Molecular spectroscopic study of river nile sediment in the greater cairo region

The greater Cairo region is the most populated area in Egypt. The aquatic environment of the Nile River in this area is being affected by industrial activities. The study of the molecular structure of sediment may provide a good trace for such changes. Both Fourier transform infrared spectroscopy (FT-IR) and density functional theory (DFT) were used to study the effect of industrial waste disposal south of Cairo on the molecular structure of Nile River sediment. Four seasonal samples were collected from six sites covering 75 km along the Nile River. Grain sizes of 200 microm, 125 microm, 65 microm, and 32 microm, respectively, were examined. The results indicate that hydrated aluminum hydroxide controls the distribution of organic matter in the different grain sizes. Furthermore, the hydration of phenol may take place in grain sizes lower than 200 microm, which is indicated by the OH stretching at 3550 cm(-1) and verified by the obtained model. The formation of metal carboxylate bonds at 1638 cm(-1) (asymmetric) and 1382 cm(-1) (symmetric) indicate the possible interaction between heavy metals and other organic structures, mainly humic substances.     

NbN and NbS2 nanobelt arrays: in-situ conversion preparation and field-emission performance

NbN nanobelt arrays were prepared by an in-situ conversion of aligned NbS3 nanobelts in the flowing NH3 at 950 degrees C, meanwhile, NbS2 nanobelt arrays were produced by a pyrolysis of aligned NbS3 nanobelts in the flowing argon atmosphere. The morphology and size of those nanobelts are close to the NbS3 nanobelt precursors, having a reactangular section of about 11 x 250 - 520 x 3100 nm2, and a length of about 120 microm. The microstructures were characterized by high-resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectroscopy (EDX). Magnetic measurements showed that the NbN nanobelts have superconductivity below 14.1 K. Field-emission experiments showed that the turn-on and threshold fields of the NbN nanobelt arrays (which are defined to be the macroscopic field to produce a current density of 10 microA/cm2 and 1 mA/cm2, respectively) are 0.61 and 2.3 V/microm, respectively, whereas the turn-on and threshold fields of the NbS2 nanobelt arrays are 0.61 and 3.5 V/microm, respectively, suggesting that they are decent field emitters.     

Determination of hydrocarbons using sapphire fibers coated with poly(dimethylsiloxane)

A poly(dimethylsiloxane) (PDMS) coated sapphire fiber has been investigated as a sensor for hydrocarbons (HCs) in the mid-infrared region around 3000 cm(-1). In order to optimize and predict sensor response, the diffusion behavior of the analytes into the PDMS preconcentration medium has been examined. A diffusion model based on Fickian diffusion was used to quantify diffusion. The model incorporated such factors as film thickness, refractive index of the polymer and the fiber core, and principal wavelength at which the analyte absorbs. A range of hydrocarbons, from hexane to pentadecane, was analyzed at 2930 cm(-1) using both fiber-coupled Fourier transform infrared spectroscopy and a modular prototype system. Diffusion coefficients were determined for these compounds and diffusion behavior examined and related to factors such as analyte polarity and molecular size. The diffusion coefficients were found to range from 6.41 x 10(-11) 5 x 10(-12) to 5.25 x 10(-11) +/- 9 x 10(-13) cm2 s(-1) for hexane and pentadecane into a 2.9 microm PDMS film, respectively. The diffusion model was also used to examine the effect of changing system parameters such as film thickness in order to characterize sensor response.     

FT-IR study of a chemically amplified resist for X-ray lithography

Microelectronic devices for future applications demand lithographic performance that falls within the 0.10 microm region and below. Chemically amplified resists (CARs), such as the positive tone commercial UVIII resist, offer a substantial gain in sensitivity, resolution, and process efficiency in deep ultraviolet, e-beam, and X-ray lithographies. In this work, the UVIII resist is characterized for X-ray lithographic applications by studying the "deprotection" or acid generation-diffusion process of the resist under different conditions of post-exposure bake (PEB) temperature and time, and of X-ray exposure dose. The X-ray irradiation from a copper anode at a wavelength of 1.33 nm was at an intensity of 30 microW/cm2 on the resist surface. The deprotection process of the resist during PEB was accurately monitored by using Fourier transform infrared (FT-IR) spectroscopy. The infrared absorption peaks at 1151, 1369, and 2977 cm(-1) in the spectrum of the UVIII resist were found to be useful indicators for the completion of deprotection. Results of the experiments showed that the performance of UVIII could be optimized at the PEB temperature of 140 degrees C, a time of 2 min, and X-ray exposure dose of 12 mJ/cm2. The change in resist thickness after PEB was also measured. The results were confirmed by scanning electron microscopy (SEM) in which a test structure as small as 0.12 microm was obtained in a 1-microm-thick UVIII resist layer.     

