Intrinsic and extrinsic factors in anion electron-stimulated desorption: D- from deuterated hydrocarbons condensed on Kr and water ice films

The results of D(-) ion desorption induced by 3-20 eV electrons incident on condensed CD(4), C(2)D(6), C(3)D(8), C(2)D(4), and C(2)D(2) are presented. These compounds were deposited in submonolayer amounts on the surfaces of multilayer solid films of Kr and nonporous and porous amorphous ice. While desorption of the D(-) anions proceeds via well-known processes, i.e., dissociative electron attachment (DEA) and dipolar dissociation, significant perturbations of these processes due to presence of the different film substrates are observed. We have shown that it is possible to distinguish between the character and nature of these perturbations. The presence of the nonporous ice perturbs the D(-) desorption intensity by affecting the intrinsic properties of the intermediate anion states through which dissociation proceeds. On the other hand, the presence of the porous ice introduces extrinsic effects, which can affect electron energy losses prior to their interaction with the hydrocarbon molecule and/or the energies and intensities of the fragment species after dissociation. Simple mechanisms responsible for the observed variations in the intensities of desorbed anionic signals are proposed and discussed. Electron transfer from transient anion states to electron states of the substrate film or nearby hydrocarbon molecules appear as the most efficient mechanism to reduce the magnitude of the DEA process.     

Kinetic parameters from thermogravimetric study of used rubber granulates–polyurethane composites

From the TG data of rubber granulates, different polyurethane and composites it can be seen that the thermal decomposition for the rubber granulate and all of the composites start above 520 K. Two major mass losses for the rubber granulates and majority of the composites were observed and thermal decomposition is essentially complete by ~820 K. The changes of activation energies of lower and higher temperature decomposition, calculated according to the different equations were observed for a priori assumed first-order reaction for devolatilisation. Differences between determined and calculated results could suggest a possible reaction between polyurethane agents and rubber granulate during the composites formations.     

Association equlibria in acetonitrile solution of tetracyanoquinodimethanides

Trimetric ion (TCNQ)^2?₃ has been discovered in mixed solutions of TCNQ and LiTCNQ in acetonitrile. The estimated association constant isK_T = 5.6 × 10¹⁰ øl² mol^?2.     

Enhancement of dielectric and electro-optical parameters of a newly prepared ferroelectric liquid crystal mixture by dispersing nano-sized copper oxide

ABSTRACT

Here, we present the effect of copper (II) oxide nanoparticles (nCuO) on dielectric and electro-optical parameters of a newly prepared ferroelectric liquid crystal (FLC) mixture, namely W302. The FLC mixture, comprising of pyrimidine compounds, was characterised through dielectric spectroscopy, differential scanning calorimetry (DSC), polarising optical microscopy (POM) and other electro-optical methods. The material parameters such as spontaneous polarisation, rotational viscosity, response time and tilt angle of W302 were found to be 14 nC/cm², 240 mPa.s, 150 µs and 28^?, respectively. The phase transition temperatures of W302 were observed through DSC and further confirmed by the dependence of dielectric loss factor in homogeneously aligned FLC sample with temperature. We also demonstrate the observance of a low-frequency dielectric relaxation mode due to the unwinding of the helix, called as partially unwound helical mode (p-UHM) along with Goldstone mode. The behaviour of p-UHM has been systematically studied with temperature and applied bias field. Further, dispersion of nCuO into host W302 has shown a significant increase in dielectric permittivity. Also, the p-UHM relaxation peak in the dielectric regime has disappeared with the incorporation of nCuO. These studies would be useful to fabricate better electro-optical devices for display, switching and beam steering applications. The formulation and characterization of a ferroelectric liquid crystal (FLC) mixture W302 composed of pyrimidine compounds is presented. Then, we observed the effect of copper (II) oxide nanoparticles (nCuO) on dielectric and electro-optical parameters of a newly prepared and characterized FLC mixture.     

