Effect of Thiourea on the Kinetics of the Hydrogen Evolution Reaction at Iron and the Transport of Hydrogen through a Steel Membrane in Solutions of C<Subscript>2</Subscript>H<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>-H<Subscript>2</Subscript>O-HCl

The effect of thiourea (0.5–10 mM) on the kinetics of the hydrogen evolution reaction (HER) at iron and the hydrogen transport through a steel membrane out of ethylene glycol (containing 2 and 10 wt % H₂O) and aqueous solutions containing HCl (0.1–0.99 M) with a constant ionic strength equal to unity is studied in parallel experiments. The presence of 0.5 mM of thiourea in the solutions raises the overvoltage of hydrogen evolution, while a subsequent increase in its concentration does not effect the HER kinetics. The dependence of the flux of hydrogen diffusion through the membrane on the thiourea content passes through a maximum.     

Bayesian sequential reliability for Weibull and related distributions

Assume that the probability density function for the lifetime of a newly designed product has the form: [H(t)/Q()] exp{–H(t)/Q()}. The Exponential(), Rayleigh, WeibullW(, ) and Pareto pdf's are special cases.Q() will be assumed to have an inverse Gamma prior. Assume thatm independent products are to be tested with replacement. A Bayesian Sequential Reliability Demonstration Testing plan is used to eigher accept the product and start formal production, or reject the product for reengineering. The test criterion is the intersection of two goals, a minimal goal to begin production and a mature product goal. The exact values of various risks and the distribution of total number of failures are evaluated. Based on a result about a Poisson process, the expected stopping time for the exponential failure time is also found. Included in these risks and expected stopping times are frequentist versions, thereof, so that the results also provide frequentist answers for a class of interesting stopping rules.This research was supported by NSF grants DMS-8703620 and DMS-8923071, and forms part of the Ph.D. Thesis of the first author, the development of which was supported in part by a David Ross grant at Purdue University. The authors thank the editors and a referee for insightful comments and suggestions.     

一种新的弹道目标成像匹配识别算法

为了能充分利用目标的散射中心对弹道目标进行识别,提出利用解线频调的方法,通过对距离向和方位向进行快速傅里叶变换,实现对目标散射中心成像,然后从目标ISAR像中提取目标特征信息,提出了一种新的匹配识别的方法实现对目标的分类识别。该方法利用提取的散射中心的位置和幅度信息,通过构造匹配度矩阵,进而与预设门限比较,判定目标类别。仿真实验及识别性能评估表明,该方法在设定情况下具有良好的目标识别能力。     

高等级公路施工测量

讨论全站仪配合ＰＣ－Ｅ５００袖珍计算机使用统一坐标系统进行高等级公路施工测量,重点分析高等级公路施工阶段,控制点、细部点的坐标计算方法和测设方法．     

Interior-point algorithm for quadratically constrained entropy minimization problems

In this paper, we develop an interior point algorithm for quadratically constrained entropy problems. The algorithm uses a variation of Newton's method to follow a central path trajectory in the interior of the feasible set. The primal-dual gap is made less than a given in at most steps, wheren is the dimension of the problem andm is the number of quadratic inequality constraints.     

The heliobacteria, a new group of photosynthetic bacteria

A review is given of the photosynthetic properties of the heliobacteria, a new group of photosynthetic bacteria, discovered only 14 years ago. These bacteria contain a “new” pigment, bacteriochlorophyll g, and they have a relatively simple pigment system, consisting of a core-reaction center complex only. Like the green sulfur bacteria, they have a Photosystem I-type reaction center, with a chlorophyll a derivative as primary electron acceptor. Because of the absence of an extensive peripheral antenna system, the reaction center processes in these bacteria are much easier to study than those in the green sulfur bacteria.     

Synthetic analogs of active centers of iron-sulfur proteins: Reactions with phosphates

The interaction of synthetic analogs of active centers of iron-sulfur proteins with phosphates of different structures was studied. It was shown that the process involves ligand exchange and obeys the first-order reaction kinetic equation. The most rapid exchange occurred with the most acidic compound diphenyl phosphate.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2301–2305, October, 1992.     

Sensitively probing the cofactor redox species and photo-induced electron transfer of wild-type and pheophytin-replaced photosynthetic proteins reconstituted in self-assembled monolayers

An ultrathin, ordered, and packed protein film, consisting of the 2-mercaptoacetic acid (MAA), polydimethyldiallylammonium chloride (PDDA), and wild-type (WT) photosynthetic reaction center (RC; termed as WT-RC) or its pheophytin (Phe)-replaced counterpart (termed as Phe-RC), was fabricated by self-assembling technique onto gold electrode for facilitating the electron transfer (ET) between RC and the electrode surface. Near-infrared (NIR)-visible (Vis) absorption and fluorescence (FL) emission spectra revealed the influence of pigment substitution on the cofactors arrangement and excitation relaxation of the proteins, respectively. Square wave voltammetry (SWV) and photoelectric tests were employed to systematically address the differences between the WT-RC films and mutant ones on the direct and photo-induced ET. The electrochemical results demonstrated that ET initiated by the oxidation of the primary donor (P) was obviously slowed down, and the formed P⁺ had more population as well as more positive redox potential in the Phe-RC films compared with those in the WT ones. The photoelectrochemical results displayed the dramatically enhanced photoelectric performances of the mutant ones, further suggesting the slow-down formation of final charge-separated state in Phe-RC. The functionalized protein films introduced in this paper provided an efficient approach to sensitively probe the redox cofactors and ET differences resulting from only minor changes in pigment arrangement in the pigment–protein complex. The favored ET process observed for the membrane proteins RC was potentially valuable for a deep understanding of the multi-step biological ET process and development of versatile bioelectronic devices.     

Nature of the active center in the cyclotrimerization of isocyanates catalyzed by the tertiary amine—α-oxide—protondonor system

The structure of the dimethylbenzylamine (DMBA)—phenylglyc idyl ether (PGE)—phenol complex was studied by IR and¹H NMR spectroscopy under various conditions of its formation. The active catalyst in the cyclotrimerization of isocyanates is a complex of composition DMBA : PGE : PhOH = 1 : 1 : 2, in which the oxygen atom of the zwitter-ion PhCH₂N⁺Me₂CH₂CH(O^–)CH₂OPh that forms after opening, of the epoxide cycle is bound to two phenol molecules by a very strong hydrogen bonds. In this complex, the oxygen atom of both the zwitter-ion and the phenolate anion can be catalytic centers. Two schemes of the cyclotrimerization of isocyanate in the presence of the aforementioned catalytic system are suggested, depending on whether the catalytic complex has time to form or not.For Part I, see Ref. 1.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1662–1668, July, 1996.