Intermolecular Se···I Interactions Identified in Cu11(μ9‐Se)(μ3‐I)3[Se2P(OEt)2]6 Form a One Dimensional Polymeric Chain

The undecanuclear copper cluster Cu₁₁(μ9‐Se)(μ₃‐I)₃[Se₂P(OEt)₂]₆ 1 , has been isolated along with Cu₈(μ₈‐Se)[Se₂P(OEt)₂]₆ 2 , from the reaction of NH₄Se₂P(OEt)₂, Cu(CH₃CN)₄PF₆, and Bu₄NI in a molar ratio of 3:2:2 in diethyl ether. The molecular formulation of 1 was confirmed by elemental analysis, positive FAB mass spectrometry, multinuclear NMR (¹H, ³¹P, and ⁷⁷Se), and X‐ray diffraction. In cluster 1 eleven copper atoms adopt the geometry of a 3,3,4,4,4‐pentacapped trigonal prism with a selenium atom in the center. The coordination geometry for the central, nonacoordinated selenium atom is tricapped trigonal prismatic. In addition, the central core Cu₁₁Se is further stabilized by three iodides and six dsep ligands. Besides, weak inter‐molecular Se···I interactions (3.949–3.972 Å) are uncovered and form a one dimensional polymeric chain.     

Synthesis, characterization and spectroscopic studies of cyclometalated platinum(II) complexes containing meta-bis(2-pyridoxy)benzene

A series of mononuclear and binuclear cyclometalated platinum(II) complexes containing new terdentate meta-bis(2-pyridoxy)benzene ligands: 3,5-bis(2-pyridoxy)toluene (L₁H) and 3,5-bis(2-pyridoxy)-2-dodecylbenzene (L₂H): [Pt(L₁)Cl] (1), [Pt(L₂)Cl] (2), [Pt(L₁)(CH₃CN)](ClO₄) (3), {[Pt(L₁)]₂(μ-dppm)}(ClO₄)₂ (4), {[Pt(L₂)]₂(μ-dppm)}(ClO₄)₂ (5), {[Pt(L₁)]₂(μ-pyrazole)}(ClO₄) (6), {[Pt(L₂)]₂(μ-pyrazole)}(ClO₄) (7), {[Pt(L₁)]₂(μ-imidazole)}(ClO₄) (8) and {[Pt(L₂)]₂(μ-imidazole)}(ClO₄) (9), have been synthesized and characterized. These ligands are coordinated to platinum(II) in a “pincer”-like manner and the presence of pyridyl donors enhances the availability of the ligand π^∗ orbitals for electronic transition. Spectroscopic properties of these cyclometalated complexes were studied. While the non-coplanar nature of the ligands hinders ligand-ligand and metal-metal interactions in these cyclometalated complexes, the presence of long hydrocarbon side chain on ligand L₂H seems to alleviate such hindrance. Intermolecular π-π, and possibly Pt-Pt interactions were observed in complex 2 at high concentration.     

Trichodiene Synthase: Synthesis and Inhibition Kinetics of 12‐Fluoro‐farnesylphosphonophosphate for Sesquiterpene Cyclases

trans, trans‐Farnesyl diphosphate (FPP) serves as a universal substrate for a large family of sesquiterpene cyclases that are responsible for biosynthesis of more than 300 structurally diverse sesquiterpenes in nature. A new FPP substrate analogue, 12‐fluoro‐farnesylphosphonophosphate (12‐F‐F‐CH₂PP), was synthesized in this paper for applications on kinetic and mechanistic studies of the enzyme family. Trichodiene synthase (TS), a sesquiterpene cyclase, catalyzes the conversion of trans, trans‐farnesyl diphosphate (FPP) to trichodiene. 12‐F‐F‐CH₂PP was tested as a potential inhibitor of TS. Inactivation and inhibition kinetic experiments showed that 12‐F‐F‐CH₂PP was not a mechanism‐based inactivator for TS; instead, a mixed‐type reversible inhibition was observed with inhibition constants K_i1 = 2.33 ± 0.50 μM and K_i2 = 25.80 ± 7.70 μM, values close to those previously determined for farnesylphosphonophosphate, K_i1 = 3.25 μM and K_i2 = 9.10 μM. Although 12‐F‐F‐CH₂PP did not irreversibly inactivate TS, this new analogue serves as a potential active‐site directed inactivator and mechanistic probe of other sesquiterpene cyclases and FPP‐utilizing enzymes, which utilize FPP as a common acyclic substrate.     

Isolation and determination of toxic congeners of polychlorinated biphenyls in environmental samples

A Method has been developed for the separation and enrichemen of there non-ortho, eight mono-ortho, and di-ortho substituted polychlorinated biphenyls (PCBs) from Aroclor formulations and environmental samples. The fractionation is accomplished using high performance liquid chromatography (HPLC) with a 2-(1-pyrenyl)ethyldimethylsilysily silca column. GC-MSD with an optimized temperature program was used for quantitation, Hexane, pentane, cyclohexane, iso-octane, and 2-propanol were tested as a mobile phase for the isolation of the thirteen target PCBs in a Aroclor 1242, 1254, and 1260 (1:1:1) misture, Pentane at room temperature with a slow rate of 0.7 ml/min is the condition of choice. The average recovery of thirteen target PCBs spiked in the Aroclor mixture is 99.5% with an average relative standard deviation of 4.5%. The average method detection limit is 8pg/μl. Targer PCBs in the reference solis, incinarator ash, and sediment samples were measured.     