Polarization-dependent interference effects in grazing-angle Fourier transform infrared reflection-absorption spectroscopy to determine the thickness of water-ice films

Interference fringes appeared between 6000 and 4095 cm(-1) in the infrared spectra of thin water-ice films vapor deposited on an aluminum substrate and probed with grazing-angle Fourier transform infrared reflection-absorption spectroscopy. At grazing incidence the position of the fringe under perpendicularly polarized light (E(sigma)) is 180 degrees out of phase with the position of the fringe under parallel polarized light (E(pi)). This shift in fringe position with polarization offers a convenient way to estimate the thickness (+/-5%) of water-ice films between 0.5 and 1.4 microm.     

Study of a chemically amplified resist for X-ray lithography by Fourier transform infrared spectroscopy

Future applications of microelectromechanical systems (MEMS) require lithographic performance of very high aspect ratio. Chemically amplified resists (CARs) such as the negative tone commercial SU-8 provide critical advantages in sensitivity, resolution, and process efficiency in deep ultraviolet, electron-beam, and X-ray lithographies (XRLs), which result in a very high aspect ratio. In this investigation, an SU-8 resist was characterized and optimized for X-ray lithographic applications by studying the cross-linking process of the resist under different conditions of resist thickness and X-ray exposure dose. The exposure dose of soft X-ray (SXR) irradiation at the average weighted wavelength of 1.20 nm from a plasma focus device ranges from 100 to 1600 mJ/cm(2) on the resist surface. Resist thickness varies from 3.5 to 15 mum. The cross-linking process of the resist during post-exposure bake (PEB) was accurately monitored using Fourier transform infrared (FT-IR) spectroscopy. The infrared absorption peaks at 862, 914, 972, and 1128 cm(-1) in the spectrum of the SU-8 resist were found to be useful indicators for the completion of cross-linking in the resist. Results of the experiments showed that the cross-linking of SU-8 was optimized at the exposure dose of 800 mJ/cm(2) for resist thicknesses of 3.5, 9.5, and 15 microm. PEB temperature was set at 95 degrees C and time at 3 min. The resist thickness was measured using interference patterns in the FT-IR spectra of the resist. Test structures with an aspect ratio 3:1 on 10 microm thick SU-8 resist film were obtained using scanning electron microscopy (SEM).     

Nonaligned carbon nanotubes anchored on porous alumina: formation, process modeling, gas-phase analysis, and field-emission properties

We have developed a chemical vapor deposition (CVD) process for the catalytic growth of carbon nanotubes (CNTs), anchored in a comose-type structure on top of porous alumina substrates. The mass-flow conditions of precursor and carrier gases and temperature distributions in the CVD reactor were studied by transient computational fluid dynamic simulation. Molecular-beam quadrupole mass spectroscopy (MB-QMS) has been used to analyze the gas phase during ferrocene CVD under reaction conditions (1073 K) in the boundary layer near the substrate. Field-emission (FE) properties of the nonaligned CNTs were measured for various coverages and pore diameters of the alumina. Samples with more dense CNT populations provided emitter-number densities up to 48,000 cm(-2) at an electric field of 6 V microm(-1). Samples with fewer but well-anchored CNTs in 22-nm pores yielded the highest current densities. Up to 83 mA cm(-2) at 7 V microm(-1) in dc mode and more than 200 mA cm(-2) at 11 V microm(-1) in pulsed diode operation have been achieved from a cathode size of 24 mm2.     

Application of infrared emission spectroscopy to the thermal transition of indium hydroxide to indium oxide nanocubes

Cubic indium hydroxide nanomaterials were obtained by a low-temperature soft-chemical method without any surfactants. The transition of nano-cubic indium hydroxide to cubic indium oxide during dehydroxylation has been studied by infrared emission spectroscopy. The spectra are related to the structure of the materials and the changes in the structure upon thermal treatment. The infrared absorption spectrum of In(OH)(3) is characterized by an intense OH deformation band at 1150 cm(-1) and two O-H stretching bands at 3107 and 3221 cm(-1). In the infrared emission spectra, the hydroxyl-stretching and hydroxyl-bending bands diminish dramatically upon heating, and no intensity remains after 200 °C. However, new low intensity bands are found in the OH deformation region at 915 cm(-1) and in the OH stretching region at 3437 cm(-1). These bands are attributed to the vibrations of newly formed InOH bonds because of the release and transfer of protons during calcination of the nanomaterial. The use of infrared emission spectroscopy enables the low-temperature phase transition brought about through dehydration of In(OH)(3) nanocubes to be studied.     

