Titanocene complexes with nonlinear pseudohalide ligands: Synthesis, spectroscopic characterization and crystal structure

Binuclear titanocene complexes [Cp₂Ti(tcm)]₂O (4), [Cp₂Ti(dca)]₂O (5) and [Cp₂Ti(dcnm)]₂O (6) (tcm⁻ = tricyanomethanide, dca⁻ = dicyanamide and dcnm⁻ = dicyanonitrosomethanide) were synthesized in moderate yields by the reaction of Cp₂TiCl₂ (1) with respective alkali metal pseudohalide salts in the aqueous solution. When the reaction was carried out in dry organic solvents, mononuclear compounds Cp₂Ti(tcm)₂ (2) and Cp₂Ti(dca)₂ (3) were isolated. Preparation of dipseudohalide complex Cp₂Ti(dcnm)₂ by this manner was unsuccessful due to decomposition of dcnm ligand resulting in formation of oxygen-bridged compound 6. All prepared compounds were characterized by elemental analysis, NMR, Raman, infrared and UV-Vis spectroscopy. Molecular structures of 2, 4 and 6 (two polymorphs) have been determined by single-crystal X-ray diffraction analysis.     

Hybrid scorpionate/cyclopentadienyl titanium and zirconium complexes with alkoxide and imido ligands

The reactivity of hybrid scorpionate/cyclopentadienyl ligand-containing trichloride zirconium complexes [ZrCl₃(bpzcp)] (1) [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] and [ZrCl₃(bpztcp)] (2) [bpztcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethylcyclopentadienyl] toward several lithium alkoxides has been carried out. Thus, alkoxide-containing complexes [ZrCl₂(OR)(bpzcp)] (R = Me, 3; Et, 4; ⁱPr, 5; (R)-2-Bu, 6), [ZrCl₂(OR)(bpztcp)] (R = Me, 7; Et, 8; ⁱPr, 9; (R)-2-Bu, 10) and [Zr(OR)₃(bpztcp)] (R = Et, 11; ⁱPr, 12) were prepared by deprotonation of the appropriate alcohol group with BuⁿLi followed by reaction with 1 or 2. In addition, the imido-complex [Ti(N^tBu)Cl(bpztcp)(py)] (13) were also prepared. The structures of these complexes have been proposed on basis of spectroscopic and DFT methods.     

A Flexible Hingeless Control Surface Inspired by Aquatic Animals

##正## A flexible hingeless control surface model was proposed for motion control of Underwater Vehicles (UVs),which is inspiredby the flexible bending control surfaces of underwater creatures,such as fish and squid.Computational Fluid Dynamics(CFD) simulation demonstrates that,in comparison with the hinged or rigid control surface,the proposed flexible bendingcontrol surface can suppress the flow separation so as to improve the turning performance.A prototype of the flexible controlsurface was fabricated,in which Shape Memory Alloy (SMA) wires were selected as the actuators.The elastic energy storageand exchange mechanism was incorporated into the actuation of the control surface to improve the efficiency.Thermal analysisof SMA wires was performed to find proper actuating condition.Open-loop bending experiments were carried out.The resultsshow that the proposed control surface can achieve the maximum bending angle of 104°.Moreover,the power and energyconsumption under different pulse conditions were compared.     

Preferential selection of titanium-bearing minerals in agglutinated Foraminifera: Ilmenite (FeTiO3) in Textularia hauerii d’Orbigny from the Bazaruto Archipelago, Mozambique

The biserial agglutinated foraminifer Textularia hauerii d’Orbigny frequently occurs at shallow depths in reefal habitats off Bazaruto Island, Mozambique. X-ray diffraction, scanning electron- and light microscopy analyses show the enhanced concentration of the titanium-bearing mineral ilmenite (FeTiO₃) in the agglutinated tests of this species. The mineral constitutes an insignificant component in the surrounding sediment (< 1%), but accounts for more than 26% of the foraminiferal test content. The accumulation of ilmenite in T. hauerii and its absence in co-occurring agglutinated Foraminifera suggest the preferential selection for ilmenite. The tendency for ilmenite particles to be arranged along sutures and on the apertural face (1) provides further evidence that certain Foraminifera can specifically select grains, and (2) implies that there exists a selective mechanism to control the timing and placement during test and chamber construction. The preferential uptake represents the first record of ilmenite selection in Foraminifera. Potential driving forces controlling the selective agglutination of Ti minerals, the preferential adsorption to Ti surfaces, and interactions between cellular compounds of the foraminiferal reticulopods and the mineral surfaces are explored.     

A large‐scale gene discovery for the red palm weevil Rhynchophorus ferrugineus (Coleoptera: Curculionidae)

The red palm weevil (RPW; Rhynchophorus ferrugineus) is a devastating pest of palms, prevalent in the Middle East as well as many other regions of the world. Here, we report a large‐scale de novo complementary DNA (cDNA) sequencing effort that acquired ～5 million reads and assembled them into 26 765 contigs from 12 libraries made from samples of different RPW developmental stages based on the Roche/454 GS FLX platform. We annotated these contigs based on the publically available known insect genes and the Tribolium castaneum genome assembly. We find that over 80% of coding sequences (CDS) from the RPW contigs have high‐identity homologs to known proteins with complete CDS. Gene expression analysis shows that the pupa and larval stages have the highest and lowest expression levels, respectively. In addition, we also identified more than 60 000 single nucleotide polymorphisms and 1 200 simple sequence repeat markers. This study provides the first large‐scale cDNA dataset for RPW, a much‐needed resource for future molecular studies.     

