Role of (La, Gd) co-doping on the enhanced dielectric and magnetic properties of BiFeO3 ceramics

The effect of the La3+ and Gd3+ co-doping on the structure, electric and magnetic properties of BiFeO3 (BFO) ceramics are investigated. For the compositions (x=0 and 0 <= y <= 0.15) in the perovskite structured LaxGdyBi1-xFeO3 system, a tiny residual phase of Bi2Fe4O9 is noticed. Such a secondary phase is suppressed with the incorporation of `La' content (x). The magnitude of dielectric constant (epsilon(r) increases progressively by increasing the `La' content from x=0 to 0.15 with a remarkable decrease of dielectric loss. For x=0.15, the system LaxGdyBi1-x(x+y)FeO3 exhibits highest remanent magnetization (M-r) of 0.18 emu/g and coercive magnetic field (H-c) of similar to 1 Tin the presence of external magnetic field of 9 T at 300 K. The origin of enhanced dielectric and magnetic properties of LaxGdyBil (x+y)Fe03 and the role of doping elements, La3+, Gd3+ has been discussed. (C) 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Structural studies on chimeric Sesbania mosaic virus coat protein: Revisiting SeMV assembly

The capsid protein (CP) of Sesbania mosaic virus (SeMV, a T=3 plant virus) consists of a disordered N-terminal R-domain and an ordered S-domain. Removal of the R-domain results in the formation of T=1 particles. In the current study, the R-domain was replaced with unrelated polypeptides of similar lengths: the B-domain of Staphylococcus aureus SpA, and SeMV encoded polypeptides P8 and P10. The chimeric proteins contained T=3 or larger virus-like particles (VLPs) and could not be crystallized. The presence of metal ions during purification resulted in a large number of heterogeneous nucleoprotein complexes. N Delta 65-B (R domain replaced with B domain) could also be purified in a dimeric form. Its crystal structure revealed T=1 particles devoid of metal ions and the B-domain was disordered. However, the B-domain was functional in N Delta 65-B VLPs, suggesting possible biotechnological applications. These studies illustrate the importance of N-terminal residues, metal ions and robustness of the assembly process. (C) 2015 Elsevier Inc. All rights reserved.

Multiple oligomeric structures of a bacterial small heat shock protein

Small heat shock proteins are ubiquitous molecular chaperones that form the first line of defence against the detrimental effects of cellular stress. Under conditions of stress they undergo drastic conformational rearrangements in order to bind to misfolded substrate proteins and prevent cellular protein aggregation. Owing to the dynamic nature of small heat shock protein oligomers, elucidating the structural basis of chaperone action and oligomerization still remains a challenge. In order to understand the organization of sHSP oligomers, we have determined crystal structures of a small heat shock protein from Salmonella typhimurium in a dimeric form and two higher oligomeric forms: an 18-mer and a 24-mer. Though the core dimer structure is conserved in all the forms, structural heterogeneity arises due to variation in the terminal regions.

A Deep-Blue Electroluminescent Device Based on a Coumarin Derivative

The design and synthesis is reported of 7-(9H-carbazol-9-yl)-4-methylcoumarin (Cz-Cm), comprising a carbazole donor moiety and a 4-methylcoumarin acceptor unit, for use in a blue organic light-emitting diode. A detailed solid state, theoretical and spectroscopic study was performed to understand the structure-property relationships. The material exhibits deep-blue emission and high photoluminescence quantum yield both in solution and in a doped matrix. A deep-blue electroluminescence emission at 430nm, a maximum brightness of 292cdm(-2) and an external quantum efficiency of 0.4% was achieved with a device configured as follows: ITO/NPD (30nm)/TCTA (20nm)/CzSi(10nm)/10wt% Cz-Cm:DPEPO (10nm)/TPBI (30nm)/LiF (1nm)/Al ITO=indium tin oxide, NPD=N,N-di(1-naphthyl)-N,N-diphenyl-(1,1-biphenyl)-4,4-diamine, TCTA=tris(4-carbazoyl-9-ylphenyl)amine, CzSi=9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole, DPEPO=bis2-(diphenylphosphino)phenyl]ether oxide, TPBI=1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene].

