diode laser with a flat field imaging spectrograph provided with a fiber optic interface with the sample.
Raman spectrometry instrumentation that combines a single dispersive grating spectrograph with a CCD detector, single-mode diode laser, fiber optic cables, a fiber optic probe, and a suitable computer may be able to accomplish in seconds what used to take minutes to hours with traditional instrumentation. However, mechanical stability of the spectrograph and detector system and other optical interfaces as well as the diode laser instabilities cause severe limitations to the ultimate quantitative capability.
Fourier Transform (FT) Raman spectrometry has been proposed for quantitative chemical analysis. However, due to instrumental variations, the analysis is generally limited to, at best, about one percent reproducibility, as described in Seasholtz et al., Appl. Spec., 1989, Vol. 43, pp. 1067-1072, and in Smith and Walder, "Quantitative Analysis Using FT-Raman Spectroscopy," Nicolet Instrument Corporation technical publication AN-9145, 1991. This level of uncertainty is inadequate for many quantitative applications.
The use of Raman instruments to obtain spectra for quantitative chemical determinations is limited by the considerable extent of system variability. This variability in Raman spectrometry apparatus has many sources, including the following:
(a) variation in the intensity and/or wavelength of the source radiation, which can be in the energy profile (wavelength) of the incident beam or the wavelength position (energy of incident radiation) of the profile;
(b) variation in optical alignment, for example, in the input optical components;
(c) variation in the characteristics of the spectrograph;
(d) variation in the position of the detector; and
(e) random detector noise variation arising from photon counting statistics (referred to as "shot noise"), random movement of molecules and electrons in the detector component (referred to as "dark noise"), and instabilities arising during conversion of the electronic signal from the detector to an analog signal (referred to as "read noise").
Different analyses have unique spectral quality requirements. For example, an analysis for the ratio of two materials for which the spectra of the components are different and non-overlapping would be relatively tolerant of both intensity and wavelength instability. U.S. Pat. No. 5,139,334, the disclosures of which are incorporated herein by reference, describes a method of analyzing hydrocarbon mixtures in which a Raman spectrum of a sample is separated into two non-overlapping ranges, the intensity of scattered radiation in each range is integrated, and the integrated intensity values are compared to provide a measurement of the sample properties. However, in a complex analysis of many components that may have similar spectra, there may not be two non-overlapping ranges with the necessary properties for adequate analysis. Compensation for the variabilities in the radiation source and other components of the Raman spectrometry apparatus, as is provided by the present invention, would enable the use of statistically based procedures such as multiple linear regression or partial least squares to achieve an accurate analysis of a complex mixture.
A simple test of the quantitative reproducibility of a spectrometer apparatus is to collect two spectra of the same material of interest at two different times. One spectrum is subtracted from the other to produce a difference spectrum, in which can be seen a residue that is the consequence of the non-reproducible features of the two spectra. In the optimum situation, the residue, which derives from such sources as read noise from the detector and shot noise from the fluctuations in the photon arrival rate, would be of random intensity difference with wavelength. Any residue that looks like the original spectrum (intensity instability), the first derivative of the original spectrum (wavelength position shifts between the two spectra), the second derivative of the original spectrum (relative broadening between the spectra), or combinations of the above, indicates instabilities in the components of the apparatus.
A Raman spectrometry apparatus that is capable of measuring and compensating for variabilities in the apparatus comprises a source of substantially monochromatic radiation, means for simultaneously interfacing the radiation with a sample and reference material, means for simultaneously acquiring at more than one wavelength the convolved Raman spectrum of the sample and a convolved spectrum of the reference material, and means for determining the convolution function of the convolved spectra and applying the convolution function to adjust the convolved Raman spectrum of the sample to produce thereby the standard Raman spectrum of the sample.
A method for obtaining the standard Raman spectrum of a sample comprises:
(a) simultaneously irradiating the sample and a reference material with a substantially monochromatic radiation source;
(b) simultaneously acquiring at more than one wavelength a convolved Raman spectrum of the sample and a convolved spectrum of the reference material;
(c) choosing the standard spectrum of the reference material;
(d) from the convolved Raman spectrum of the sample and the convolved spectrum of the reference material and the standard spectrum of the reference material, determining the convolution function of the convolved spectra; and
(e) applying the convolution function to adjust the convolved Raman spectrum of the sample to produce thereby the standard Raman spectrum of the sample.
The Raman spectrometry apparatus and spectrum standardization method of this invention allows one to measure and compensate for variabilities in the spectra of the sample and the reference material owing to instabilities in various components in the apparatus so that, after standardization, the difference spectrum shows only fluctuations characteristic of random detector noise. The standard Raman spectrum obtained in accordance with the present invention enables precise quantitative measurements of a sample, which find use in monitoring the course of a variety of chemical processes such as, for example, distillation or polymerization.
FIG. 1 is a schematic diagram of a single probe Raman spectrometer.
FIG. 2 is a schematic diagram of a double probe Raman spectrometer.
FIG. 3 is an illustration of a procedure for obtaining the convolved spectra of a sample and a reference.
FIG. 4 is an illustration of the Fourier transform process of measuring differences between standard and convolved reference spectra for the purpose of standardizing the convolved sample spectrum.
FIG. 5 is a schematic diagram of a multi-probe Raman spectrometer.
FIG. 6 is a schematic diagram of a multi-source Raman spectrometer.
FIG. 7 is an illustration of the reduced variation in standardized spectra.
FIG. 8 is an illustration of the reduced variation in standardized spectra following variations in the apparatus.
FIG. 9 is an illustration of reduced variation in standardized spectra from a gas laser in a dual beam spectrometer.
FIG. 10 is an illustration of reduced variation in standardized spectra from a multi-mode diode laser in a dual beam spectrometer.
The Raman spectrometry apparatus of the present invention is capable of measuring and compensating for both long-term and short-term variations and instabilities in its component parts. It uses a referencing technique that simultaneously acquires the convolved spectra of samples with unknown characteristics and a reference material, where all spectra have been subjected to the same instabilities. This Raman spectrometry apparatus is particularly useful in applications where precise quantitative determinations of structural or compositional properties of matter are required, and where it is convenient to use unstable or variable spectrometer components for reasons of ruggedness, simplicity, cost, speed, and the like.
U.S. Pat. No. 4,620,284, the disclosures of which are incorporated herein by reference, describes a method and apparatus for comparing the Raman spectrum of an unknown sample with reference spectra of known materials, the reference spectra being stored in digital form in a computer, and the comparison of the spectra being accomplished by the computer. There is no provision, however, for the detection of and compensation for long-term and short-term variations and instabilities in the spectrophotometric apparatus.
The present invention describes a Raman spectrometry apparatus and a method in which variations from source, detector, and/or mechanical positioning instabilities are measured for an acquired Raman spectrum so that the necessary compensation can be provided. A preferred embodiment of this apparatus utilizes an instrument constructed with a radiation source, optics, a dispersive element, and a multichannel array detector, together with a mathematical procedure for obtaining the convolution function and providing the standard Raman spectrum of a sample.
Minimizing instabilities in diode lasers may be achieved through proper control of temperature and unwanted emissions, as described in Carrabba et al., "Compact Raman Instrumentation for Process and Environmental Monitoring," SPIE 1991 Vol 1434, Environmental Sensing and Combustion Diagnostics, pp. 127-134, the disclosures of which are incorporated herein by reference. For the control of undesirable laser emissions, Carrabba et al. describes holographic optical edge filters which have very high optical density at the laser wavelength.
