Studies on base-boronated oligonucleotides. 2 (1). Incompatibility of DMT and cyanoborane groups during oligonucleotide synthesis

The cyanoborane (-BH2CN) nucleosides and nucleotides are a new class of compounds that mimic natural and synthetic congeners in many ways and exhibit interesting biochemical and biophysical properties. The B-N bond is isoelectronic with the C-N+ bond of N7-alkylated 2'-nucleosides, as well as the C-C bond of naturally occurring 7-alkyl-7-deazanucleosides. These compounds differ from normal guanosine in that they are incapable of hydrogen bonding at the 7-position. The syntheses of N7-cyanoborane 2'-deoxyguanosine, N2-(dimethylaminomethylene)-N7-cyanoborane 5'-(dimethoxytrityl)-2'-deoxyguanosine (3), and N2-isobutyryl-N7-cyanoborane 5'-(dimethoxytrityl)-2'-deoxyguanosine (9) are described. Removal of the dimethoxytrityl (DMT) group from 3 or 9 is accompanied by significant loss of the cyanoborane moiety. Additionally, dimethoxytritylation of a cyanoboronated nucleoside leads to partial deboronation, thus limiting use of the commercially available 5'-DMT nucleosides as viable precursors in base-boronated oligonucleotide synthesis. The incompatibility of the cyanoborane moiety under DMT removal/addition conditions necessitated the search for an alternative method of protecting the 5'-hydroxyl of the nucleoside. This paper addresses the possible cause of deboronation and describes the synthesis of N7-cyanoboronated nucleosides by a method that avoids transient protection of the sugar hydroxyls.     

Serine derived NK1 antagonists. 2: A pharmacophore model for arylsulfonamide binding

Modifications to the spirocyclic aryl sulfonamide portion of serine derived NK1 antagonists allow a partial pharmacophore model to be developed.     

Structural and magnetic properties of MnAs/GaAs ferromagnetic semiconductor nanocomposite material

Self-organized (Ga,Mn)As nanoclusters, embedded in GaAs and formed during thermal annealing of Ga_1-xMn_xAs layer at 500 °C or 600 °C, were studied using Transmission Electron Microscopy (TEM) and Magnetic Force Microscopy (MFM). We found that 10–20 nm large NiAs-type hexagonal MnAs nanocrystals gave magnetic contrast in MFM images, whereas smaller zinc-blende nanoinclusions were not visible by means of this technique. Theoretical simulations showed that MFM contrasts reflect interaction between magnetic tip and many randomly distributed MnAs nanocrystals.     

Calibration and evaluation of seven fracture models

Over the past 5 years, there has been increasing interest of the automotive, aerospace, aluminum, and steel industries in numerical simulation of the fracture process of typical structural materials. Accordingly, there is a pressure on the developers of leading commercial codes, such as ABAQUS, LS-DYNA, and PAM-CRASH to implement reliable fracture criteria into those codes. Even though there are several options to address fracture in these and other commercial codes, no guidelines are given for the users as to which fracture criterion is suitable for a particular application and how to calibrate a given material for fracture. The objective of the present paper is to address the above issues and present a thorough comparative study of seven fracture criteria that are included in libraries of material models of non-linear finite element codes. A set of 15 tests recently conducted by the authors on 2024-T351 aluminum alloy is taken as a reference for the present study. The plane stress prevails in all these tests. These experiments are compared with the constant equivalent strain criterion, the Xue–Wierzbicki (X–W) fracture criterion, the Wilkins (W), the Johnson–Cook (J–C) and the CrachFEM fracture models. Additionally, the maximum shear (MS) stress model, and the fracture forming limit diagram (FFLD) are included in the present evaluation. All criteria are formulated in the general 3-D case for the power law hardening materials and then are specified for the plane stress condition. The advantage of working with plane stress is that there is one-to-one mapping from the stress to the strain space. Therefore, the fracture criteria formulated in the stress space can be compared with those expressed in the strain space and vice versa. Fracture loci for all seven cases were constructed in the space of the equivalent fracture strain and the stress triaxiality. Interesting observations were made regarding the range of applicability and expected errors of some of the most common fracture criteria. Besides evaluating the applicability of several fracture criteria, a detailed calibration procedure for each criterion is presented in the present paper. It was found rather unexpectedly that the MS stress fracture model closely follows the trend of all tests except the round bar tensile tests. The X–W criterion and the CrachFEM models predict correctly fracture in all types of experiments. The W criterion is working well in certain ranges of the stress triaxiality.     

单晶金刚石外延层生长工艺研究

目的 研究高质量单晶金刚石外延生长工艺。方法 使用X射线白光形貌束分析了等离子体表面刻蚀处理前后单晶金刚石位错密度的变化,随后使用等离子体刻蚀预处理工艺,通过改变沉积温度研究了其对金刚石质量的影响。为了表征温度对单晶金刚石质量的影响程度,使用拉曼光谱和X射线衍射摇摆曲线等方法分析了单晶金刚石质量以及位错密度的变化情况,进而确定沉积高质量单晶金刚石最佳的沉积温度。结果 X射线白光形貌束结果显示,未进行氢氧等离子体表面刻蚀的籽晶生长之后,由于表面微加工、抛光引入的位错或者微裂纹,导致生长层位错增多;同时,氢氧等离子体表面刻蚀实验结果显示,刻蚀时间并非越长越好;使用刻蚀处理过的单晶金刚石籽晶进行不同温度外延生长实验,籽晶刻蚀后生长的金刚石拉曼峰位均在1332.5 cm?1附近,半高宽为2~3 cm?1之间。在900 ℃沉积之后,X射线摇摆曲线半高宽仅为0.009。结论 使用氢氧微波等离子体刻蚀单晶金刚石,800 ℃刻蚀40 min,可以基本消除因微加工或者抛光引入的位错或者缺陷。经过刻蚀处理的籽晶在900 ℃制备出的单晶金刚石质量最高,位错最少,可以满足高质量单晶金刚石的制备。     

