Search

Molecular vibrations that bear information about intrinsic properties of chemical compounds are challenging to detect at submonolayer densities. Surface-enhanced infrared absorption (SEIRA) spectroscopy has been proven to be a viable approach to enhance and detect weak vibration signals. Here, we report a SEIRA sensor based on mid-infrared surface plasmon resonances supported by single-walled carbon nanotubes (SWCNTs). Due to the 1D nature of SWCNTs, their plasmon modes are highly polarized with the electromagnetic fields spatially confined to nanometer scales. Leveraging these characteristics of SWCNTs, we observe a polarization selective coupling between their surface plasmons and vibrational modes of chemical bonds introduced onto their surfaces. A maximum modulation of ∼15% to the plasmon resonance peak is obtained for a submonolayer chemical group coverage. These findings suggest that SWCNTs may potentially serve as a highly sensitive SEIRA platform for revealing intricate information about molecular compositions and bond orientations.

A greenhouse gas sensor has been developed to simultaneously detect multiple gas species within a hollow-core photonic bandgap fiber (HC-PBF) structure entirely composed of fibers. To enhance sensitivity, the gas cell consists of HC-PBF enclosed between two single-mode fibers fused with a reflective end surface to double the absorption length. The incorporation of side holes for gas diffusion allows for analysis of the relationship between gas diffusion speed, number of drilled side holes, and energy loss. As the number of drilled holes increases, the response time decreases to less than 3 min at the expense of energy loss. Gas experiments demonstrated detection limits of 0.1 ppm for methane and 2 ppm for carbon dioxide, with an average time of 50 s. In-situ testing conducted in rice fields validates the effectiveness of the developed gas detection system using HC-PBF cells, establishing all-fiber sensors with high sensitivity and rapid response.

The evolution of time-resolved spectroscopies has resulted in significant advancements across numerous scientific disciplines, particularly those concerned with molecular electronic states. However, the intricacy of molecular vibrational spectroscopies, which provide comprehensive molecular-level information within complex structures, has presented considerable challenges due to the ultrashort dephasing time. Over recent decades, an increasing focus has been placed on exploring the temporal progression of bond vibrations, thereby facilitating an improved understanding of energy redistribution within and between molecules. This review article focuses on an array of time-resolved detection methodologies, each distinguished by unique technological attributes that offer exclusive capabilities for investigating the physical phenomena propelled by molecular vibrational dynamics. In summary, time-resolved vibrational spectroscopy emerges as a potent instrument for deciphering the dynamic behavior of molecules. Its potential for driving future progress across fields as diverse as biology and materials science is substantial, marking a promising future for this innovative tool., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Drug checking is increasingly being explored outside of festivals and events to be an ongoing service within communities, frequently integrated within responses to illicit drug overdose. The choice of instrumentation is a common question, and the demands on these chemical analytical instruments can be challenging as illicit substances may be more complex and include highly potent ingredients at trace levels. The answer remains nuanced as the instruments themselves are not directly comparable nor are the local demands on the service, meaning implementation factors heavily influence the assessment and effectiveness of instruments. In this perspective, we provide a technical but accessible introduction to the background of a few common drug checking methods aimed at current and potential drug checking service providers. We discuss the following tools that have been used as part of the Vancouver Island Drug Checking Project in Victoria, Canada: immunoassay test strips, attenuated total reflection IR-absorption spectroscopy, Raman spectroscopy from powder samples, surface-enhanced Raman scattering in a solution of colloidal gold nanoparticles, and gas chromatography-mass spectrometry. Using four different drug mixtures received and tested at the service, we illustrate the strengths, limitations, and capabilities of such instruments, and expose the scientific theory to give further insight into their analytical results. Each case study provides a walk-through-style analysis for a practical comparison between data from several different instruments acquired on the same sample. Ideally, a single instrument would be able to achieve all of the objectives of drug checking. However, there is no clear instrument that ticks every box; low cost, portable, rapid, easy-to-use and provides highly sensitive identification and accurate quantification. Multi-instrument approaches to drug checking may be required to effectively respond to increasingly complex and highly potent substances demanding trace level detection and the potential for quantification., (© 2023. The Author(s).)

