NIR Calibrations for Soybean Seeds and Soy Food Composition Analysis: Total Carbohydrates, Oil, Proteins and Water Contents

Conventional chemical analysis techniques are expensive, time consuming, and often destructive. The non-invasive Near Infrared (NIR) technology was introduced over the last decades for wide-scale, inexpensive chemical analysis of food and crop seed composition (see Williams and Norris, 1987; Wilcox and Cavins, 1995; Buning and Diller, 2000 for reviews of the NIR technique development stage prior to 1998, when Diode Arrays were introduced to NIR). NIR spectroscopic measurements obey Lambert and Beer’s law, and quantitative measurements can be successfully made with high speed and ease of operation. NIR has been used in a great variety of food applications. General applications of products analyzed come from all sectors of the food industry including meats, grains, and dairy products (Shadow, 1998)

NIR Calibrations for Soybean Seeds and Soy Food Composition Analysis: Total Carbohydrates, Oil, Proteins and Water Contents [v.2]

Conventional chemical analysis techniques are expensive, time consuming, and often destructive. The non-invasive Near Infrared (NIR) technology was introduced over the last decades for wide-scale, inexpensive chemical analysis of food and crop seed composition (see Williams and Norris, 1987; Wilcox and Cavins, 1995; Buning and Diller, 2000 for reviews of the NIR technique development stage prior to 1998, when Diode Arrays were introduced to NIR). NIR spectroscopic measurements obey Lambert and Beer’s law, and quantitative measurements can be successfully made with high speed and ease of operation. NIR has been used in a great variety of food applications. General applications of products analyzed come from all sectors of the food industry including meats, grains, and dairy products (Shadow, 1998).
Novel NIR calibrations for rapid, reliable and accurate composition analysis of a variety of several soy based foods and bulk soybean seeds were developed and validated in a six-year collaborative project with a large number of different samples (N >~12, 000). The availability of such calibrations is important for establishing NIR as a secondary method for composition analysis of foods and soybeans both in applications and fundamental research

Low-temperature formation of polycyclic aromatic hydrocarbons in Titan’s atmosphere

The detection of benzene in Titan’s atmosphere led to the emergence of polycyclic aromatic hydrocarbons (PAHs) as potential nucleation agents triggering the growth of Titan’s orange-brownish haze layers. However, the fundamental mechanisms leading to the formation of PAHs in Titan’s low-temperature atmosphere have remained elusive. We provide persuasive evidence through laboratory experiments and computations that prototype PAHs like anthracene and phenanthrene (C14H10) are synthesized via barrierless reactions involving naphthyl radicals (C10H7•) with vinylacetylene (CH2=CH–C≡CH) in low-temperature environments. These elementary reactions are rapid, have no entrance barriers, and synthesize anthracene and phenanthrene via van der Waals complexes and submerged barriers. This facile route to anthracene and phenanthrene—potential building blocks to complex PAHs and aerosols in Titan—signifies a critical shift in the perception that PAHs can only be formed under high-temperature conditions, providing a detailed understanding of the chemistry of Titan’s atmosphere by untangling elementary reactions on the most fundamental level

Plasma assisted deposition of thin films using molecular titanium alkoxide and amido precursors

Metal-containing polymer thin films are known to possess interesting electrical, magnetic, optical or barrier properties. Such coatings can be deposited by plasma assisted chemical vapour deposition (PACVD). This technique comprises the fragmentation and rearrangement of metallorganic precursors within a low pressure non-equilibrium electrical discharge. In this work, the deposition of titanium containing species embedded into a polymeric network from titanium tetraisopropoxide (TiTP), Ti[OCH(CH(_3))(_2)](_4), and tetrakis (dimethylamido) titanium (TMT), Ti[N(CH(_3))(_2)](_4), precursors has been investigated as a function of glow discharge power and substrate location. In addition these precursors have been mixed with hydrogen and ammonia gases during PACVD. These metal-containing plasma polymers layers have been characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and atomic force microscopy (AFM).It has been demonstrated that Ti02/polymer composite layers can be produced using the TiTP precursor with a wide range of stoichiometries. The mixing of hydrogen gas with TiTP create films which are stable towards oxidation and aging. TiTP/ammonia mixtures produced Ti(0,N)/polymer films which contained Ti-N bonds. Injection of TMT into a glow discharge has been found to result in a non-thermally assisted intramolecular alkyl (3-hydrogen activation mechanism to produce Ti(0,C,N)/polymer composite films. The film composition is found to be independent of glow discharge power beyond 5 W. Mixing with hydrogen gas lowers the carbon content due to recombination reactions competing with plasma polymerization. TMT/ammonia mixtures result in a gas phase transamination reaction prior to and during plasma activation causing a drop in the total carbon content due to replacement of the -N(CH(_3))(_2) ligand by –NH(_x)