Mass spectrometric analysis of dimer-disrupting mutations in Plasmodium triosephosphate isomerase

Electrospray ionization mass spectrometry (ESI MS) under nanospray conditions has been used to examine the effects of mutation at two key dimer interface residues, Gln (Q) 64 and Thr (T) 75, in Plasmodium falciparum triosephosphate isomerase. Both residues participate in an intricate network of intra- and intersubunit hydrogen bonds. The gas phase distributions of dimeric and monomeric protein species have been examined for the wild type enzyme (TWT) and three mutants, Q64N, Q64E, and 175S, under a wide range of collision energies (40-160 eV). The results established the order of dimer stability as TWT > T75S > Q64E similar to Q64N. The mutational effects on dimer stability are in good agreement with the previously reported estimates, based on the concentration dependence of enzyme activity. Additional experiments in solution, using inhibition of activity by a synthetic dimer interface peptide, further support the broad agreement between gas phase and solution studies. (C) 2016 Elsevier Inc. All rights reserved.

基体对氮化钛膜的微力学和摩擦性能的影响

采用等离子电弧沉积的方法分别在GT35和40CrNiMo钢上沉积厚约为0.5mm 的TiN膜。为了检测成膜质量，在较宽的载荷范围内分别使用显微硬度、纳米压痕和纳米划痕技术表征钢基材和TiN/基材的微机械和摩擦性能。同TiN/40CrNiMo相比，TiN/GT35的硬度高和固体润滑效果显著，GT35是较为理想的基体材料。对这种亚微米厚的膜，纳米压痕技术和纳米划痕技术能提供丰富的近表面的弹塑性变形、断裂和摩擦等的信息。

氮化钛沉积膜的摩擦性能研究

采用等离子电弧沉积法在9Cr18钢表面制备了厚约0.5 μm的TiN薄膜，通过显微硬度测试以及纳米压痕和纳米划痕试验，对比考察了9Cr18钢及其表面TiN薄膜的机械和摩擦性能。结果表明，9Cr18钢及其表面TiN沉积膜的纳米硬度分别为8GPa和38GPa，弹性模量分别为250GPa和580 GPa，9Cr18、TiN和有机薄膜的摩擦系数分别为0.40、0.12和、0.10；TiN沉积膜可显著提高基体钢的承载和耐磨能力。

Characterization of a liquid crystal microlens array using multiwalled carbon nanotube electrodes.

Reconfigurable liquid crystal microlenses employing arrays of multiwalled carbon nanotubes (MWNTs) have been designed and fabricated. The cells consist of arrays of 2 microm high MWNTs grown by plasma-enhanced chemical vapor deposition on silicon with a top electrode of indium tin oxide coated glass positioned 20 microm above the silicon and the gap filled with the nematic liquid crystal BLO48. Simulations have found that, while its nematic liquid crystal aligns with MWNTs within a distance of 10nm, this distance is greatly enhanced by the application of an external electric field. Polarized light experiments show that light is focused with focal lengths ranging from approximately 7 microm to 12 microm.

亚微米氮化钛膜的纳米压痕和划痕测定Coatings

采用等离子电弧沉积的方法分别在GT35和40CrNiMo钢上沉积厚约为0.5mm 的氮化钛(TiN)膜。为了筛选基材，采用纳米压痕和划痕技术评价膜基界面结合和固体润滑效果。纳米压痕结果，采用等离子电弧沉积的方法，分别在GT35和40CrNiMo钢上沉积厚约为0.5$\mu $m 的氮化钛(TiN)膜。为了筛选基材，采用纳米压痕和划痕技术，评价膜基界面结合和固体润滑效果。纳米压痕结果，GT35，40CrNiMo和TiN的纳米硬度/弹性模量的典型值分别约为11.5 Gpa/330 Gpa，6.0 Gpa/210 Gpa，30 Gpa/450 Gpa。纳米划痕结果，GT35有较理想的膜基结合能力；GT35，40CrNiMo，TiN及其有机膜的摩擦系数分别约为0.25，0.45，0.15，0.10。同40CrNiMo相比，GT35是较为理想的基体材料。纳米压痕和划痕技术能提供丰富的近表面的弹塑性变形、断裂和摩擦等的信息，是评价亚微米薄膜力学性能的有效手段。

