IR Fingerprint Regions Research Articles

Infrared Fingerprint Engineering: A Molecular-Design Approach to Long-Wave Infrared Transparency with Polymeric Materials.

Optical technologies in the long-wave infrared (LWIR) spectrum (7-14 μm) offer important advantages for high-resolution thermal imaging in near or complete darkness. The use of polymeric transmissive materials for IR imaging offers numerous cost and processing advantages but suffers from inferior optical properties in the LWIR spectrum. A major challenge in the design of LWIR-transparent organic materials is that nearly all organic molecules absorb in this spectral window which lies within the so-called IR-fingerprint region. We report on a new molecular-design approach to prepare high refractive index polymers with enhanced LWIR transparency. Computational methods were used to accelerate the design of novel molecules and polymers. Using this approach, we have prepared chalcogenide hybrid inorganic/organic polymers (CHIPs) with enhanced LWIR transparency and thermomechanical properties via inverse vulcanization of elemental sulfur with new organic co-monomers.

Modified Quadrupole Ion Trap Mass Spectrometer for Infrared Ion Spectroscopy: Application to Protonated Thiated Uridines.

Modifications to a Paul-type quadrupole ion trap mass spectrometer providing optical access to the trapped ion cloud as well as hardware and software for coupling to a table-top IR optical parametric oscillator laser (OPO) are detailed. Critical experimental parameters for infrared multiple photon dissociation (IRMPD) on this instrument are characterized. IRMPD action spectra, collected in the hydrogen-stretching region with this instrument, complemented by spectra in the IR fingerprint region acquired at the FELIX facility, are employed to characterize the structures of the protonated forms of 2-thiouridine, [s2Urd+H]+, and 4-thiouridine, [s4Urd+H]+. The measured spectra are compared with predicted linear IR spectra calculated at the B3LYP/6-311+G(d,p) level of theory to determine the conformers populated in the experiments. This comparison indicates that thiation at the 2- or 4-positions shifts the protonation preference between the 2,4-H tautomer and 4-protonation in opposite directions versus canonical uridine, which displays a roughly equal preference for the 2,4-H tautomer and O4 protonation. As found for canonical uridine, protonation leads to a mixture of conformers exhibiting C2'-endo and C3'-endo sugar puckering with an anti nucleobase orientation being populated for both 2- and 4-thiated uridine. Graphical Abstract ᅟ.

Nanoliter Sensing for Infrared Bioanalytics.

Nondestructive label-free bioanalytics of microliter to nanoliter sample volumes with low analyte concentrations requires novel analytic approaches. For this purpose, we present an optofluidic platform that combines surface-enhanced in situ infrared spectroscopy with microfluidics for sensing of surface-immobilized ultrathin biomolecular films in liquid analytes. Submonolayer sensitivity down to surface densities of few ng/cm2 is demonstrated for the adsorption of the thiolate tripeptide glutathione and for the recognition of streptavidin on a biotinylated enhancement substrate. Nonfunctionalized and functionalized metal island films on planar oxidized silicon substrates are used for signal enhancement with quantifiable enhancement properties. A single-reflection geometry at an incidence angle below the attenuated-total-reflection (ATR) regime is used with ordinary planar, IR-transparent windows. The geometry circumvents the strong IR absorption of common polymer materials and of aqueous environments in the IR fingerprint region. This practice enables straightforward quantitative analyses of, e.g., adsorption kinetics as well as chemical and structural properties in dependence of external stimuli.

Analysis of Australian Beers Using Fluorescence Spectroscopy

Classification of a series of Australian beers was performed using synchronous scanning fluorescence spectroscopy and emission-excitation matrices based on the IR fingerprint regions. The results indicate that synchronous scanning fluorescence spectroscopy is a robust and valuable method to discriminate between Australian lager beers based on their brand name. In addition, a subsequent spoiling study revealed that when beers are opened and stored at 4 °C for 4 weeks, the results demonstrated that the beers were not statistically different. The methods and techniques outlined may be of interest to brewing companies and microbrewers to determine the unique beer spectrum.

