Topography and surface free energy of DPPC layers deposited on a glass, mica, or PMMA support

An investigation of energetic properties of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) layers deposited on glass, mica, and PMMA (poly(methyl methacrylate)) surfaces was carried out by means of contact angles measurements (advancing and receding) for three probe liquids (diiodomethane, water, and formamide). DPPC was deposited on the surfaces from water (on glass and mica) or methanol (on PMMA) solutions. The topography of the tested surfaces was determined with a help of scanning electron microscopy (SEM) and atomic force microscopy (AFM). Using the measured contact angles, the total apparent surface free energy and its components of the studied layers were determined from van Oss et al.'s (Lifshitz-van der Waals and acid-base components, LWAB) and contact angle hysteresis (CAH) approaches. It allowed us to learn about changes in the surface free energy of the layers (hydrophobicity/hydrophilicity) depending on their number and kind of support. It was found that the changes in the energy greatly depended on the surface properties of the substrate as well as the statistical number of monolayers of DPPC. However, principal changes took place for first three monolayers.     

NMR studies of chloroform@cryptophane-A and chloroform@bis-cryptophane inclusion complexes oriented in thermotropic liquid crystals

Oriented inclusion complexes of chloroform@cryptophane-A and chloroform@bis-cryptophane were prepared using a nematic thermotropic liquid crystal (ZLI 1132), and the alignment and magnetic resonance properties of these host-guest systems were studied via (13)C NMR of the labeled guests. Large (1)H-(13)C dipolar splittings for (13)CHCl(3) guests indicated significantly enhanced (approximately 2-fold) ordering for the trapped vs. free ligands under all conditions studied, with similar ordering observed for the two complexes-despite significant differences in size and motional freedom between the hosts. For each environment, variable-temperature studies permitted the sign and magnitude of the order parameter for chloroform's C-H bond to be independently determined from the (13)C chemical shift anisotropy (CSA) shifts (via the gradient method) and the restored (1)H-(13)C dipolar couplings. In both systems, the results are consistent with overall alignment of the complexes such that the cage principal axis lies roughly perpendicular to the LC director.     

Bisignate resonance Raman optical activity: a pseudo breakdown of the single electronic state model of RROA?

Raman optical activity (ROA) spectra were calculated for a set of conformers of astaxanthin, which is a non‐rigid molecule exhibiting strong resonance enhancement in the visible range. Single electronic state theory of the Resonance ROA (RROA) predicts the spectrum to be monosigned. For astaxanthin, it appeared that some of the conformers exhibit different sign of the bands than the other conformers. As a result, the conformer population averaged spectrum of astaxanthin can exhibit both signs of the bands, or be monosigned depending on which conformers are dominating, that reflects a departure from the single electronic state approximation. Moreover, use of different basis sets and/or density functional theory (DFT) functionals results in different conformer populations, thus yielding again either monosigned ROA spectrum or with bands of both signs. Consequences of these two findings for the astaxanthin RROA spectrum are discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Solvent effects on electron-driven proton-transfer processes: adenine-thymine base pairs

Time-Dependent Density Functional Theory (TD-DFT) computations, with M05-2X and PBE0 functionals, have been employed for a detailed study of the Electron-Driven Proton-Transfer (PT) processes in an Adenine-Thymine Watson-Crick Base Pair in the gas phase and in solution, with the bulk solvent described by the polarizable continuum model. In the gas phase, TD-DFT computations predict that the Adenine → Thymine Charge Transfer (CT) excited state undergoes a barrierless PT reaction, in agreement with CC2 computations (S. Perun, A. Sobolewski, W. Domcke, J. Phys. Chem. A, 2006, 110, 9031.). The good agreement between the TD-DFT approach and CC2 results validates the former for the studies of excited state properties, excited state proton transfer reaction, and deactivation mechanisms in the DNA base pairs. Next, it is shown that inclusion of solvent effects significantly influences the possibility of both barrier-less excited state proton transfer and radiation-less deactivation through conical intersection with the ground state, affecting the energy of the CT excited state in the Franck-Condon region, the energy barrier associated to the PT process and the energy gap with the ground electronic state. These findings clearly indicate that environmental effects, with a special attention to proper treatment of dynamical solvation effects, have to be included for reliable computational analysis of photophysical and photochemical processes occurring in condensed phases.     