电弧离子镀薄膜中的颗粒尺寸及其影响的扫描电镜观察

用扫描电镜对比分析了电弧离子镀增加直线磁场过滤对沉积TiN和TiAlN薄膜中颗粒的密度和尺寸的影响，，结果表明，TIN薄膜中颗粒的最大直径，从14μm减小到3μm，颗粒密度从lO~9／cm~2。降低到10~5／cm~2.TilN薄膜由于靶材中含有低熔点金属Al，因而发射出更大的颗粒，有的颗粒集团达到20μm，磁场过滤后颗粒尺寸减小，颗粒密度降低到10~6／cm~2。分析了脉冲叠加直流偏压对TiCrZrN复合薄膜相组成的影响。颗粒可使电弧离子镀rriN／crN多层膜的结合力降低，并使针孔产生遗传。使用直线型磁场过滤及脉冲叠加直流偏压不仅使颗粒密度和尺寸显著降低和减小，而且多层化对小颗粒产生了包覆作用。

亚微米氮化钛膜的纳米压痕和划痕测定

采用等离子电弧沉积的方法，分别在GT35和40CrNiMo钢上沉积厚约为0.5μm的氮化钛(TiN)膜。为了筛选基材，采用纳米压痕和划痕技术，评价膜基界面结合和固体润滑效果。纳米压痕结果，GT35，40CrNiMo和TiN的纳米硬度/弹性模量的典型值分别约为11.5 GPa/330GPa, 6.0 GPa/210GPa, 30GPa/450GPa。纳米划痕结果，GT35有较理想的膜基结合能力；GT35，40CrNiMo，TiN及其有机膜的磨擦系数分别约为0.25，0.45，0.15, 0.10。同40CrNiMo相比，GT35是较为理想的基体材料。纳米压痕和划痕技术能提供丰富的近表面的弹塑性变形、断裂和磨擦等的信息，是评价亚微米薄膜力学性能的有效手段。

真空磁过滤电弧离子镀法制备类金刚石涂层方法及性能研究

采用真空磁过滤电弧离子镀方法，在GT35基体上沉积类金刚石膜。通过对清洗工艺及弧电流、工件所加负偏压、沉积温度等参数的研究，制定出了合理的工艺路线，并对这种膜层进行了X-射线光电子谱（XPS）分析，利用干涉仪、纳米硬度计对膜层的粗糙度、纳米硬度作了进一步检测。结果表明，采用此种方法制备的类金刚石膜层，SP^3含量约为40．1％；组织致密，无大的颗粒；镀膜后的粗糙度可以达到0．015μm；纳米硬度约为55GPa。并将膜层与TiN膜层组成摩擦副，进行了耐磨性试验。结果表明膜层的耐磨性较好。

Magnitude and Extent of Contaminated Sediment and Toxicity in Chesapeake Bay

INTRODUCTION: This report summarizes the results of NOAA's sediment toxicity, chemistry, and benthic community studies in the Chesapeake Bay estuary. As part of the National Status and Trends (NS&T) Program, NOAA has conducted studies to determine the spatial extent and severity of chemical contamination and associated adverse biological effects in coastal bays and estuaries of the United States since 1991. Sediment contamination in U.S. coastal areas is a major environmental issue because of its potential toxic effects on biological resources and often, indirectly, on human health. Thus, characterizing and delineating areas of sediment contamination and toxicity and demonstrating their effect(s) on benthic living resources are viewed as important goals of coastal resource management. Benthic community studies have a history of use in regional estuarine monitoring programs and have been shown to be an effective indicator for describing the extent and magnitude of pollution impacts in estuarine ecosystems, as well as for assessing the effectiveness of management actions. Chesapeake Bay is the largest estuarine system in the United States. Including tidal tributaries, the Bay has approximately 18,694 km of shoreline (more than the entire US West Coast). The watershed is over 165,000 km2 (64,000 miles2), and includes portions of six states (Delaware, Maryland, New York, Pennsylvania, Virginia, and West Virginia) and the District of Columbia. The population of the watershed exceeds 15 million people. There are 150 rivers and streams in the Chesapeake drainage basin. Within the watershed, five major rivers - the Susquehanna, Potomac, Rappahannock, York and James - provide almost 90% of the freshwater to the Bay. The Bay receives an equal volume of water from the Atlantic Ocean. In the upper Bay and tributaries, sediments are fine-grained silts and clays. Sediments in the middle Bay are mostly made of silts and clays derived from shoreline erosion. In the lower Bay, by contrast, the sediments are sandy. These particles come from shore erosion and inputs from the Atlantic Ocean. The introduction of European-style agriculture and large scale clearing of the watershed produced massive shifts in sediment dynamics of the Bay watershed. As early as the mid 1700s, some navigable rivers were filled in by sediment and sedimentation caused several colonial seaports to become landlocked. Toxic contaminants enter the Bay via atmospheric deposition, dissolved and particulate runoff from the watershed or direct discharge. While contaminants enter the Bay from several sources, sediments accumulate many toxic contaminants and thus reveal the status of input for these constituents. In the watershed, loading estimates indicate that the major sources of contaminants are point sources, stormwater runoff, atmospheric deposition, and spills. Point sources and urban runoff in the Bay proper contribute large quantities of contaminants. Pesticide inputs to the Bay have not been quantified. Baltimore Harbor and the Elizabeth River remain among the most contaminated areas in the Unites States. In the mainstem, deep sediment core analyses indicate that sediment accumulation rates are 2-10 times higher in the northern Bay than in the middle and lower Bay, and that sedimentation rates are 2-10 times higher than before European settlement throughout the Bay (NOAA 1998). The core samples show a decline in selected PAH compounds over the past several decades, but absolute concentrations are still 1 to 2 orders of magnitude above 'pristine' conditions. Core data also indicate that concentrations of PAHs, PCBs and, organochlorine pesticides do not demonstrate consistent trends over 25 years, but remain 10 times lower than sediments in the tributaries. In contrast, tri-butyl-tin (TBT) concentrations in the deep cores have declined significantly since it=s use was severely restricted. (PDF contains 241 pages)