钛合金人工听小骨与自体组织在开放室鼓室成形听力重建中的疗效对比研究

目的：探讨钛合金人工听小骨与自体组织在开放室鼓室成形听力重建中的疗效。方法：回顾性分析2008年7月-2012年7月入住我院的120例接受开放式鼓室成形手术的患者的临床资料,并将其按照奇偶数法随机地分为对照组与治疗组,分别给予自体骨组织治疗以及钛合金人工听小骨治疗,听力统计根据0．5、1．0、2．0及4．0kHz的评价气岛差值进行计算,比较两组的治疗效果。结果：对照组手术前后气导值及气骨导差值差异无统计学意义（P〉0．05）,治疗组手术前后气导值及气骨导差值方面具有显著的统计学意义（P〈0．01）,且治疗组手术后与对照组手术后相比,差异具有统计学意义（P〈0．05）。结论：钛合金人工听小骨与自体组织在开放室鼓室成形听力重建中的疗效明显优于自体骨组织治疗,应加以推广并应用。     

Predicting bone remodeling around tissue- and bone-level dental implants used in reduced bone width

The objective of this study was to predict time-dependent bone remodeling around tissue- and bone-level dental implants used in patients with reduced bone width. The remodeling of bone around titanium tissue-level, and titanium and titanium–zirconium alloy bone-level implants was studied under 100 N oblique load for one month by implementing the Stanford theory into three-dimensional finite element models. Maximum principal stress, minimum principal stress, and strain energy density in peri-implant bone and displacement in x- and y- axes of the implant were evaluated. Maximum and minimum principal stresses around tissue-level implant were higher than bone-level implants and both bone-level implants experienced comparable stresses. Total strain energy density in bone around titanium implants slightly decreased during the first two weeks of loading followed by a recovery, and the titanium–zirconium implant showed minor changes in the axial plane. Total strain energy density changes in the loading and contralateral sides were higher in tissue-level implant than other implants in the cortical bone at the horizontal plane. The displacement values of the implants were almost constant over time. Tissue-level implants were associated with higher stresses than bone-level implants. The time-dependent biomechanical outcome of titanium–zirconium alloy bone-level implant was comparable to the titanium implant.     

Thermal and pressure-induced martensitic phase transformations in a Ni–Al alloy modelled by Sutton–Chen embedded atom method

The Ni–Al alloys which exhibit the thermoelastic martensitic phase transformations in the composition range from 60 to 65 atomic percentage (at.%) of Ni are widely used in the high technology applications. In this study, both thermal and pressure-induced phase transformations in Ni-37.5 at.%Al alloy model were investigated by a molecular dynamics (MD) method. Physical interactions between atoms in the alloy system were modelled using the Sutton–Chen version of the embedded atom method based on many-body interactions. The potential parameters for cross interactions between Ni and Al atoms were estimated by optimising the results obtained from the MD simulations, taking into account the experimental data including the crystal lattice properties of the model alloy in high temperature phase.     

Heteroannelated and 7-deoxygenated goniofufurone mimics with antitumour activity: Design,synthesis and preliminary SAR studies

Cytotoxic (+)-goniofufurone mimic such as benzoxepane 2 was preferentially formed after the treatment of 7-O-benzoyl-5-O-benzyl (+)-goniofufurone derivative 6 with titanium(IV) fluoride. However, the corresponding 7-epimer 5 (derivative of 7-epi-goniofufurone) under the similar reaction conditions gave mainly 7-deoxy derivative 7 as a result of an unexpected 1,5-hydride shift. Extension of this methodology to the enantiomer ent-6 provided cytotoxic (?)-goniofufurone mimics ent-2 and ent-7. Synthesized compounds showed diverse growth inhibitory effects against selected tumour cell lines, but were devoid of any significant toxicity towards the normal foetal lung fibroblasts (MRC-5). A SAR study reveals the structural features of these lactones that are beneficial for their antiproliferative activity, such as presence of an additional oxepane ring, the absolute stereochemistry and the presence of a deoxy function at the C-7 position.     

Morphological,biochemical and kinetic properties of lipase from Candida rugosa immobilized in zirconium phosphate

Zirconium phosphate (ZrP), a low-cost inorganic material with well-defined physicochemical properties, was successfully used as support for immobilizing Candida rugosa lipase by covalent bonding. The immobilized derivative showed high catalytic activity in both aqueous and non-aqueous media. Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy measurements demonstrated that the ZrP fulfilled the morphological requirements for use as a matrix for immobilizing lipases. The free and immobilized lipases were compared in terms of pH, temperature and thermal stability. The immobilized lipase had a higher pH optimum (7.5) and higher optimum temperature (50°C) than the free lipase. Immobilization also increased the thermal stability. The hydrolysis of p-nitrophenyl palmitate (pNPP) by immobilized lipase, examined at 37°C, followed Michaelis–Menten kinetics. Values for K_m=1.18 µM and V_max=325Umg^?1 indicated that the immobilized system was subject to mass transfer limitations. The immobilized derivative was also tested under repetitive reaction batches in both ester hydrolysis and synthesis.