Probing UPD-induced surface atomic rearrangement of polycrystalline gold nanofilms with surface plasmon resonance spectroscopy and cyclic voltammetry

Silver underpotential deposition (UPD)-induced surface atomic rearrangement of polycrystalline gold nanofilms was probed with use of surface plasmon resonance spectroscopy (SPRs) as a novel probe tool in combination with cyclic voltammetry. Interestingly, upon repetitive electrochemical UPD and stripping of Ag, the surface structure of the resulting bare Au film is rearranged due to strong adatom-substrate interactions, which causes a large angle shift of SPR R-theta curves, in a good linear relationship with the number of UPDs, to a lower SPR angle. The n, K values of the surfacial Au monolayers before and after the repetitive Ag UPD and stripping for 27 times are found to be 0.133, 3.60 and 0.565, 9.39, respectively, corresponding to the huge shift of 1.61degrees to the left of the SPR minima. Cyclic voltammetry experiments in 0.10 M H2SO4 are carried out before and after the UPD treatment to examine the quality of the whole electrode surface and confirmed this change. To correlate the angle change in SPRs with the profile change in the cyclic voltammogram, the UPD treatment was also performed on a Au(111) textured thin film. It was therefore confirmed that the resonance position of the SPR spectrum is very sensitive to the surface crystallographic orientation of the bare Au substrates. Some surface atomic rearrangement can cause a pronounced SPR angle shift.

A temperature-dependent interaction of neutral red with calf thymus DNA

Neutral red (NR) is used as a probe to study the temperature and concentration dependent interaction of a cationic dye with nucleic acid. A temperature-dependent interaction of NR with calf thymus DNA (CT DNA) has been studied by differential pulse voltammetry (DPV), UV-Visible absorption, circular dichroism (CD) and fluorescence spectroscopy. The experimental results of increasing peak current, changes in the UV-Visible absorption and fluorescence spectra of NR and decreasing the induced circular dichroism (ICD) intensity show that (i) the binding mode of NR molecules is changed from intercalating into DNA base pairs to aggregating along the DNA double helix and (ii) the orientation of NR chromophore in DNA double helix is also changed with the temperature.

Conformational and orientational analyses of 2,2 '-bithiophene under interaction of external electric field constructed by point charges

The fully relaxed single-bond torsional potentials and orientation-related rotational potentials of 2,2'-bithiophene (BT) under the interaction of an external electric field (EF) constructed by point charges have been evaluated with semi-empirical AMI and PM3 calculations. The torsional potentials are sensitive to both EF strength and direction. While the EF is parallel to the molecular long axis, the torsional barrier around C-x-C-x' bond obviously rises with increasing the EF strength, whereas the relative energies of syn and anti minima show a slight change. The interaction between the EF and the induced dipole moment has been proposed to elucidate this observation. On the other hand, the relative energy difference between the syn and anti minima shows an obvious change, while the EF is perpendicular to the molecular long axis. This feature has been ascribed to the interaction between the EF and the permanent dipole moment of BT. Furthermore, conformational and orientational analyses in two dimensions have been carried out by changing the torsional and rotational angles in the different EF. The conformation and orientation of a gas-phase BT in the EF are governed by both the above factors.

The single crystal-like banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group

The banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group have been studied by means of transmission electron microscopy(TEM), electron diffraction(ED) and atomic force microscopy (AFM). The crystallization-induced Landed texture without external shear can be formed when the thin films were annealed at the temperature range(320-330 degrees C) of the liquid crystalline state from the melt, The results show that the banded regions have high orientation of single crystal based on the orthorhombic packing and the growing direction of the Lands is along the b axis of the crystals, This kind of single crystal-like bands is due to the different orientation of the packing molecular chains, The molecular chains of the dark bands in the bright field electron micrograph are perpendicular to the film plane, while the ones of the bright Lands are tilt along the b axis with the tilt angle upto +/-20 degrees.

