Relativistic molecular orbitals for the double group D3h

Relativistic symmetry orbitals are given for the double group D_3h. For atomic orbitals at the symmetry center a general expression is presented. The atomic orbitals of the s, p_½, and p_3/2 variety outside the center are also considered. The representation matrices are given in explicit form.     

Synthesis, characterization and thermal properties of new aromatic quaternary ammonium bromides: precursors for ionic liquids and complexation studies

Series of new aromatic R₂R′₂N⁺Br⁻ (R=benzyl, 4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl; R′=ethyl, methyl, isopropyl) or RR′₂NH⁺Br⁻-type (R=benzyl, R′=isopropyl) quaternary ammonium bromides were prepared by using novel synthetic route in which a formamide (N,N-diethylformamide, N,N-dimethylformamide, N,N-diisopropylformamide) is treated with aralkyl halide in presence of a weak base. The compounds were characterized by ¹H-NMR and ¹³C-NMR spectroscopy and mass spectrometry. Structures of the crystalline compounds were determined by X-ray single crystal diffraction, and in addition the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. Three of the compounds crystallized in monoclinic, two in orthorhombic and one in triclinic crystal system, showing ion pairs, which are interconnected by weak hydrogen bonds and weak π-π interactions between the phenyl rings. Three of the compounds appeared as viscous oil or waxes. Finally, TG/DTA and DSC methods were used to analyze thermal properties of the prepared compounds. The lowest melting points were obtained for diethyldi-(2-phenylethyl)ammonium bromide (122.2 °C) and for diethyldi-(3-phenylpropyl)-ammonium bromide (109.1 °C). In general, decomposition of the compounds started at 170-190 °C without identifiable cleavages, thus liquid ranges of 30-70 °C were observed for some of the compounds.     

Adaptation of the human skin by chronic solar-simulating UV irradiation prevents ultraviolet-B irradiation-induced rise in serum C-reactive protein levels

Exposure of the skin to UV radiation induces local inflammation. We hypothesized that inflammation induced by erythemal UV-B irradiation could elevate levels of serum C-reactive protein (CRP) and that suberythemal repeating doses of solar-simulating UV radiation (SSR) would produce photoadaptation to such inflammation. Separation-free high-sensitivity assays of CRP show an increase by 42% (P = 0.046) in CRP concentrations in healthy human subjects 24 h after a 3 minimal erythemal dose (MED) dose of UV-B delivered onto a 100 cm2 skin area. Preceding daily suberythemal doses of whole-body SSR for 10 or 30 consecutive days completely prevented the CRP increase. UV-B-induced skin erythema was partially attenuated by 30 preceding days of SSR only (P = 0.00066). After 10 daily SSR doses, the mean baseline CRP concentrations (0.24 +/- 0.21 mg/L) declined by 35% (P = 0.018). Using high-sensitivity analysis of serum CRP as the endpoint marker for cutaneous inflammation, we show that acute exposure of even a relatively small skin area to erythemal UV-B induces skin inflammation detectable also at the systemic level and that photoadaptation by preceding repeating suberythemal doses of SSR reduces signs of inflammation. Our data complement the view given by previous studies in that local photoadaptation also has systemic manifestations.     

Determination of the Dissociation Constants of Urocanic Acid Isomers in Aqueous Solutions

Summary. (E)- and (Z)-Urocanic acids are endogenous chemicals in the normal mammalian skin. The first and the second thermodynamic dissociation constants (pK _a1 and pK _a2) of urocanic acid isomers were determined using UV spectrophotometry in aqueous solutions. The values with standard deviation (pK _a1 = 3.43 ± 0.12 and pK _a2 = 5.80 ± 0.04) and (pK _a1 = 2.7 ± 0.3 and pK _a2 = 6.65 ± 0.04) were obtained to (E)- and (Z)-urocanic acids, respectively. The second dissociations were studied also by potentiometric titration in aqueous sodium chloride solutions up to the isotonic salt concentration (0.154 mol dm⁻³), and the second thermodynamic dissociation constants as well as activity parameters for both isomers were determined at temperature 25°C and for (E)-urocanic acid also at 37°C. The obtained pK _a2 values were close to those found by UV spectrophotometry. The equations for the calculation of the second stoichiometric dissociation constants of urocanic acid isomers on molality and molarity scale in aqueous sodium chloride solutions were derived. The obtained pK _a1 and pK _a2 values for (Z)-urocanic acid appear to be essentially lower than some previously reported values in literature. An erratum to this article is available at .     