Thermally expandable microspheres (TEMs) are hollow polymeric particles in which a blowing gas has been encapsulated. This property makes them excellent for thermal insulation applications, such as lightweight fillers. This study has developed a viable technology for further improving thermal insulation properties in the field that needs excellent thermal insulation of textile fabrics. The ATO/TEMs composites were designed and prepared to reduce sunlight radiation by the charge gravity method. The test results showed that the ATO-coated TEMs effectively block thermal radiation from sunlight. The temperature difference between ATO/TEMs treated cotton and the uncoated cotton fabric was 9 °C, and the thermal conductivity coatings were 0.0432 W/m⋅K. The UPF value of ATO/TEMs (ILs) coated cotton fabric is 440, significantly higher than pure cotton. This approach can provide insight into the design of high-performance solar insulation composite structures., (© 2023 Wiley-VCH GmbH.)

The parameters of the shell and interface in semiconductor core/shell nanocrystals (NCs) are determinant for their optical properties and charge transfer but are challenging to be studied. Raman spectroscopy was shown earlier to be a suitable informative probe of the core/shell structure. Here, we report the results of a spectroscopic study of CdTe NCs synthesized by a facile route in water, using thioglycolic acid (TGA) as a stabilizer. Both core-level X-ray photoelectron (XPS) and vibrational (Raman and infrared) spectra show that using thiol during the synthesis results in the formation of a CdS shell around the CdTe core NCs. Even though the spectral positions of the optical absorption and photoluminescence bands of such NCs are determined by the CdTe core, the far-infrared absorption and resonant Raman scattering spectra are dominated by the vibrations related with the shell. The physical mechanism of the observed effect is discussed and opposed to the results reported before for thiol-free CdTe Ns as well as CdSe/CdS and CdSe/ZnS core/shell NC systems, where the core phonons were clearly detected under similar experimental conditions.

Lithium niobate is a ferro- and piezoelectric material with excellent optical properties and a wide variety of applications. The defect structures of congruent and Mg-doped crystals are still under intense discussion. In this work, undoped lithium niobate and magnesium-doped lithium niobate grown from congruent melt with the addition of 0 to 9 mol% MgO were investigated by infrared absorption, establishing the dependence of the absorbance on the Mg-doping level in two bands related to OH- stretching vibrations. The absorption band at 3485 cm-1 peaks at a MgO concentration in melt of 1 mol% and vanishes for MgO concentrations above the threshold level for optical damage suppression (4.8 mol%). A corresponding peak occurs in the minimum yield of the 7Li(p,α)4He reaction during ion channeling measurements, indicating a maximum of disorder in the Li sublattice. A possible explanation for this correlation is the attribution of this absorption band to ilmenite stacking fault sequences instead of isolated NbLi antisites in undoped and low-doped material. On the other hand, the OH- absorption band at 3535 cm-1 stays weak up to the MgO concentration threshold, and then increases, hinting to a defect related to the increase of vacancies due to the lack of charge compensation.

The present work applied the methods of density functional theory and the van der Waals interaction PBE + D3(BJ) on the basis of localized orbitals of the CRYSTAL17 package. It featured the effect of interactions between structural elements of fluorocarbonates ABCO 3 F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd) on their elastic and vibrational properties. The hexagonal structures proved to consist of alternating ···B-CO 3 ··· and ···A-F··· layers in planes ab , interconnected along axis c by infinite chains ···F-B-F···, where cations formed polyhedra AO n F 3 and BO m F 2 . The calculations included the band energy structure, the total and partial density of electron states, the energy and band widths of the upper ns - and np -states of alkali and alkaline-earth metals, as well as nd -zinc and nd- cadmium. For hydrostatic compression, we calculated the parameters of the Birch - Murnaghan equation of state and the linear compressibility moduli along the crystal axes and bond lines. We also defined the elastic constants of single crystals to obtain the Voigt-Reuss-Hill approximations for the elastic moduli of polycrystalline materials. The study also revealed the relationship between the elastic properties and the nature of the chemical bond. Hybrid functional B3LYP made it possible to calculate the modes of normal long-wavelength oscillations, which provided the spectra of infrared absorption and Raman scattering. Intramolecular modes ν1 and ν4 with one or two maxima were found to be intense, and their relative positions depended on the lengths of nonequivalent C-O bonds.

