Theoretical study of the surface energy and electronic structure of pyrite FeS2 (100) using a total-energy pseudopotential method, CASTEP

The geometric and electronic structures of FeS(2) (100) surface have been studied by a quantum-mechanical calculation using a total-energy pseudopotential code, CASTEP. The (100) surface is very stable and does not give any significant geometric relaxation. The electronic structure of FeS(2) (100) surface is characterized by the appearance of new native surface states in the bulk band gap, which correspond to antibonding mixed Fea-Ssp(3) states. These surface states play an important role as mediators of electron transfer on both anodic and cathodic sites in the incipient oxidation of pyrite. Moreover, the (100) surface has small band gaps and shows some metallic character. It is predicted that the rate of cathodic reductive reaction of O(2) in the incipient oxidation of pyrite is much faster than previously considered. The transport of electrons from the anodic sites to the cathodic sites on the (100) surface is faster and hole injection of anodic sites is not the rate-determining step. So we can deduce that the rate-determining step of incipient oxidation for pyrite consists of both electron transfer of pyrite/aqueous O(2) interface and the splitting of H(2)O.     

Determination of lactate or oxalate using injected lactate oxidase and peroxidase by capillary electrophoresis with UV detection

Two reactions, catalyzed by lactate oxidase (LO) and peroxidase, are initiated by a single injection of the enzymes and the substrate 2,2'-azino-bis(3-ethylene-thiazoline-6-sulfonic acid) (ABTS) into the capillary previously filled with the sample (lactate or lactate-oxalate mixture) and the run buffer containing NADH. The oxidized ABTS product upon reaction with NADH is converted to NAD(+) which is separated and detected in less than 2 min at 266 nm with a sample throughput of 7 min (including wash steps between samples). Simplex trade mark software is used to optimize the enzyme concentrations and reaction temperature. Consumption of the more expensive LO enzyme is only 1.4 x 10(-3) U per assay assuming 27 nL per injection. Linearity is established within the range from 0.0025 to 1 mM with R(2) of 0.9982. Recoveries of lactate from five spiked serum samples averaged 101%. Application of this method for the determination of oxalate as an inhibitor of LO is demonstrated.     

Fe(II) in different macrocycles: electronic structures and properties

A theoretical comparative study of complexes of porphyrin (P), porphyrazine (Pz), phthalocyanine (Pc), porphycene (Pn), dibenzoporphycene (DBPn), and hemiporphyrazine (HPz) with iron (Fe) has been carried out using a density functional theory (DFT) method. The difference in the core size and shape of the macrocycle has a substantial effect on the electronic structure and properties of the overall system. The ground states of FeP and FePc were identified to be the 3A2g [(d(xy))2(d(z)2)2(d(pi))2] state, followed by 3E(g) [(d(xy))2(d(z)2)1(d(pi))3]. For FePz, however, the 3E(g)-3A2g energy gap of 0.02 eV may be too small to distinguish between the ground and excited states. When the symmetry of the macrocycle is reduced from D4h to D2h, the degeneracy of the d(pi) (d(xz), d(yz)) orbitals is removed, and the ground state becomes 3B2g [(d(xy))2(d(z)2)1(d(yz))2(d(xz))1] or 3B3g [...(d(yz))1(d(xz))2] for FePn, FeDBPn, and FeHPz. The calculations also show how the change of the macrocycle can influence the axial ligand coordination of pyridine (Py) and CO to the Fe(II) complexes. Finally, the electronic structures of the mono- and dipositive and -negative ions for all the unligated and ligated iron macrocycles were elucidated, which is important for understanding the redox properties of these compounds. The differences in the observed electrochemical (oxidation and reduction) properties between metal porphycenes (MPn) and metal porphyrins (MP) can be accounted for by the calculated results (orbital energy level diagrams, ionization potentials, and electron affinities).     

LiM2(NCN)Br3 (M = Sr,Eu): Synthesis and Crystal Structures of Solid‐State Carbodiimides with Empty Tetrahedral Metal Entities

Two solid‐state carbodiimide compounds, LiM₂(NCN)Br₃ (M = Sr, Eu), with characteristic empty tetrahedral M₄ entities have been synthesized using a flux route, and their structures were determined by single‐crystal X‐ray diffraction. The new phases LiSr₂(NCN)Br₃ and LiEu₂(NCN)Br₃ are isotypical with the corresponding iodides and crystallize in the cubic system (( , Z = 16) but with smaller unit cells (a = 14.641(1) Å for LiSr₂(NCN)Br₃ and 14.572(1) Å for LiEu₂(NCN)Br₃). The extended structures comprise two interpenetrating three‐dimensional networks: the first one is built from isolated M₄ tetrahedra capped by NCN^2? anions on their triangular faces while the second is made from vertex‐sharing LiBr₆ octahedra. The linear NCN^2? anions exhibit the symmetrical carbodiimide shape and serve as linkers between the tetrahedral entities.     

Synthesis, Structure and Conductivity of the New Charge-transfer Salt (ET)_2(CH_2=CH-CH_2-SO_3)·H_2O

ET is one of the most famous electron-donor molecules, which forms charge-transfer complexes (abbr. CT-complexes) with various types of counterions. These complexes have received intense attention because a wide range of physical properties such as conductivity and superconductivity1, ferromagnetism2-4 and nonlinear optical properties5 was found in these materials. Although the majority of the ET-based CT-complexes were prepared by combining with inorganic counterions, CT-complexes with o…     

Synthesis and mesomorphic properties of n-butyl-4- [4-((4-n-alkoxyl-tetrafluorophenyl)ethynyl)benzyloxy]benzoates

A homologous series of n-butyl-4-[4-((4-n-alkoxyl-tetrafluorophenyl)ethynyl)benzyloxy]benzoates have been synthesized.Their phase transition temperatures have also measured by polarizing textural observation and confirmed by DSC.     

