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Ga speciation in Ga/H-ZSM-5 by in-situ transmission FTIR spectroscopy

H-ZSM-5 supported Ga (Ga/H-ZSM-5) has long been recognized as a promising catalyst for nonoxidative dehydrogenation and dehydroaromatization of alkanes. However, Ga speciation under reaction conditions remains controversial. In this work, in-situ transmission Fourier Transform infrared (FTIR) spectroscopy is employed to systematically investigate Ga speciation in Ga/H-ZSM-5 with three Si/Al ratios (15, 28 and 39) and a wide range of Ga/Al ratios (0–1.7). Quantitative FTIR spectroscopy with pyridine reveals that one Ga atom roughly replaces one Brønsted acid site (BAS) at Ga/BAS ratio up to 0.7, however, only up to ~80% of the BAS on the H-ZSM-5 can be exchanged even with excess amounts of Ga. At a low Si/Al ratio of 15, the intensity of GaH x bands on reduced Ga/H-ZSM-5 at 550 °C increases almost linearly at low Ga loadings (Ga/Al < 0.13), and then levels off. In contrast, no detectable GaH x bands are observed on Ga/H-ZSM-5 with a high Si/Al ratio of 39, with Ga/Al ratios up to 1.3. The dependence of GaH x bands on both the Si/Al ratios and the Ga/Al ratios shows that Ga speciation varies with BAS density in the zeolite. We hypothesize that paired BAS sites are preferentially exchanged with Ga + , leading to the formation of Ga + –H + pair sites, while the exchange of isolated BAS form isolated Ga+ species. Using water as a probe molecule, we show that isolated Ga + and Ga + –H + pair sites have distinct properties, i.e., the former can be easily oxidized by water at 150 °C to form GaOOH species, while the latter is inactive under the same conditions. Furthermore, these results provide direct experimental evidence for the existence of two types of Ga species on reduced Ga/H-ZSM-5, highlighting the possibility that they have different catalytic activities in alkane dehydrogenation reactions.

03 NATURAL GAS↗

Multiplicity of Th(IV) and U(VI) HEH[EHP] Chelates at Low Temperatures from Concentrated Nitric Acid Extractions

Organophosphorus extractants have been widely investigated for lanthanide recovery from ore and for application in the reprocessing of spent nuclear fuel, such as in Advanced TALSPEAK schemes. Determining the speciation of the extracted metal complex in the organic phase remains a significant challenge. A better understanding of the variability of HEH[EHP]–actinide complexes and the speciation of chelates for tetra- and hexavalent actinides can improve the predictability of actinide phase transfer in such biphasic systems. Here, the extraction of Th(IV) and U(VI) from nitric acid media using HEH[EHP] in heptane is examined. The distribution ratio as a function of nitric acid concentration was quantified using UV–vis spectroscopy, and then the speciation of HEH[EHP]–metal complexes in the organic phase was investigated using Fourier transform infrared (FTIR) spectroscopy and low-temperature 31 P nuclear magnetic resonance (NMR) spectroscopy. In addition to perturbation of the vibrational modes proximal to the phosphonic moiety in HEH[EHP] in the FTIR spectra, the appearance of a nitrate signal was found in the organic phase following extraction from the highest acidity conditions for U(VI). The 31 P NMR spectra of the organic phase at a low temperature (-70 °C) exhibited a surprising number (n) of resonances (n ≥ 7 for Th(IV) and n ≥ 11 for U(VI)), with the distribution between these resonances changing with the initial concentration of nitric acid in the aqueous phase. These results indicate that the compositions of the inner and outer spheres of the extracted actinides in the organic phase are more diverse than initially thought.