High-resolution Infrared Spectroscopy of the v23 and v22 Vibrational Bands of Methyl Vinyl Ketone

The high-resolution Infrared spectrum of methyl vinyl ketone (C4H6O) has been acquired in the region containing the v22 and v23 bands near 987 cm-1 and 1001cm-1, respectively, using a quantum cascade laser-based spectrometer. All acquired spectra underwent frequency calibrations that will prove useful during future atmospheric measurements of methyl vinyl ketone. Anharmonic calculations were performed at the MP2/ccp-pVTZ level of theory to obtain the vibrational frequencies and the excited state rotational constants of cis-methyl vinyl ketone. These calculations supported the assignment of the Q-branch features at 1001.031 and 987.592 cm-1 to the v22 and v23 fundamental vibrations of the molecule. Additionally, the Q-branch feature at 998.98 cm-1 was assigned as a hot band of the v23 mode arising from the v26 mode. The calculated rotational constants were used as starting points to begin preliminary spectral simulations of the v22 and v23 bands

Grating-Coupler Assisted Infrared Reflection Absorption Spectroscopy for the Characterization of Organic Thin Films

We demonstrate how grating-coupler assisted infrared reflection absorption spectroscopy can be used to simultaneously determine the chemical identity and relative thickness of organic thin films. With a grating substrate, a threshold anomaly associated with passing off of the −1 diffracted order occurs at grazing angles of incidence, resulting in a sharp absorbance in the infrared. The position of this peak is sensitive to the grating geometry as well as the dielectric environment near its surface. Thus, shifts in the peak position can be used to determine the relative thickness of adsorbed films or quantify molecular adsorption events. To illustrate the characteristics and sensitivity of this phenomenon, several samples were prepared and tested, including self-assembled alkanethiolate monolayers with 11-mercaptoundecanoic acid, 11-mercapto-1-undecanol, decanethiol, and a covalently linked layer of bovine serum albumin on a commercial, gold-coated grating. For these samples, the position of the threshold absorbance peak shifted to lower wavenumbers as film thickness increased, which is consistent with calculated shifts based upon an increasing refractive index at the interface. The sensitivity of this shift was measured to be 3.7 cm-1 nm-1. These results illustrate how a grating substrate can be exploited in a standard infrared reflectance measurement to provide additional information about the relative thickness of adsorbed surface films

Application And Development Of Advanced Atomic-Scale Analysis And Simulations For Complex Systems

A series of studies have investigated the applicability of kerogen, which is an amorphous and insoluble organic matter abundant in unconventional shale formations. This geo−materials are known to have undergone significant alteration in chemical structure during thermal maturation which is characterized using a combination of solid−state 1H & 13C−NMR, X−ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR), Matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF-MS) techniques. For these studies, four kerogen samples (type−II) from the Bakken Formation were selected based on the differences in their thermal maturity, as well as representing the pre−oil and oil window stages as measured through organic petrology and bulk geochemical screening of the samples. Results documented a systematic structural change in these four samples where the ratio of CH3/CH2 increased when the maturity increases, along with the presence of shorter aliphatic chain length. Furthermore, the aromatic carbon structure becomes more abundant in higher maturities and oil window stages. It concluded that, the structural and chemical changes that occurs in the organic matter involves defunctionalization of heteroatom functional groups, coupled with an increase in cross−linked carbon in the residual remaining kerogen. Also molecular weight distribution variations in kerogen samples revealed the rate of change in molecular mass populations as a function of thermal maturity. The studies using computational simulation techniques investigated the applicability of kerogen for separation of the mixture of gases (CO2 and CH4) in dry and wet (brine) conditions for an effective storage and injection operation. Here, through grand canonical Monte Carlo (GCMC)/molecular dynamics (MD) simulations, the studies of thermodynamics and kinetics investigated the CO2 transportation and adsorption behavior on three-dimensional (3D) kerogen molecular models from the Bakken, which contains non-periodically arrayed functional groups. The stronger interaction of CO2 molecules with the model leads to the penetration of CO2 molecules to the sub-surface levels. And, the concentration of brine shows a positive effect for CO2/CH4 selectivity that supports our goals of sequestration and enhanced production. These results suggest the important role of kerogen in the separation and transport of gas in organic−rich shale plays that are the target for sequestration of CO2 and/or enhanced oil recovery (EOR)