Luminescent Di‐ and Polynuclear Organometallic Gold(I)–Metal (Au2, {Au2Ag}n and {Au2Cu}n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents

The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au₂(mes)₂(μ‐LL)] (LL=dppe: 1,2‐bis(diphenylphosphano)ethane 1 a , and water‐soluble dppy: 1,2‐bis(di‐3‐pyridylphosphano)ethane 1 b ) with Ag⁺ and Cu⁺ lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au₂M(μ‐mes)₂(μ‐LL)][A] (M=Ag, A=ClO₄^?, LL=dppe 2 a , dppy 2 b ; M=Ag, A=SO₃CF₃^?, LL=dppe 3 a , dppy 3 b ; M=Cu, A=PF₆^?, LL=dppe 4 a , dppy 4 b ). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au₂(mes)₂(μ‐dppy)] ( 1 b ) and [Au₂Ag(μ‐mes)₂(μ‐dppe)][SO₃CF₃] ( 3 a ) were determined by a single‐crystal X‐ray diffraction study. 3 a in solid state is not a cyclic trinuclear Au₂Ag derivative but it gives an open polymeric structure instead, with the {Au₂(μ‐dppe)} fragments “linked” by {Ag(μ‐mes)₂} units. The very short distances of 2.7559(6) Å (Au? Ag) and 2.9229(8) Å (Au? Au) are indicative of gold–silver (metallophilic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self‐aggregation of [Au₂M(μ‐mes)₂(μ‐LL)]⁺ units (M=Ag or Cu; LL=dppe or dppy) into an extended chain structure, through Au? Au and/or Au? M metallophilic interactions, as that observed for 3 a . In solid state the heterometallic Au₂M complexes with dppe ( 2 a – 4 a ) show a shift of emission maxima (from ca. 430 to the range of 520‐540 nm) as compared to the parent dinuclear organometallic product 1 a while the complexes with dppy ( 2 b–4 b ) display a more moderate shift (505 for 1 b to a max of 563 nm for 4 b ). More importantly, compound [Au₂Ag(μ‐mes)₂(μ‐dppy)]ClO₄ ( 2 b ) resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au₂Cl₂(μ‐LL)] (LL dppy 5 b ) was also studied for comparative purposes. The antimicrobial activity of 1–5 and Ag[A] (A=ClO₄^?, SO₃CF₃^?) against Gram‐positive and Gram‐negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au₂M derivatives with dppe ( 2 a – 4 a ) were the more active (minimum inhibitory concentration 10 to 1 μg mL^?1). Compounds containing silver were ten times more active to Gram‐negative bacteria than the parent dinuclear compound 1 a or silver salts. Au₂Ag compounds with dppy ( 2 b , 3 b ) were also potent against fungi.     

The effect of mechanical activation on the thermal reactions of P2O5–Al2O3–Fe2O3–Na2O phosphate glasses

The effect of mechanical activation on the structure and thermal reactions of glasses has been studied on the example of Na–Al–Fe phosphate glasses. These glasses are used in nuclear technology for immobilization of radioactive waste. The glasses were activated by grinding in a planetary mill. Mechanical activation causes a decrease of the T _g temperature as well as of the glass crystallization temperature. The type of crystalline phases formed and the quantitative proportions between them are changing. Analysis of inter-atomic interactions in the structure of glass was applied to explain the observed regularities governing the crystallization of the activated glasses.     

Bio-dissolution of colloidal-size clay minerals entrapped in microporous silica gels

Four colloidal-size fractions of strongly anisotropic particles of nontronite (NAu-2) having different ratios of basal to edge surfaces were incubated in the presence of heterotrophic soil bacteria to evaluate how changes in mineral surface reactivity influence microbial dissolution rate of minerals. To avoid any particle aggregation, which could change the reactive surface area available for dissolution, NAu-2 particles were immobilized in a biocompatible TEOS-derived silica matrix. The resulting hybrid silica gels support bacterial growth with NAu-2 as the sole source of Fe and Mg. Upon incubation of the hybrid material with bacteria, between 0.3% and 7.5% of the total Fe included in the mineral lattice was released with a concomitant pH decrease. For a given pH value, the amount of released Fe varied between strains and was two to twelve-fold higher than under abiotic conditions. This indicates that complexing agents produced by bacteria play an important role in the dissolution process. However, in contrast with proton-promoted NAu-2 dissolution (abiotic incubations) that was negatively correlated with particle size, bacterial-enhanced dissolution was constant for all size fractions used. We conclude that bio-dissolution of nontronite particles under acidic conditions seems to be controlled by bacterial metabolism rather than by the surface reactivity of mineral.     

Interval methods of Adams-Bashforth type with variable step sizes

Numerical Algorithms - In a number of our previous papers, we have proposed interval versions of multistep methods (explicit and implicit), including interval predictor-corrector methods, in which...     

A Parallel Algorithm for Multiple Objective Linear Programs

This paper presents an ADBASE-based parallel algorithm forsolving multiple objective linear programs (MOLPs). Job balance,speedup and scalability are of primary interest in evaluatingefficiency of the new algorithm. The scalability of a parallelalgorithm is a measure of its capacity to increase performance withrespect to the number of processors used. Implementation results onIntel iPSC/2 and Paragon multiprocessors show that the algorithmsignificantly speeds up the process of solving MOLPs, which isunderstood as generating all or some efficient extreme points andunbounded efficient edges. The algorithm is shown to be scalable andgives better results for large problems. Motivation andjustification for solving large MOLPs are also included.