31P NMR↗

Detailed Characterization of Vitrinite-Rich Subbituminous and Bituminous Coals for Utilization in Carbon Fiber Precursor Production

Chemical structures of candidate coals (one subbituminous coal from the Powder River Basin and three bituminous Eastern US coals) were examined for potential low-cost carbon fiber precursor production. Here, the structural evaluation examined the carbon skeleton ( 13 C nuclear magnetic resonance (NMR) and high-resolution transmission electron microscopy (HRTEM)), the heteroatom functionality (X-ray photoelectron spectroscopy (XPS) Fourier transform infrared spectroscopy (FTIR) and NMR), the structural ordering and distribution of PAH sizes (HRTEM), and an estimation of the molecular weight distribution (laser desorption ionization mass spectrometry, LDIMS). The molecular compositional distributions were also evaluated for a mixed solvent extract (atmospheric pressure photoionization, 21 T Fourier transform ion cyclotron resonance mass spectrometry, FT-ICR MS). Significant structural differences existed between the subbituminous and bituminous coals, as expected with coalification (with the bituminous coals having a higher carbon content, lower oxygen content, higher aromaticity values, larger cluster sizes, and so forth). While the bituminous coals were similar in structure (close in rank with Blue Gem being hvAb and the rest being hvBb), structural differences were still evident. Specifically, structural similarities were evident for the average properties of Herrin and Springfield coals: same rank, similar moisture, and volatile matter yields, along with similar aromaticity and carbon and hydrogen content. However, significant structural differences were observed at the molecular level by 21 T FT-ICR MS, which showed that the Springfield coal was structurally more complex. Specifically, 21740, 16931, 30190, and 12982 unique elemental compositions were identified for the Monarch, Herrin, Springfield, and Blue Gem coals, further illustrating the complexity of the coal.

01 COAL, LIGNITE, AND PEAT↗

Interconnection of the Antenna Pigment 8-HDF and Flavin Facilitates Red-Light Reception in a Bifunctional Animal-like Cryptochrome

Cryptochromes are ubiquitous flavin-binding light sensors closely related to DNA-repairing photolyases. The animal-like cryptochrome CraCRY from the green alga Chlamydomonas reinhardtii challenges the paradigm of cryptochromes as pure blue-light receptors by acting as a (6-4) photolyase, using 8-hydroxy-5-deazaflavin (8-HDF) as a light-harvesting antenna with a 17.4 Å distance to flavin and showing spectral sensitivity up to 680 nm. The expanded action spectrum is attributed to the presence of the flavin neutral radical (FADH•) in the dark, despite a rapid FADH• decay observed in vitro in samples exclusively carrying flavin. Herein, the red-light response of CraCRY carrying flavin and 8-HDF was studied, revealing a 3-fold prolongation of the FADH• lifetime in the presence of 8-HDF. Millisecond time-resolved ultraviolet-visible spectroscopy showed the red-light-induced formation and decay of an absorbance band at 458 nm concomitant with flavin reduction. Time-resolved Fourier transform infrared (FTIR) spectroscopy and density functional theory attributed these changes to the deprotonation of 8-HDF, challenging the paradigm of 8-HDF being permanently deprotonated in photolyases. FTIR spectra showed changes in the hydrogen bonding network of asparagine 395, a residue suggested to indirectly control flavin protonation, indicating the involvement of N395 in the stabilization of FADH•. Fluorescence spectroscopy revealed a decrease in the energy transfer efficiency of 8-HDF upon flavin reduction, possibly linked to 8-HDF deprotonation. Finally, the discovery of the interdependence of flavin and 8-HDF beyond energy transfer processes highlights the essential role of the antenna, introducing a new concept enabling CraCRY and possibly other bifunctional cryptochromes to fulfill their dual function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The preparation and characterization of chemically deuterium incorporated cotton fibers