Restoration and spectral recovery of mid-infrared chemical images

Fourier transform infrared (FTIR) microspectroscopy is a powerful technique for label-free chemical imaging that has supplied important chemical information about heterogeneous samples for many problems across a variety of disciplines. State-of-the-art synchrotron based infrared (IR) microspectrometers can yield high-resolution images, but are truly diffraction limited for only a small spectral range. Furthermore, a fundamental trade-off exists between the number of pixels, acquisition time and the signal-to-noise ratio, limiting the applicability of the technique. The recently commissioned infrared synchrotron beamline, infrared environmental imaging (IRENI), overcomes this trade off and delivers 4096-pixel diffraction limited IR images with high signal-to-noise ratio in under a minute. The spatial oversampling for all mid-IR wavelengths makes the IRENI data ideal for spatial image restoration techniques. Here, we measured and fitted wavelength-dependent point-spread-functions (PSFs) at IRENI for a 74× objective between the sample plane and detector. Noise-free wavelength-dependent theoretical PSFs are deconvoluted from images generated from narrow bandwidths (4 cm(-1)) over the entire mid-infrared range (4000-900 cm(-1)). The stack of restored images is used to reconstruct the spectra. Restored images of metallic test samples with features that are 2.5 μm and smaller are clearly improved in comparison to the raw data images for frequencies above 2000 cm(-1). Importantly, these spatial image restoration methods also work for samples with vibrational bands in the recorded mid-IR fingerprint region (900-1800 cm(-1)). Improved signal-to-noise spectra are reconstructed from the restored images as demonstrated for a mixture of spherical polystyrene beads in a polyurethane matrix. Finally, a freshly thawed retina tissue section is used to demonstrate the success of deconvolution achievable with a heterogeneous, irregularly shaped, biologically relevant sample with distinguishing spectroscopic features across the entire mid-IR spectral range.     

Doppler-free nonlinear absorption in ethylene by use of continuous-wave cavity ringdown spectroscopy

We report what we believe to be the first systematic study of Doppler-free, nonlinear absorption by use of cavity ringdown spectroscopy. We have developed a variant of cavity ringdown spectroscopy for the mid-infrared region between 9 and 11 microm, exploiting the intracavity power buildup that is possible with continuous-wave lasers. The infrared source consists of a continuous-wave CO2 laser with 1-mW tunable infrared sidebands that couple into a high-finesse stable resonator. We tune the sideband frequencies to observe a saturated, Doppler-free Lamb dip in the nu7, 11(1,10) <-- 11(2,10) rovibrational transition of ethylene (C2H4). Power studies of the Lamb dip are presented to examine the intracavity effects of saturation on the Lamb-dip linewidth, the peak depth, and the broadband absorption.     

Vapor-phase infrared laser spectroscopy: from gas sensing to forensic urinalysis

Numerous gas-sensing devices are based on infrared laser spectroscopy. In this paper, the technique is further developed and, for the first time, applied to forensic urinalysis. For this purpose, a difference frequency generation laser was coupled to an in-house-built, high-temperature multipass cell (HTMC). The continuous tuning range of the laser was extended to 329 cm(-1) in the fingerprint C-H stretching region between 3 and 4 microm. The HTMC is a long-path absorption cell designed to withstand organic samples in the vapor phase (Bartlome, R.; Baer, M.; Sigrist, M. W. Rev. Sci. Instrum. 2007, 78, 013110). Quantitative measurements were taken on pure ephedrine and pseudoephedrine vapors. Despite featuring similarities, the vapor-phase infrared spectra of these diastereoisomers are clearly distinguishable with respect to a vibrational band centered at 2970.5 and 2980.1 cm(-1), respectively. Ephedrine-positive and pseudoephedrine-positive urine samples were prepared by means of liquid-liquid extraction and directly evaporated in the HTMC without any preliminary chromatographic separation. When 10 or 20 mL of ephedrine-positive human urine is prepared, the detection limit of ephedrine, prohibited in sports as of 10 microg/mL, is 50 or 25 microg/mL, respectively. The laser spectrometer has room for much improvement; its potential is discussed with respect to doping agents detection.     

