Particle-swarm structure prediction on clusters

We have developed an efficient method for cluster structure prediction based on the generalization of particle swarm optimization (PSO). A local version of PSO algorithm was implemented to utilize a fine exploration of potential energy surface for a given non-periodic system. We have specifically devised a technique of so-called bond characterization matrix (BCM) to allow the proper measure on the structural similarity. The BCM technique was then employed to eliminate similar structures and define the desirable local search spaces. We find that the introduction of point group symmetries into generation of cluster structures enables structural diversity and apparently avoids the generation of liquid-like (or disordered) clusters for large systems, thus considerably improving the structural search efficiency. We have incorporated Metropolis criterion into our method to further enhance the structural evolution towards low-energy regimes of potential energy surfaces. Our method has been extensively benchmarked on Lennard-Jones clusters with different sizes up to 150 atoms and applied into prediction of new structures of medium-sized Li(n) (n = 20, 40, 58) clusters. High search efficiency was achieved, demonstrating the reliability of the current methodology and its promise as a major method on cluster structure prediction.     

Solvothermal synthesis of zincblende and wurtzite CuInS2 nanocrystals and their photovoltaic application

We report a simple solvothermal synthesis approach to the growth of CuInS(2) nanocrystals with zincblende- and wurtzite-phase structures. Zincblende nanocrystals with particle sizes of 10-20 nm were produced using oleylamine as the solvent. When ethylenediamine was used as the solvent, similarly sized wurtzite nanocrystals with some degree of particle aggregation were formed. Use of a mixture of these solvents gave products with mixed phases including some polyhedral nanostructures. The crystal phases of these nanocrystals were carefully determined by X-ray diffraction and transmission electron microscopy analysis. All the samples exhibit strong absorption from the entire visible light region to the near-infrared region beyond 1300 nm. Pure-phase zincblende and wurtzite CuInS(2) nanocrystals were employed as ink in the fabrication of solar cells. The spray-coated nanocrystal layer was subjected to a selenization process. A power conversion efficiency of ~0.74% and a good external quantum efficiency profile over broad wavelengths have been measured. The results demonstrate that wurtzite and zincblende CuInS(2) nanocrystals may be attractive precursors to light-absorbing materials for making efficient photovoltaic devices.     

3-D phase diagram of HPC/H2O/H3PO4 tertiary system

A 3-D phase diagram of the HPC/H₂O/H₃PO₄ tertiary system against various temperatures was established. Four distinct phases—the completely separated phase (S), the cloudy suspension phase (CS), the liquid crystalline miscible phase (LC), and the isotropically miscible phase (I)—were identified. The S phase shrank as the temperature increased, revealing that the HPC solubility increased with temperature, regardless of the LCST (lower critical solution temperature) characteristic. The addition of H₃PO₄ suppressed the formation of LC phase. However, as the temperature was raised sharply from 50 to 70?°C, the LC phase could only be maintained at high H₃PO₄ concentration region; it was a triangular shape, and the top apex of the triangle was the temperature-invariant L* point (HPC/H₂O/H₃PO₄ 38/9/53?wt%). The CS phase expanded considerably into the H₂O-rich but H₃PO₄-poor region when the temperature continued to increase over 48?°C. The LCST points of the CS phase that contained 0 and 15?wt% of H₃PO₄ were 34 and 38?°C, respectively. These CS results demonstrate that H₃PO₄ suppresses the occurrence of LCST behavior. Additionally, the binodal curve exhibits a weak or even zero dependence of binodal temperature on the HPC concentration at HPC concentrations of less than 30?wt% in a pure water system. A hypothesis concerning the sequential desorption of water molecules was proposed to explain such behavior.     

蒸馏法测定一次性筷子中二氧化硫浸出量的不确定度评定

依照GB 19790.1-2005,GB 19790.2-2005和GB/T 5009.34-2003(第二法),选取含量接近法规限值的代表性样品,从基准物质和标准滴定溶液溯源,探索测定一次性筷子中二氧化硫浸出量的数学模型,对检测过程中引入的不确定度进行了分类和量化,系统地评定了各个不确定度分量,得到该方法的相对标准不确定度为0.0043.     

Synthesis and Characterization of Ultraviolet Light-Emitting Organic Acids

Three ultraviolet light-emitting organic acids of 3,3′-(4-phenyl-4H-1,2,4-triazole-3,5-diyl)dibenzoic acid (Tz-1), 4,4′,4″-(4H-1,2,4-triazole-3,4,5-triyl)tribenzoic acid (Tz-2), and 4,4′-(4-(4′-carboxy-[1,1′-biphenyl]-4-yl)-4H-1,2,4-triazole-3,5-diyl)dibenzoic acid (Tz-3) were successfully synthesized and fully characterized by the ¹H NMR, the IR absorption spectra, and the X-ray single crystal diffraction. It was found that Tz-1, Tz-2, and Tz-3 could give out the ultraviolet photoluminescent spectra centered at 369 nm, 365 nm and 350 nm, respectively. The luminescence quantum yields of Tz-1 and Tz-2 were measured to be 0.20 and 0.14, respectively. Additionally, the density functional theory (DFT) and the time-dependent DFT calculations were also carried out for Tz-1, Tz-2, and Tz-3.     