Study of the mechanism for controlled crystallization of BaF2 under two kinds of monolayers

Controlled crystallization of BaF2 under two different kinds of monolayers, octadecylamine [CH3(CH2)(17)NH2] and hexadecanol [CH3(CH2)(14)CH2OH], has been studied by using x-ray diffraction (XRD) and scanning electron microscope. It was found that the monolayer headgroup, the degree of ionization of the headgroup, etc., had a complicated effect on the selectivity of monolayers for crystal and on the morphology and orientation of crystals grown under the compressed monolayers. At pH = 7.0, XRD analysis showed that (100)-oriented BaF2 crystals were formed under the octadecylamine monolayer, while several kinds of crystals were found under the hexadecanol monolayer. In comparison, at pH = 8.5, both (100)-oriented BaF2 and (111)-oriented Ba(NO3)(2) crystals were obtained under the monolayer of octadecylamine. However, crystals formed under hexadecanol monolayer consist of BaF2, Ba(NO3)(2), etc. The detailed mechanism for crystallization was discussed in terms of the specific interaction and lattice matching between the monolayer headgroup and the nucleating species.

FTIR-ATR study of self-assembled thiol monolayers on gold

Self-assembled monolayers of 1-teradecanethiol on gold were characterized by means of FTIR-ATR measurements, XPS and contact angle measurements. Linear dichroism measurements using FTIR-ATR are used to estimate the orientation of the alkyl chains. An equation for calculating the orientation angles of the alkyls chains was deduced. (C) 1998 Elsevier Science Limited. All rights reserved.

Effect of lamellar thickness on the epitaxial crystallization of PE on oriented iPP films

The effects of lamellar thickness on the epitaxial crystallization of polyethylene on the oriented isotatic polypropylene have been studied by means of transmission electron microscopy. The results obtained from the bright field electron microscopy and electron diffraction show that the epitaxial orientation of the PE crystals on the iPP substrate depends not only on the thickness of the oriented iPP lamellae, but also on the lamellar thickness of PE crystals. No epitaxial orientation relationship between PE crystal and iPP substrate can be found, when the PE crystals are thicker than the lamellar thickness of iPP along the matching direction. This suggests, that the epitaxial nucleation of PE in the PE/iPP epitaxial system is controlled not only by the chain-row matching, but also by a secondary nucleation process.

2D NMR and FT-Raman spectroscopic studies on the interaction of lanthanide ions and Ln-DTPA with phospholipid bilayers

The interactions of lanthanide ions and the Ln-DTPA (DTPA = diethylenetriaminepentaacetate) complex with di palmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylethanolamine (DPPE) bilayers are studied by 2D NOESY and FT-Raman spectroscopy. Proton NMR spectroscopic results show that lanthanide ions combine with phosphate groups in the polar region of the outer layer of DPPC liposomes, leading to the separation in chemical shift of the proton signal of N(CH3)(3) The conformational change of the O-C-C-N+ backbone from the gauche conformer to the trans one is not found; i.e., the orientation of the polar headgroup is still parallel to the surface of the bilayers. The Ln-DTPA complex at low concentration in a pH 7.4 solution localizes far away from bilayers and thereby has little effect on the structure of bilayers. The FT-Raman spectroscopic results indicate that lanthanide ions affect strongly the fluidity of acyl chains of DPPE bilayers while the Ln-DTPA complex affects it slightly.

Recrystallization of HDPE in HDPE/iPP quenched films

Epitaxial crystallization behavior of HDPE/iPP double layers under quenching and annealing conditions has been studied by means of transmission electron microscopy (TEM). The results obtained from bright field TEM observations indicate that in the as-quenched state the HDPE that is in direct contact with the surface of the oriented iPP substrate recrystallizes in the form of oriented crystallites dispersed on the iPP substrate. The electron diffraction results show that besides the two normally observed epitaxial orientations between HDPE and iPP, there is also a special orientation with [001](HDPE)parallel to[001](iPP). The HDPE which is in contact with the clean surface of a glass slide crystallizes in small lamellae with random orientation. In the boundary region, the epitaxially crystallized HDPE small lamellae stop right on the boundary of the oriented iPP film. If the quenched samples are annealed at 128 degrees C (below T-m of HDPE) for 2 h, the small HDPE crystals grow to thick lamellae in both areas. But only the epitaxial orientation of HDPE with [001](HDPE)parallel to[101](iPP) has been observed.

PREPARATION AND CHARACTERIZATION OF LANGMUIR-BLODGETT-FILMS OF PORPHYRINS WITHOUT LONG ALKYL CHAINS

A number of synthetic and natural source porphyrins without long alkyl chains have been examined in the form of monolayers and multilayers on solid substrates. These compounds formed stable solid condensed films with measured molecular areas compatible with a vertical or tilted orientation of these molecules on the substrate. Spectral study and fluorescence lifetime measurement, in particular, revealed the formation of aggregates as the main species in these films.

