In vivo temporal EPR imaging for estimating the kinetics of a nitroxide radical in the renal parenchyma and pelvis in rats

The kinetics of a nitroxide radical in the renal parenchyma and pelvis in rats were investigated by employing an in vivo EPR imaging system equipped with a surface-coil-type resonator (SCR). The exposed kidney of a living rat was inserted into the single-turn coil of the SCR, with the renal major axis aligned with the direction of alternative magnetic field (B(1)). After the injection of nitroxide radical via the tail vein, EPR measurements were repeated. From the temporal EPR images of the kidney on the 2-D projection to the plane which is perpendicular to the direction of B(1,) the decay rate of nitroxide radical in the renal parenchyma and pelvis was estimated. The parenchymal decay rate was found to be significantly shorter than that for the pelvis.     

New regioselective synthesis of metalinked aromatic polyketones from metasubstituted bis(arylsilane)s and aromatic dicarboxylic acid chlorides

A new regioselective synthesis of metalinked aromatic polyketones was achieved for the first time. New metaconnected aromatic polyketones with inherent viscosities of up to 0.49 dL/g were regioselectively synthesized by the solution polycondensation of metasubstituted bis(arylsilane)s with aromatic dicarboxylic acid chlorides in the presence of aluminum chloride in 1,2‐dichloroethane along with the elimination of chlorotrimethylsilane. The polycondensation proceeded through aromatic electrophilic ipso‐substitution. The metalinked aromatic polyketones had considerably lower glass‐transition temperatures and 10% weight‐loss temperatures than those of their counterpart paracatenated aromatic polyketones. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1428–1434, 2003     

Basic design and synthesis of sulfonated contrast agents for magnetic resonance imaging based on gadolinium complexes.

Magnetic resonance angiography (MRA) is an imaging method to examine blood vessels based on the magnetic resonance imaging (MRI) technique. For this purpose, blood pool contrast agents have been developed to selectively increase the signal intensity of the intravascular lumen for improvement of the contrast-to-noise ratio in MR images. Here, we describe the design and the syntheses of six novel sulfonated contrast agents (KMR-Sulfo1 - 6), their chemical properties and their in vivo applications. In this study, we investigated the lipophilicity and the hydrophilicity of a gadolinium complex using a convenient two-step synthesis route, with the goal of prolonging the plasma half-life by binding mainly to human serum albumin. We confirmed that KMR-Sulfo5 fulfilled the requirements as a blood pool contrast agent: it showed a sufficient relaxivity r(1) of 5.9 mM(-1) s(-1), a long plasma half-life of 25.7 min and complete elimination from the body within 12 h after the administration.     

斜拉桥拉索-阻尼器系统非线性响应分析

考虑索的抗弯刚度、垂度及几何非线性的影响，得出了索一阻尼器系统的空间非线性振动偏微分方程，用中心差分法将微分方程在空间内离散，导出了系统的非线性振动常微分方程组。结合Newmark法及虚拟力法提出了一种用于求解非线性振动瞬态响应的杂交分析算法。并以典型的斜拉桥拉索为研究对象，给出了数值算例，并与Runge—Kutta直接积分法进行了比较，说明了杂交算法的准确性及有效性。     

Structure Determination and Total Synthesis of (+)‐16‐Hydroxy‐16,22‐dihydroapparicine

Herein, we describe the first asymmetric total synthesis and determination of the relative and absolute stereochemistry of naturally occurring 16‐hydroxy‐16,22‐dihydroapparicine. The key steps include 1) a novel phosphinimine‐mediated cascade reaction to construct the unique 1‐azabicyclo[4.2.2]decane core, including a pseudo‐aminal‐type moiety; 2) a highly stereospecific 1,2‐addition of 2‐acylindole or a methylketone through a Felkin–Anh transition state for the construction of a tetrasubstituted carbon center; and 3) an intramolecular chirality‐transferring Michael reaction of the ketoester, with neighboring‐group participation, to introduce a chiral center at C15 in the target molecule. In addition, we evaluated the antimalarial activity of synthetic (+)‐(15S,16R)‐16‐hydroxy‐16,22‐dihydroapparicine and its intermediate against chloroquine‐resistant Plasmodium falciparum (K1 strain) parasites.     