Synthesis of Ag2O nanocrystals with systematic shape evolution from cubic to hexapod structures and their surface properties

We report the development of a facile method for the synthesis of Ag(2)O crystals with systematic shape evolution from cubic to edge- and corner-truncated cubic, rhombicuboctahedral, edge- and corner-truncated octahedral, octahedral, and hexapod structures by mixing AgNO(3), NH(4)NO(3), and NaOH at molar ratios of 1:2:11.8. A sufficient volume of NaOH solution was first added to a mixture of AgNO(3) and NH(4)NO(3) solution to promote the formation of Ag(NH(3))(2)(+) complex ions and the growth of Ag(2)O nanocrystals with good morphological control. The crystals are mostly submicrometer-sized. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy characterization has been performed to determine the crystalline surface facets. A band gap value of approximately 1.45 eV has been found for the octahedral Ag(2)O crystals. By changing the molar ratios of AgNO(3)/NH(4)NO(3)/NaOH to 1:2:41.8, corner-depressed rhombicuboctahedra and elongated hexapods were obtained as a result of enhanced crystal growth along the [100] directions. Smaller nanocubes with average sizes of approximately 200 and 300 nm and octapods can also be prepared by adjusting the reagent molar ratios and their added volumes. Both the octahedra and hexapods with largely silver atom-terminated {111} surface facets responded repulsively and moved to the surface of the solution when dispersing in a solution of positively charged methylene blue, but can be suspended in a negatively charged methyl orange solution. The cubes and octapods, bounded by the {100} faces, were insensitive to the molecular charges in solution. The dramatic facet-dependent surface properties of Ag(2)O crystals have been demonstrated.     

Circular permutation of the starch-binding domain: inversion of ligand selectivity with increased affinity

Proteins containing starch-binding domains (SBDs) are used in a variety of scientific and technological applications. A circularly permutated SBD (CP90) with improved affinity and selectivity toward longer-chain carbohydrates was synthesized, suggesting that a new starch-binding protein may be developed for specific scientific and industrial applications.     

Organometallic modification approach to the control of push-pull architectures: Synthesis, properties and radical polymerization of chromium N-vinylcarbazole derivatives

In an effort to combine the donor character of the carbazole unit with the electron-withdrawing nature of the chromiumtricarbonyl moiety, which can be further modified by exchange of the CO ligand, a new series of vinyl-type monomers with organometallic push-pull chromophores, (N-vinylcarbazole)Cr(CO)₂L (L = CO (2), PPh₃ (4), (5)) and (N-vinylcarbazole)bisCr(CO)₃ (3), have been synthesized and isolated, wherein 2 could be converted into 3 under appropriate conditions. All compounds were characterized spectroscopically, and X-ray crystal structure analyses were performed for 2-4. The coordination-induced geometrical changes occur predominantly on the N-center and its attached double bond. PPh₃ replaces a CO group leading to the N-vinyl double bond length shortening from 1.274 (12) to 1.245 (9) Å. The distance of Cr from the carbazole plane, which allows estimates of the strength of the metal-ligand π-bonding, is shorter in 3 than in 2 as a result of an electronic communication between the two Cr(CO)₃ groups on each aryl ring of carbazole molecule. Electronic absorption and fluorescence spectral features of these complexes have been studied in terms of the electronic nature of the ligands. The change from 2 to 3 causes a subtle red-shift of the absorption bands due to the electronic transitions within dinuclear-carbazole ring system. The polymerization studies of these complexes under free-radical conditions lead to a better understanding of how the organometallic moiety affects the vinyl polymerization. The intriguing effect of the organometallic moiety on the intrachain excimer formation in the resultant polymers have been shown to be likely.     

Energy transfer of highly vibrationally excited azulene: collisions between azulene and krypton

The energy-transfer dynamics between highly vibrationally excited azulene molecules and Kr atoms in a series of collision energies (i.e., relative translational energies 170, 410, and 780 cm(-1)) was studied using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. "Hot" azulene (4.66 eV internal energy) was formed via the rapid internal conversion of azulene initially excited to the S4 state by 266-nm photons. The shapes of the collisional energy-transfer probability density functions were measured directly from the scattering results of highly vibrationally excited or hot azulene. At low enough collision energies an azulene-Kr complex was observed, resulting from small amounts of translational to vibrational-rotational (T-VR) energy transfer. T-VR energy transfer was found to be quite efficient. In some instances, nearly all of the translational energy is transferred to vibrational-rotational energy. On the other hand, only a small fraction of vibrational energy is converted to translational energy (V-T). The shapes of V-T energy-transfer probability density functions were best fit by multiexponential functions. We find that substantial amounts of energy are transferred in the backward scattering direction due to supercollisions at high collision energies. The probability for supercollisions, defined arbitrarily as the scattered azulene in the region 160 degrees 2000 cm(-1) is 1% and 0.3% of all other collisions at collision energies 410 and 780 cm(-1), respectively.     

Generation and characterization of highly vibrationally excited molecular beam

A simple method to generate and characterize a pure highly vibrationally excited azulene molecular beam is demonstrated. Azulene molecules initially excited to the S4 state by 266-nm UV photons reach high vibrationally excited levels of the ground electronic state upon rapid internal conversion from the S4 electronically excited state. VUV laser beams at 157 and 118 nm, respectively, are used to characterize the relative concentrations of the highly vibrationally excited azulene and the rotationally and vibrationally cooled azulene in the molecular beam. With a laser intensity of 34 mJ/cm2, 75% of azulene molecules absorb a single 266-nm photon and become highly vibrationally excited molecules. The remaining ground-state azulene molecules absorb two or more UV photons, ending up either as molecular cations, which are repelled out of the beam by an electric field, or as dissociation fragments, which veer off the molecular-beam axis. No azulene without absorption of UV photons is left in the molecular beam. The molecular beam that contains only highly vibrationally excited molecules and carrier gas is useful in various experiments related to the studies of highly vibrationally excited molecules.