Gas samples were collected from the air surrounding single and mixed laboratory cultures, and preliminary data on human breath samples were also obtained. The infrared spectra of a variety of gasses were measured at high resolution (0.5 cm -1 ) to obtain information about the infrared absorption bands to be used as indicators. These key bands enable bacterial classification, and the discrimination rates can be improved by observing multiple infrared absorptions. The air around Pseudomonas aeruginosa was distinguished from the other gas samples by the infrared absorptions at wavenumbers of 778.4 cm -1 and 2213.2 cm -1 . For Acinetobacter baumannii, infrared absorptions at 1215.0 cm -1 and 2982.3 cm -1 were used; furthermore, adding those at 4768.7 cm -1 and 5353.8 cm -1 was shown to improve identification., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The development of ultrafast kinetic methods is one of the factors that allowed the research on protein folding to flourish over the last 20 years. The introduction of new optical triggering techniques enabled to experimentally investigate the protein dynamics at the nanosecond to millisecond timescale, allowing researchers to test theoretical predictions and providing experimental benchmarks for computer simulations. In this work, the details of how to perform kinetic experiments by the laser-induced temperature-jump technique, using the two most commonly used probing techniques (namely infrared absorption and fluorescence spectroscopy) are given, with a strong emphasis on the practical details., (© 2022. Springer Science+Business Media, LLC, part of Springer Nature.)

Vertically aligned carbon nanotube (VACNT) arrays have been explored as an absorber of thermal-type photodetectors. A long and dense VACNT array absorbs a wide spectral range of incident light with high absorption rate, but has a high thermal mass that results in a low response speed. To achieve a small thermal mass, a shorter and less dense VACNT array is needed. In addition, the high temperature needed to grow the VACNTs is detrimental to the functional sensing materials of the photodetector. The height, density, and growth temperature of VACNTs need to be optimized to achieve a working absorber that has high absorption rate and a high response speed. In this work, a low-temperature plasma enhanced chemical vapor deposition process is used to prepare various VACNT arrays with different heights and densities by controlling the CNT growth parameters. The absorption coefficients of the resulting samples are measured with Fourier transform infrared spectroscopy. An effective medium theory (EMT) is adopted to establish a working model of the VACNTs. Using experimentally extracted CNT density and height as fitting parameters, the EMT model is fitted to obtain theoretical absorption coefficients, which are found to be comparable to the experimentally measured absorption coefficients. Our experimental and theoretical investigations pave the way for future studies to integrate CNTs with infrared photodetectors., (© 2021 IOP Publishing Ltd.)

AgBiS 2 nanocrystals (NCs) are nontoxic, lead-free, and near-infrared absorbing materials. Eco-friendly solar cells were constructed using interdigitated layers of ZnO nanowires (NWs) and AgBiS 2 NCs, with the aim of elongating the otherwise short carrier diffusion length of the AgBiS 2 NC assembly. AgBiS 2 NCs were uniformly infiltrated into the ZnO NW layers using a low-cost and easily scalable dip coating method. The resulting ZnO NW/AgBiS 2 NC interdigitated structures provided efficient carrier pathways in constructed nanowire solar cells (NWSCs), composed of a transparent electrode/ZnO NW/AgBiS 2 NC interdigitated layer/P3HT hole transport layer/Au. The photocurrent external quantum efficiency (EQE) in the visible to near-infrared regions was enhanced compared to those of the control solar cells made with ZnO/AgBiS 2 tandem layered structures. The maximum EQE for the NWSCs reached 82% in the visible region, which is higher than the EQE values previously reported for solar cells fabricated with ZnO/AgBiS 2 NCs. Air stability tests on unsealed NWSCs demonstrated that 90% or more of the initial power conversion efficiency was maintained even after 6 months.

