Study on the Vortex of the Qinghai-Xizang (Tibet) Plateau in Summer

In this paper an ideal model for the formation and development of the Qinghai-Xizang Plateau vortex is presented by a large number of statistical data and typical case studies. It points out that the Plateau vortex is shallow and thermal originated from a strong heat source near the surface of the west of the Plateau. Then moving eastward , it develops and becomes stronger and thicker with larger upward vertical velocity, and causes great precipitation in the middle Plateau. But at this time the heat source in the vortex becomes weaker, and even the heat sink occurs near the surface. Consequently, it disappears in a cold trough with a strong heat sink in the east of the Plateau. The heat source (sink) is mainly determined by the vertical eddy flux convergence (divergence) of the sensible heat caused by the cumulus convection and turbu-lance. Both the nonuniform heating (cooling) at the surface and the convergence (divergence) of the eddy kinetic energy coact and play an important role in the genesis (di     

Speciation in the Vanadium(III)–Carnosine System

Speciation in the aqueous V(III)–carnosine system has been determined from potentiometric and spectroscopic (UV-Vis absorption and CD) data. Application of the Hyperquad program to the experimental potentiometric data indicates that under our experimental conditions (I=0.5 mol⋅L⁻¹ NaClO₄, pH=2 to 6.5, and L/M>5) only ML₂H₄, ML₂H₃, ML₂H₂ and ML₂H form. These potentiometric results prove that stable complexes form and, with use of the spectroscopic methods, the binding sites are identified.     

Ultrastructures in the Spirotheca of Fusulinella (Fusulinid foraminifer)

An SEM study has been conducted to examine the ultrastructures in the spirotheca of Fusulinella and to reveal the ultra-features of the basic layers consisting of the spirotheca of Fusulinella. The study has demonstrated that the diaphanotheca in the spirotheca of Fusulinella could be considered as a secondary structure.     

Studies on the Glycosides in the Leaves ofOplopanax elatus NAKAI(Ⅰ)

ＳｔｕｄｉｅｓｏｎｔｈｅＧｌｙｃｏｓｉｄｅｓｉｎｔｈｅＬｅａｖｅｓｏｆＯｐｌｏｐａｎａｘｅｌａｔｕｓＮＡＫＡＩ（Ⅰ）ＷＡＮＧＧｕａｎｇ－ｓｈｕ，ＺＨＡＯＣｈｕｎ－ｆａｎｇａｎｄＸＵＪｉｎｇ－ｄａ（ＢｅｔｈｕｎｅＵｎｉｖｅｒｓｉｔｙｏｆＭｅｄｉｃａｌＳ...     

In situ study of the breakout crystallization in the poly(butadiene)-block-poly(ε-caprolactone) thin film

Despite its wide occurrence in soft confined block co-polymers, breakout crystallization remains poorly understood and is difficult to control. In this work, thin films of cylinder-forming poly(butadiene)-block-poly(ε-caprolactone) (PB-b-PCL) diblock co-polymers, with PCL being the minority block, have been chosen as the study subject. We demonstrate a new route to study the breakout crystallization by obtaining the microphase separation structure within terraced lamellae first and then in situ tracking down the lamellar coalescence, resulting from the development of the crystal growth front. We find that the crystal growth front has sucked materials from the surrounding amorphous lamellae, which lead to the decrease of the lamellar zones and coalescence of the microphase separation structure. Dividing the breakout crystallization into parallel breakout and vertical breakout, we illustrate that it is the crystallization-driven molecular diffusion that make the molecules overcome the topography constraint and grow into large-scale spherulite. Moreover, the results show that the polymer microphase separation structure has a significant influence on the crystal nucleation and greatly retarded the crystal growth rate. With a well-designed microphase separation structure within terraces and an easily tunable atomic force microscopy in situ imaging technique, an intensive study of the breakout crystallization and concomitant microdomain coalescence has been offered.     