Without controls such as those described, diode lasers are unstable and thus regarded as of little use for Raman spectroscopic investigations. Further, the wavelength of any diode laser device will gradually shift as the device ages. A diode laser device, though stable for short times, is characterized by long-term instabilities which produce a slow drift, resulting in reduced instrument reliability. To date there have been no published solutions to these long-term instability difficulties with diode laser devices when applied to Raman spectrometry.
Typical single mode diode lasers are relatively inexpensive but perform with substantially less output power compared to gas lasers. Multi-mode diode lasers, which have inherent wavelength instabilities, generate substantially more laser power output than single mode diode laser devices, but they exhibit a constantly changing wavelength intensity profile. Thus, multi-mode diode lasers, while attractive because of their large power output, have not heretofore been considered useful in providing reproducible Raman spectra.
Normally, Raman spectra are obtained by scattering laser radiation with a wavelength spread and variation much smaller than the resolution of the instrument. However, by reducing resolution, additional signal throughput can be obtained and broader bands may be used. For example, a multi-mode diode laser has less spectral purity and stability than traditional sources but could provide a greater signal at a reduced cost. Though it may appear that less resolution provides less information, broad signals often contain information similar to narrow signals, which can be extracted by proper mathematical routines.
Another source of variation in a spectrometer used in an on-line process control environment is related to maintenance or repair operations. For example, a major component in the spectrometer might need to be replaced because of malfunction. If a detector is removed and remounted, position inaccuracies of as little as a few micrometers will lead to spectral errors sufficient to destroy quantitative calibration. If a diode laser were to be replaced, the new laser could have characteristics significantly different from the replaced item. In the chemical process industry, these and other changes in spectrometric instrumentation are likely to occur. To provide a useful process analysis tool, the spectrometer apparatus must be robust enough to permit these changes without major disruption of its operation.
In a Raman spectral determination, the observed signal will always be a convolution of the desired signal and an instrumental response. In general, instrumental responses broaden, shift, or otherwise distort the desired signal.
The convolution process, though non-linear in an observed spectrum, can be represented as a multiplication in the time domain. FT techniques are commonly used to accomplish the conversion to and from the time domain. In the time domain, the deconvolution process is a straightforward division, using complex numbers (which consist of both a real and imaginary component), of the observed signal by the instrumental response function.
Under ideal conditions, the instrument response may be determined either experimentally or by a theoretical calculation. However, when the apparatus response changes with time, as is the case with unstable lasers or other components, traditional methods of using FT deconvolution to compensate for instrumental effects are inadequate.
A Raman spectrometer useful for the practice of the present invention may be constructed such that the radiation from a laser is optically filtered and transmitted to the sampled matter; the Raman scattered radiation is then collected, optically filtered, and transmitted to the dispersive element, where individual wavelengths are separated and monitored with a multichannel array detector.
The detector continuously monitors the spectra of both the sampled matter and that of a suitable reference material. The convolved spectrum of the reference material, also referred to herein as the convolved reference spectrum, consists of a spectral fragment with known spectral characteristics convolved with all random instabilities in the radiation source and/or mechanical instabilities in the instrument. The convolved reference spectrum is convolved by the apparatus in the same way as the convolved spectrum of the sample, also referred to herein as the convolved sample spectrum.
There are two general situations encountered in the practice of the invention: one in which the sample provides a suitable spectral fragment to serve as the convolved reference spectrum, and the other in which no such spectral fragment exists. In general, it is rare that a sample will exhibit a suitable convolved reference spectral fragment, and thus the latter is a more general and more preferred embodiment of the method of the invention.
The reference material may be mixed with a sample either homogeneously, for example, as a solvent for the sample, or heterogeneously, for example, as small particles. The reference material may be included in a window or cell that is irradiated by the same beam that irradiates the sample. Alternatively, the reference material sample may be irradiated by separate beams with the same characteristics.
FIG. 1 schematically illustrates a Raman spectrometry apparatus that can be used when a suitable reference spectral fragment exists in a sample 20. Such an instrument is composed of a radiation source 1, an excitation optical waveguide 2A and 2B, excitation filtering means 3, an optical probe 4, incident wavelength rejection means 5, a collection optical waveguide 6A and 6B, a spectrograph interface 7, a spectrograph 8, a detector 9, and a computer 19 provided with appropriate mathematical routines.
FIG. 2 illustrates a more general Raman spectrometry apparatus that can be used where no reference spectral fragment exists in the spectrum of the sample. This instrument differs from that described in FIG. 1 by the addition of a beam splitter 10, additional excitation optical waveguides 2, 2C and 2D, additional excitation filtering means 3A and 3B, an additional optical probe 13, additional incident wavelength rejection means 5A and 5B, additional collection optical waveguides 6C and 6D, and a requirement that the array detector 16 be multidimensional.
Excitation optical waveguides 2, 2A, 2B, 2C, and 2D may be various lenses, mirrors, fiber optic cables, or combinations thereof that are capable of transmitting radiation over the desired distance. Commonly, the waveguides are low hydroxyl content quartz fiber optic cables.
Excitation filtering means 3, 3A, and 3B are required to remove stray radiation from the source beam prior to laser radiation interaction with the sampled matter. Such means may be placed near the unstable laser, near the optical probe, or at any location between. Typical filtering means include grating dispersion, dielectric interference, or holographic bandpass filters to isolate the incident radiation from undesired stray radiation.
Incident wavelength rejection means 5, 5A, and 5B are used to remove elastically scattered radiation from Raman scattered radiation. Such means may be placed near the optical probe, near the entrance optics, at any location between the optical probe and the entrance optics, or as part of the spectrograph system. Typical means include combinations of dispersive gratings, holographic notch rejection filters, indium-doped cadmium telluride crystals, dielectric notch rejection filters, and dielectric long pass edge filters. In general, such rejection means must be capable of rejecting greater than 100,000 elastically scattered photons for every Raman photon.
Optical probes 4 and 13 are used to interface the incident radiation with the sample and reference material, respectively. Such devices generally comprise a combination of lenses, mirrors, windows, and/or fiber optic cables through which the incident radiation may interact with the sampled matter and/or reference material and through which the Raman scattered radiation is collected. U.S. Pat. No. 4,573,761, the disclosures of which are incorporated herein by reference, describes a fiber optic probe that comprises at least one optical fiber for transmitting radiation into a sample and at least two optical fibers for collecting radiation from the sample. U.S. Pat. No. 5,112,127, the disclosures of which are incorporated herein by reference, discloses a fiber optic probe with optics that filter scattering and fluorescence by the fiber, focus the filtered light on an external sample, collect the scattered radiation from the sample, and refocus the scattered radiation to the exit fiber.
Beam splitter 10 performs the function of splitting incident laser radiation into two or more distinct paths. Such devices are typically constructed either by fusing together two or more optical fibers or using special beam splitting optics such as prisms or half-silvered mirrors. The specific construction of beam splitting devices is not crucial to the invention so long as each path contains a similar representation of the incident radiation. Such devices, several of which are commercially available, include prism- and plate-type beam splitters, from Melles Griot, Irvine, Calif., fiber-coupled prisms, from Oz Optics, Carp, Ontario, Canada, and fused fiber optic beam splitters, from Oz Optics and C-Technologies, Trenton, N.J.
The spectrograph interface 7 usually contains spectrograph entrance optics and an adjustable slit for the monochromator. Entrance optics are used to match the aperture of the collection waveguide to the aperture of the spectrograph. The adjustable slit influences the resolution of the resultant Raman spectrum.