Accurate laser-flash measurements of thermal diffusivity ( D ) of diverse bulk solids at moderate temperature ( T ), with thickness L of ~0.03 to 10 mm, reveal that D ( T ) = D ∞ ( T )[1 - exp(- bL )]. When L is several mm, D ∞ ( T ) = F T -G + H T , where F is constant, G is ~1 or 0, and H (for insulators) is ~0.001. The attenuation parameter b = 6.19 D ∞ -0.477 at 298 K for electrical insulators, elements, and alloys. Dimensional analysis confirms that D → 0 as L → 0, which is consistent with heat diffusion, requiring a medium. Thermal conductivity ( κ ) behaves similarly, being proportional to D . Attenuation describing heat conduction signifies that light is the diffusing entity in solids. A radiative transfer model with 1 free parameter that represents a simplified absorption coefficient describes the complex form for κ ( T ) of solids, including its strong peak at cryogenic temperatures. Three parameters describe κ with a secondary peak and/or a high- T increase. The strong length dependence and experimental difficulties in diamond anvil studies have yielded problematic transport properties. Reliable low-pressure data on diverse thick samples reveal a new thermodynamic formula for specific heat (∂ln( c P )/∂ P = -linear compressibility), which leads to ∂ln( κ )/∂ P = linear compressibility + ∂lnα/∂ P , where α is thermal expansivity. These formulae support that heat conduction in solids equals diffusion of light down the thermal gradient, since changing P alters the space occupied by matter, but not by light.

A nondispersive infrared gas analyzer was demonstrated for investigating metal alkylamide precursor delivery for microelectronics vapor deposition processes. The nondispersive infrared analyzer was designed to simultaneously measure the partial pressure of pentakis(dimethylamido) tantalum, a metal precursor employed in high volume manufacturing vapor deposition processes to deposit tantalum nitride, and dimethylamine, the primary decomposition product of pentakis(dimethylamido) tantalum at typical delivery conditions for these applications. This sensor was based on direct absorption of pentakis(dimethylamido) tantalum and dimethylamine in the fingerprint spectral region. The nondispersive infrared analyzer optical response was calibrated by measuring absorbance as a function of dimethylamine and pentakis(dimethylamido) tantalum density. The difference between the mass of material removed from the ampoule during flow tests as measured gravimetrically and as determined optically, by calculating flow rates from the nondispersive infrared analyzer measurements, was only ≈2 %. The minimum detectable molecular densities for pentakis(dimethylamido) tantalum and dimethylamine were ≈2 × 10 13  cm -3 and ≈5 × 10 14  cm -3 , respectively (with no signal averaging and for a sampling rate of 200 Hz), and the corresponding partial pressures were ≈0.1 Pa and ≈2 Pa for pentakis(dimethylamido) tantalum and dimethylamine, respectively (for an optical flow cell temperature of 93 ℃). Pentakis(dimethylamido) tantalum could be detected at all conditions of this investigation and likely the majority of conditions relevant to high volume manufacturing tantalum nitride deposition. Dimethylamine was not detected at all conditions in this study, because of a lower nondispersive infrared analyzer sensitivity to dimethylamine compared to pentakis(dimethylamido) tantalum and because conditions of this study were selected to minimize DMA production. While this nondispersive infrared gas analyzer was specifically developed for pentakis(dimethylamido) tantalum and dimethylamine, it is suitable for characterizing the vapor delivery of other metal alkylamide precursors and the corresponding amine decomposition products, although in the case of some metal alkylamides a different bandpass filter would be required.

