Predictive Abilities of Scaled Quantum Mechanical Molecular Force Fields: Application to 1,3-Butadiene

The positions of some IR bands of the s-trans-1,3-butadiene-h ₆ and -1,1,2-d ₃ isotopomers in the gas phase have been measured using a Brucker IFS 120 HR spectrometer with a resolution of 2 cm^–1. The structural parameters of the s-trans- and s-gauche-1,3-butadiene conformers were optimized completely at the MP2/6-31G* theoretical level and their MP2/6-31G*//MP2/6-31G* quantum mechanical force fields (QMFFs) were calculated. Using only the experimental vibrational frequencies of s-trans-1,3-butadiene-h ₆ the QMFF of the s-trans conformer was corrected by Pulay's scaling method (eight scale factors were involved). The scaled QMFF was used to calculate the mean vibrational amplitudes and the Coriolis coupling constants of s-trans-1,3-butadiene-h ₆ and the vibrational frequencies of 12 of its deuterated isotopomers. The set of scale factors obtained for correction of the s-trans QMFF was transferred to the QMFF of the s-gauche conformer. Its theoretical vibrational spectrum and those of some deuterated and C¹³ isotopomers were calculated. The ability of this scaling approach (transferring of scale factors) to predict the vibrational frequencies of rotational conformers and their isotopomers, as well as other molecular characteristics, and to permit detection of perturbations of the experimental bands are discussed.     

Chemical and Pharmacological Potential of Coccoloba cowellii,an Endemic Endangered Plant from Cuba

Coccoloba cowellii Britton (Polygonaceae) is an endemic and critically endangered plant that only grows in Camagüey, a province of Cuba. In this study, a total of 13 compounds were identified in a methanolic leaf extract, employing a dereplication of the UHPLC-HRMS data by means of feature-based molecular networking (FBMN) analysis in the Global Natural Products Social Molecular Network (GNPS), together with the interpretation of the MS/MS data and comparison with the literature. The major constituents were glucuronides and glycosides of myricetin and quercetin, as well as epichatechin-3-O-gallate, catechin, epicatechin and gallic acid, all of them being reported for the first time in C. cowellii leaves. The leaf extract was also tested against various microorganisms, and it showed a strong antifungal effect against Candida albicans ATCC {"type":"entrez-nucleotide","attrs":{"text":"B59630","term_id":"2614348"}}B59630 (azole-resistant) (IC₅₀ 2.1 µg/mL) and Cryptococcus neoformans ATCC {"type":"entrez-nucleotide","attrs":{"text":"B66663","term_id":"2640641"}}B66663 (IC₅₀ 4.1 µg/mL) with no cytotoxicity (CC₅₀ > 64.0 µg/mL) on MRC-5 SV2 cells, determined by the resazurin assay. Additionally, the extract strongly inhibited COX-1 and COX-2 enzyme activity using a cell-free experiment in a dose-dependent manner, being significantly more active on COX-1 (IC₅₀ 4.9 µg/mL) than on COX-2 (IC₅₀ 10.4 µg/mL). The constituents identified as well as the pharmacological activities measured highlight the potential of C. cowellii leaves, increasing the interest in the implementation of conservation strategies for this species.     

Effects of Adsorbed Polyaniline on Redox Processes on As(2)O(3) Surfaces

Polyaniline deposited on As(2)O(3) surface resulted in a new material, which was characterized by infrared spectoscopy, thermogravimetry, differential scanning calorimetry, scanning electron microscopy, X-ray diffraction, and cyclic voltammetry. The mass percentage of polymer deposited on oxide surface is approximately 13%. The scanning electron microscopy images as well as the X-ray diffraction patterns provided conclusive evidence that the oxide surface is coated by the polymer. The cyclic voltammograms of the polyaniline adsorbed on As(2)O(3) surface showed that the adsorbate exerts remarkable effects on redox processes on this oxide. The pure oxide exhibited two oxidation/reduction peaks at 0.25/-0.06 and 0.47/-0.25 V attributed tentatively to the processes As(2)O(3)(s)+6H(+)+6e(-)=2As(s)+3H(2)O and As(s)+3H(+)+3e(-)=AsH(3)(g), respectively. The polyaniline-coated sample exhibited a better-defined voltammogram in which the first oxidation peak of the oxide had its intensity increased about four times. Copyright 2000 Academic Press.     