The spectrograph 8 functions to disperse the individual wavelength of the Raman radiation. Such devices are typically composed of dispersive grating elements, mirrors, and/or lenses.. Commercially available spectrographs such as single grating dispersion instruments from Instruments S. A., Inc., Edision, N.J., Chromex, Albuquerque, N.M., or Acton Inc., Acton, Mass., holographic dispersion instruments from Kaiser Optics, Ann Arbor, Mich., or FT-interferometers from Nicolet Instrument Corp., Madison, Wis., are suitable for the practice of the invention.
The detector element 16 for a dispersion instrument may be a multi-channel array detector, such as a PDA or CCD, which enables all wavelengths of the spectrum to be simultaneously monitored. When distinct reference and sample channels are used, it is necessary that the detector be multidimensional. Useful multi-channel array detectors include photo-diode arrays, intensified photo-diode arrays, charge-coupled devices (CCD), photographic films, Vidicon tubes, and charge injection devices. It is important that the detector have very low noise characteristics, such that measurements are limited by photon shot noise rather than detector read or dark current noise. A suitable and preferred detector that meets these requirements is a charge-coupled device (CCD).
Suitable mathematical routines are also useful for the practice of this invention. The collected spectra are mathematically treated with a standardization process that compensates for all but random detector noise variability. In this process, the following spectral information is important: the convolved sample spectrum, the convolved reference spectrum, the standard reference spectrum, the standard sample spectrum, and the convolution function.
The convolved sample spectrum, S'(x), is a digital representation of the Raman spectrum of the unknown sample material, as obtained from the spectrograph detector. This spectrum is influenced by variations from both instrumental (laser and/or mechanical) instabilities and structural changes in the sample.
As described above, the convolved reference spectrum, R'(x), contains a spectral fragment with known shape characteristics convolved with all instrument instabilities. This spectral fragment must be convolved with the same convolution function as the convolved sample spectrum.
The convolution function, c(x), which enables one to compensate for the variations resulting from radiation source variability and/or instrument mechanical instabilities, contains the information necessary to transform a standard spectrum into a convolved spectrum, and vice versa.
The standard reference spectrum, R(x), is a selected spectrum that should be a true representation of the underlying shape of the convolved reference spectrum. The standard reference spectrum may be a theoretical mathematical representation of the invariant portion of the convolved reference spectrum; it may also be a previously acquired convolved spectrum of the reference material that has been adjusted or smoothed. Preferably, it is a spectrum obtained by averaging a multiplicity of previously acquired convolved spectra of the reference material. It is not necessary, however, that a spectrum used to provide the standard reference spectrum be obtained from the same instrument as that used to acquire the convolved spectra of the sample and the reference material.
The standard sample spectrum, S(x), which is produced by the apparatus and method of the present invention, is the resultant sample spectrum after all random instrument variations except random detector noise have been removed. This spectrum will vary according to chemical composition and thus enables a precise quantitative analysis of the sample.
As previously discussed, there are two general situations for the practice of the invention. FIG. 3 illustrates a procedure for obtaining the unknown convolved sample spectrum and the convolved reference spectrum for either situation. In case A, where a suitable reference spectral fragment in the Raman sample spectrum exists, collection of the sample spectrum, FIG. 3(a), is sufficient for the standardization process. A suitable spectral fragment is one which remains unchanged as the sample undergoes composition or temperature changes. Mathematical routines may be used to isolate this reference fragment from extraneous portions of the spectrum, for example, multiplication of the function in trace (a) by the function in trace (b) to get the function in trace (c). The resultant waveform becomes the convolved reference spectrum, FIG. 3(c).
In a variation of case A, elastically scattered radiation may be employed as the convolved spectrum of the reference material.
In case B, where no suitable reference spectral band exists in the sample spectrum, the laser beam is split into two beams or channels, one of which enters into the reference material and the other into the sample. A suitable reference material is one that exhibits a consistent, reliable spectral fragment. Diamond, whose Raman spectrum has a single strong vibration at about 1332 cm-1, which lies in the middle of the 500-2000 cm-1 "fingerprint" region, is an especially suitable and preferred reference material. In this way, a convolved sample spectrum, FIG. 3(d), and a convolved reference spectrum, FIG. 3(e), are simultaneously measured with a two-dimensional array detector. Extraneous bands may be removed from the reference spectrum by a mathematical routine, for example, multiplication of function (e) by function (f) to get function (g), which provides the convolved reference spectrum, FIG. 3(g).
FIG. 4 schematically illustrates the general process of measuring the spectral variations between the standard and convolved reference spectra and utilizing those measurements to adjust the convolved sample spectrum to obtain the standard sample spectrum. Carrying out this process by iterative computation is possible, although extremely arduous. Preferably, after the spectra R'(x) and S'(x) have been obtained, they can be transformed into the time domain using a FT method as described in, for example, W. H. Press et al., Numerical Recipes: The Art of Scientific Computing, 1986, Cambridge University Press, pp. 381-383 and 407-412, the disclosures of which are incorporated herein by reference. R(x) is also transformed into the time domain and c(x) is determined by dividing the FT of R(x) into the FT of R'(x). As the matrices for the FT of R(x) and R'(x) include complex numbers, this division must properly account for both the real and imaginary components. The symbols [/] and [*] used in FIG. 4 represent complex division and multiplication, respectively, in the FT time domain.
The calculated convolution function, c(x), contains the necessary information to decode the variations and instabilities of the instrument occurring during the spectral acquisition. The FT of S'(x) is then divided (again both matrices contain complex numbers) with c(x) to result in the FT of S(x). By calculating the inverse FT on this result, a standard sample spectrum, S(x), which accurately represents the composition of the sample, is obtained.
If desired, S(x) may be treated by procedures to achieve curve smoothing or to obtain the spectral derivatives, for example. These procedures may be useful when the spectra are used for reproducibly extracting quantitative compositional information. Curve smoothing methods are described in A. Savitsky and M. J. E. Golay, Anal. Chem., 1964, vol. 36, pp. 1627-1639.
The method for obtaining the standard sample spectrum may be carried out with instruments of various forms. It is required, however, that the convolved reference spectrum derive from the same convolution function as the convolved sample spectrum. Two additional embodiments are described in FIGS. 5 and 6.
FIG. 5 shows the components of a Raman apparatus that is capable of simultaneously monitoring three materials. It consists of one radiation source with a four way beam splitter which directs radiation toward three separate samples and one reference material. The individual components are similar to those used in construction of the instrument shown in FIG. 2, where individual sample channels are denoted by (a), (b), and (c). The apparatus can be constructed with as many sample channels as desired, being limited by the acceptable radiation throughput of the radiation source and/or the physical dimensions of the two dimensional array detector. It has previously been shown by Angel et al. "Simultaneous Multi-point Fiber-Optic Raman Sampling for Chemical Process Control Using Diode Lasers and a CCD Detector" SPIE, 1991, Vol 1587, Chemical, Biochemical, and Environmental Fiber Sensors III, pp. 219-231, and Vess and Angel, "Near-Visible Raman Instrumentation for Remote Multi-Point Process Monitoring Using Optical Fibers and Optical Multiplexing," SPIE 1992, Vol 1637 Environmental and Process Monitoring Technologies, pp. 118-125, the disclosures of which are incorporated herein by reference, that a CCD detector is capable of simultaneously monitoring up to ten channels. The present invention is general and not limited by current physical dimensions of the detector; with correctly sized components, more than 100 samples may be monitored simultaneously on one Raman instrument.
FIG. 6 schematically illustrates another embodiment of the invention, in which multiple lasers, each with a reference and sample arm, are used. This embodiment is similar to that shown in FIG. 5, except that each sample channel has a corresponding reference channel to provide the necessary information for the standardization process.
Further embodiments maybe any combination of the above embodiments wherein multiple radiation sources are directed at multiple samples, each source having a respective reference sample. When multi-channel instruments are used, there may be differences in the instrument response between the channels. It is commonly known in the art that many differences in instrument response between channels may be determined and described by convolution functions derived by comparing the spectra of a common material acquired through the different channels. When multi-channel instruments are used in the practice of this invention, these channel-to-channel variations in instrument response may be corrected by applying the appropriate convolutions in addition to the standardization convolution of the invention.