Broadband absorption in the mid-infrared region is of significance for wide applications, such as photo/thermal detection, infrared stealth, and thermal imaging. Recently, metal-based plasmonic absorbers have been developed in the mid-infrared region. However, the fabrication cost, thickness, and bandwidth of these absorbers applied in aerospace still need to be improved. In this study, we propose and experimentally demonstrate a large-area, rather thin, metal-free absorber with broadband mid-infrared absorption based on a low-cost self-assembly process. The metal-free absorber is fabricated by spraying carbon black nanoparticles onto 5 μm-thick transferrable anodic aluminum oxide (AAO) templates on nanoporous Si graded-index films, which are fabricated by ion irradiation. Experimental results show that the average absorbance can reach 97.5% in the range of 2.5-15.3 μm. Full-wave numerical simulations show that the electromagnetic fields are greatly enhanced into pores, as these random carbon black particles serve as scatter centers and couple light into 5 μm-thick AAO templates, enhancing the interaction of light with carbon black significantly, and reveal that the high-performance broadband absorption is attributed to the light-trapping effect. The significant light absorption combined with a low-cost, high-production self-assembly technique suggests that the absorber can be used in the fields of optoelectronics and integrated photonics.

We report updated infrared (IR) absorption measurements on vapor-deposited cryogenic parahydrogen (pH 2 ) solids that indicate a ≈10% systematic error in our previous approach for determining a pH 2 solid's thickness (S. Tam and M.E. Fajardo. Appl. Spectrosc. 2001. 55(12): 1634-1644). We provide corrected values for the integrated absorption intensities of the Q 1 (0)+S 0 (0) and S 1 (0)+S 0 (0) bands calculated over the 4495-4520 cm -1 and 4825-4855 cm -1 regions, respectively. New polarized IR absorption spectroscopy data demonstrate the insensitivity to polarization effects of the peak intensity of the Q R (0) phonon sideband near 4228 cm -1 . This feature provides an even quicker way for determining the thickness of a pH 2 solid than via the integrated absorptions.

Mashing is an enzymatic procedure for the extraction of sugars from malt. It has strong temperature dependence, so monitoring the sugar production is very important for optimization of the brewing process. In this work, Fourier transform infrared spectroscopy (FTIR) was used to monitor three different mashing programs. These all presented high concentrations of maltose and dextrin, enabling their differentiation according to the FTIR absorption bands at 991 and 1022 cm -1 , characteristic of maltose and dextrin, respectively. The absorption intensities of these bands were used to monitor the concentrations of the compounds during mashing, and the values were compared to HPLC data. Multivariate analysis of variance was applied to the FTIR absorption intensities in order to separate groups corresponding to the temperature steps of each mashing program. The results demonstrated that infrared absorption offers an alternative to the HPLC method for monitoring the mashing process., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Gas leak detection is an important issue in infrastructure monitoring and industrial production. In this context, infrared (IR) absorption spectroscopy is a major measurement method. It can be applied in an extractive or remote detection scheme. Tunable laser spectroscopy (TLS) instruments are able to detect CH₄ leaks with column densities below 10 ppm·m from a distance of 30 m in less than a second. However, leak detection of non-IR absorbing gases such as N₂ is not possible in this manner. Due to the fact that any leaking gas displaces or dilutes the surrounding background gas, an indirect detection is still possible. It is shown by sensitive TLS measurements of the ambient background concentration of O₂ that N₂ leaks can be localized with extractive and standoff methods for distances below 1 m. Minimum leak rates of 0.1 mbar·L/s were determined. Flow simulations confirm that the leakage gas typically effuses in a narrow jet. The sensitivity is mainly determined by ambient flow conditions. Compared to TLS detection of CH₄ at 1651 nm, the indirect method using O₂ at 761 nm is experimentally found to be less sensitive by a factor of 100. However, the well-established TLS of O₂ may become a universal tool for rapid leakage screening of vessels that contain unknown or inexpensive gases, such as N₂., Competing Interests: The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