Planar Schlegel Diagram's Illustrations of Fullerene's Structural Changes and Fullerene's Cage Interactions with Metals and Hydrogens

Two-dimensional planar Schlegel diagrams are used to displace fullerenes and to exhibit cage cluster's vertices, faces and edges as well as cluster's extensions and changes such as isomerization, addition, elimination etc. The Schlegel diagrams also show the possible π bondings and free π radicals to determine symmetry group structures as well as to interact with the corresponding number of electrons in metals. The diagrams also show the possible addition of outside hydrogens and their movements.     

Microgel formation in the free radical crosslinking polymerization of ethylene glycol dimethacrylate (EGDMA). II. Simulation

The simulation of free radical crosslinking polymerizations of multifunctional monomer by a percolation model was performed on a two-dimensional lattice with periodical boundaries. The model was formulated in such a way that a variety of monomers, translational diffusion of monomer and polymer molecules, segmental diffusion of polymer, shielding effects, microgel formation, and unequal reactivities of vinylene bonds can be considered. Simulation results of the 2-D model agreed well with those of a 3-D model. The percolation model was able to qualitatively verify several experimental results. © 1995 John Wiley & Sons, Inc.     

Optical excitation and absorption spectra of C50Cl10

C50Cl10 [S. Y. Xie et al., Science 304, 699 (2004)] has been synthesized in large quantities enabling the capture of the labile fullerene C50. In this Communication, we report ab initio calculations on the optical excitation and absorption spectra of C50Cl10. We successfully explain and assign the measured UV-visible absorption spectrum of C50Cl10. The first singlet excitation for C50Cl10 is optically forbidden, and its optical absorption gap is redshifted by 0.6 eV (110 nm) relative to that of C60. We demonstrate that passivating C50 with 10 hydrogen atoms and replacing one Cl in C50Cl10 by one methoxy group lead to 100 nm blueshift and 90 nm redshift of the optical gap predicted for C50Cl10, respectively, suggesting C50 derivatives are suitable for tunable optical applications.     

Biohydrogen Production from Mushroom Cultivation Waste by Anaerobic Solid‐state Fermentation

Mushroom cultivation waste (MCW) is a polypropylene bag stuffed with wood flour and nutrients for growing mushroom, which is a feasible feedstock for anaerobic biohydrogen production owing to its abundant availability, high organic and nutrient content. This study optimized the seed inoculum from various waste sludges (sewage sludge, cow dung and pig slurry), nutrient addition and operation conditions (moisture content and MCW powder particle size) for maximal biohydrogen production by solid‐state fermentation (SSF). SSF batch test was operated at a MCW 3 g total volatile solid (TVS)/L, temperature 55 °C and rotation speed of 15 rpm with a vertical rotative shaker. The peak hydrogen production performance of hydrogen production rate (HPR) 9.50 mol H₂/kg‐d and hydrogen yield (HY) 0.29 mmol H₂/g TVS) are obtained using sewage sludge 2 seed inoculum, nutrients addition, moisture content 70 % and particle size of 1.190～0.590 mm. The results show that the MCW has the potential for hydrogen production by anaerobic mixed microflora using solid‐state fermentation. The bioenergy of 1842 kWh while using SSF to conver MCW to produce biohydrogen and it could reduce CO₂ emission of 114–178 kg per year comparing using fossil fuel such as coal, fuel oil and natural gas.     

D3R grand challenge 2015: Evaluation of protein–ligand pose and affinity predictions

The Drug Design Data Resource (D3R) ran Grand Challenge 2015 between September 2015 and February 2016. Two targets served as the framework to test community docking and scoring methods: (1) HSP90, donated by AbbVie and the Community Structure Activity Resource (CSAR), and (2) MAP4K4, donated by Genentech. The challenges for both target datasets were conducted in two stages, with the first stage testing pose predictions and the capacity to rank compounds by affinity with minimal structural data; and the second stage testing methods for ranking compounds with knowledge of at least a subset of the ligand–protein poses. An additional sub-challenge provided small groups of chemically similar HSP90 compounds amenable to alchemical calculations of relative binding free energy. Unlike previous blinded Challenges, we did not provide cognate receptors or receptors prepared with hydrogens and likewise did not require a specified crystal structure to be used for pose or affinity prediction in Stage 1. Given the freedom to select from over 200 crystal structures of HSP90 in the PDB, participants employed workflows that tested not only core docking and scoring technologies, but also methods for addressing water-mediated ligand–protein interactions, binding pocket flexibility, and the optimal selection of protein structures for use in docking calculations. Nearly 40 participating groups submitted over 350 prediction sets for Grand Challenge 2015. This overview describes the datasets and the organization of the challenge components, summarizes the results across all submitted predictions, and considers broad conclusions that may be drawn from this collaborative community endeavor.     

Spectral characteristics for a fiber grating external cavity laser

A numerical investigation has been carried out on the influence of the antireflection (AR) coating of laser, the coupling efficiency of laser and fiber (), and the reflectivity of fiber grating (R _g) on the side-mode suppression ratio (SMSR) of the fiber grating external cavity laser (FGECL). The FGECL was fabricated by the assembly of the multimode Fabry–Perot (FP) laser chip and fiber grating. The results showed that the FGECL with a lower AR coating, higher and R _g exhibited a better SMSR. A comparison of the SMSR dependence on the and R _g showed that SMSR increased more rapidly with increasing than SMSR for R _g. These spectral characteristic studies of the SMSR dependence on the device parameters of the AR coating, , and R _g may provide useful device designs for the practical fabrication of a FGECL for use in dense wavelength division multiplexing (DWDM) applications.