Polymerization of α-methylstyrene in the solid (frozen) state

Russian Chemical Bulletin -     

The role of CH-π interaction in the charge transfer properties in tris(8-hydroxyquinolinato)aluminium(III)

The charge mobility is a key property in many electro-optical materials, with charge transfer (CT) taking place in a solid matrix of molecules. Large intermolecular electronic interaction is one of the key factors for a good CT rate, which is dependent on both intra- and intermolecular structures. The connection of the molecular structure with the intermolecular CT property would facilitate the search for a new material with desirable CT property, but currently it is still quite limited by the lack of knowledge for intermolecular configurations. In the present work, we study factors influencing the intermolecular configurations, and subsequently the CT property, in tris(8-hydroxyquinolinato) aluminium(III) (AlQ(3)) from all currently available crystal structures. We found that there exists a pair of CH-π interactions in a good majority of the π-π stacked bimolecular configurations. Such CH-π and π-π interacting structures are also seen in the crystal structures of many other similar molecules. With both experimental and simulated structures, we show that the CH-π interaction stabilizes the bimolecular configurations, and drives the structure towards a region with a higher electron transfer coupling and lower hole transfer coupling. This effect likely affects the electron transport property of AlQ(3), since it is consistent with recent experimental results, where AlQ(3) analogs with their CH-π interaction blocked either require a higher operating voltage in light-emitting devices [Sapochak et al., J. Am. Chem. Soc., 2001, 123, 6300], or become bipolar in their charge mobilities [Liao et al., J. Am. Chem. Soc., 2009, 131, 763]. CH-π interaction is commonly seen in aromatic molecules, which are frequently used as building blocks in molecules for electro-optical applications. Our work points out a possible way to enhance the desired CT property in the design of new materials.     

Effects of Y (Ⅲ) Ions on the Fluorescence Properties of Ce(Ⅲ) Ion and the Organic Ligands in the Complex

The enhancement effects of Y ( Ⅲ) ions on the fluorescence of Ce ( Ⅲ) in Ce ( Ⅲ)-Y ( Ⅲ)-PMMA (polymethylmethacrylate ) or Ce ( Ⅲ)-Y ( Ⅲ)-PVC (polyvinyl chloride ) complex systems were observed. The influence of Y ( Ⅲ) ions on the emission spectra of PMMA ligands in PMMA-Y ( Ⅲ) and the fluorescent enhance- ment of Y( Ⅲ) on Ce( Ⅲ) emission in PMMA-Ce-Y by Y( Ⅲ) ion were studied. It was also of interest to note that when Y ( Ⅲ) ions were added into PMMA and into bpy(bipyridine ), respectively, the emission spectrum of PMMA ligands was split into fine structure bands by Y ( Ⅲ), and the fluorescence intensities of bpy ligands in bpy-Y ( Ⅲ) complexes were considerably increased.     

Modeling the similarities and differences between the sodalite cages (β-cages) in the generic materials

Initially in this review the sodalite framework [T₁₂O₂₄]^6– (T=Al, Si] is modeled with regular tetrahedra and disordered T atoms. Equations are given for calculating atomic coordinates from the unit cell parameter a and the T—O distancet; the expansion or contraction of the sodalite-cage is related quantitatively to changes ina through the cooperative twists of TO₄ tetrahedra about 4 axes and changes in < TOT bridge angles. The fully expanded cage has=0° and the maximum value ofa. The equations are general for any framework formed by isomorphous substitution of T by atoms other than Al, Si and for any SiAl ratio. The model and equations are extended to the zeolite A framework, which can be built from fully expanded sodalite cages. With the cooperative tilt of the TO₄ tetrahedra of zeolite A, described by Depmeier, the major variable features of the zeolite A framework are explained quantitatively. The faujasite framework has twisted-cages (>0), as in sodalite examples, and is quantitatively modeled most conveniently from sodalite examples with similar-cage contents. The review is extended to structures with T-ordering and distorted tetrahedra. Methods are given for estimating a for sodalites from a knowledge of the cavity contents, especially the sizes of cations and anions, and so on, present. Ways of predicting cavity sites in zeolite A as a function of cation size are presented, and the principal cavity sites in the faujasite-cage region are discussed. Finally the review considers isomorphous replacement of T atoms (Si or Al) by B, Be, Fe, Ga, Ge, and P; many of these substituted frameworks are stabilized by templates, or guest molecules, which reside in the cavities. Templates also stabilize Si, Al frameworks with high SiAl ratios. The modeling approach reviewed here is tested on a range of isomorphously substituted frameworks isotypic with sodalite; observed and calculated values of twist and 12O₂₄]^12– with distorted tetrahedra; these are structures with Al-O-Al bridges, which violate Loewenstein's Rule.     