有关铜锌原电池的问题讨论

针对铜锌原电池中锌电极冒气泡的“异常”现象,通过分析不同类型原电池的工作原理,认为即使使用纯度极高的锌也会产生气泡,并给出其缘由。对在教学中如何处理这一棘手的难题,提出个人见解。同时,建议中学化学教材将“锌片上产生气泡”的现象明确地描述出来。     

Tests for specific nonparametric relations between two distribution functions with applications

Let (X,Y) be a random vector and let G and H be the marginal distributions of X and Y, respectively. In this paper, we propose two tests, one of Kolmogorov‐Smirnov type and the other of Wilcoxon type, for the null hypothesis Ψ(G) = H against the alternative Ψ(G) < H, where Ψ() is a function such that Ψ(G) is a distribution function. The tests are based on the empirical distribution functions of the observations on X and Y, which are dependent. We obtain their asymptotic null distributions. A suspected relationship between the distribution functions of two dependent outcomes can be specified as a hypothesis to be tested in examples like the load sharing models, record values, and auction bidding models. As an application, we consider in detail the problem of testing the effect of load sharing in two component parallel systems.     

The HITRAN 2008 molecular spectroscopic database

This paper describes the status of the 2008 edition of the HITRAN molecular spectroscopic database. The new edition is the first official public release since the 2004 edition, although a number of crucial updates had been made available online since 2004. The HITRAN compilation consists of several components that serve as input for radiative-transfer calculation codes: individual line parameters for the microwave through visible spectra of molecules in the gas phase; absorption cross-sections for molecules having dense spectral features, i.e. spectra in which the individual lines are not resolved; individual line parameters and absorption cross-sections for bands in the ultraviolet; refractive indices of aerosols, tables and files of general properties associated with the database; and database management software. The line-by-line portion of the database contains spectroscopic parameters for 42 molecules including many of their isotopologues.     

New High-Resolution Analysis of the ν7 and ν9 Fundamental Bands of trans-Formic Acid by Fourier Transform Infrared and Millimeter-Wave Spectroscopy

The high-resolution (0.002 cm⁻¹) spectrum of the ν₇ (OCO scissor mode) and ν₉ (COH torsion mode) fundamental bands of trans-formic acid (HCOOH) at 15.8 μm was recorded by Fourier transform infrared spectroscopy. In addition, millimeter-wave transitions within the 7¹ and 9¹ vibrational states were measured in the spectral range 340-600 GHz. Using these new experimental data, an extensive analysis of the ν₇ and ν₉ bands was performed. The model we have used accounts for the strong A- and B-type Coriolis interactions which couple the 7¹ and 9¹ vibrational states and which were already pointed out in the literature [J. C. Deroche, J. Kauppinen and E. Kyrö, J. Mol. Spectrosc.78, 379-394 (1979); E. Willemot, J. Mol. Spectrosc.120, 246-275 (1986)]. The observed levels are fit to within the experimental accuracy leading to the determination of a precise set of band centers of ν₇ and ν₉ at 686.1656 cm⁻¹ and 640.7251 cm⁻¹, respectively, and rotational and Coriolis constants.     

New combination bands in CCH2 around 0.83 μm recorded using FT-ICLAS

Fourier-transform intracavity laser absorption spectroscopy allowed five ¹²C¹³CH₂ Σ⁺-Σ⁺ bands, all from the ground state, to be identified in the 0.83 μm range. Their rotational analysis was performed and rotational constants are provided. Three of these bands, with origins at 11616.9684(18), 11737.2356(14), and 11761.0322(23) cm⁻¹, have never been reported before. Their upper states are assigned to , respectively.     

Synchrotron FTIR spectroscopy of weak torsional bands: A case study of cis-methyl formate

The far infrared spectrum of cis-methyl formate has been recorded on the AILES beamline of the synchrotron SOLEIL using a Fourier transform infrared spectrometer coupled to a long path cell. The very weak fundamental band associated with the methyl-top torsion mode (ν(18)) was observed. The frequency analysis was performed using the "rho axis method", and the microwave and millimeter-wave data from the literature. A precise determination of the band origins (ν(18) (A) = 132.4303 cm(-1) and ν(18) (E) = 131.8445 cm(-1)) and of the barrier height [V(3) = 370.7398 (58) cm(-1)] have been obtained. The intensity of the ν(18) fundamental band was determined to be 3.4 × 10(-21) cm(-1)∕(molecule cm(-2)) at 297 K, equally shared among A-A and E-E transitions, thus leading to a dipole moment component μ(c) ((3)) equal to 0.0483 D. The results were compared with the ab initio calcula-tions of Senent et al. [Astrophys. J. 627, 567 (2005)].