Effects of soluble surfactants on the deformation and breakup of stretching liquid bridges

Surfactants are routinely used to control the breakup of drops and jets in many applications such as inkjet printing, crop spraying, and DNA or protein microarraying. The breakup of surfactant-free drops and jets has been extensively studied. By contrast, little is known about the closely related problem of interface rupture when surfactants are present. Solutions of a nonionic surfactant, pentaethylene glycol monododecyl ether, or C12E5, in water and in 90 wt % glycerol/water are used to show the effects of surfactant and viscosity on the deformation and breakup dynamics of stretching liquid bridges. Equilibrium surface tensions for both solutions can be fitted with the Langmuir-Szyskowski equation. All experiments have been done at 24 degrees C. The critical micelle concentrations for C12E5 are 0.04 and 0.4 mM in water and the glycerol/water solution, respectively. With high-speed imaging, the dynamic shapes of bridges held captive between two rods of 3.15 mm diameter are captured and analyzed with a time resolution of 0.1-1 ms. The bridge lengths are 3.15 mm initially and about 5-7 mm at pinch-off. Breakup occurs after stretching for about 0.2-0.3 s, depending on the solution viscosity and the surfactant concentration. When the liquid bridges break up, the volume of the sessile drop left on the bottom rod is about 3 times larger than that of the pendant drop left on the top rod. This asymmetry is due to gravity and is influenced by the equilibrium surface tensions. Surfactant-containing low-viscosity water bridges are shown to break up faster than surfactant-free ones because of the effect of gravity. With or without surfactant, water bridges form satellite drops. Surfactant-containing high-viscosity glycerol/water bridges break up more slowly than surfactant-free ones because of strong viscous effects. Moreover, the shapes of the sessile drops close to breakup exhibit a "pear-like" tip; whether a satellite forms depends on the surface age of the bridge before stretching commences. These unexpected effects arising from the addition of surfactants are due to the capillary pressure reduction and Marangoni flows linked to dynamic surface tension.     

The effect of phenyl substituents on the release rates of esterase-sensitive coumarin-based prodrugs

A coumarin-based prodrug system has been recently developed in our laboratory for the preparation of esterase-sensitive prodrugs of amines, peptides, and peptidomimetics. The drug release rates from this prodrug system were found to be dependent on the structural features of the drug moiety. In certain cases, the release can be undesirably slow for drugs that are secondary amines with relatively high pKa's. Aimed at finding ways to manipulate the release rates to suit the need of different drugs, we have examined the effect of the phenyl ring substitutions on the release kinetics of such prodrugs and found that appropriately positioned alkyl substituents on the phenyl ring could help to facilitate the release by as much as 16-fold. Therefore, introduction of alkyl substituents on the phenyl ring should allow us to manipulate the release rates and, therefore, time profiles for different drugs.     

振动噪声等高图的电驱动桥噪声预测及优化*

在项目开发前期通过优化电驱动桥扭矩特性的设计,可以规避噪声大问题。根据电驱动桥台架在对应扭矩下的振动噪声特性,提出了一套稳定高效的测试流程和分析方法。首先设计了一套完整的试验流程,制定了精准的数据分析方法。然后绘制出能够全面反映电驱动桥振动噪声特性的等高图。最后利用电驱动桥台架的振动噪声等高图,准确评估电驱动桥加速工况下振动噪声风险,为主机厂和电驱动桥零部件企业提供电驱动桥扭矩特性设计前期指导。利用该方法成功识别到某电驱动桥匀速及加速工况下电机及齿轮的啸叫问题。通过优化电驱动桥扭矩特性设计,电机48阶噪声峰值降低了8.5dB(A),确认该方法准确可靠,具备推广应用价值。     

Synthesis of PNIPAAm-g-P4VP Microgel as Draw Agent in Forward Osmosis by RAFT Polymerization and Reverse Suspension Polymerization to Improve Water Flux

Microgels have unique and versatile properties allowing their use in forward osmosis areas as a draw agent. In this contribution, poly(4-vinylpyridine) (P4VP) was synthesized via RAFT polymerization and then grafted to a poly(N-Isopropylacrylamide) (PNIPAAm) crosslinking network by reverse suspension polymerization. P4VP was successfully obtained by the quasiliving polymerization with the result of nuclear magnetic resonance and gel permeation chromatography characterization. The particle size and particle size distribution of the PNIPAAm-g-P4VP microgels containing 0, 5, 10, 15 and 20 wt% P4VP were measured by means of a laser particle size analyzer. It was found that all the microgels were of micrometer scale and the particle size was increased with the P4VP load. Inter/intra-molecular-specific interactions, i.e., hydrogen bond interactions were then investigated by Fourier infrared spectroscopy. In addition, the water flux measurements showed that all the PNIPAAm-g-P4VP microgels can draw water more effectively than a blank PNIPAAm microgel. For the copolymer microgel incorporating 20 wt% P4VP, the water flux was measured to be 7.48 L∙m⁻²∙h⁻¹.