Simple isotopic product rules valid for absolute and integrated infrared intensities

Microwave spectra of CH¹⁸ OCOOH, CHOC¹⁸ OOH, CHOCO¹⁸ OH, ¹³ CHOCOOH and CHO¹³ COOH are reported and have been used in combination with data on CHOCOOH and CHOCOOD to determine the molecular structure as r(C=O)_ald. = 1.174 ± 0.006 Å, r(C=O)_acid = 1.203 ±0.006 Å, r(C—O) = 1.313 ± 0.010 Å, r(C—C) = 1.535 ± 0.005 Å, r(O—H) = 0.948 ± 0.004 Å, r(C—H) = 1.104 ±0.010 Å, ald. = 123.7 ± 0.4<, 相似文献   

The Composition of the Milk Fat Globule Surface Alters the Structural Characteristics of the Coagulum

The effects of the composition of a fat globule surface in reconstituted milks on the properties of rennet-induced coagulums were studied by rheological measurements and by front-face fluorescence spectroscopy in combination with a multivariate statistical method to investigate, at a molecular level, the evolution of the structure during the milk coagulation process. Reconstituted milks used in this study were prepared from different fat-in-water emulsions stabilized by whole skim-milk proteins, beta-casein, or beta-lactoglobulin. Coagulation of milk reconstituted with natural fat globules was also investigated. The study showed that the fat droplet/water interface influences the rheological properties (G' modulus) of the reconstituted milks during the coagulation process. The tryptophan fluorescence emission spectra of proteins were recorded during the kinetics of coagulation. The results of the principal component analysis performed on the spectral data showed a discrimination in the different systems investigated. It was shown that the fluorescence properties of protein tryptophans and, consequently, the structures of the protein networks were different for the investigated systems. The development of fluorescence transfer between protein tryptophans and fat-globule vitamin A during the coagulation kinetics agreed with the interactions between the protein network and fat globules. Copyright 2001 Academic Press.     

Reactions CO/H2 en phase liquide. Synthese de precurseurs de l'ethanol par homologation du methanol.: I. Influences de la temperature et de la pression

The CO/H₂ homologation of methanol to acetaldehyde and subsequently to its dimethyl acetal in the presence of cobalt acetate promoted by iodine was examined under various conditions. Temperature and pressure were found as critical parameters. High pressures (140 MPa) and low temperatures (160–170°C) give optimal yields and selectivity to acetaldehyde. According to pressure, temperature, contact time, gas ratio and ligand/catalyst ratio, the reaction is oriented towards acetaldehyde, its dimethyl acetal or methyl acetate.     

Etude quantitative de la distinction entre une liaison de covalence et une liaison de coordination: les molecules de borazane et d'aminoborane

Résumé On propose un exemple quantitatif de la distinction entre une liaison de covalence et une liaison de coordination; cette différenciation, fondée sur les propriétés de la molécule une fois formée, semble très nette pour les énergies de liaison, les populations de recouvrement et les charges des groupes; en particulier, un critère récent, proposé par deux des auteurs, est remarquablement vérifié. Enfin, on essaie de préciser la signification des symboles chimiques traditionnels.

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Quantitative studies of the difference between a covalence and a coordination bond: The molecules of amine-borane and aminoborane

An illustration of the distinction between these two types of chemical bonds is proposed, which is based on the properties of the molecule once built. Bond energies, overlap populations and group charges vary considerably from one compound to the other; more, a recent criterion given by two of the authors seems to be particularly suitable for describing the character of the bond. Lastly, one tries to give an explicit signification to the usual chemical symbols.

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Zusammenfassung Es wird ein quantitatives Beispiel der Unterscheidung zwischen einer kovalenten und einer koordinativen Bindung angegeben, die auf den Eigenschaften des vorliegenden Moleküls beruht. Sie erscheint sehr günstig für die Bindungsenergien, die Überlagerungspopulationen und die Gruppenladungen. Insbesondere wird ein Kriterium, das kürzlich von zwei der Autoren angegeben wurde, gut verifiziert. Schließlich wird versucht, die üblichen chemischen Symbole zu präzisieren.

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Les auteurs tiennent à remercier très vivement M. M. Berthier et Millié d'avoir mis à leur disposition le programme de localisation indispensable à ce travail, ainsi que Mademoiselle Le Guen et le C.I.R.C.E. pour la réalisation des calculs sur l'ordinateur IBM 360-75.     

Electronic properties of 2D and 3D hybrid organic/inorganic perovskites for optoelectronic and photovoltaic applications

We herein investigate theoretically both 2D and 3D Hybrid Organic/inorganic perovskite crystal structures based on density functional theory (DFT) calculations and symmetry analyses. Our findings reveal the universal features of the electronic band structure for the class of lead-halide hybrids (R-NH \(_{3})_{n}\hbox {PbX}_{m}\) , where \((\mathrm{{n}}, \mathrm{{m}})=(2,4)\) and (1,3) respectively for 2D and 3D structures. Among those, the large spin-orbit coupling acting on the conduction band is shown to play a major role on the band gap of these materials. Moreover, this approach can easily be generalized to related layered and 3D hybrids, thus providing a clear-sighted inside in their electronic and optical properties.     

