Mononitrosyl tris(thiolate) iron complex [Fe(NO)(SPh)3]- and dinitrosyl iron complex [(EtS)2Fe(NO)2]-: formation pathway of dinitrosyl iron complexes (DNICs) from nitrosylation of biomimetic rubredoxin [Fe(SR)4]2-/1- (R = Ph, Et)

Nitrosylation of the biomimetic reduced- and oxidized-form rubredoxin [Fe(SR)4]2-/1- (R = Ph, Et) in a 1:1 stoichiometry led to the formation of the extremely air- and light-sensitive mononitrosyl tris(thiolate) iron complexes (MNICs) [Fe(NO)(SR)3]- along with byproducts [SR]- or (RS)2. Transformation of [Fe(NO)(SR)3]- into dinitrosyl iron complexes (DNICs) [(RS)2Fe(NO)2]- and Roussin's red ester [Fe2(mu-SR)2(NO)4] occurs rapidly under addition of 1 equiv of NO(g) and [NO]+, respectively. Obviously, the mononitrosyl tris(thiolate) complex [Fe(NO)(SR)3]- acts as an intermediate when the biomimetic oxidized- and reduced-form rubredoxin [Fe(SR)4]2-/1- exposed to NO(g) were modified to form dinitrosyl iron complexes [(RS)2Fe(NO)2]-. Presumably, NO binding to the electron-deficient [Fe(III)(SR)4]- and [Fe(III)(NO)(SR)3]- complexes triggers reductive elimination of dialkyl/diphenyl disulfide, while binding of NO radical to the reduced-form [Fe(II)(SR)4]2- induces the thiolate-ligand elimination. Protonation of [Fe(NO)(SEt)3]- yielding [Fe(NO)(SPh)3]- by adding 3 equiv of thiophenol and transformation of [Fe(NO)(SPh)3]- to [Fe(NO)(SEt)3]- in the presence of 3 equiv of [SEt]-, respectively, demonstrated that complexes [Fe(NO)(SPh)3]- and [Fe(NO)(SEt)3]- are chemically interconvertible. Mononitrosyl tris(thiolate) iron complex [Fe(NO)(SPh)3]- and dinitrosyl iron complex [(EtS)2Fe(NO)2]- were isolated and characterized by X-ray diffraction. The mean NO bond distances of 1.181(7) A (or 1.191(7) A) in complex [(EtS)2Fe(NO)2]- are nearly at the upper end of the 1.178(3)-1.160(6) A for the anionic {Fe(NO)2}9 DNICs, while the mean FeN(O) distances of 1.674(6) A (or 1.679(6) A) exactly fall in the range of 1.695(3)-1.661(4) A for the anionic {Fe(NO)2}9 DNICs.     

Modified sublayer approach model for analysis of turbulent particle transports

Attempt is to extend the sublayer approach model to capture the combined effects of thermophoresis and turbophoresis on the particle transport in the turbulent boundary flow with thermal gradients. Analytical solution relying on a more detailed picture of the periodic sublayer development in the wall region has been obtained. During the average growth period of viscous sublayer, the physical trend of the modeling parameters has been quantitatively revealed in some extent, and the calculated results of the particle deposition rate for the different ranges of the particle relaxation time are in general agreement with available particle transport data.     

An efficient algorithm for computing traffic equilibria using TRANSYT model

Computing traffic equilibria with signal settings using TRANSYT model for an area traffic control road system is considered in this paper. Following Wardrop’s first principle, this problem can be formulated as a variational inequality problem. In this paper, we propose a novel algorithm to efficiently solve this equilibrium traffic assignment with global convergence. Numerical calculations are conducted on a grid-size road network. As it shows, the proposed method achieved greater savings in computational overheads than did those conventional methods for solving traffic equilibria when signal settings are particularly taken into account.     