By removing the uncertainties in laser stability, detector position, etc., the changes that occur between subsequent standardized spectra can be correlated to compositional changes in the sampled matter. Standardized spectra can be used to monitor compositional concentrations, reaction rates., or other important variables that relate to changes in the sample through time.
Another additional embodiment of the invention is the use of standardization of Raman spectra collected with a radiation source in a Raman system in which the detector is a Fourier transform spectrometer rather than an array detector. The Fourier transform spectrometer also collects the entire spectrum simultaneously. If the radiation characteristics change more slowly than the scan of the spectrometer, a spectral fragment from the spectrum may be used to standardize the spectrum. In the Fourier transform spectrometer, the spectrum commonly includes the excitation wavelength in the scan. Thus, the filters may be selected to leak enough light to act as the spectral fragment for the convolved reference spectrum.
Other multiplex detector arrangements as in, for example, a Hadamard spectrometer, may be used in the practice of the present invention. Hadamard transform spectroscopy, in which a dispersion spectrometer is employed in combination with a movable mask that contains a series of slits and is positioned in the focal plane, is described in J. A. Decker, Jr., Applied Optics, 1971, vol. 10, pp. 510-514, and D. A. Skoog and D. M. West, Principles of Instrumental Analysis, 2nd ed. 1980, Saunders College, Philadelphia, p. 254, the disclosures of which are incorporated herein by reference.
Raman spectra were collected on a Nicolet 60SX Fourier transform spectrometer equipped with a Nicolet FT Raman accessory. The Raman spectra were excited with a 5 watt CVI Nd:YAG laser operating in multi-mode configuration with about 1.25 watts at the sample, and were collected with 180 degree scattering geometry. Toluene (Burdick and Jackson High Purity Solvent) was placed in a quartz tube at the position that gives maximum signal. A spectrum consisted of 1000 scans co-added with a scan time of 2 seconds/scan. The resolution was 8 wavenumbers. The data were transferred to a personal computer, where the data processing was done.
Each spectral fragment was collected so that the elastically scattered radiation was also observed. As this spectral fragment is indicative of laser fluctuations, it was used for the convolved reference spectrum. The standard reference spectrum was chosen to be a delta function spike, which was later smoothed to a Gaussian shape in the Fourier domain. The convolution function was determined and each spectrum standardized using the described process. Spectrum to spectrum variation was significantly reduced.
An example of the reduction in noise is shown in FIG. 7. Traces B and A are the Raman spectra of toluene shown as collected (convolved) and after the standardization process, respectively. Traces C and D show a difference spectrum from an average spectrum for the standardized spectra and as collected, respectively. (Traces A and C have been offset for the purpose of clarity). It is readily apparent from traces C and D that the standardized spectrum has a significant reduction in variation.
A Raman spectrograph was assembled as in FIG. 1 to contain one optical probe. The radiation from a Lexel krypton ion gas laser operating at 752 nm was used to illuminate a toluene sample through the optical probe. A 0.3 meter single grating spectrograph from Instruments SA, Inc. (model number HR320) with a fiber optic spectrograph interface assembly and a liquid nitrogen cooled CCD detector (578×416 pixels each 25 microns square) was used to collect, disperse, and monitor the Raman signal. A series of spectra was acquired while adjusting the position of the spectrograph grating and spectrograph interface slit width. These minor adjustments caused dramatic changes in the spectrum appearance by shifting band positions and broadening or narrowing bands.
The Raman vibrational bands between 950 cm-1 and 1050 cm-1 (249-314 pixels in FIG. 8) were used as the spectral fragment to determine the convolved reference spectrum. The initially collected convolved reference spectrum was used as the standard spectrum. Each subsequently acquired spectrum was standardized using the mathematical procedure described to determine a standard sample spectrum.
FIG. 8 shows a spectrum of the toluene sample, trace A, the residual variation caused from the shifting of the spectrograph position, trace B, and the residual variation after the standardization process, trace C. (The scale of 0-500 pixels on the x-axis corresponds to the range of 540-1330 cm-1.) Note that trace B indicates a typical variation pattern for an unstable instrument, with the greatest degree of variation occurring at inflection point regions. In trace C, this variation has been all but eliminated.
The same spectrograph and detector from example 2 was used in conjunction with a 1.2 watt multi-mode gallium-aluminum-arsenide (GaAlAs) diode laser (Spectra Diode Labs) with a center wavelength of 800 nm. Such a laser exhibits a constantly changing wavelength and energy profile. The radiation was directed toward a diamond fragment, and the Raman scattered radiation was detected. A Raman spectrum of diamond exhibits one strong band located at 1332 cm-1. A series of 200 sequential files was acquired and standardized to a theoretically shaped Gaussian curve.
An analysis of the experimental data showed that the raw spectra had a standard deviation as great as 3%. This degree of variation is excessive for precise quantitative work. The raw spectra were analyzed by using the 1332 cm-1 spectral fragment in each diamond spectrum as the convolved reference spectrum. A mathematically derived three point half width Gaussian band was used as the standard reference spectrum. After the standardization process, analysis of the data indicated that the largest standard deviation across the entire data set of 200 sequential spectra was less than 0.2% deviation. The majority of this deviation was due to the fundamental shot noise limitations in the detection.
A Raman spectrograph was assembled with the same detector and spectrograph as in Example 3, with a two probe set-up similar to FIG. 2. The radiation from a Lexel krypton ion gas laser operating at 752 nm was split into each probe with a beam splitter (Oz Optics) and used to illuminate liquid toluene (sample) and a diamond fragment (reference material). A series of 200 sequential spectral pairs were collected and saved from both samples.
The 1332 cm-1 band from each diamond spectrum was used as the convolved reference spectrum and a mathematically derived three point half width Gaussian band as the standard reference spectrum. A convolution function was determined for each spectral pair and used to standardize each toluene convolved sample spectrum. The variation in the resultant standard sample spectra was near that limited by shot noise.
This reduction in variation is indicated in FIG. 9, which shows the root mean square (RMS) variation for the as collected (convolved) toluene spectra, trace a, the RMS variation for the standard toluene spectra, trace b, and an estimate of expected shot noise variation based on photon counting statistics, trace c. (The scale of 0-500 pixels on the x-axis corresponds to the range of 360-1940 cm-1.) The small inset is an enlargement of traces b and c to show additional detail. It is clear that the standardization process is effective at removing a great portion of the random instrument instabilities which occur in the system.
A Raman spectrograph was assembled with the same detector and spectrograph as in Example 3, with a two probe set-up similar to FIG. 2. The radiation from a 1.2 Watt GaAlAs multi-mode diode laser (Spectra Diode Labs) operating at 800 nm was split into each probe with a beam splitter (Oz Optics) and used to illuminate liquid toluene (sample) and a diamond fragment (reference material). A series of 200 sequential spectral pairs were collected and saved from both samples.
The 1332 cm-1 band from each diamond spectrum was used as the convolved reference spectrum and a mathematically derived three point half width Gaussian band as the standard reference spectrum. A convolution function was determined for each spectral pair and used to standardize each toluene convolved sample spectrum. The variation in the resultant standard sample spectra was near that limited by shot noise.
The multi-mode laser is inherently unstable and exhibits a rapidly changing spectral profile. This is indicated by the RMS variation of the raw convolved spectra shown in FIG. 10. After the standardization process (lower curve and inset), the variation was significantly reduced, again being on the order of the expected shot noise variation. In this example, it would be impossible to use the raw convolved spectra for any sensitive quantitative analytical work; after standardization, however, virtually all instabilities have been eliminated, enabling quantitative determinations to be made.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
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|20 juil. 1994||AS||Assignment|
Owner name: EASTMAN CHEMICAL COMPANY, TENNESSEE
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Effective date: 20071003