Preparation of deuterium incorporated cellulose is a vital tool to investigate cellulose internal structure and to expand the application fields of cellulose materials. In this study, cellulosic cotton fibers with anti-rehydration (exchange-resistant) deuterium incorporated in cellulose were prepared by chemical hydrogen–deuterium exchange treatment. The chemical hydrogen–deuterium exchange process, along with exchange time, were characterized by nuclear magnetic resonance hydrogen spectroscopy (1H-NMR). The anti-rehydration deuterium incorporation was determined by Fourier Transform infrared spectroscopy (FTIR) and Stable Isotope Ratio Mass Spectrometer (IRSM). Here, the effect of the deuterium hydroxyl substitution on cotton fiber’s spectral data, microstructure, crystalline information, degree of polymerization, as well as it’s thermogravimetric analysis (charcoalization and combustion) are explored. Analysis of the chemical exchange process indicated that the hydrogen–deuterium exchange occurred preferentially in the amorphous cellulose component over the first several minutes. Deuterium exchange in the anti-rehydration crystalline phase took several hours. Increasing the treatment time, enhanced exchange-resistant deuterium incorporation to as high as about 60% of the cotton fibers’ cellulose hydroxyl groups was achieved. The characterization of FTIR, Fourier transform Raman (FT-Raman), and near-infrared spectra (NIR) all exhibited the deuterium spectral isotope effect on cellulose hydroxl groups. While, apart from the effect of reaction temperature, deuterium incorporation isotope effect did not affect the cellulose microstructure, crystalline index and the degree of polymerization properties. Furthermore, the thermogravimetric analysis of deuterated cotton fibers under N 2 and air atmosphere were both altered due to the thermodynamic isotope effect. These observations revealed the hydrogen–deuterium exchange treatment process and impacts on cellulose fiber properties, which helped us to better understand the cellulose internal structure and may facilitate the potential utilization of deuterated cellulosic materials.

59 BASIC BIOLOGICAL SCIENCES↗

Crosslinked Polyethyleneimine Gel Polymer Interface to Improve Cycling Stability of RFBs

Redox flow batteries are considered a promising technology for grid energy storage. However, capacity decay caused by crossover of active materials is a universal challenge for many flow battery systems, which are based on various chemistries. In this paper, using the vanadium redox flow battery as an example, we demonstrate a new gel polymer interface (GPI) consisting of crosslinked polyethyleneimine with a large amount of amino and carboxylic acid groups introduced between the positive electrode and the membrane. The GPI functions as a key component to prevent vanadium ions from crossing the membrane, thus supporting stable long-term cycling. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted to investigate the effect of GPI on the electrochemical properties of graphitic carbon electrodes (GCFs) and redox reaction of catholyte. X-ray photoelectron spectroscopy (XPS) and 1 H nuclear magnetic resonance (NMR) spectra demonstrated that the crosslinked GPI is chemically stable for 100 cycles without dissolution of polymers and swelling in the strong acidic electrolytes. Results from inductively coupled plasma mass spectrometry (ICP-MS), Fourier-transform infrared (FTIR) spectroscopy, and energy-dispersive X-ray (EDX) spectroscopy proved that the GPI is effective in maintaining the concentration of vanadium species in their respective half-cells, resulting in improved cycling stability because of it prevents active species from crossing the membrane and stabilizes the oxidation states of active species.

Lim, Hyung-Seok↗

Use of kaolinite clays in development of a low carbon MgO-clay binder system

Magnesium oxide based cements may provide a promising alternative to the conventional Portland cement in many applications. This study investigates the feasibility of using calcined kaolinitic clay to produce an MgO binder. The MgO-based binder were prepared using a low kaolinite content clay and metakaolin and were compared with a silica fume system. Implications of the addition of magnesium carbonate in the binder were also investigated. Isothermal calorimetry, X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) were used to study the hydration characteristics of the binder system whereas compressive strength and porosity were measured to determine mechanical and durability attributes. The economic and environmental aspects of the binder system is also discussed. Hydrotalcite like phases were clearly produced on hydration in the clay mixes containing carbonate additions. The compressive strength of clay mixes was at par or better compared to systems containing silica fume, and the clay systems had significantly lower porosity levels. The presence of magnesium carbonate further enhanced the physical properties of the clay mixes.