Trend of lower stratospheric methane (CH4) from atmospheric chemistry experiment (ACE) and atmospheric trace molecule spectroscopy (ATMOS) measurements

The long-term trend of methane (CH₄) in the lower stratosphere has been estimated for the 1985-2008 time period by combining spaceborne solar occultation measurements recorded with high spectral resolution Fourier transform spectrometers (FTSs). Volume mixing ratio (VMR) FTS measurements from the ATMOS (atmospheric trace molecule spectroscopy) FTS covering 120-10 hPa (∼16-30 km altitude) at 25°N-35°N latitude from 1985 and 1994 have been combined with Atmospheric Chemistry Experiment (ACE) SCISAT-1 FTS measurements covering the same latitude and pressure range from 2004 to 2008. The CH₄ trend was estimated by referencing the VMRs to those measured for the long-lived constituent N₂O to account for the dynamic history of the sampled airmasses. The combined measurement set shows that the VMR increase measured by ATMOS has been replaced by a leveling off during the ACE measurement time period. Our conclusion is consistent with both remote sensing and in situ measurements of the CH₄ trend obtained over the same time span.     

Temperature-dependent characteristics of pulse-laser-deposited (Pb,Sr)TiO<Subscript>3</Subscript> films at low temperatures

Pulsed laser deposition (PLD) of (Pb,Sr)TiO₃ (PSrT) film on Pt/SiO₂/Si at low substrate temperatures (T_s), ranging from 300–450 °C, has been investigated. As T_s increases, the films reveal coarsening clusters, improved crystallization of the perovskite phase, distinct capacitance–electric field (C–E) hysteretic loops and a larger dielectric constant. The 350 °C-deposited film shows strong (100) preferred orientation and optimum dielectric properties with the dielectric constant of ∼620. The current density increases as the measurement temperature and the electric field increase. Moreover, PSrT films exhibit a strong negative temperature coefficient of resistance (NTCR) behavior at temperatures ranging from 100 to 390 °C. PACS 81.15.Fg; 77.22.Ch; 68.60.Dv     

Synthesis and study of a lipophilic alpha-keto amide inhibitor of pancreatic lipase

[reaction: see text] A lipophilic alpha-keto amide, inhibitor of pancreatic lipase, was synthesized using a lipidic 2-amino alcohol as backbone. The chiral key intermediate 2-(tert-butyloxycarbonylamino)-D-undecen-5-ol was synthesized starting from D-glutamic acid. The inhibitor formed a stable monomolecular film at the air/water interface as shown by a force/area curve. Inhibition studies using the monomolecular film technique with mixed films of 1,2-dicaprin containing variable proportions of the inhibitor showed a 50% decrease in lipase activity at a 0.14 molar fraction.     

Laminar natural convection over a slender vertical frustrum of a cone with constant wall heat flux

The problem of laminar natural convection flow over a slender frustrum of a cone with constant wall heat flux is treated in this paper. The governing differential equations are solved by a combination of quasilinearization and finite-difference methods. Numerical solutions are obtained for Prandtl numbers from 0.1 to 100 for a range of values of transverse curvature parameter. It is found that the effect of transverse curvature is of great significance in such flows.

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Laminare natürliche Konvektion über einem dünnen, senkrechten Kegelstumpf mit konstantem Wand wär mestrom

Zusammenfassung In dieser Arbeit wird das Problem der laminaren, natürlichen Konvektionsströmung öber einem dünnen Kegelstumpf mit konstantem Wandwärmestrom behandelt. Die maßgeblichen Differentialgleichungen werden mit Hilfe einer Kombination von Quasilinearisierung und Differenzenverfahren gelöst. Numerische Lösungen werden für die Prandtl ' sehen Zahlen zwischen 0. l und 100 innerhalb eines Bereiches von Querkrüm mungswerten erhalten. Es wird gezeigt, daß der Einfluß der Querkrümmung in solchen Strömungen von großer Bedeutung ist.