Single-site mutation and secondary structure stability: an isodesmic reaction approach. The case of unnatural amino acid mutagenesis Ala-->Lac

A method is described to evaluate backbone interactions in proteins via computational unnatural amino acid mutagenesis. Several N-acetyl polyalanyl amides (AcA(n)NH(2)) were optimized in the representative helical (3(10)-, 4(13)-, and a "hybrid" kappa-helix, n = 7, 9, 10, 14) and hairpin (two- and three-stranded antiparallel beta-sheets with type I turns betaalphaalphaepsilon, n = 6, 9, 10) conformations, and extended conformers of N-acetyl polyalanyl methylamides (n = 2, 3) were used to derive multistranded beta-sheet fragments. Subsequently, each residue of every model structure was substituted, one at a time, with l-lactic acid. The resulting mutant structures were again optimized, and group-transfer energies DeltaE(GT) were obtained as heats of the isodesmic reactions: AcA(n)NHR + AcOMe --> AcA(x)LacA(y)NHR + AcNHMe (R = H, CH(3)). These group-transfer energies correlate with the degree of charge polarization of the substituted peptide linkages as measured by the difference Deltae in H and O Mulliken populations in HN-C=O and with the H-bond distances in the "wild-type" structures. A good correlation obtains for the HF/3-21G and B3LYP/6-31G* group-transfer energies. The destabilization effects are interpreted in terms of loss of interstrand and intrastrand H-bonds, decrease in Lewis basicity of the C=O group, and O...O repulsion. On the basis of several comparisons of Ala --> Lac DeltaE(GT)'s with heats of the NH --> CH(2) substitutions, the latter contribution is estimated (B3LYP/6-31G*) to range between 1.5 and 2.4 kcal mol(-1), a figure close to the recent experimental DeltaDeltaG(o) value of 2.6 kcal mol(-1) (McComas, C. C.; Crowley, B. M.; Boger, D. L. J. Am.Chem. Soc. 2003, 125, 9314). The partitioning yields the following maximum values of the electronic association energy of H-bonds in the examined sample of model structures (B3LYP/6-31G* estimates): 3(10)-helix D(e) = -1.7 kcal mol(-1), alpha-helix D(e) = -3.8 kcal mol(-1), beta-sheet D(e) = -6.1 kcal mol(-1). The premise of experimental evaluations of the backbone-backbone H-bonding that Ala --> Lac substitution in proteins is isosteric (e.g., Koh, J. T.; Cornish, V. W.; Schultz, P. G. Biochemistry 1997, 36, 11314) is often but not always corroborated. Examination of the integrity of H-bonding pattern and phi(i), psi(i) distribution identified several mutants with significant distortions of the "wild-type" structure resulting inter alia from the transitions between i, i + 3 and i, i + 4 H-bonding in helices, observed previously in the crystallographic studies of depsipeptides (Ohyama, T.; Oku, H.; Hiroki, A.; Maekawa, Y.; Yoshida, M.; Katakai, R. Biopolymers 2000, 54, 375; Karle, I. L.; Das, C.; Balaram, P. Biopolymers 2001, 59, 276). Thus, the isodesmic reaction approach provides a simple way to gauge how conformation of the polypeptide chain and dimensions of the H-bonding network affect the strength of backbone-backbone C=O...HN bonds. The results indicate that the stabilization provided by such interactions increases on going from 3(10)-helix to alpha-helix to beta-sheet.     

Application of kinetic investigations for interpretation ofn-hexane and benzene adsorption on active carbon

Differencies between the mechanism ofn-hexane and benzene adsorption on active carbon were investigated on the ground of kinetic measurements. As it has been stated, the kinetic measurements show fundamental differencies between the mechanism of adsorption in spite of analogy existing in the state of adsorption equilibrium. Within the range investigated, only the adsorption ofn-hexane follows the model of volume filling of micropores. Existence of those differencies is also confirmed by measurements of effective diffusion coefficient values as well as changes of activation energy of the diffusion—adsorption process.

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Anwendung kinetischer Untersuchungen zur Interpretation des Adsorptionsverhaltens vonn-Hexan und Benzol an Aktivkohle

Zusammenfassung Mittels kinetischer Messungen untersuchte man die Unterschiede im Mechanismus des Adsorptionsverlaufes vonn-Hexan und Benzol an Aktivkohle. Man stellte fest, daß trotz der Analogie im Adsorptionsgleichgewichtszustand die kinetischen Messungen auf prinzipielle Unterschiede im Adsorptionsmechanismus hinweisen. Im untersuchten Bereich verläuft nur die Adsorption vonn-Hexane nach dem Modell der Mikroporenvolumenausfüllung. Die auftretenden Unterschiede wurden auch durch die Berechnungen der Werte der effektiven Diffusionskoeffizienten sowie Änderungen der Aktivierungsenergie des Diffusions-Adsorptionsprozesses bestätigt.