High-power laser with Nd:YAG single-crystal fiber grown by the micro-pulling-down technique

We present optical characterization and laser results achieved with single-crystal fibers directly grown by the micro-pulling-down technique. We investigate the spectroscopic and optical quality of the fiber, and we present the first laser results. We achieved a cw laser power of 10 W at 1064 nm for an incident pump power of 60 W at 808 nm and 360 kW peak power for 12 ns pulses at 1 kHz in the Q-switched regime. It is, to the best of our knowledge, the highest laser power ever achieved with directly grown single-crystal fibers.     

The Cellular Interactions of PEGylated Gold Nanoparticles: Effect of PEGylation on Cellular Uptake and Cytotoxicity

Poly(ethylene glycol) (PEG) is frequently used to coat various medical nanoparticles (NPs). As PEG is known to minimize NP interactions with biological specimens, the question remains whether PEGylated NPs are intrinsically less toxic or whether this is caused by reduced NP uptake. In the present work, the effect of gold NP PEGylation on uptake by three cell types is compared and evaluated the effect on cell viability, oxidative stress, cell morphology, and functionality using a multiparametric methodology. The data reveal that PEGylation affects cellular NP uptake in a cell‐type‐dependent manner and influences toxicity by different mechanisms. At similar intracellular NP numbers, PEGylated NPs are found to yield higher levels of cell death, mostly by induction of oxidative stress. These findings reveal that PEGylation significantly reduces NP uptake, but that at similar functional (= cell‐associated) NP levels, non‐PEGylated NPs are better tolerated by the cells.     

Experimental low energy values of CH4 transitions near 1.33 μm by absorption spectroscopy at 81 K

The high resolution absorption spectrum of methane has been recorded at liquid nitrogen temperature by direct absorption spectroscopy between 1.36 and 1.30 μm (7351-7655 cm⁻¹) using a cryogenic cell and a series of distributed feed back (DFB) diode lasers. The investigated spectral range corresponds to the high energy part of the icosad dominated by the ν₂+2ν₃ band near 7510 cm⁻¹. The positions and strengths at 81 K of 3473 transitions were obtained from the spectrum analysis. The minimum value of the measured line intensities (at 81 K) is on the order of 10⁻²⁶ cm/molecule, i.e. significantly lower than the intensity cut off of the HITRAN database in the region (4×10⁻²⁵ cm/molecule at 296 K). From the variation of the line strength between 81 and 296 K, the low energy values of 1273 transitions could be determined. They represent 69% and 81% of the absorbance in the region at 296 and 81 K, respectively. The obtained results are discussed in relation with the few rovibrational assignments previously reported in the region.     

Quasi-solitonic behavior of self-written waveguides created by photopolymerization

We investigated the condition of unique self-written channel and multichannel propagation inside bulk photopolymerizable materials. Light was introduced in the medium by a single-mode optical fiber. At a very low beam power of 5 muW , a unique uniform-channel waveguide without any broadening was obtained by polymerization. When the input power is increased to 100 muW , the guide becomes chaotic and multichannel. We connected two fibers separated by a 1-cm distance. The results open the door to studies of the optical and electro-optical properties of photopolymerized guides doped by nonlinear optical chromophores and to possible applications in integrated optical devices.     

Rotational Analysis of the ΔvSiH=3-6 Stretching Vibrational Overtones of HSiD3

The nν₁ SiH stretching overtone transitions of trideuterosilane, HSiD₃, have been recorded by Fourier transform spectroscopy (n=3 and 4) and by intracavity laser absorption spectroscopy (n=5 and 6). The unusually weak 3ν₁ band is affected by considerable intensity and energy perturbations. The 4ν₁ band is also strongly perturbed but the interaction with the dark states is more limited and part of the rotational structure of the v₁=4 upper state could be satisfactorily modeled. Less pronounced perturbations affect the v₁=5 level, newly detected by ICLAS. Its rotational structure is locally perturbed by anharmonic coupling with an unidentified vibrational dark state. The global modeling of the interacting dyad allowed the determination of the perturber parameters and the assignment of extra lines due to an intensity transfer from the v₁=5 bright state to the dark state. In agreement with a previous ICLAS study, the 6ν₁ band near 12 113 cm⁻¹ was found free of perturbation. About six hundred line positions could be reproduced with an rms of 4.6×10⁻³ cm⁻¹, leading to a significantly improved set of rovibrational parameters. The striking evolution of the rotational structure, which exhibits fewer and fewer perturbations when the SiH excitation increases, is discussed.