Energy relationship and the polarization of C_(60) cage in the endohedral complexes (X@C_(60))

In this paper, we carry out the calculation on the system (X@C60)(X=Li, Na, K, Kb, Cs; F, Cl, Br, I), where the position of X changes along 5 typical symmetry directions. For the calculation of quantum chemistry we use EHMO/ASED method, for the calculation of molecular mechanics we use Buckingham potential (exp-6-1) function, and for the calculation of thermo-chemical cycle we use individually isolating the processes such as the structure variation, charge transfer and charge distribution, and their interactions etc. The calculation results show that (1) In the region of radius r≈0.2 nm of the Ceo cage, the potential field is nearly spherical; (2) Except for Li and Na, the systems are the most stable with minimum energies at the center of C60 cage. For Li and Na, the systems are the most stable with minimum energies at r≈0.16 nm and r≈0.13 nm, respectively. In view of the interactive region of chemical bonds, the interactions between X and the C60 cage do not belong to the classical chemical bonds; (     

Chemical Studies on the Glycosides in the Leaves of Oplopanax Elatus Nakai(Ⅳ)

ＣｈｅｍｉｃａｌＳｔｕｄｉｅｓｏｎｔｈｅＧｌｙｃｏｓｉｄｅｓｉｎｔｈｅＬｅａｖｅｓｏｆＯｐｌｏｐａｎａｘＥｌａｔｕｓＮａｋａｉ（Ⅳ）＊ＷＡＮＧＧｕａｎｇ－ｓｈｕａｎｄＸＵＪｉｎｇ－ｄａ（ＮｏｒｍａｎＢｅｔｈｕｎｅＵｎｉｖｅｒｓｉｔｙｏｆＭｅｄｉｃａｌ...     

Characterization of the bis(β-diimino-tetracyano-pyrrolizinido)-metal(II) complexes incorporated in polymeric matrices

The bis(-diimino-tetracyano-pyrrolizinido)-Cu(II) complex (CuL₂) has been incorporated in polystyrene (0.28% w/w), by evaporating tetrahydrofuran solutions either at room temperature (a) or at 100°C (b). From IR and UV-vis measurements and optical microscopy on the resulting films (a orb, thickness 50 m) it is concluded that CuL₂ is present as a concentrated (C10^–1 M) THF solution ina and as small solid particles (diameter <1 m) inb. The difference in colour of the films (dark bluea, light blueb), due to the different physical state of CuL₂ in the matrix, is expected, and has been preliminarily shown using similar films based on NiL₂, to be useful for sensing organic vapours in the atmosphere.     

Studies of the Intramolecular Aromatic-ring Stacking Interactions in the Ternary Platinum(Ⅱ) Complexes

The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA) , where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.     

(η6-Anisole) (η2-benzene) dicarbonylchromium(0): an intermediate in the photochemical carbonyl substitution of (η6-anisole)tricarbonylchromium(0) in benzene

The photochemical carbonyl substitution of (η⁶-anisole)Cr(CO)₃ has been investigated by laser flash photolysis. Both transient spectra and second-order rate constants for the reactions of transients with nucleophiles are found to be extremely variable depending upon solvents used. The coordination of benzene to the transient in cyclohexane forms the transient in benzene, indicating two discrete chemical species: (η⁶-anisole)Cr(CO)₂ and (η⁶-anisole)Cr(CO)₂(η²-benzene). The latter type of transient was observed also for fluorobenzene and mesitylene, leading to the assignment of a weak band in the visible region as η²-arene → Cr charge transfer. The existence of (η⁶-arene)Cr(CO)₂(η²-arene′) may throw light on what have been described as solvent effects in organometallic reactions.     

Nucleotide hydrolysis in the presence of μ-hydroxo-bridged-cobalt(III) complexes

Abstract

Two cobalt(III) complexes with tridentate ligands, the acyclic diethylenetriamine and macrocyclic 1,4,7-triazacyclononane, were examined as potential catalysts for the hydrolysis of adenosine 5′-triphosphate (ATP). Studies were performed primarily at pH 4.5, where the two complexes were in the binuclear di-μ-hydroxo forms. For both complexes, a rapid initial hydrolysis with first order dependence on the concentration of ATP was observed, k_obs of approximately 0.20 min^?1, followed by very slow hydrolysis. Deuterium isotope studies done in D₂O showed a normal isotope effect with k_H/k_D = 1.8. Spectral investigations and ⁵⁹Co NMR studies indicated that the biphasic nature of the hydrolysis reaction may be due to the formation of a complex in which inorganic phosphate is coordinated to the cobalt, effectively poisoning the catalyst.     

