Molecular dynamics simulation of thermomechanical properties of montmorillonite crystal. 1. Isolated clay nanoplate

The structure and mechanical properties of clay nanoparticles is a subject of growing interest because of their numerous applications in engineering. We present the results of molecular dynamics simulation for a single nanoplate of pyrophyllite - a 2:1 clay mineral consisting of two tetrahedral sheets of SiO4 and an intervening octahedral AlO6 sheet. Simulations were performed in the temperature interval from 5 to 750 K using the ionic-type potentials of Cygan et al. On this basis the temperature dependences of structural parameters, characterizing both tetrahedral and octahedral sheets as well as single lamella, have been studied. Two slightly different structures were observed in this wide temperature interval. The mechanical properties of the nanoplate were calculated from stress-strain diagrams, which have been obtained at relatively slow rates of deformation (for molecular simulations). Using different types of loading, we calculated the full elasticity tensor and estimated the influence of temperature on its components. We estimated also the bending and torsion stiffnesses of the nanoplate as specific characteristics of this type of particle. Because the nanoplate is atomically thin, a reasonable determination of the thickness is a nontrivial problem, both in the modeling of mechanical properties and in physical interpretation of the obtained data. We propose a procedure for its calculation.     

The enthalpies of formation and reorganization of aromatic radicals

The enthalpies of formation of some biphenyl derivatives were determined. A "double difference" method for calculating the enthalpies of formation of aromatic radicals and the bond dissociation energies was proposed. The enthalpies of formation of the radicals biphenyl, diphenyl oxide, and phenyl oxide were determined. The energies of reorganization of these radicals as well as phenyl and 4-, 3-, and 2-pyridyls were calculated. The sums of the energies of the chemical bonds in the molecular moieties transformed into radicals upon the decomposition of chemical compounds were found to be constant for different compounds. The energies of the chemical bonds in arenes were determined.     

Self‐assembly of mono‐ and multilayers of polyconjugated conducting polymers

To obtain organised mono‐ and multilayers of policonjugated polymers or oligomers by self assembly techniques has recently attracted much attention. This is due to the simplicity of the method and to the fact that no sophisticated apparatus is required. In the present feature the state of the art in this field is discussed including our own research results. A survey on self assembly of thiols, disulfides, and alkylsilanes on gold or glass surfaces is presented as well as self assembly of ferrocenylalkyl‐substituted heterocycle adsorbates on ITO surfaces. Carboxyalkyl bithiophenes and terthiophenes, in which the oligothiophene tail is either perpendicularly or linearly linked to the tethering carboxyalkyl chain form stable monolayers on ITO electrodes and are anodically oxidised to produce polymer layers or to couple with oligothiophenes in solution, depending on the structure. As for multilayers, an introductory survey on the self assembly technique usually employed is given. Several examples of multilayers constituted of electroconductive polymers are discussed. Finally our recent results concerning different multilayers from polythiophenes bearing anionic and cationic moieties are discussed.     

Structural Factors and Mechanisms Underlying the Improved Photodynamic Cell Killing with Silicon Phthalocyanine Photosensitizers Directed to Lysosomes Versus Mitochondria

The phthalocyanine photosensitizer Pc 4 has been shown to bind preferentially to mitochondrial and endoplasmic reticulum membranes. Upon photoirradiation of Pc 4-loaded cells, membrane components, especially Bcl-2, are photodamaged and apoptosis, as indicated by activation of caspase-3 and cleavage of poly(ADP-ribose) polymerase, is triggered. A series of analogs of Pc 4 were synthesized, and the results demonstrate that Pcs with the aminopropylsiloxy ligand of Pc 4 or a similar one on one side of the Pc ring and a second large axial ligand on the other side of the ring have unexpected properties, including enhanced cell uptake, greater monomerization resulting in greater intracellular fluorescence and three-fold higher affinity constants for liposomes. The hydroxyl-bearing axial ligands tend to reduce aggregation of the Pc and direct it to lysosomes, resulting in four to six times more killing of cells, as defined by loss of clonogenicity, than with Pc 4. Whereas Pc 4-PDT photodamages Bcl-2 and Bcl-xL, Pc 181-PDT causes much less photodamage to Bcl-2 over the same dose–response range relative to cell killing, with earlier cleavage of Bid and slower caspase-3-dependent apoptosis. Therefore, within this series of photosensitizers, these hydroxyl-bearing axial ligands are less aggregated than is Pc 4, tend to localize to lysosomes and are more effective in overall cell killing than is Pc 4, but induce apoptosis more slowly and by a modified pathway.     

Observation of non-Förster-type energy-transfer behavior in quantum dot-phthalocyanine conjugates

The effect of linker chain length on the energy transfer from CdSe quantum dots (QDs) to silicon phthalocyanine (Pc) photodynamic therapy agents was investigated by steady-state and femtosecond time-resolved spectroscopy with 500 nm light for the specific excitation of the QD energy donor. The conjugation between the QD and the Pc was achieved with linker chains varying from 4 to 9 bond lengths by incorporating 1-6 methylene groups into the axial ligand of the Pc. With increasing chain length, the energy-transfer efficiency increased, which appears to be opposed to a purely F?rster-type resonance energy-transfer behavior that is commonly discussed for the energy transfer in QD conjugates. The obtained results provide strong evidence for a capping-layer-mediated energy transfer in the QD-based donor-acceptor conjugates.     

Kinetics of photochemical reactions of a new biphotochromic compound upon photolysis with light of different wavelengths

Using the method of microsecond flash photolysis with UV and visible light, the spectral and kinetic characteristics of intermediate products of photolysis in toluene and methanol solutions of a new biphotochromic compound have been studied, in which two photochromic moieties, spironaphthoxazine and azomethine, are linked to each other in such a way that there is conjugation between π-electronic systems of the moieties in the ground state of the molecule. Two intermediate products have detected, whose relative efficiency of formation substantially depends on the solvent and the wavelength of excitation light.     

Simulation of melting in crystalline polyethylene

We carry out a molecular dynamics simulation of the first stages of constrained melting in crystalline polyethylene (PE). When heated, the crystal undergoes two structural phase transitions: from the orthorhombic (O) phase to the monoclinic (M) phase, and then to the columnar (C), quasi-hexagonal, phase. The M phase represents the tendency to the parallel packing of planes of PE zigzags, and the C phase proves to be some kind of oriented melt. We follow both the transitions O→M and M→C in real time and establish that, at their beginning, the crystal tries (and fails) to pass into the partially ordered phases similar to the RI and RII phases of linear alkanes, correspondingly. We discuss the molecular mechanisms and driving forces of the observed transitions, as well as the reasons why the M and C phases in PE crystals substitute for the rotator phases in linear alkanes.     

激光光束传输因子M~2的一些问题

本文讨论与 M2 因子有关的一些问题 ,指出在近轴近似条件下由光束的二阶强度矩定义的 M2 因子满足 M2 ≥ 1 ,其中只有对基模高斯光束等式才成立 .由光束的功率通量值定义的 M2 因子 ( M2pc)有可能小于 1 ,M2pc的大小取决于所定义的光斑半径内包含的光功率的百分数 .通过计算光场的二阶矩 ,我们获得了轴向相干叠加的高斯光束的 M2 因子的解析解