Dissecting the Genetic Basis for Seed Coat Mucilage Heteroxylan Biosynthesis in Plantago ovata Using Gamma Irradiation and Infrared Spectroscopy

Seeds from the myxospermous species Plantago ovata release a polysaccharide-rich mucilage upon contact with water. This seed coat derived mucilage is composed predominantly of heteroxylan (HX) and is utilized as a gluten-free dietary fiber supplement to promote human colorectal health. In this study, a gamma-irradiated P. ovata population was generated and screened using histological stains and Fourier Transform Mid Infrared (FTMIR) spectroscopy to identify putative mutants showing defects in seed coat mucilage HX composition and/or structure. FTMIR analysis of dry seed revealed variation in regions of the IR spectra previously linked to xylan structure in Secale cereale (rye). Subsequent absorbance ratio and PCA multivariate analysis identified 22 putative mutant families with differences in the HX IR fingerprint region. Many of these showed distinct changes in the amount and subtle changes in structure of HX after mucilage extrusion, while 20% of the putative HX mutants identified by FTMIR showed no difference in staining patterns of extruded mucilage compared to wild-type. Transcriptional screening analysis of two putative reduced xylan in mucilage (rxm) mutants, rxm1 and rxm3, revealed that changes in HX levels in rxm1 correlate with reduced transcription of known and novel genes associated with xylan synthesis, possibly indicative of specific co-regulatory units within the xylan biosynthetic pathway. These results confirm that FTMIR is a suitable method for identifying putative mutants with altered mucilage HX composition in P. ovata, and therefore forms a resource to identify novel genes involved in xylan biosynthesis.

Interval ANOVA simultaneous component analysis (i-ASCA) applied to spectroscopic data to study the effect of fundamental fermentation variables in beer fermentation metabolites

This study explores the effect of different settings on beer fermentation process applying an interval-based version of ASCA on FT-IR data. Three main factors (yeast type, temperature, fermentation time) are included in the experimental design, being high sources of variation in brewing and strictly interdependent; thus, difficult to be studied through a univariate approach. The three-factor full factorial design leads to a spectral multi-set data, with a total of 12 independent fermentations, which is explored combining ASCA and an interval adaptation of ASCA (interval-ASCA or i-ASCA). The ASCA models calculated on two separate regions (2900–2250cm−1 and 1500–980cm−1) shows differences for average time levels and the interaction between yeast types and time linked to carbon dioxide, maltose consumption and ethanol production, respectively. To better investigate the punctual influence of the studied factors on the so-called IR fingerprint region, permutation testing of ASCA in variable intervals is investigated. The analysis highlights the significant effect not only of the fermentation in all intervals considered, but also the role of other factors, such as time × yeast, yeast and temperature, in smaller variable regions. The proposed approach demonstrates how interval-ASCA on FT-IR data, isolating the variation in the data according to the experimental design used, allows a rapid and accurate test for parameter control in beer manufacturing.

Gas-phase conformations and energetics of protonated 2'-deoxyadenosine and adenosine: IRMPD action spectroscopy and theoretical studies.

The gas-phase conformations of protonated 2'-deoxyadenosine, [dAdo+H](+), and its RNA analogue protonated adenosine, [Ado+H](+), generated upon electrospray ionization are examined using infrared multiple photon dissociation (IRMPD) action spectroscopy techniques and supported by complementary theoretical electronic structure calculations. IRMPD action spectra are measured over the IR fingerprint region using the FELIX free-electron laser and the hydrogen-stretching region using an optical parametric oscillator/amplifier laser system. The measured IRMPD spectra are compared to linear IR spectra predicted for the stable low-energy conformations of [dAdo+H](+) and [Ado+H](+) computed at the B3LYP/6-311+G(d,p) level of theory to determine the preferred site of protonation and to identify the structures populated in the experiments. N3 is found to be the most favorable site of protonation for both [dAdo+H](+) and [Ado+H](+), whereas conformers protonated at the N1 and N7 positions are much less stable by >25 kJ/mol. The 2'-hydroxyl substituent of Ado does not lead to a significant change in the structure of the ground-state conformer of [Ado+H](+) as compared to that of [dAdo+H](+), except that it provides additional stabilization via the formation of an O2'H···O3' hydrogen bond. Therefore, [dAdo+H](+) and [Ado+H](+) exhibit highly parallel IRMPD spectral features in both the fingerprint and hydrogen-stretching regions. However, the additional 2'-hydroxyl substituent markedly affects the IRMPD yield of the measured IR bands. The spectral signatures in the hydrogen-stretching region provide complementary information to that of the fingerprint region and enable facile differentiation of the conformers that arise from different protonation sites. In spite of the relative gas-phase stabilities of the N3 and N1 protonated conformers, present results suggest that both are accessed in the experiments and contribute to the measured IRMPD spectrum, indicating that the relative stabilities in solution also influence the populations generated by electrospray ionization.