Synthetic scope and DFT analysis of the chiral binap-gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

he 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(S-a)-Binap.AuTFA](2). The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF) level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

Iso-specific Ziegler-Natta polymerization of α-olefins with a single-component organoyttrium catalyst

The synthesis of a sterically tailored ligand array (M)_2((C_5H_2-2-Si(CH_3)_3-4-C(CH_3)_3)S_2i(CH_3)_2]("M_2Bp") (M = Li, 16; K, 19) is described. Transmetallation of Li_2Bp with YCl_3(THF)_3 affords exclusively the C_2 symmetric product rac-[BpY(µ_2-Cl)_2Li(THF)_2], 20. A X-ray crystal structure of 20 has been determined; triclinic, P1, a= 13.110 (8), b = 17.163 (15), c = 20.623 (14) Å, α = 104.02 (7), β = 99.38 (5), γ = 100.24 (6)° , Z = 4, R = 0.056. Transmetallation of K_2Bp with YCl_3(THF)_3 affords the halide free complex rac-BpYCl, 23. The corresponding rac-BpLaCl, 28, is prepared in an anlogous manner. In all cases the achiral meso isomer is not obtained since only for the racemic isomers are the unfavorable steric interactions between the Si(CH3)_3 groups in the narrow portion of the [Cp-M'-Cp] wedge avoided. Alkylation of 20 or 23 with LiCH(Si(CH_3)_3)_2 affords rac-BpYCH(Si(CH_3)_3)_2, 26 in good yield. Alkylation of 28 with LiCH(Si(CH_3)_3)_2 affords rac-BpLaCH(Si(CH_3)_3)_2 29. Hydrogenation of 26 cleanly affords the bridging hydride species [BpY(µ_2-H)]_2, 27, as the homochiral (R,R) and (S,S) dimeric pairs. 26 is an efficient initiator for the polymerization of ethylene to high molecular weight linear polyethylene. 27 catalyzes the polymerization of propylene (25% v/v in methylcyclohexane) and neat samples of 1-butene, 1-pentene, 1-hexene to moderately high molecular weight polymers: polypropylene (M_n = 4,200, PDI 2.32, T_m 157 °C); poly-1-butene (M_n = 8,500, PDI 3.44, T_m 105 °C); poly-1-pentene (M_n = 20,000, PDI 1.99, T_m 73 °C); poly-1-hexene (M_n = 24,000, PDI 1.75, T_m < 25 °C). ^(13)C NMR spectra at the pentad analysis level indicates that the degree of isotacticity is 99% mmmm for all polymer samples. 27 is the first single component iso-specific α-olefin polymerization catalyst. The presumed origins of the high isospecificity are presented.