Combined application of comprehensive analysis for DNA modification and reporter gene mutation assay to evaluate kidneys of gpt delta rats given madder color or its constituents

DNA adductome analysis using liquid chromatography–tandem mass spectrometry is a promising tool to exhaustively search DNA modifications. Given that the molecular weight of chemical-specific adducts is determined by the total molecular weights of the active form and nucleotide bases, we developed a new method of comprehensive analysis for chemical-specific DNA adducts based on the principle of adductome analysis. The actual analytical mass range was 50 mass units up or down from the average molecular weight of the four DNA bases plus the molecular weight of the expected active form of the chemical. Using lucidin-3-O-primeveroside (LuP), lucidin-modified bases formed by its active form were exhaustively searched using this new method. Various DNA adducts, including Luc-N ²-dG and Luc-N ⁶-dA, were identified in the kidneys of rats given LuP. Together with measurement of 8-hydroxydeoxyguanosine (8-OHdG) levels, the combined application of this new method with a reporter gene mutation assay was performed to clarify renal carcinogenesis induced by madder color (MC) that includes LuP and alizarin (Alz) as constituent agents. A DNA adductome map derived from MC-treated rats was almost identical to that of LuP-treated rats, but not Alz-treated rats. Although 8-OHdG levels were elevated in MC- and Alz-treated rats, significant increases in gpt and Spi^? mutant frequencies were observed only in MC- and LuP-treated rats. In addition, the spectrum of gpt mutants in MC-treated rats showed almost the same pattern as those in LuP-treated rats. The overall data suggest that LuP may be responsible for MC-induced carcinogenicity and that the proposed methodology is appropriate for exploring and understanding mechanisms of chemical carcinogenesis.

Oxidative dimerization of primary alcohols to esters catalyzed by iridium complexes

Primary alcohols undergo efficiently oxidative dimerization by iridium complexes under air without any solvent to form esters in fair to good yields. For instance, the reaction of 1-dodecanol in the presence of [IrCl(coe)₂]₂ (3 mol %) at 95 °C for 15 h produced dodecyl dodecanoate in 91% isolated yield. This is the first successful Ir-catalyzed oxidative dimerization of primary alcohols to esters using air as an oxidant. Various primary alcohols are converted to the corresponding esters in fair to good yields.     

Sooner and later waiting time problems for success and failure runs in higher order Markov dependent trials

The probability generating functions of the waiting times for the first success run of length k and for the sooner run and the later run between a success run of length k and a failure run of length r in the second order Markov dependent trials are derived using the probability generating function method and the combinatorial method. Further, the systems of equations of 2^.m conditional probability generating functions of the waiting times in the m-th order Markov dependent trials are given. Since the systems of equations are linear with respect to the conditional probability generating functions, they can be solved exactly, and hence the probability generating functions of the waiting time distributions are obtained. If m is large, some computer algebra systems are available to solve the linear systems of equations.This research was partially supported by the Natural Sciences and Engineering Research Council of Canada.     

Joint distributions of numbers of success-runs and failures until the first consecutivek successes

Joint distributions of the numbers of failures, successes and success-runs of length less thank until the first consecutivek successes are obtained for some random sequences such as a sequence of independent and identically distributed integer valued random variables, a {0, 1}-valued Markov chain and a binary sequence of orderk. There are some ways of counting numbers of runs with a specified length. This paper studies the joint distributions based on three ways of counting numbers of runs, i.e., the number of overlapping runs with a specified length, the number of non-overlapping runs with a specified length and the number of runs with a specified length or more. Marginal distributions of them can be derived immediately, and most of them are surprisingly simple.This research was partially supported by the ISM Cooperative Research Program (93-ISM-CRP-8).     

Behavior of thin rectangular ANCF shell elements in various mesh configurations

The absolute nodal coordinate formulation (ANCF) is characterized by being developed specifically for dynamic analysis of large deformation problems. The objective of the study is to investigate how the shape of the initial mesh configuration influences the obtained numerical solution. After a thorough review of three available formulations, they are used in three different convergence studies. Initially a reference study is conducted to determine how the ANCF performs in an uniform and rectangular mesh. Subsequently, the ANCF methods sensitivity to irregular mesh is investigated and finally, the ability of the ANCF method to describe curved structures is evaluated. This study concludes that thin ANCF shell elements are sensitive to both the initial shape and their loading condition. Furthermore, both the initial configuration and the loading condition affect how the ANCF-based models converge. It is suggested that models containing thin ANCF shell elements are subjected to extensive validation studies, before they are used in a design process.