36 MATERIALS SCIENCE↗

Air Contamination Quantification by FTIR with Gas Cell

Air quality is of utmost importance in environmental studies and has many industrial applications such as aviators grade breathing oxygen (ABO) for pilots and breathing air for fire fighters. Contamination is a major concern for these industries as identified in MIL-PRF-27210, CGA G-4.3, CGA G-7.1, and NFPA 1989. Fourier Transform Infrared Spectroscopy (FTIR) is a powerful tool that when combined with a gas cell has tremendous potential for gas contamination analysis. Current procedures focus mostly on GC-MS for contamination quantification. Introduction of this topic will be done through a comparison of the currently used deterministic methods for gas contamination with those of FTIR gas analysis. Certification of the mentioned standards through the ISOIEC 17065 certifying body A2LA will be addressed followed by an evaluation of quality information such as the determinations of linearity and the limits of detection and quantitation. Major interferences and issues arising from the use of the FTIR for accredited work with ABO and breathing air will be covered.

Freischlag, Jason↗

A parametric study of accelerated carbonation in alkali-activated slag

Resistance to carbonation is one important attribute that low-CO{sub 2} cement alternatives must possess, and is particularly crucial for cement alternatives subjected to aggressive CO{sub 2} concentrations such as those used in construction of oil wells and wells for below ground carbon sequestration. Here, a parametric study of alkali-activated slag (AAS) carbonation in aggressive environments has been conducted to examine (i) calcium carbonate polymorphism using X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy, and (ii) the extent of calcium carbonate formation and CO{sub 2} adsorption using thermogravimetric analysis (TGA). A range of AASs have been studied by varying the magnesium content of the slag, the activator type (sodium hydroxide and sodium silicate), the activator concentration, and the curing time prior to carbonation. It was uncovered that both (i) magnesium from the slag and (ii) silica from the activating solution are needed to reduce the propensity for the sodium-containing calcium-alumino-silicate-hydrate gel to undergo decalcification.

36 MATERIALS SCIENCE↗

Extreme Thermal Stabilization of Carborane–Cyanate Composites via B–N Dative-Bonded Boroxine Barriers

Enhancing the thermal stability of cyanate ester (CE) resins is crucial for high-temperature aerospace applications. This study elucidates the degradation mechanisms of CE composites reinforced with carborane additives, focusing on the formation of boron–nitrogen (B–N) dative bonds and their role in improving thermal resistance. Using thermogravimetric analysis, we examined char formation and evolved gases at multiple degradation stages. Reaction sequences and char products were characterized via Fourier transform infrared spectroscopy (FTIR), solid-state 13C and 11B NMR, and evolved gas analysis using mass spectrometry and FTIR. The solid-state 11B NMR was instrumental in detecting various boron oxidation states and the formation of B–N dative bonds during decomposition. These bonds facilitate cross-linking in the char phase, enhancing material integrity at elevated temperatures. However, in inert environments, the volatility of boron additives like carborane limits their effectiveness. These findings advance the understanding of CE composite degradation mechanisms and offer critical insights for developing high-temperature-resistant materials for aerospace applications.

Fourier transform infrared spectroscopy↗

Polyvinyl Alcohol (PVA)–Azadirachta indica (Neem) Nanofibrous Mat for Biomedical Application: Formation and Characterization

The present study provides credence to the formation of polyvinyl alcohol (PVA)–Azadirachta indica (neem) nanofibrous mat (PNNM) under optimum processing conditions of electrospinning technique from a mixer of PVA and neem extract to utilize the inherent medicinal properties of this herb for biomedical application. The bonding behavior, orientation of fibers, thermal behavior, and moisture management properties were evaluated by Fourier transforms infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermo gravimetric analysis (TGA) and moisture management tester (MMT) reports respectively. The antibacterial activity of the developed sample at the maximum mixing ratio of neem extract (80%) was tested against Gram-positive (S. aureus) bacteria using agar disc diffusion method. The results reveal that the prepared nanofibrous mat exhibited better thermal and moisture management properties in comparison with PVA nanofiber alone. The formation of smooth fibers was confirmed by SEM images having average diameter of 185 nm under 5k, 10k and 15k magnifications. The characteristic peaks of PVA and neem constituents in FTIR spectra of the developed mat confirmed the presence of both components. Bacterial resistance was reached up to 20 mm due to the antibacterial constituents of neem extract. Thus the developed mat could be used as a biocompatible and bio based in biomedical applications. Graphic Abstract: .