domain: chemistry


text:
Research & Publications
I seek to advance equity and social justice through my research. I do so by conducting community-based studies with state and municipal agencies, schools, and community-based organizations to promote resilience, help individuals recover from trauma or crises, prevent substance misuse, or to develop systems or population-based solutions to human challenges. My work is done collaboratively in which I work with community stakeholders to co-create interventions and evaluation designs to address challenges that result from stress, trauma, mental illness, addiction, or systemic oppression (based on race, ethnicity, gender, social class, ability status, indigenous background or other social differences). The ultimate goal of my work is to transform settings and communities so that they are more equitable and just, and better able to promote resilience, thriving, and well-being. I also have scholarly interests in community research methods, program evaluation, philosophy of science, and team science.
My research is conceptualized from an equity and social justice perspective and usually examines multiple levels simultaneously (e.g., the individual, the family, peers, the school, the neighborhood or community). This work takes place in community settings that involve populations who are at risk, in crisis, have experienced adverse or traumatic circumstances, or have a clinical disorder. Some of my research involves randomized controlled trials and some involves evaluations of programs, services, or social change interventions by community coalitions. Through my research, evaluation, and scholarly work, my collaborators and I have developed principles for conducting community-based research, created innovative programs to assess systems change, helped define the field of community science, developed strategies for using data to inform practice and policy, described participatory approaches to interdisciplinary team science, proposed a framework for understanding historical trauma, and developed a population health model for trauma-informed practice. I feel fortunate to have had extraordinary collaborators and community partners to do this work.
Extensive Research Description
Below is a more extensive summary my research and scholarly work on 1) resilience; 2) prevention of adolescent substance use; 3) incorporating equity and social justice principles into research, and 4) community research methodology, program evaluation, philosophy of science, and team science.
Resilience. Resilience is characterized by normative development despite adverse circumstances. My colleagues and I have identified risk and protective factors associated with resilience among vulnerable populations, and that promote resilience among at-risk groups. My early research examined risk processes among women who had primary caregiving responsibilities for a child as well as an elder family member, which led to a statewide randomized trial of the effectiveness of self-help/mutual support groups for these “sandwiched generation” women. This trial was among the first to examine the health impacts of self-help/mutual support groups on the children of caregivers. In other studies, my colleagues and I examined resilience processes among bereaved young adults, children of mothers with serious mental illnesses, maltreated and foster care children in the child welfare system, and multi-system involved youth.
I have also examined the effectiveness of interventions that promote community adaptation and resilience to trauma among various clinical populations. These have included randomized controlled trials of community-based programs, such as crisis-respite services for persons with serious mental illness and peer support services for persons in recovery from serious mental illness. Along with colleagues I have also studied the effectiveness of statewide services, such as community support services for persons in recovery, system of care services for children with serious emotional disorders, multi-systemic therapy for juvenile offenders and their families, and risk and protective factors for well-being among family caregivers of persons living with schizophrenia. In other studies, I have examined the impact of participatory, interdisciplinary approaches on creating environments that can promote resilience and well-being in the aftermath of trauma or adverse experiences. In one study, my colleagues and I examined how participatory public art, created jointly by adults in recovery from mental illness or addiction and neighborhood residents, can help revitalize under-resourced urban neighborhoods. In another study, we examined how a community coalition organized to prevent the negative impact of adverse childhood experiences (ACEs) can promote trauma-informed schools and services for children and families. The latter research was guided by a comprehensive population health model of trauma-informed practice. More recent research has focused on how interactive virtual stress and resilience town halls that use mutual support and psychoeducation can promote resilience and well-being in healthcare workers and their family members during the COVID-19 pandemic.
Prevention of adolescent substance use. My colleagues and I have also conducted school- and community-based studies to prevent adolescent substance use and problem behaviors. Most of our research with adolescents has used a social-cognitive approach to prevent substance use in which we examine the effectiveness of teaching decision-making skills in schools or after-school programs to middle and high school youth to prevent substance use. The focus of several studies has been to help youth critically examine influences from parents, peers, and the media to make their own decisions about using substances. In a series of studies, we demonstrated the effectiveness of a school-based program to prevent substance use among middle and high school students in suburban school districts. We then adapted the program for use in urban after-school settings, where it also was found to be effective. That adaptation was based on a collaboration with a youth services coalition that incorporated cultural heritage and positive youth development activities into the updated program. In other research, we developed and examined a school-based mentoring program to prevent substance use among urban, high school youth that was also effective in preventing substance use. More recently we implemented and evaluated a school-wide prevention program with urban high school students that promotes healthy decision-making. Drawing on a population health approach, this research involves a partnership that includes youth, teachers, school administrators, parents, and youth service providers, among others, to use social media and school activities to foster school-wide norms for healthy decision-making about nutrition, sleep, exercise, relationships, activity involvements, and substance use.
Incorporating equity, social justice, and anti-oppressive principles into research. Most of my research -- including the studies described above -- incorporates equity, social justice, and anti-oppressive principles into how the research is conceptualized, designed, implemented, used, and disseminated. This involves infusing the voices of public stakeholders into one or more phases of the research, as is common in community-based participatory research or in what we have called "participatory team science." Depending on the study, public stakeholders could be: youth, family, and community members; persons in recovery from mental illness or addiction; teachers, school staff, and service providers; neighborhood leaders and residents; municipal and state representatives; funders, and healthcare workers.
My research and scholarship, as well as my related practice and teaching, also seeks to incorporate an understanding of culture -- defined in terms of gender, race, ethnicity, social class, sexual orientation, religion, ability status, indigenous background, and other social identities – into how research is conducted, services are designed and delivered, and policies established. Incorporating culture into any professional endeavor is essential to uncovering hidden and systemic inequities, disparities, and oppression. Throughout my career, and in collaboration with colleagues, I have led seminars or workshops on this issue for Yale faculty, fellows, staff, or professional staff from community organizations. For example, my colleagues and I worked with an urban police department to train officers and command staff to identify and act on issues of diversity, equity, and inclusion in the workplace.
Community research methodology, program evaluation, philosophy of science, and team science. I have a longstanding interest in how we conceptualize and conduct research in community settings, how we evaluate programs and services, and in the philosophy of science. My scholarship in these areas has examined philosophical roots of community research and community psychology, mixed methods approaches, and interdisciplinary team science, and has intersected with my research and scholarship on resilience, substance use prevention, equity, and social justice.
Professional roles that draw on research and scholarship. As a clinical/community psychologist, I feel fortunate to have been able to pursue professional roles that developed from my research and scholarship that have direct public health benefit. These roles have included: collaborator on community intervention research with colleagues and community stakeholders; consultant to national, state, and municipal agencies to promote data-driven decision making and evidence-based practice; trainer and coach to build program evaluation capacity and enhance the performance of community organizations, healthcare settings, and service systems; evaluator of public and non-profit programs and services; and testifying expert on federal class action litigation to address health inequities. These roles have allowed me to blend research and practice, and to create opportunities for teaching and mentoring doctoral and postdoctoral fellows, and early career faculty.
Primary Prevention; Public Health; Social Change; Social Justice; Program Evaluation; Cultural Diversity; Vulnerable Populations; Resilience, Psychological; Community-Based Participatory Research
Public Health Interests
Community Health; Mental Health
- Evaluation in prevention and health promotion.Tebes J.K., Kaufman JS, Connell C, Crusto, CA, & Thai, ND. (2014). In: T Gugliotta & M Bloom (Eds). Encyclopedia of Primary Prevention and Health Promotion, 2nd Edition (pp. 69-101). NY: Springer.
- Beauty, connection, healing, and behavioral health: The role of public art in promoting wellness.Matlin, S. L., Evans, A. C., & Tebes, J. K. (2014). In: Golden, J. & Mural Arts Associates (Eds). Mural Arts at 30: Growing Up, Growing Out, Putting Down Roots. (pp. 121-127). Philadelphia Mural Arts Program, Philadelphia, PA.
- Adult Smoking Initiation Is on the Rise in the US, But Among Whom?Thompson, A.B., Tebes, J. K., McKee. S. A. (2013). Journal of Women’s Health, 22, 140.
- Philosophical foundations of mixed methods research: Implications for research practice.Tebes, J.K. (2012). In Jason, L. & Glenwick, D. (Eds.). Innovative methodological approaches to community-based research. Washington, DC: APA Books, 2012, 13-28.
- Service access and service system development in a children's behavioral health system of care.Tebes, J. K., Bowler, S. M., Shah, S., Connell, C. M., Ross, E., Simmons, R., Tate, D., Chinman, M. J., & Kaufman, J. S. (2005). Evaluation & Program Planning, 28, 151-160.
- Resilience and family psychosocial processes among children of parents with serious mental disorders.Tebes, J. K., Kaufman, J. S., Adnopoz, J. & Racusin, G. R. (2001). Journal of Child and Family Studies, 10, 115-136.
- Promoting resilience in children of sandwiched generation caregiving women through caregiver mutual support.Tebes, J. K., & Irish, J. T. (2000). Journal of Prevention and Intervention in the Community, 20, 139-158.