A nondispersive infrared (NDIR) gas analyzer was demonstrated for measuring the vapor-phase density of the carbonyl-containing organometallic cobalt precurso μ 2 -η 2 -( t Bu-acetylene) dicobalthexacarbonyl (CCTBA). This sensor was based on direct absorption by CCTBA vapor in the C≡O stretching spectral region and utilized a stable, broadband IR filament source, an optical chopper to modulate the source, a bandpass filter for wavelength isolation, and an InSb detector. The optical system was calibrated by selecting a calibration factor to convert CCTBA absorbance to a partial pressure that, when used to calculate CCTBA flow rate and CCTBA mass removed from the ampoule, resulted in an optically determined mass that was nominally equal to a gravimetrically-determined mass. In situ Fourier transform infrared (FT-IR) spectroscopy was performed simultaneously with the NDIR gas analyzer measurements under selected conditions in order to characterize potential spectroscopic interferences. Interference due to CO evolution from CCTBA was found to be small under the flow conditions employed here. A CCTBA minimum detectable molecular density as low as ≈3 × 10 13  cm -3 was calculated (with no signal averaging and for a sampling rate of 200 Hz). While this NDIR gas analyzer was specifically tested for CCTBA, it is suitable for characterizing the vapor delivery of a range of carbonyl-containing precursors.

This theoretical work exhibits a new systematic study of structural parameters, electronic properties, infrared vibration modes, and molecular topography of hydrogen complexes, namely linear-type HCN⋯HX and T-type C 2 H 2 ⋯HX (X = F, Cl, CN, and CCH). Ideally, the knowledge of the ternary systems of C 2 H 2 ⋯HCN⋯HF and HCN⋯HCN⋯HF whose subparts integrate the linear and T-shaped complexes were used to give support in this current research. By means of computational calculations carried out in both levels B3LYP and MP2, the variations of the HX bond lengths are clearly overestimated in the HCN⋯HX linear complexes. In agreement with the analyses of the electrostatic potentials, the higher intermolecular energies of these complexes agree with the larger red-shifts in the stretch frequencies in HX. Also, the QTAIM descriptors and NBO calculations were used to inspect the interaction strength as well as to confirm the π cloud as a proton accepting center. By taking into account the absorption intensity ratio as a standard parameter to predict the interaction strength and intermolecular characterization, the formalism of the charge-charge flux-overlap modified (CCFO) was applied.

We propose the use of thin Ag film deposition to remedy the degradation of near-infrared (NIR) absorption of black Si caused by high-temperature thermal annealing. A large amount of random and irregular Ag nanoparticles are formed on the microstructural surface of black Si after Ag film deposition, which compensates the degradation of NIR absorption of black Si caused by thermal annealing. The formation of Ag nanoparticles and their contributions to NIR absorption of black Si are discussed in detail.

In this study, we present a comprehensive investigation of graphene's optical and conductive properties using confocal Raman and a Drude model. A comparative analysis between experimental findings and theoretical predictions of the material's changes and improvements as it transitioned from three-dimensional graphite is also presented and discussed. Besides spectral recording by Raman, which reveals whether there is a single, a few, or multi-layers of graphene, the confocal Raman mapping allows for distinction of such domains and a direct visualization of material inhomogeneity. Drude model employment in the analysis of the far-infrared transmittance measurements demonstrates a distinct increase of the material's conductivity with dimensionality reduction. Other particularly important material characteristics, including carrier concentration and time constant, were also determined using this model and presented here. Furthermore, the detection of micromolar concentration of dopamine on graphene surfaces not only proves that the Raman technique facilitates ultrasensitive chemical detection of analytes, besides offering high information content about the biomaterial under study, but also that carbon-based materials are biocompatible and favorable micro-environments for such detection. Such information is valuable for the development of bio-medical sensors, which is the main application envisioned for this analysis.