36 MATERIALS SCIENCE↗

Sublimation of Laboratory Ices Millimeter/Submillimeter Experiment (SubLIME): Structure-Specific Identifications of Products from UV-photolyzed Methanol Ice

Submillimeter/far-IR spectroscopy was used to detect and quantify organic molecules sublimated after the ultraviolet photolysis (at 12 K) and warm-up (up to 300 K) of a methanol (CH3OH) ice sample. Eleven sublimated photoproducts were uniquely identified: carbon monoxide (CO), formaldehyde (H2CO), ketene (C2H2O), acetaldehyde (CH3CHO), ethylene oxide (CH2OCH2), vinyl alcohol (CH2CHOH), ethanol (CH3CH2OH), dimethyl ether (CH3OCH3), methyl formate (HCOOCH3), glycolaldehyde (HOCH2CHO), and acetone ((CH3)2CO). Two additional products were detected in the photolyzed ice by Fourier-transform infrared (FTIR) spectroscopy: carbon dioxide (CO2) and methane (CH4). The rotational temperatures and gas densities were calculated for the organics containing two or more C atoms via a rotation diagram analysis, and the gas-phase submillimeter/far-IR technique was used in tandem with mass spectrometry and FTIR spectroscopy of the ice during photolysis. The abundance ratios of the sublimated species (normalized to methanol) were compared to those observed in hot cores (Orion-KL, Sagittarius B2(N), and IRAS 16293-2422(B)) and in comets C/2014 Q2 (Lovejoy) and 67P/Churyumov–Gerasimenko.

K M Yocum↗

Sublimation of Laboratory Ices Millimeter/Submillimeter Experiment (SubLIME): Structure-Specific Identifications of Products from UV-photolyzed Methanol Ice

Submillimeter/far-IR spectroscopy was used to detect and quantify organic molecules sublimated after the ultraviolet photolysis (at 12 K) and warm-up (up to 300 K) of a methanol (CH3OH) ice sample. Eleven sublimated photoproducts were uniquely identified: carbon monoxide (CO), formaldehyde (H2CO), ketene (C2H2O), acetaldehyde (CH3CHO), ethylene oxide (CH2OCH2), vinyl alcohol (CH2CHOH), ethanol (CH3CH2OH), dimethyl ether (CH3OCH3), methyl formate (HCOOCH3), glycolaldehyde (HOCH2CHO), and acetone ((CH3)2CO). Two additional products were detected in the photolyzed ice by Fourier-transform infrared (FTIR) spectroscopy: carbon dioxide (CO2) and methane (CH4). The rotational temperatures and gas densities were calculated for the organics containing two or more C atoms via a rotation diagram analysis, and the gas-phase submillimeter/far-IR technique was used in tandem with mass spectrometry and FTIR spectroscopy of the ice during photolysis. The abundance ratios of the sublimated species (normalized to methanol) were compared to those observed in hot cores (Orion-KL, Sagittarius B2(N), and IRAS 16293-2422(B)) and in comets C/2014 Q2 (Lovejoy) and 67P/Churyumov–Gerasimenko.