domain: psychology


text:
What to say about a book that a reader should know nothing about before opening
the cover? One’s tongue must tread very carefully, while exuberantly bandying about ones utter enchantment with the work, least it slip and let out one of the book’s many, many delightful secrets. With a great deal of care and some trepidation, here are a few things that I would like to say:
Now comes the moment when I introduce a little device I am going to call the Kid Lit Social Club (KLSC). This is where I get to break down the barriers of time, location, publishers, genre, and book binding to throw characters from the currently discussed book into the path of other characters from children's literature.
The Gang from When You Reach Me at the KLSC
Miranda will naturally be BFFs with Meg Murry, after all they will always be the same age.
Miranda can also form a support group with Lynne Rae Perkins' Debbie for the recovery of those who have been dumped by long-time best friends.
Miranda and Richard can both join Lucky's friend Lincoln, as members of The International Guild of Knot Tyers.
Marcus should enroll in a social skill awareness class with Emma Jean Lazarus.
Marcus and Julia will most likely get a scholarship to attend Connie Willis' Oxford.

domain: literature


text:
The Los Angeles Dodgers begin their final homestand of the regular season Monday with a 4.5-game lead in the National League West.
All the Dodgers need to accomplish is win two of the three games against the San Francisco Giants to clinch their second consecutive division title. While that certainly would be a team accomplishment, they have two players whom manager Don Mattingly believes have reached statistical milestones.
The Dodgers return to Chavez Ravine with Clayton Kershaw, who has already won 20 games this season and Adrian Gonzalez, who leads the team and the Majors with 112 RBIs. Mattingly said he views the two stats as a sign of a great season, via ESPN LA’s Mark Saxon:
From my childhood, I remember you hear about Baltimore’s five [actually, four] 20-game winners and stuff like that,” Dodgers manager Don Mattingly said. “That’s a landmark. It’s like 100 RBIs for a hitter. Twenty wins, I think, is something we’ve always put out there as a landmark and a great year.”
Kershaw’s 20 wins lead the Majors and so too does his 1.80 ERA and 0.86 WHIP. He threw his first career no-hitter this season and had an 11-game winning streak. Making his list of accomplishments more impressive is he missed one month due to injury.
Kershaw’s last start Sept. 19 didn’t fall in line with what’s been expected from him and he benefitted from his offense hitting well. Among the bats that picked up the ace was Gonzalez.
Giancarlo Stanton’s injury opened the door for Gonzalez to take the RBI lead and the first baseman certainly has taken advantage of the opportunity. In the four-game series with the Chicago Cubs, Gonzalez hit two home runs and drove in six runs, with five of the RBIs coming in one game.
Gonzalez has six games remaining to add to his RBI total and Kershaw is scheduled to start the series finale against the Giants Wednesday.

domain: news


text:
Patient Access Representative
Company: CHRISTUS Health
Posted on: June 12, 2021
To accurately collect socio-economic information for proper
utilization by all hospital departments to ensure proper care for
the patient and to effectively maximize reimbursement.
High school diploma or equivalent preferred Hospital or
physician office-helpful Insurance knowledge-helpful Good
Keywords: CHRISTUS Health, Longview , Patient Access Representative, Other , Marshall, Texas
Didn't find what you're looking for? Search again!

domain: medical


text:
well, this is an interesting concept- an online course about what happens when stories and films are turned into online games
and you can take it for free
Starts July 14th, so if you’re interested, better jump on it now.
(My favorite part?
“•What is the coolest thing about this class?
The chance to meet in-game with your instructor and fellow classmates.” )
from Catherine Kane
For more information on Catherine’s books, “Adventures in Palmistry”, “The Practical Empath – Surviving and Thriving as a Psychic Empath”, “Manifesting Something Better” , her urban fantasy “The Lands That Lie Between” and her new book “The Psychic Power of Your Dreams”, all from Foresight Publications, click here


text:
Smještaji za odmor – Kalinga
Pronađite i rezervirajte jedinstvene smještaje na Airbnbu
Kalinga – smještaji za odmor s najboljim ocjenama
Gosti su se složili: ti smještaji imaju visoke ocjene u pogledu lokacije, čistoće i drugih kriterija.
Privatna soba u mjestu Tabuk
8 rooms with own toilet/bath
Close to everything when you stay at this centrally-located place. Building is 100m away from the provincial road. 8 rooms available. All rooms are good for two person. Each room has its own toilet and bath. Silog breakfast will be available in the morning. Units are located at the 3rd floor. Good way to have your legs and thighs exercised. :) 1st and 2nd floors are commercial areas so there’s a bit of things going on during the day. These does not affect much the 3rd floor though.
$35 po noćenju
Smještajna jedinica u mjestu Tabuk city
A 3-BR PENTHOUSE in Tabuk City Kalinga Philippines
This is a 3-storey residential building. The 1st floor is parking space and an office. The 2nd floor is the owner’s house. The Penthouse is on the 3rd floor. It has 3 bedrooms with individual air conditioners and 3 full bathrooms with water heaters. The living, dining and kitchen are one big room. It has also a huge veranda with a nice view of the ricefields. It is suitable for a big group of up to 12 people. However, it can also be booked per bedroom if only 2-4 guests with different rate.
$110 po noćenju
Kampiralište u mjestu Tabuk
Our humble place is 17 minutes away from Tabuk Center. Marvel on the scenic Mountain View and Chico River from our campsite. We also offer freshly picked veggies and home cooked meals. We also offer day tour package for a day well spent during your stay.
$10 po noćenju
Smještaji za odmor za svačiji stil
Pronađite prostor koji vam najbolje odgovara po veličini.