Use of the subcutaneous venous network of the forearm to create an arteriovenous fistula

The reconstruction of vascular access in patients with kidney allograft failure is a challenging problem. A case of a 62‐year‐old man with transplanted kidney insufficiency is described. The patient was initially dialyzed with a wrist radial‐cephalic arteriovenous fistula. In the post‐transplantation period, the enormously dilated venous part of the anastomosis was ligated and the part of the vein suspected of being the source of bacteremia was excised. The man was referred to our department due to kidney allograft failure for vascular access creation. During preoperative assessment, we unexpectedly found a soft thrill on the forearm. Doppler ultrasound confirmed fistula patency, although the blood supply was not sufficient to perform dialysis. Angiography showed the blood flow from the radial artery to the cephalic vein, through a complicated vessel system consisting of inter alia a dilated vein of the subcutaneous venous network. We successfully used this vein as the vascular access outflow for fistula recreation. In conclusion, making use of veins of the subcutaneous venous network of the forearm for creation of a native fistula should be considered in selected cases.     

Effect of Various SPD Techniques on Structure and Superplastic Deformation of Two Phase MgLiAl Alloy

MgLiAl alloy containing 9 wt% Li and 1.5% Al composed of hexagonal α and bcc β phases was cast under protecting atmosphere and hot extruded. Various methods of severe plastic deformation were applied to study their effect on structure and grain refinement. Rods were subjected to 1–3 passes of Twist Channel Angular Pressing TCAP (with helical component), cyclic compression to total strain ε?=?5 using MAXStrain Gleeble equipment, both performed at temperature interval 160–200 °C and, as third SPD method, KOBO type extrusion at RT. The TCAP pass resulted in grain refinement of α phase from 30 μm down to about 2 μm and that of β phase from 12 to 5 μm. Maxstrain cycling 10?× up to ε?=?5 led to much finer grain size of 300 nm. KOBO method performed at RT caused average grain size refinement of α and β phases down to about 1 μm. Hardness of alloy decreased slightly with increasing number of TCAP passes due to increase of small void density. It was higher after MAXStrain cycling and after KOBO extrusion. TEM studies after TCAP passes showed higher dislocation density in the β region than in the α phase. Crystallographic relationship (001) α|| (110) β indicated parallel positioning of slip planes of both phases. Electron diffraction technique confirmed increase of grain misorientation with number of TCAP passes. Stress/strain curves recorded at temperature 200 °C showed superplastic forming after 1st and 3rd TCAP passes with better superplastic properties due to higher elongation with increasing number of passes. Values of strain rate sensitivity coefficient m were calculated at 0.29 after 3rd TCAP pass for strain rate range 10^?5 to 5?×?10^?3 s^?1. Deformation by MAXStrain cycling caused much more effective grain refinement with fine microtwins in α phase. Superplastic deformation was also observed in alloy deformed by KOBO method, however the value of m?=?0.21 was obtained at lower temperature of deformation equal to 160 °C and deformation rate in the range 10^?5 to 5?×?10^?3. Tensile samples deformed superplastically showed grain growth and void formation caused by grain boundary slip. Summarizing, all methods applied resulted in sufficient grain refinement to obtain the effect of superplastic deformation for alloys of two phase α?+?β structure.     

Multiscale analyses and characterizations of surface topographies

This work studies multiscale analyses and characterizations of surface topographies from the engineering and scientific literature with an emphasis on production engineering research and design. It highlights methods that provide strong correlations between topographies and performance or topographies and processes, and methods that can confidently discriminate topographies that were processed or that perform differently. These methods have commonalities in geometric characterizations at certain scales, which are observable with statistics and measurements. It also develops a semantic and theoretical framework and proposes a new system for organizing and designating multiscale analyses. Finally, future possibilities for multiscale analyses are discussed.     

ND++ – an extended IPv6 Neighbor Discovery protocol for enhanced stateless address autoconfiguration in MANETs

Recent trends in information and communications technologies are oriented toward the design of the Future Internet and the Internet of Things. While IPv6‐based mobile ad hoc networks (MANETs) are emerging as an important building block of these new technologies, it is necessary to come up with adequate self‐configuration capabilities allowing for seamless and automated configuration of addresses in mobile environment. The mechanisms of stateless address autoconfiguration proposed for IPv6 networks are supposed to automate some configuration steps; however, they would need to be aligned with the requirements imposed by MANET networks. Therefore, in this article, we present Neighbor Discovery ++ – an extended IPv6 Neighbor Discovery protocol for enhanced duplicate address detection in MANETs, which provides increased coverage of network nodes, while minimizing protocol overhead. It exploits efficient flooding mechanism on the basis of the multipoint relay concept, which makes it an interesting approach also for large‐scale networks. Trials performed on the designated real‐world testbed platform indicate that ND++ is a promising solution to support efficient address autoconfiguration in MANETs. Copyright © 2012 John Wiley & Sons, Ltd.