K. M. Yocum↗

Operando Measurements of Electrolyte Li-ion Concentration during fast charging with FTIR/ATR

The ability to charge a Li-ion battery at high charging rates is critical for electric vehicle adoption; however, further study of ion transport is required to develop electrolytes suitable for fast charge. Fourier transform infrared spectroscopy (FTIR) used with attenuated total reflection (ATR) enables operando measurements of liquid electrolytes. This research focused on solvation shifting of solvent infrared absorption bands in the presence of lithium ions. Lithium-shifted infrared absorption bands and non-shifted bands of ethyl methyl carbonate (EMC) and ethylene carbonate (EC) were compared to infer ion concentration changes during cycling. Lithium concentrations were calibrated using EC/EMC/LiPF 6 electrolytes with known lithium concentrations. A Li-ion half-cell with a graphite anode and EC/EMC/LiPF 6 electrolyte was observed with FTIR/ATR. The results showed that the magnitude of lithium concentration changes increased with increasing C-rate. During a galvanostatic intermittent titration technique (GITT) test, changes in lithium concentration could be observed. During intercalation, a lithium depletion occurred when a negative current was applied, and a lithium surplus occurred during deintercalation when a positive current was applied. The capability of observing lithium concentration has significant implications for the utility of operando studies and the potential to link lithium movement to battery performance.

25 ENERGY STORAGE↗

Analysis of Material Properties of Aged Rigid Polyurethane Foam

Foams are classified as either rigid or flexible and are commonly used in applications such as pipe insulation, carpet fibers, and chair foam cushions. Polyurethane foams are excellent thermal insulators, have excellent mechanical properties, and are chemically inert. With the addition of fire protective additives, polyurethane foams have the ability to intumescence when exposed to high temperatures. For the future storage of the 9977 nuclear shipping packages, the material properties of the General Plastics 3716 rigid polyurethane foam were evaluated for long term performance by comparing aged samples to unaged samples. General Plastics 3716 rigid polyurethane foam was aged from November 2014 to June 2019 at varying temperatures of: 160 deg. F, 160 deg. F + 50% relative humidity (RH), 185 deg. F, 215 deg. F, and 250 deg. F. The foam was then analyzed via Fourier Transform Infrared Spectroscopy (FTIR), 3D Optical Microscope, Thermal Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC). FTIR and Optical Microscope: No significant change to chemical or physical structure was evident by FTIR or optical microscope analysis. DSC: Decrease of heat capacity over time for all oven temperatures except a slight increase for the 185 deg. F conditioned foams. Largest decrease evident with foams conditioned at 250 deg. F. A slight increase in heat capacity for humid samples. Similar trends in heat capacities at 71 deg. C and 102 deg. C. TGA: As conditioning temperature increased, a decline was evident in the average percent weight loss, onset temperature, and first derivative peak temperature. No significant effect due to humidity except for a decrease in first derivative peak temperature. Unaged samples exhibited strong intumescence. Foams conditioned at 160 deg. F exhibited slight intumescence. Results suggest fire protective additives decomposed at higher temperatures, which contributed to a lower average percent mass loss in higher temperature conditioning. Further thermal degradation testing would be beneficial to evaluate the ability of the conditioned foams to intumesce. Evaluate irradiation dose rate effects on conditioned foam. Possible conditioning in an environment with a known humidity or analyzing a new aliquot of sample for each trial to achieve a more representative heat capacity calculation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

SPRUCE FT-ICR MS, Bulk Chemistry, and Mass Loss from Litter Decomposition Study in Experimental Plots, Marcell Experimental Forest, Minnesota, 2015-2017