domain: travel


text:
Liverpool winger Raheem Sterling brought into England squad ahead of qualifier with Poland
Liverpool winger Raheem Sterling has been called into the England squad for Tuesday's World Cup qualifier with Poland.
Last Updated: 13/10/13 8:19am
Manager Roy Hodgson lost two members of his squad on Friday, in the shape of Tom Cleverley and Kyle Walker.
Cleverley returned to Manchester United before the 4-1 win over Montenegro with a calf injury that is likely to keep him out for up to three weeks, while Walker picked up a booking in the match which means he is suspended for the clash with Poland.
Either Phil Jones or Chris Smalling are likely to replace the Tottenham man at right-back, but Hodgson has called on Sterling, who was part of Gareth Southgate's Under-21 squad that beat San Marino on Thursday, to bolster numbers ahead of a game England must win to guarantee qualification for next summer's Finals in Brazil.
Sterling became the fifth-youngest player in England history when he made his debut in the friendly defeat to Sweden last November, but the 18-year-old has not featured since.
England head into the final set of fixtures with a one-point lead at the top of Group H.
But with Ukraine's final game being a trip to San Marino, who have lost every game in qualifying, Hodgson knows his side must win to avoid November's playoffs.


text:
The Spanish political scientist and humanitarian activist Enrique Refoio said that the murder of the head of the Donetsk People’s Republic will not lead to the end of the war in the Donbass, Kiev should use other instruments to solve the problem in the southeast of the country, he said.
Kiev will always lose, using political assassinations. The death of the head of the DPR, Alexander Zakharchenko, can lead to another confrontation between the soldiers of the people’s republics and the AFU. He noted that if the Ukrainian army tries to use this situation, it will never win, but will only continue fighting with numerous losses.
After the terrorist attack in Donetsk, the threat of a new round of war will only grow, the political scientist is sure.

domain: politics


text:
Government relaxes export curbs on 24 pharma ingredients, medicines
Government has relaxed export curbs on 24 pharma ingredients and medicines including vitamin B1 and B12.
Government has relaxed export curbs on 24 pharma ingredients and medicines including vitamin B1 and B12. The Directorate General of Foreign Trade (DGFT) issued a notification in this regard yesterday.
Paracetamol, a common pain reliever, and its formulations were not included in the list of drugs freed up for export.
On March 3, DGFT, under the commerce ministry, had imposed export restrictions on 26 active pharmaceutical ingredients (APIs) and formulations, under which exporter has to obtain a licence or permission from the DGFT.
Easing of curbs on 24 APIs and its formulations assumed significance as certain pharma companies have raised concerns over these restrictions. With this, the export of these items is allowed freely without any restrictions.
Besides Vitamin B1, B6 and B12, the other APIs and formulations over which the export restrictions have been eased include Tinidazole, Metronidazole, Acyclovir, Progesterone, Chloramphenicol, Ornidazole, formulations made of Chloramphenicol, formulations made of Clindamycin Salts, and formulations made of Neomycin.
The APIs and formulations included common antibiotics and vitamins.
India has exported APIs worth about USD 225 million last year.
The country's API imports stood at around USD 3.5 billion per year. Out of this, about USD 2.5 billion is from China.
It was not clear what prompted India to lift the restrictions, but it seems that the decision is a follow up of a telephone call between Indian Prime Minister Narendra Modi and US President Donald Trump on Saturday. "The two leaders agreed to remain in touch on the issue of global supply chains for critical pharmaceuticals and medical supplies and to ensure they continue to function as smoothly as possible during the global health crisis," White House spokesman Judd Deere, said in a tweet on Saturday following the leaders` call.
Today, @realDonaldTrump spoke with Prime Minister Narendra Modi of India to discuss how the two countries can work together to combat the coronavirus pandemic.— Judd Deere (@JuddPDeere45) April 5, 2020
Besides, India has also placed restrictions on the export of most diagnostic testing kits. And in recent weeks it had also banned the export of ventilators, masks and other protective gear needed by both patients and medical staff.


text:
By this point, anyone interested in equity in retail should be familiar with the 15 Percent Pledge, the initiative launched by Brothers Vellies founder Aurora James in June 2020, in response to both calls for racial justice and equity and the largely performative promises of the beauty and fashion industries. Calling out one of the most basic metrics of equity, Vellies challenged retailers to make their stores more accurately reflect the demographics America, by delegating a minimum of 15 percent of their offerings to Black-owned brands.
Beauty emporium Sephora was the first of a still-growing number of retailers to sign on to the pledge, which it added to its ongoing efforts to combat racial bias in its stores and corporate structure. Part of that effort included commissioning the Racial Bias in Retail Study, the result of which were published this January. Now, a more recent report measures how far the retailer has come in the DE&I Action Plan it shared in that study—and gives us an idea of what 15 percent might actually look like in practice.
Per a press release shared with The Glow Up: “Supported by its 11 internal task forces, this work is focused on tackling bias across all areas of the organization including marketing, merchandising, education, hiring, recruiting, operations and the in-store experience. With this work, the prestige retailer set out to make the Sephora experience more inclusive and equitable, for team members, clients, and the broader beauty community.”
Sephora also provided highlights from the report:
- At the time of the 15 Percent Pledge in June 2020, Sephora carried eight Black-owned brands. By the end of 2021, Sephora will more than double their assortment overall, including achieving the 15% benchmark in prestige haircare.
- Within the Action Plan share-out in January, Sephora pledged to establish new guidelines to ensure its campaigns, social media and marketing content included a diverse array of backgrounds, identities, ages, and body types.
- Black-owned brands now comprise 15% of Sephora’s total social and digital content, up from 11% in June 2020. In addition, in 2021 Sephora implemented dedicated quarterly campaigns to drive awareness of Black-owned brands including a Sephora.com landing page.
- To broaden inclusion for Sephora’s LatinX clients, the retailer has doubled the number of Spanish-language YouTube videos produced each month and have incorporated closed-captioning on all Sephora-produced IGTVs, to improve the accessibility of their content.
- Since June of last year, Sephora has grown Black or African American leadership across stores, distribution centers and corporate offices from 6% to 9%. Black or African American Store Director representation increased from 6 to 11%.
- 64% of Sephora’s total workforce is comprised of People of Color, with 16% Black or African American.
- Sephora created 20 new inclusivity training modules required to be taken by all Sephora retail employees, including a series which trains all Sephora employees to recognize and mitigate their unconscious biases.
Shopping at Sephora this July, beauty and haircare aficionados will find the retailer’s expanded offering now includes Black-owned brands Adwoa Beauty, Bread Beauty Supply, Briogeo, Danessa Myricks Beauty, Fenty Beauty and Fenty Skin by Rihanna, Jackie Aina’s FORVR Mood, Grace Eleyae, KNC Beauty, LYS Beauty, Pat McGrath Labs, Rose Ingleton, MD, Shani Darden Skin Care, Sunday II Sunday, Topicals and Qhemet Biologics. This fall will see the launch of several more Black-owned brands in store and online, including but not limited to Fashion Fair and Hyper Skin.
You can read Sephora’s entire report here.