Chinikomycins A and B: Isolation, structure elucidation, and biological activity of novel antibiotics from a marine Streptomyces sp isolate M045

In our screening of marine Streptomycetes for bioactive principles, two novel antitumor antibiotics designated as chinikomycins A (2a) and B (2b) were isolated together with manumycin A (1), and their structures were elucidated by a detailed interpretation of their spectra. Chinikomycins A (2a) and B (2b) are chlorine-containing aromatized manumycin derivatives of the type 64-pABA-2 with an unusual para orientation of the side chains. They exhibited antitumor activity against different human cancer cell lines, but were inactive in antiviral, antimicrobial, and phytotoxicity tests.

Characteristics and Formation Mechanism of Polygonal Faults in Qiongdongnan Basin, Northern South China Sea

Based on high-resolution 3D seismic data, we document the polygonal faults within the Miocene Meishan (sic) Formation and Huangliu (sic) Formation of the Qiongdongnan (sic) basin, northern South China Sea. Within the seismic section and time coherent slice, densely distributed extensional faults with small throw and polygonal shape were identified in map view. The orientation of the polygonal faults is almost isotropic, indicating a non-tectonic origin. The deformation is clearly layer-bounded, with horizontal extension of 11.2% to 16%, and 13.2% on average. The distribution of polygonal faults shows a negative correlation with that of gas chimneys. The development of polygonal faults may be triggered by over-pressure pore fluid which is restricted in the fine-grained sediments of bathyal facies when the sediments is compacted by the burden above. The polygonal faults developed to balance the volumetric contraction and restricted extension. The product of hydrocarbon in the Meishan Formation may have contributed to the development of the polygonal faults. In the study area, it was thought that the petroleum system of the Neogene post-rift sequence is disadvantageous because of poor migration pathway. However, the discovery of polygonal faults in the Miocene strata, which may play an important role on the fluid migration, may change this view. A new model of the petroleum system for the study area is proposed.

Docking and molecular dynamics study on the inhibitory activity of coumarins on aldose reductase

In order to explore the inhibitory mechanism of coumarins toward aldose reductase (ALR2), AutoDock and Gromacs software were used for docking and molecular dynamics studies on 14 coumarins (CM) and ALR2 protease. The docking results indicate that residues TYR48, HIS110, and TRP111 construct the active pocket of ALR2 and, besides van der Waals and hydrophobic interaction, CM mainly interact with ALR2 by forming hydrogen bonds to cause inhibitory behavior. Except for CM1, all the other coumarins take the lactone part as acceptor to build up the hydrogen bond network with active-pocket residues. Unlike CM3, which has two comparable binding modes with ALR2, most coumarins only have one dominant orientation in their binding sites. The molecular dynamics calculation, based on the docking results, implies that the orientations of CM in the active pocket show different stabilities. Orientation of CM1 and CM3a take an unstable binding mode with ALR2; their conformations and RMSDs relative to ALR2 change a lot with the dynamic process. While the remaining CM are always hydrogen-bonded with residues TYR48 and HIS110 through the carbonyl O atom of the lactone group during the whole process, they retain the original binding mode and gradually reach dynamic equilibrium.

On the formation of vertically oriented MCM-22 zeolite crystal films

Growth of MCM-22 zeolite films on glass substrates was studied with the focus on the understanding of the unusual vertical crystal orientation. The films formed were characterized by scanning electron microscopy and X-ray diffraction. Separate thin disk-like MCM-22 crystals were found vertically oriented at the early crystallization stage. With crystallization the crystals grew into thick disks and finally into continuous films. The vertically oriented MCM-22 thin crystals could be developed from the orientation of columnar MCM-22 nuclei, which have larger parameters in their c-directions than those in a and b directions. The preferred orientation of MCM-22 nuclei and the fast growth rate in the layer direction are responsible for the vertical growth of MCM-22 zeolite films. (C) 2001 Elsevier Science B.V. All rights reserved.

可动凝胶渗流规律研究现状与发展方向

系统分析了可动凝胶与聚合物体系驱油机理和适用条件的区别以及在渗流规律方面的研究现状，总结出了聚合物凝胶一般分类及其特性。提出了研究可动凝胶渗流规律需要分段试验研究流变关系来确定视黏度的变化规律，需要确定视黏度下的相渗规律变化，需要对可动凝胶的整个驱替过程统一考虑，具体研究工作中应该进行分段研究的观点。该研究对指导可动凝胶渗流规律研究和可动凝胶在提高采收率中的应用具有一定的借鉴意义。