Protonation Preferentially Stabilizes Minor Tautomers of the Halouracils: IRMPD Action Spectroscopy and Theoretical Studies

Tautomerization induced by protonation of halouracils may increase their efficacy as anti-cancer drugs by altering their reactivity and hydrogen bonding characteristics, potentially inducing errors during DNA and RNA replication. The gas-phase structures of protonated complexes of five halouracils, including 5-fluorouracil, 5-chlorouracil, 5-bromouracil, 5-iodouracil, and 6-chlorouracil are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical electronic structure calculations. IRMPD action spectra were measured for each complex in the IR fingerprint region extending from ~1000 to 1900 cm(-1) using the free electron laser (FELIX). Correlations are made between the measured IRMPD action spectra and the linear IR spectra for the stable low-energy tautomeric conformations computed at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G* level of theory. Absence of an intense band(s) in the IRMPD spectrum arising from the carbonyl stretch(es) that are expected to appear near 1825 cm(-1) provides evidence that protonation induces tautomerization and preferentially stabilizes alternative, noncanonical tautomers of these halouracils where both keto functionalities are converted to hydroxyl groups upon binding of a proton. The weak, but measurable absorption, which does occur for these systems near 1835 cm(-1) suggests that in addition to the ground-state conformer, very minor populations of excited, low-energy conformers that contain keto functionalities are also present in these experiments.

Confirmation of NH species in the framework of nitrogen-incorporated ZSM-5 zeolite by experimental and theoretical studies

Nitrogen-incorporated zeolites have drawn much attention as a new family of basic solid materials and N atoms are expected to be introduced into the frameworks of zeolites. In this study, nitrogen-incorporated ZSM-5 zeolites were prepared by temperature-programmed nitridation and their physicochemical properties were characterized by means of XRD, SEM and BET techniques. Combined a detailed IR characterization with a theoretical IR simulation, the bands relating to bridging Si–N(H)–Si groups at 1151 and 985 cm −1 were observed in the IR fingerprint region of nitrogen-incorporated zeolites. The results confirmed that N atoms have been introduced into the framework of ZSM-5 zeolites by nitridation to form basic –NH– species, which was also supported by results of 29Si MAS NMR characterization. Furthermore, the basic catalytic properties of nitrogen-incorporated ZSM-5 zeolites were evaluated by Knoevenagel condensation of benzaldehyde and malononitrile and enhanced conversion of benzaldehyde was achieved.

Rapid evaluation and quantitative analysis of thyme, origano and chamomile essential oils by ATR-IR and NIR spectroscopy

The essential oils obtained from various chemotypes of thyme, origano and chamomile species were studied by ATR/FT-IR as well as NIR spectroscopy. Application of multivariate statistics (PCA, PLS) in conjunction with analytical reference data leads to very good IR and NIR calibration results. For the main essential oil components (e.g. carvacrol, thymol, γ-terpinene, α-bisabolol and β-farnesene) standard errors are in the range of the applied GC reference method. In most cases the multiple coefficients of determination ( R 2) are >0.97. Using the IR fingerprint region (900–1400 cm −1) a qualitative discrimination of the individual chemotypes is possible already by visual judgement without to apply any chemometric algorithms.The described rapid and non-destructive methods can be applied in industry to control very easily purifying, blending and redistillation processes of the mentioned essential oils.