High-pressure infrared spectroscopy has been used to study the eigenvectors and eigenvalues of the vibrational modes of crystalline adenosine at 298 K by evaluating the logarithmic derivative of the vibrational frequency with respect to pressure: [Formula: see text]. Crystalline samples of molecular materials such as adenosine have vibrational modes that are localized within a molecular unit ("internal" modes) as well as modes in which the molecular units vibrate against each other ("external" modes). The value of the logarithmic derivative is that it is a diagnostic probe of the nature of the eigenvector of these vibrational modes. Stretching modes, which are predominantly internal to the molecule, have low logarithmic derivatives while external modes have higher logarithmic derivatives. Particular attention is paid to modes in the 800-1000 cm(-1) range since modes in that region of the vibrational spectrum are found to be sensitive to the conformation of double-helical DNA. Since the sugar pucker is different for the various conformations of DNA, this fact suggests that these modes involve the motion of atoms in the sugar group. The vibrations of the hydrogen atoms are also of interest to study since the vibrational frequency of hydrogen atoms involved in hydrogen bonds has a negative pressure derivative. Such behavior clearly shows which hydrogen atoms are involved in hydrogen bonding.

Total syntheses and complete characterizations of singly substituted PheCN -based analogs of alamethicin AlaP, which is active on model and natural membranes, and the TM peptide, which inserts in a transmembrane orientation in lipid bilayers, are reported. The syntheses of the AlaP analogs were performed in solution, while those of TM and its analogs were carried out by solid phase. Using the cyanophenyl fluorescence and infrared (IR) absorption probe, an in-depth investigation of the self-association, membrane-interacting, permeabilizing, and orientation properties of these peptides were conducted. The aromatic residue incorporated induces only a negligible modification to the properties of the parent peptides. The PheCN IR absorption band was located between 2228 and 2230 cm(-1) for all peptides, irrespective of the position of labeling. By contrast, as the width of this band varied significantly with the depth of probe insertion in the bilayer, it could represent a good marker of the PheCN position in phospholipid membranes., (© 2015 Wiley Periodicals, Inc.)

The rate of self-reaction of the simplest Criegee intermediate, CH2OO, is of importance in many current laboratory experiments where CH2OO concentrations are high, such as flash photolysis and alkene ozonolysis. Using laser flash photolysis while simultaneously probing both CH2OO and I atom by direct absorption, we can accurately determine absolute CH2OO concentrations as well as the UV absorption cross section of CH2OO at our probe wavelength (λ = 375 nm), which is in agreement with a recently published value. Knowing absolute concentrations we can accurately measure kself = 6.0 ± 2.1 × 10(-11)cm(3) molecule(-1) s(-1) at 297 K. We are also able to put an upper bound on the rate coefficient for CH2OO + I of 1.0 × 10(-11) cm(3) molecule(-1) s(-1). Both of these rate coefficients are at least a factor of 5 smaller than other recent measurements of the same reactions.

The peptide 2.0(5)-helix does exist. It has been experimentally authenticated both in the crystalline state (by X-ray diffraction) and in solution (by several spectroscopic techniques). It is the most common conformation for C(α)-tetrasubstituted α-amino acids with at least two atoms in each side chain, provided that cyclization on the C(α)-atom is absent. X-Ray diffraction has allowed a detailed description of its geometrical and three-dimensional (3D)-structural features. The infrared absorption and the nuclear magnetic resonance parameters characteristics of this multiple, consecutive, fully-extended structure have been described. Conformational energy calculations are in agreement with the experimental findings. As the contribution per amino acid residue to the length of this helix is the longest possible, its exploitation as a molecular spacer is quite promising. However, it is a rather fragile 3D-structure and particularly sensitive to solvent polarity. Interestingly, in such a case, it may reversibly convert to the much shorter 3(10)-helix, thus generating an attractive molecular spring., (Copyright © 2013 Wiley Periodicals, Inc.)

Memory functions, which enter into the equations of motion for time correlation functions, are constructed from neutron scattering, infrared absorption and light scattering data involving single particle motions in liquids. The qualitative features of these memory functions are related to the shape of the corresponding time correlation functions. It is found that a negative portion to the memory function is indicative of a rapid loss of correlation in time while strong temporal correlations imply a memory function which does not go negative. The mathematical structure of a memory function is examined for the case of the ideal gas by expanding and evaluating the projection operator representation of the function. The resulting expression has a rich mathematical structure and can be expressed in a closed form only for its Laplace transform.