text:
Description of Airport Taxi Service Edmonton APK
Use a map to select your pick-up location, and track the location of your taxi.
Receive notification alerts about the status of your booking, and when your taxi arrives.
TAXI BOOKING FEATURES:
• Request a taxi cab right now, or select a future date and time for pick-up.
• Don’t know your location? – Send the taxi to your current GPS position.
• You can also tap a location on a map, or type in a pick-up address.
• Select a pickup or drop-off address from your phone’s Contacts list.
• Save a pick-up address as a favorite, and use it for future bookings.
• Select booking options for your cab (wheelchair accessible, pet-friendly,etc.)
• Display the current location of your taxi on a map.
• Cancel a booking.
• Display up to three previous bookings made with your mobile device.
• Tap a button to make a phone call to Airport Taxi Service (if app is installed on an Android smartphone).
• Communicate directly with your driver.
• Receive a message sent by the driver who is on the way to your location.
Greater Edmonton Area - River Cree, Spruce Grove, Stony Plain, St. Albert, Nisku, Leduc, Sherwood Park, Devon, Calmar, Beaumont, Camrose, CFB Namao, Millet, Ponoka, Red Deer, Wetaskiwin
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domain: geography


text:
On a wet and blustery Sunday November 26th, 2017, performers and audience gathered to celebrate Canada Music Week in the sanctuary of First Baptist Church, made festive with balloons, streamers and maple leaf flags, large and small — evidence of the decorating skills of teachers Wendy Guimont and Katharine Nimmert.
This local celebration and performance of Canadian compositions, mounted by the East Kootenay Music Teachers’ Association (EKMTA) is representative of similar events across Canada.
Here, though, we must boast of the Kootenays’ one-of-a-kind emcee, Arne Sahlen, who, with his characteristic gusto and wit, and appropriately sporting a red blazer, skillfully punctuated the event with a stream of humorous and instructive remarks.
Thirty-two talented piano, violin and voice students gave polished performances of Canadian compositions including those of Alberta composer Christine Donkin, whose fun titles ranged from “T Rex Goes for a Stroll” – the monster’s heavy tread depicted by pounding chords — to “Computer Chatter”. Also included were renditions of jazz pianist Oscar Peterson’s “Jazz Exercise” and Leonard Cohen’s “Hallelujah”. A couple of students even performed their own compositions! Thanks to our three accompanists: Ellen Bailey, Tim Plait and Sooyeun Lee.
Following the recital, EKMTA distributed a variety of awards to their students, including scholarships for voice, piano and strings (based on Conservatory exam performance), as well as awards to students who had composed their own original compositions.
Finally, in celebration of Canada’s 150th anniversary, “Canada 150 achievers” – those students who leading up to the event practiced a total of 150 days, notably including the summer period – were rewarded with pizza and goodie bags.
Thanks to photographer, Cara Webb and to the EKMTA for organizing this, their most popular annual event.
EKMTA is a non-profit organization that aims to educate and musically enrich the community. For more information, please see our Facebook page ‘East Kootenay Music Teachers’ Association’, or call our President, Wendy Guimont, at 250-417-9897.

domain: artistic


text:
Reeves and Reeves
Regular price £43.95
Tax included. Shipping calculated at checkout.
A pretty necklace of two songbirds perching on a twig textured circle in silver, rose gold and gold. A beautifully delicate piece of jewellery, suitable for all occasions.
- Sterling silver with 18ct yellow and rose gold vermeil (plated)
- Adjustable 16-18" sterling silver chain
- Presented in a gift box

domain: design


Featuring WA birds located in the Banksia Garden in Kings Park.
Phylidonyris novaehollandiae - New Holland Honeyeater
Phylidonyris niger - White-cheeked Honeyeater
Lichenostomus virescens - Singing Honeyeater
Smicrornis brevirostris - Weebil
About the Artist:
Future Shelter is a small design and manufacturing workshop based in North Perth, Western Australia.
|Materials||55% Linen, 45% Cotton.|
|Care instructions||Cool, gentle hand wash or cold, delicate machine wash, using phosphate-free detergent. Do not tumble dry.|
|Dimensions||Approx. L 150cm x W 32cm|
|Origin||Made in Western Australia|
Redeemable in-store only.


Time Extension Granted to McMillan
NEWS | May 2, 2019
In 2016, the plans to redevelop the McMillan Reservoir and Sand Filtration Site were about to get started. However, an appellate court decision put a halt to the project later that year, and it has been stuck in limbo ever since.
As the controversial redevelopment plan for the site remains under appeal, the Zoning Commission unanimously approved a two-year extension for the approved planned-unit development earlier this week.
Vision McMillan Partners (VMP) plans to develop the 25-acre industrial site between North Capitol and First Streets and Michigan Avenue and Channing Street NW (map) into 146 townhouses, 531 apartments, an eight-acre park, a community center, medical office buildings, and retail including a grocery store. VMP is made up of Jair Lynch Real Estate Partners, EYA, Trammell Crow, and architects MV+A Architects, Shalom Baranes and Perkins Eastman.
With the extension approval, all portions of the PUD remain valid until March 2021, or for two years from the conclusion of the appeals.


text:
NEWS RELEASE APRIL 2015
Asian Valve Market to Reach $31 Billion By 2019
The industrial valve market in Asia will grow by $5 billion to reach more than $30 billion by 2019. The control valve market will grow by 21 percent and the on/off segment by 20 percent.
Valve Revenues ($ Millions)
There is a slowdown in China but growth will still be enviable compared to other countries. Coal gasification and liquefaction is promising to boost valve revenues substantially in China and will also impact South Korea and India.
Coal-fired power will show the greatest growth percentage in India, but many Asian countries have ambitious coal-fired generator programs. Steel, pulp and chemicals are all growth markets.
Steady growth will continue in municipal water and wastewater.
By 2019, China will be treating 30,000 MGD with secondary wastewater treatment ranking it second in the world behind the U.S. and with nearly three times the capacity of Japan.
Asian Secondary Wastewater Treatment Capacity in 2019 (MGD)
|Country||Secondary Capacity (MGD)|
|Other East Asia||1|
|Other West Asia||1|
For more information on N028 Industrial Valves: World Market, click on: http://home.mcilvainecompany.com/index.php/markets/2-uncategorised/115-n028


text:
And they that know thy name will put their trust in thee: for thou, LORD, hast not forsaken them that seek thee.
Our Christian faith requires being in a relationship and friendship with God. Our God is not our adversary or our accuser. He's our Father, friend and brother and we need to seek Him in all things. We also need to be obedient to His word and trust Him with the obedience which naturally occurs from our relationship with God, our Lord and Saviour. Christianity is a committed relationship with the Father of our faith.
Most of us want a relationship with our earthly father. Why? We desire our father's affection and approval, and because he desires to lavish his love on us. So too our heavenly Father desires to abundantly bless us. He loves us. He cares for us so much that He was willing to die for us and wants nothing more than to forgive us.
Seeking God should be the desire of our heart: desiring His grace and His will. He created us to have a relationship with Him.
And ye shall seek me, and find me, when ye shall search for me with all your heart.
Father, I want to seek a relationship with you. Teach me truth and understanding so that I may know you as I ought. My desire, Lord, is to know you more. Amen.
Scripture Verses used are from the King James Version of the Bible
Chrissy Siggee is the author of 'Glimpses of His Glory', a collection of her poetry, devotions, pencil illustrations and nature photos. - SORRY - SOLD OUT!
Chrissy is also the author of the teen novel 'Out of the Shadows - Jenna's Secret.' http://chrissysiggee.com/shadows/


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