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Nomenclature A,B,C constants in the transformation, defined in Eq.(14) - f dependent variable, defined in Eq. (7) - g dependent variable, defined in Eq. (7) - g_e gravitational acceleration - k heat conductivity - k_n -grid - L characteristic length - Nu Nusselt number - Pr Prandtl number - q_w wall heat flux - r radial distance from the axis of the cone - R_TVC transverse curvature ratio, defined in Eq.(28) - Re Reynolds number - T temperature - u,v velocity components in the x- and y-directions, respectively - x,y rectangular coordinates Greek Letters dimensionless temperature, defined in Eq.(4) - bulk modulus - cone angle - dynamic viscosity - stream function - , transformed independent variables, defined in Eq. (7) - transverse curvature parameter     

酞菁铁催化烯烃自由基膦叠氮化反应:利用叠氮快速转移合成膦叠氮的温和方法

含氮和磷原子的化合物是生命系统中不可缺少的组成部分,由于其独特的化学、生物和物理性质,已被广泛应用于农业化学、材料科学和制药学.如果一个有机化合物同时含有氮和磷原子,它可能因为胺和膦/磷酸盐基团的协同作用而具有额外的功能.2015年赵玉芬院士和唐果教授报道了一例自由基叠氮膦酰化的例子,该反应虽然有效,但因需使用化学剂量的氧化性自由基引发剂Mn(OAc)3·2H2O,因此,有必要发展一种更环保经济的方法.本文报道了铁催化烯烃的分子间自由基膦叠氮化反应.该方法使用了微量的催化剂,通过自由基接力与叠氮基团转移实现分子间自由基膦叠氮化反应.实验先进行条件筛选,考察了催化剂类型、催化剂用量、氧化剂类型、溶剂和温度对反应的影响,确定以酞菁铁为催化剂,叔丁基过氧化氢(TBHP)为引发剂,乙腈为溶剂,苯乙烯、叠氮基三甲基硅烷、二苯基膦酰为模板反应底物为最佳条件,实现了二苯基膦酰对烯烃的自由基膦酰基叠氮化反应.在最优条件下进行底物拓展,制备得到27种膦叠氮化合物,产率为23％～88％.以制得的膦叠氮产物为起始原料,通过叠氮还原和Click反应制备得到三种衍生物,产率为82％～97％,可作为药物合成中间体进行下一步研究.本文还进行了机理实验和理论计算.在自由基钟实验和自由基捕获实验中,通过两种不同速率的自由基开环反应与自由基捕获反应证实了反应的自由基路径.质谱检测到酞菁铁羟基(PcFeⅢOH)和酞菁铁叠氮(PcFeⅢN3)的存在.采用密度泛函理论计算了不同自旋态下的酞菁铁(PcFe),以确定可能的催化剂种类,并计算出三重态3pcFe最稳定.从三重态3pcFe开始计算铁催化叔丁基过氧化氢的单电子转移,并计算了从叔丁氧基自由基开始的自由基接力,证实了膦酰苄基自由基的形成是最有利的途径;研究结果发现膦酰苄基自由基能与4pcFe(N3)反应,发生叠氮基团转移生成目标产物.在叠氮基团转移计算中,考察了四种合理的途径,分别是苄基在三重态或五重态势能面接近叠氮基团的内部或端位氮原子(Ni和Nt).结果 表明,叠氮基团从叠氮基酞菁铁(Ⅲ)物种(PcFeⅢN3)转移到苄基自由基的活化能(4.8 kcal/mol)极低.据此催化循环机理可能为:酞菁铁首先与叔丁基过氧化氢发生单电子转移形成酞菁铁羟基中间体及叔丁氧自由基;然后,二苯基膦酰的氢原子被叔丁氧自由基攫取生成二苯基膦酰自由基,并加成至苯乙烯形成苄基自由基.同时,酞菁铁羟基中间体与HN3进行配体交换形成酞菁铁叠氮中间体,最后与苄基自由基进行叠氮基团转移生成产物,并重新生成酞菁铁(Ⅱ).本文证实了铁催化叠氮化反应的自由基基团转移机理(外球机理),因为很难想象如何在酞菁铁的同侧同时加成叠氮与苄基基团,通过生成高价铁物种(PcFe-N3·)的内球机理得到产物.该工作将有助于启发更多的金属催化机理研究.