A μ(1,1)- or μ(1,3)-carboxylate bridge makes the difference in the magnetic properties of dinuclear Mn(II) compounds

Six new dinuclear Mn(II) compounds with carboxylate bridges have been synthesized and characterized by X-ray diffraction: [{Mn(phen)(2)}(2)(μ-RC(6)H(4)COO)(2)](ClO(4))(2) with R = 2-Cl (1), 2-CH(3) (2), 3-Cl (3), 3-CH(3) (4), 4-Cl (5) and 4-CH(3) (6). Compounds 1 and 2 show two μ(1,3)-carboxylate bridges in a syn-anti mode while compounds 3-6 present a very uncommon coordination mode of the carboxylate ligand: the μ(1,1)-bridge. The magnetic properties of these compounds are very sensitive to the bridging mode of the carboxylate ligands. While compounds 1 and 2 (μ(1,3)-bridge) display antiferromagnetic interactions, with J values of -1.41 and -1.66 cm(-1), respectively, compounds 3-6 (μ(1,1)-bridge) show ferromagnetic interactions, with J values of 1.01, 0.98, 1.04 and 1.06 cm(-1), respectively. It is worth noting that compounds 3-6 are the first of their class to be magnetically characterized. The EPR spectra at 4 K for compounds with antiferromagnetic coupling (1 and 2) are more complex than those for compounds with a ferromagnetic interaction (3-6). Quite good simulations can be obtained with the ZFS parameters of the Mn(II) ion D(Mn) ~ 0.095 cm(-1) and E(Mn) ~ 0.025 cm(-1) for compounds 1 and 2 and D(Mn) ~ 0.060 cm(-1) and E(Mn) ~ 0.004 cm(-1) for compounds 3-6.     

Theoretical Investigations of the Inclusion Processes of (4-tert-butylphenyl) (3-sulfonatophenyl) (phenyl) Phosphine in β-Cyclodextrin

Quantum mechanical calculations on the (4-tert-butylphenyl)(3-sulfonatophenyl) (phenyl) phosphine/-cyclodextrin inclusion complex werecarried out using semi-empirical calculations. Inclusion process pathways are describedand the most probable structures of the 1:1 complex are sought through a global potentialenergy scan. The calculations suggest that the most stable structure is obtained whenthe aromatic ring bearing the tert-butyl group is includedinto the hydrophobic cavity of the -cyclodextrin from theside of the primary hydroxyl groups.     

Investigating the inclusion of the Ag(I)-nimesulide complex into β-cyclodextrin: studies in solution and in the solid state

The present work describes the preparation and characterization of inclusion systems involving β-CD and the silver(I) nimesulide coordination complex (Ag-NMS), prepared by kneading (K) and co-evaporation (CE) methods. Solid state characterization by DSC, XRD and IR vibrational spectroscopic measurements provided remarkable evidences of the formation of true inclusion systems. Solution measurements provided information about the inclusion mode. The UV–Vis spectroscopy was used to obtain the association constants by the Scatchard method, and the value obtained was 370 ± 2 L mol^?1. The ¹H NMR spectroscopic measurements indicate a total inclusion of the guest into the cavity. A 2D NOESY experiment was carried out for the inclusion complex. The spectrum shows that hydrogens 3–6 of the cyclodextrin clearly correlate with the protons of the phenoxy ring of nimesulide in the Ag-NMS coordination compound, which confirms the formation of the inclusion complex. The antibacterial activities of the Ag-NMS and CE-[(Ag-NMS)·β-CD] inclusion system were evaluated by the well diffusion method over Escherichia coli and Pseudomonas aeruginosa (Gram-negative) and Staphylococcus aureus (Gram-positive) pathogenic bacterial strains. The observed data shows the significant antibacterial activity of the Ag-NMS coordination complex, and no activity for the inclusion complex under the same considered conditions.