     

Reactions of Polycyclic Ketones with Dimethoxycarbene; a Convenient Route for a ‘One‐Pot’ Preparation of Some α‐Hydroxycarboxylic Acid Esters

Polycyclic ‘cage’ ketones, such as pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecan‐8‐one ( 10 ), pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane‐8,11‐dione ( 11 ), and adamantan‐2‐one ( 16 ) were treated with the nucleophilic dimethoxycarbene (DMC; 1 ), which was generated thermally from 2,5‐dihydro‐2,2‐dimethoxy‐5,5‐dimethyl‐1,3,4‐oxadiazole ( 4a ) in boiling toluene. In this ‘one‐pot’ procedure, the α‐hydroxycarboxylic acid ester 12 or a corresponding derivative 15 or 17 was obtained (Schemes 4–7). Additionally, ‘cage’ thione 21 was treated with DMC under the same conditions yielding dimethoxythiirane 22 (Scheme 8). Subsequent hydrolysis or desulfurization (followed by hydrolysis on silica gel) of 22 gave α‐mercaptocarboxylate 25 and the corresponding desulfurized ester 24 , respectively. In all cases, the addition of DMC occurred stereoselectively, and the addition from the exo‐face is postulated to explain the structures of the isolated products.     

Density functional theory of adsorption of mixtures of charged chain particles and spherical counterions

We propose a microscopic density functional theory to describe nonuniform ionic fluids composed of chain molecules with charged "heads" and spherical counterions. The chain molecules are modeled as freely jointed chains of hard spheres, the counterions are oppositely charged spheres of the same diameter as all segments of chain molecules. The theory is based on the approach of Yu and Wu [J. Chem. Phys. 117, 2368 (2002)] of adsorption of chain molecules and on theory of adsorption of electrolytes [O. Pizio, A. Patrykiejew, and S. Sokolowski, J. Chem. Phys. 121, 11957 (2004)]. As an application of the proposed formalism we investigate the structure and adsorption of fluids containing segments of different length in a slitlike pore.     

Determination of total carbon and total organic carbon from volatile air pollutants

Summary The method developed based on the determination of TC and TOC in the form of the total amount of CO₂ requires application of the proper techniques for the final determination of CO₂. The possibility of using a stream of carrier gas at a convenient flow-rate for desorbing quantitatively CO₂ concentrated on a molecular sieve permits use of a wide variety of known analytical techniques for the final determination of CO₂. Various methods were compared on the basis of both absolute and calibration measurements. The absolute methods chosen were gravimetric (classical or an automated version based on application of a gravimetric automat and automatic recording balance), thermogravimetric analysis and coulometry. The calibration methods included thermal conductivity, the flame-ionization detector (after conversion of CO₂ into methane) and infrared absorption. Usefulness of the methods was evaluated on the basis of comparative statistical analysis of experimental data with respect to precision (Snedecor'sF-test and Bartlett'sU ²-test) and accuracy (Student'st-test).

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Zusammenfassung Das entwickelte Verfahren zur Bestimmung des TC- und TOC-Gehaltes in Form der gesamten Menge CO₂ erfordert die Anwendung geeigneter Analysentechniken zur Endbestimmung dieser Verbindung. Die Möglichkeit einer Desorption des am Molekularsieb angereicherten CO₂ in einem Gasstrom mit geeignetem Durchfluß erlaubt zur Endbestimmung von CO₂ die Anwendung einer Reihe verschiedener Analysenverfahren. Die Anwendbarkeit verschiedener, auf Absolutverfahren und auch auf relativen Messungen beruhender Methoden wurde vergleichend untersucht. Die folgenden Methoden zur CO₂-Bestimmung wurden gewählt: die Gravimetrie (klassische oder automatisierte unter Einsatz eines Wägeautomaten und einer registrierenden Waage), die Thermogravimetrie und die Coulometrie. Von den relativen Methoden wurden die Thermokonduktometrie, der Flammenionisationsdetektor (nach Umsetzung von CO₂ zu Methan) und das IR-Absorptionsmeßverfahren geprüft. Die Anwendbarkeit der Methoden wurde mit Hilfe statistischer Prüfverfahren beurteilt, wobei die Präzision (SnedecorsF-Test und BartlettsU ²-Test) und die Genauigkeit (Studentst-Test) der erhaltenen Analysenwerte verglichen wurden.

     

Bond energy, aromatic stabilization energy and strain in IPR fullerenes

Various models applied to DFT structures and energies of 2-D and 3-D aromatic molecules shed new light on the effects of strain and aromaticity in these systems. The cyclic pi electron delocalisation does not stabilize the fullerene C60 formation; and 5-6 and 6-6 CC bonds have near-identical bond stretch potentials.