This dataset contains molecular, bulk chemical, and mass loss measurements from a litter decomposition study at the Spruce and Peatland Responses Under Changing Environments (SPRUCE) experimental site within the Marcell Experimental Forest in northern Minnesota, USA. This site is in a Sphagnum spp. ombrotrophic bog forest. Litterbags were deployed into the peat in September 2015 across three warming levels (+0, +4.5, and +9°C) under ambient and elevated carbon dioxide (CO₂ - +500 ppm) and retrieved after roughly 0.5, 1, and 2 years of field incubation (2015-09-23 to 2017-08-02). Litterbags containing six peatland litter types: black spruce needles (Picea mariana - SPL), spruce fine roots (SPR), Sphagnum angustifolium (ANG), Sphagnum magellanicum (MAG), Labrador tea leaves (Rhododendron groenlandicum - LTL), and Labrador tea roots (LTR). Molecular composition of water-soluble organic matter extracts was characterized using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) at 9.4 Tesla, operated in negative ion mode with electrospray ionization, providing molecular formula assignments and compound-class distributions across the decomposition time series. Bulk chemical characterization included elemental analysis (percent carbon, nitrogen, and phosphorus) and Fourier Transform Infrared Spectroscopy (FTIR) to quantify functional group composition. Litter mass loss was tracked gravimetrically at each retrieval interval, expressed as percent mass remaining relative to initial dry mass for each litter type and treatment combination. These data are valuable for understanding how vegetation shifts driven by increased atmospheric CO2 and temperature in peatlands alter litter inputs and organic matter stabilization trajectories, with implications for projecting and modeling peatland carbon cycling. This dataset contains two data files in comma-separated value (.csv) format. Additional metadata are provided: two data dictionaries and a file-level metadata file in comma separate (.csv) format and a user guide in PDF (*.pdf) format.

decomposition↗

Spectroscopic characterization of collagen cross-links in bone

Collagen is the most abundant protein of the organic matrix in mineralizing tissues. One of its most critical properties is its cross-linking pattern. The intermolecular cross-linking provides the fibrillar matrices with mechanical properties such as tensile strength and viscoelasticity. In this study, Fourier transform infrared (FTIR) spectroscopy and FTIR imaging (FTIRI) analyses were performed in a series of biochemically characterized samples including purified collagen cross-linked peptides, demineralized bovine bone collagen from animals of different ages, collagen from vitamin B6-deficient chick homogenized bone and their age- and sex-matched controls, and histologically stained thin sections from normal human iliac crest biopsy specimens. One region of the FTIR spectrum of particular interest (the amide I spectral region) was resolved into its underlying components. Of these components, the relative percent area ratio of two subbands at approximately 1660 cm(-1) and approximately 1690 cm(-1) was related to collagen cross-links that are abundant in mineralized tissues (i.e., pyridinoline [Pyr] and dehydrodihydroxylysinonorleucine [deH-DHLNL]). This study shows that it is feasible to monitor Pyr and DHLNL collagen cross-links spatial distribution in mineralized tissues. The spectroscopic parameter established in this study may be used in FTIRI analyses, thus enabling the calculation of relative Pyr/DHLNL amounts in thin (approximately 5 microm) calcified tissue sections with a spatial resolution of approximately 7 microm.

Non-NASA Center↗

In situ CF3 Detection in Low Pressure Inductive Discharges by Fourier Transform Infrared Spectroscopy

The detection of CF(x) (x=1-3) radicals in low pressure discharges using source gases such as CF4 and CHF3 is of importance to the understanding of their chemical structure and relevance in plasma based etching processes. These radicals are known to contribute to the formation of fluorocarbon polymer films, which affect the selectivity and anisotropy of etching. In this study, we present preliminary results of the quantitative measurement of trifluoromethyl radicals, CF3, in low pressure discharges. The discharge studied here is an inductively (transformer) coupled plasma (ICP) source in the GEC reference cell, operating on pure CF4 at pressures ranging from 10 - 100 mTorr, This plasma source generates higher electron number densities at lower operating pressures than obtainable with the parallel-plate capacitively coupled version of the GEC reference cell. Also, this expanded operating regime is more relevant to new generations of industrial plasma reactors being used by the microelectronics industry. Fourier transform infrared (FTIR) spectroscopy is employed to observe the absorption band of CF3 radicals in the electronic ground state X2Al in the region of 1233-1270/cm. The spectrometer is equipped with a high sensitivity HgCdTe (MCT) detector and has a fixed resolution of 0.125/cm. The CF3 concentrations are measured for a range of operating pressures and discharge power levels.

Kim, J. S.↗