Merged electrospray ionization mass spectrometry

Ambient ionization allows the analysis of materials in their native environment without sample preparation by creating ions outside the mass spectrometer. The goal of this research was to develop new ambient ionization techniques for application to solids, liquids and particles under ambient conditions. Samples to be analyzed were directly merged with an electrospray of droplets, and then ionized and detected by a mass spectrometer. An ion trap mass spectrometer was modified with a nanoelectrospray source and configured for three experiments: merged electrospray ionization of dry particles, merged electrospray ionization of combustion products, and infrared laser desorption/ablation using electrospray for post-ionization. In the first set of experiments, materials in powdered samples were ionized directly by interaction with an electrospray of charged solvent droplets. The powdered samples were dispersed as dry particles with an aerosol generator. The study included amino acids and antibiotics, as well as food and pharmaceutical samples. Singly-charged peaks, corresponding to major components in the powdered samples, were detected using this method. The second set of experiments directly analyzed combustion products generated from the burning of cigarettes, incense, candles, and organic fuels by merging these with electrospray for ionization. This approach allowed the detection of major components in the smoke of cigarettes, incense, and candles, and polycyclic aromatic hydrocarbons generated from combustion of organic fuels. In the third set of experiments, an infrared laser was used to desorb and ablate samples placed on a stainless steel sample target, and electropray droplets interacted with the ablated materials to generate ions. Protein standards, biological fluids, and pharmaceutical products were analyzed using this technique. The spectra of the materials analyzed were similar to conventional electrospray

Photoluminescence, Dual-Donor Energy Transfer And Single X-Ray Crystallographic Studies Of Eu3+ Andtb3+ Complexes With Pyridines And Triazaphosphaadamantane Oxide (Tpao) Ligands

Coordination of several chromophoric ligands capable of sensitizing Tb3+ and Eu3+ ions have been studied. Four new complexes of Eu3+ and Tb3+ ions were achieved by coordinating Eu with 4’, 4’’’’- (1-4 phenylene) bis (2, 2’:6’, 2-terpyridine) , pyridino [2-3-b] pyrazines and 6,6′′ dibromo-2,2′:6′,2′′-terpyridine.The crystal structure of [Tb(TPAO)2(H2O)4(Au(CN)2)3], was determined and shows a polymeric three-dimensional coordination with a monoclinic space group Cc, Z=4. The unit cell parameters are a = 17.4266(14) Å, b = 10.8224(10) Å, c = 18.0270(16) Å, α = 90° β = 109.309(3)° γ = 90°. The structure exhibits an equilateral Au-Au-Au interaction bridged to a terbium core by the C-N groups. Three other complexes, viz [Eu(ppz)2(H2O)n]Cl3, [Eu(ptpy)(H2O)n]Cl3 and [Eu(bbterp)(H2O)n]Cl3, have also been synthesized and characterized using IR and luminescence spectroscopy, although no crystal was obtained suitable for X-ray diffraction analysis. The ligand tetra(2‘-pyridyl)pyrazine (tppz) was also crystallized and its crystal structure solved. The results herein, elaborate the mode of dual donor sensitization from ligand groups to the lanthanide ions. The efficiency of energy transfer that occurs in the Ln3+ complexes has been calculated, taking into account the radiative and non radiative relaxation processes, and the limitation encountered. A broad excitation spectrum at 369, 366 and 380 nm were observed for [Eu(ppz)2(H2O)n]Cl3 , [Eu(bbterp)(H2O)n]Cl3 and [Eu(ptpy)(H2O)n]Cl3 complexes, respectively upon monitoring the Eu3+ emission indicating the presence of ET in a donor-acceptor type interaction