Alnumycins A2 and A3: new inverse-epimeric pairs stereoisomeric to alnumycin A1

Two new pairs of stereoisomeric alnumycin As, A2 {(2)-(1R,1′RS,4′SR,5′SR)} and A3 {(2)-(1R,1′RS,4′SR,5′RS)}, are described. Similar to alnumycin A1 {(2)-(1R,1′RS,4′RS,5′SR)}, each of these naturally occurring compounds is also a pair of C-1 inverse epimers. The relative configurations of the dioxane ring sidechains were assigned on the basis of ¹H NMR NOE contacts and molecular modeling using density functional theory (DFT) at the M06-2X/6-31G(d) level of theory. The absolute configurations of C-1 and the determination of inverse epimeric relationships were achieved by experimental electronic circular dichroism (ECD) measurements, with both aspects confirmed by using the chiral derivatizing agent (CDA) Mosher′s acid chloride {α-methoxy-α-trifluorophenylacetyl chloride (MTPACl)} to effect enantiodifferentiation. The absolute configurations of the dioxane ring using the CDA could only be effected in the case of alnumycin A1, the results of which were in agreement with previous assignments. The dioxane ring conformational mobility and the likely interaction between the MTPA groups coupled with the structural novelty of the diols in the dioxane ring with respect to CDA analysis precluded an absolute configuration assignment for alnumycins A2 and A3 based on empirical comparisons or by computational analysis of through-space NMR shieldings (TSNMRS) emanating from the phenyl groups of the MTPA moieties.     

The effect of side-chain length of cellulose fatty acid esters on their thermal,barrier and mechanical properties

Currently, long-chain cellulose esters are not produced commercially because of high price, and since their preparation typically requires a large quantity of chemicals. To reduce the chemical consumption, cellulose reactivity needs to be increased without losing its quality. One way to increase the reactivity of cellulose is to decrease its molar mass in a controlled manner. In this study, we have synthesized cellulose esters with different side-chain length (C6–C18) in a homogeneous system using ozone molar mass-controlled cellulose. The target was to keep the degree of substitution as low as possible while still ensuring the suitability of cellulose esters for solvent casting. Thermal, barrier and mechanical properties were studied depending on cellulose fatty acid ester side-chain length. All our molar mass-controlled cellulose esters form optically transparent, flexible and heat-sealable films with good water barrier properties and are processable without the addition of an external plasticizer. Furthermore, the films have mechanical properties comparable to some generally used plastics. These good properties suggest that our molar mass-controlled cellulose esters could be potential candidates for various applications such as films and composites.     

The role of TL dosimetry in estimating patient doses

A system of determining entrance surface doses (ESDs) from diagnostic X-ray examination is described. It is shown that the radiation yield calibrations of X-ray units (μGym²mAs⁻¹) can be based on very simple measurements with TL dosimeters. Comparisons of determined ESDs with the guidelines of international organizations are carried out with the aim of demonstrating the idea of how these values can be utilized in limiting patient doses.     

<Emphasis Type="Italic">z</Emphasis>-Scaling and high-<Emphasis Type="Italic">p</Emphasis><Subscript><Emphasis Type="Italic">T</Emphasis></Subscript> particle production in hadron-hadron and hadron-nucleus collisions at high energies

The general features of particle production in hadron-hadron and hadron-nucleus collisions at high energy and transverse momentum using the concept of z-scaling are reviewed. z-Presentation of experimental data on the inclusive cross sections obtained at ISR, SPS, and Tevatron is presented and its properties are discussed. It is argued that the properties reflect the fundamental symmetries such as self-similarity, locality, and fractality. z-Scaling is used to predict particle yields in hadron-hadron and hadron-nucleus collisions at RHIC and LHC energies. The violation of z-scaling is considered as a signature of new physics phenomena.     

FT-FIR-spectrum and the ground state constants of D2CO

The ground state spectrum of the formaldehyde D₂¹³CO molecule in the range from 25 to 360 cm⁻¹ has been recorded by a Fourier transform infrared spectrometer. The quantum number limits of the assigned transitions are J = 6-54 and K_a = 0-16. The data was fitted into Watson’s A- and S-reduced Hamiltonians in I^r-representation up to eighth order. The determinable constants calculated from both reductions are compared. The standard deviation of the far infrared data is 3.0 MHz. The spectroscopic constants are also calculated to high accuracy at the CCSD(T)/cc-pVQZ level of ab initio theory and agree well with the experimental ones.     

Black hole spectrum: continuous or discrete?

We formulate a qualitative argument, based on Heisenberg's uncertainty principle, to support the claim that when the effects of matter fields are assumed to overshadow the effects of quantum mechanics of spacetime, the discrete spectrum of black hole radiation, as predicted by Bekenstein's proposal for a discrete black hole area spectrum, reduces to Hawking's black-body spectrum.