Novel SiO2-deposited CaF2 substrate for vibrational sum-frequency generation (SFG) measurements of chemisorbed monolayers in an aqueous environment

A novel SiO(2)-deposited CaF(2) (SiO(2)/CaF(2)) substrate for measuring vibrational sum-frequency generation (SFG) spectra of silane-based chemisorbed monolayers in aqueous media has been developed. The substrate is suitable for silanization and transparent over a broad range of the infrared (IR) probe. The present work demonstrates the practical application of the SiO(2)/CaF(2) substrate and, to our knowledge, the first SFG spectrum at the solid/water interface of a silanized monolayer observed over the IR fingerprint region (1780-1400 cm(-1)) using a back-side probing geometry. This new substrate can be very useful for SFG studies of various chemisorbed organic molecules, particularly biological compounds, in aqueous environments.     

200-mW-average power ultraviolet generation at 0.193 microm in K2Al2B2O7

K2Al2B2O7 has been found to be phase matchable for type-1 sum-frequency generation (SFG) at 0.193 microm by mixing the Nd:YAG laser wavelength at 1.0642 microm and the SFG output of the RbTiOAsO4 optical parametric oscillator tuned at 0.2358 microm. An average power of 200 mW at 10 kHz was obtained in a 7-mm-long crystal. In addition, the Sellmeier equations and the thermo-optic dispersion formula, which predict well the phase-matching conditions and temperature phase-matching bandwidths (FWHM) for second-harmonic generation and SFG in the 0.193-0.669-microm range, are presented.     

Vibrational spectroscopic study on the origin of stress oscillation during step-wise stretching in poly(ethylene terephthalate)

The origin of the phenomenon of stress oscillation during step-wise stretching at room temperature for amorphous poly(ethylene terephthalate) (PET) was investigated using vibrational spectroscopy. For the first time, transmission Fourier transform infrared (FT-IR), attenuated total reflection (ATR) FT-IR, and micro-Raman spectroscopies were used in order to investigate the correlation of the orientation of the molecular chains, their conformational transformations, and the appearance of stress-induced crystallization to the phenomenon of stress oscillation during the step-wise stretching procedure. The phenomenon of stress oscillation occurs when amorphous PET is exposed to mechanical stress during which the extension rate is increased in a step-wise manner. This phenomenon leads to the formation of a pattern of opaque and transparent stripes ('striated' or oscillating region), clearly distinguished from the unstretched ('bulk') and the 'necking' regions. Both infrared and Raman spectroscopic investigations revealed that the main conformational transformations and a significant increase of the crystallinity occur simultaneously in the 'striated' region. Polarized infrared experiments showed the presence of increased molecular orientation, which is more profound for the 'intense striated' region. Finally, micro-Raman spectroscopy allowed the study of opaque and transparent stripes individually and showed that the opaque stripes are more crystalline. Thus, our findings provide conclusive experimental support for the theory, which directly correlates the appearance of the stress-oscillation phenomenon with the induction of crystallinity and heat release and is based on Barenblatt's model. Our study also provides new conformational assignments for the infrared bands in PET for the high-frequency region from 3200 to 3800 cm(-1). Specifically, the bands at 3336 cm(-1) and at 3298 cm(-1) have been attributed to the trans and gauche conformations, respectively.     

Crystallization of polylactide and its stereocomplex investigated by two-dimensional fourier transform infrared correlation spectroscopy employing carbonyl overtones

The band origins and transitions of weak vibrational modes developed in the 3500 cm(-1) region of polylactide (PLA) spectra during crystallization are investigated. The band assignment to the OH stretching mode of terminal hydroxyls is unlikely because the trace amount of chain-ends is negligible considering the long chain of high molecular weight polymer. The band intensity can be enhanced for quantitative study by increasing the sample film thickness. The results show that the transition patterns of these bands mimic those of C=O stretching modes. Therefore, these are assigned to C=O overtones. Two bands associated with crystalline and amorphous characteristics are revealed during cold crystallization. The crystalline C=O bands of PDLA and its stereocomplex counterpart are located at 3510 cm(-1) and 3482 cm(-1), respectively, indicating a weaker C=O bond in the latter crystal structure. Two-dimensional Fourier transform infrared (2D-FT-IR) correlation spectroscopy is then applied to study the correlation between C=O overtones and the crystalline characteristic band located near 900 cm(-1). The transitions of the two vibrational modes observed in crystallization of the stereocomplex are in-phase with each other. This reflects an involvement of short-range hydrogen bonding in the stereocomplex crystal structure. In contrast, crystallization of PDLA shows that the C=O overtone varies prior to that of the C-H character, indicating that dipole-dipole force is a crystal-induced interaction.     

Broadly Tunable, Mode-Hop-Tuned cw Optical Parametric Oscillator Based on Periodically Poled Lithium Niobate

We describe a broadly tunable, cw optical parametric oscillator (OPO) based on periodically poled lithium niobate. The OPO can be tuned over a broad region in the mid IR (2900-3100 cm(-1)) covering the important C-H stretch region while a high spectral resolution (<0.1 cm(-1)) is maintained. The OPO is the light source for a field-portable photoacoustic spectrometer for gas-phase monitoring of volatile organic compounds.     

Differentiation of selected Salmonella enterica serovars by Fourier transform mid-infrared spectroscopy

Salmonella enterica serovars include pathogens responsible for high numbers of foodborne salmonellosis. Fourier transform infrared (FT-IR) spectroscopy can be used to rapidly and accurately identify microorganisms based on unique spectra of bacterial cell components. The objectives of this study were to discriminate closely related Salmonella enterica serovars by using FT-IR spectroscopy and multivariate analysis and to compare the performance of three techniques for differentiating among Salmonella serovars. Selected serovars of S. enterica were streaked onto plate count agar and incubated (37 degrees C, 24 h). Isolated colonies were suspended in phosphate buffer or 50% ethanol (10 microL). Suspensions were placed on (1) ZnSe crystals for transmission, (2) disposable polyethylene membranes (DPM) for transmission, and (3) diamond crystal plate for attenuated total reflectance (ATR) analyses; all samples were dried under vacuum. Classification models, soft independent modeling of class analogy (SIMCA), from derivatized infrared spectra (1300-900 cm(-1)), discriminated among Salmonella serovars presumably attributed to cell's lipopolysaccharides (1000-980 cm(-1)). Samples on DPM required high cell density for reliable spectra. High-quality spectra were obtained when a single colony was suspended in ethanol or buffer and mounted on ZnSe crystals for transmission or diamond plate for ATR analysis. Prediction of unknowns, representative of serovars used to construct classification models, showed that all techniques were suitable for the rapid and accurate differentiation of Salmonella serovars.     

Structural changes of milk components during acid-induced coagulation kinetics as studied by synchronous fluorescence and mid-infrared spectroscopy

Dynamic oscillatory experiments and front-face synchronous fluorescence spectroscopy and mid-infrared (mid-IR) spectroscopy have been used to investigate structure evolution, at the macroscopic and molecular levels, during milk acidification kinetics. The studies were performed using skim milk, at two different temperatures (30 °C and 40 °C), to which was added glucono-δ-lactone (GDL) to generate different structural changes in casein micelles and gels. Synchronous fluorescence spectra were recorded in the 250-500 nm excitation wavelength range using an offset of 80 nm between the excitation and emission monochromators for each system during the 300 min acidification kinetics. The change in the fluorescence intensity at 281 nm reflects the pH-induced physicochemical changes of casein micelles and, in particular, structural changes in the micelles in the pH range 5.5-5.0. Regarding mid-infrared spectroscopy, the region located between 1700 and 1500 cm(-1), corresponding to the amide I and II bands, and the 1500-900 cm(-1) region, called the fingerprint region, were considered for the characterization of milk coagulation kinetics. Changes in the absorbance at 1063 cm(-1) as a function of pH for kinetics recorded at 30 °C and 40 °C reflected pH-induced phosphate dissolution in the pH range 5.5-5.0. Compared to rheometry, which reveals microstructure changes only in the gel state, spectroscopic methods make it possible to monitor molecular structure changes in micelles throughout the acidification processes.     

Ultrasensitive near-infrared integrated cavity output spectroscopy technique for detection of CO at 1.57 microm: new sensitivity limits for absorption measurements in passive optical cavities

A robust absorption spectrometer using the off-axis integrated cavity output spectroscopy (ICOS) technique in a passive cavity is presented. The observed sensitivity, conceptually the detection threshold for the absorption cross section (cm2) multiplied by the concentration (cm(-3)) and normalized by the averaging time, is measured to be 1.9 x 10(-12) (1/cm square root of Hz). This high sensitivity arises from using the optical cavity to amplify the observed path length in the spectrometer while avoiding cavity resonances by careful design of the spot pattern within the cavity. The instrument is ideally suited for routine monitoring of trace gases in the near-infrared region. A spectrum showing ambient carbon monoxide at 1.57 microm is presented.