Opto-Electronic Block-Cipher Based on Iteration of the 2-D Toggle Cellular Automata: Algorithm

Parallel architectures and algorithms may offer a solution to the system bottleneck arising from the need to encrypt a very large amount of data without compromising security. In this respect the use of cellular automata with their parallel, simple, regular and modular structure is very promising. We extend the blockcipher algorithm, based on the iterations of so called “toggle” cellular automata rules to two dimensions.The advantages are higher complexity of the crypt-analytical attacks and substantial increase in the speed of the algorithm. Due to its massive parallelism and interconnectivity, the algorithm is very suitable for opto-electronic implementation.     

Synthesis and polymerization of long alkyl acetylenic compounds

A variety of long alkyl acetylenic compounds was synthesized and polymerized by using Rh(I) catalysts. Particularly, the monomer having a terminal hydroxyl group was converted into the high molecular weight of polymer in good conversion, which was soluble in THF, DMSO, and DMF. The high stereoregularity (cis) in the main chain was confirmed by ¹H‐NMR in DMSO‐d₆ and the rod‐like structure by wide‐angle X‐ray diffraction. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3419–3427, 2000     

Novel photosensitive polymer based on polycarbodiimide and photoamine generator

A novel photosensitive polymer based on end‐capped polycarbodiimide (E‐PCD) and the photoamine generator N‐{[(4,5‐dimethoxy‐2‐nitrobenzyl)oxy]carbonyl}‐2,6‐dimethylpiperidine (1) was developed. The E‐PCD was prepared by polycondensation of tolylene‐2,4‐diisocyanate in the presence of 3‐methy‐1‐phenyl‐2‐phospholene‐1‐oxide as a catalyst. The reaction of carbodiimide and secondary amine was studied. The nucleophilic addition of amine to the carbodiimide moiety proceeded smoothly and provided a guanidine base that acted as a crosslinking agent. A lithographic evaluation of the system of E‐PCD and 1 revealed that the dissolution rate of the exposed area after the postexposure bake decreased drastically, although no obvious change of the dissolution rate in the unexposed area was observed. The E‐PCD containing 10 wt % 1 functioned as a negative working photosensitive polymer when it was exposed to 365‐nm UV light, postbaked at 120 °C for 5 min, and developed with toluene at 25 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 329–336, 2000     

Cu纳米针上电场促进C-C耦合增强CO2电还原生成C2产物

电催化CO₂减排技术利用电能将过量的CO₂转化为有附加值的化学品,是解决能源危机、实现碳中和的有效途径之一.电催化CO₂还原反应(CO₂RR)中的多碳产物(C₂),如乙烯和乙醇,因其比C1产物具有更高的能量密度和更广泛的应用而受到较大关注.目前为止,Cu基催化剂被认为是获得C₂产物的独特材料.研究者在提高Cu基催化剂C₂产物的活性和选择性方面做了大量的工作,如催化剂形貌工程、活性位点设计和中间吸附性能调控等.许多理论和实验研究已经证明,Cu基催化剂上的C-C偶联过程是C₂产物生成的速率决定步骤.优化C-C偶联过程的能垒是提高C₂产物活性和选择性的重要而直接的策略.CO₂RR在Cu上是由CO₂还原吸附CO(*CO)并二聚生成C₂产物引起的.C-C偶联过程与*CO的吸附性能密切相关.众所周知,CO是一种典型的极性分子,因此其在催化剂表面的吸附性能可能会受到活性位点周围的局部电场的影响.构建合适的局部电场是调节CO吸附性能和C-C偶联过程的潜在手段之一.前期工作(Nature,2016,537,382-386)证明了高曲率金纳米针可以在尖端产生高的局部电场.高局域电场诱导K+聚集,使活性位点周围CO₂浓度升高,大大促进了Au纳米针上的CO生成.基于Au纳米针的局域电场促进了CO₂RR的CO生成.本文利用Cu纳米针促进并优化C-C偶联反应来提高C₂产物活性和选择性.结果表明,局部电场可以促进C-C偶联过程,进而增强CO₂电还原生成C₂产物.有限元模拟结果表明,高曲率铜纳米针处存在较强的局部电场;密度泛函理论计算结果表明,强电场能促进C-C耦合过程.在此基础上,制备了一系列不同曲率的Cu催化剂,其中,Cu纳米针(CuNNs)的曲率最高,Cu纳米棒(CuNRs)和Cu纳米颗粒(CuNPs)曲率次之.实验测得CuNNs上吸附的K+浓度最高,证明了纳米针上的局部电场最强.同时,CO吸附传感器测试表明,CuNNs对CO的吸附能力最强,原位傅里叶变换红外光谱显示,CuNNs的*COCO和*CO信号最强.由此可见,高曲率铜纳米针可以诱导高局部电场,从而促进C-C耦合过程.催化性能测试结果表明,在低电位(-0.6 V vs.RHE)下,Cu NNs对CO₂RR的生成C₂产物的法拉第效率值为44%,约为Cu NPs的2.2倍.综上,本文为CO₂RR过程中提高多碳产物提供了新的思路.     

Monolithic silica column for in-tube solid-phase microextraction coupled to high-performance liquid chromatography

In-tube solid-phase microextraction (SPME) has successfully been coupled to capillary LC, and further an automated in-tube SPME system has been developed using a commercially available HPLC auto-sampler. However, an open tubular capillary column with a thick film of polymer (stationary phase) is unfavorable because the ratio of the surface area of coating layer contacted with sample solution to the volume of the capillary column is insufficient for mass transfer. A highly efficient SPME column is. therefore, required. We introduced a C18-bonded monolithic capillary column that was used for in-tube SPME. The column consisted of continuous porous silica having a double-pore structure. Both the through-pore and the meso-pore were optimized for in-tube SPME, and the optimized capillary column was connected to an HPLC injection valve for characterization. The results demonstrated that the pre-concentration efficiency is excellent compared with the conventional in-tube SPME. The novel method for both introduction and concentration of the samples was effective. satisfactory and suitable for use in the SPME medium.     

Structural and Spectroscopic Characterization of a Mononuclear Hydroperoxo–Copper(II) Complex with Tripodal Pyridylamine Ligands

A model for the key intermediate in copper oxygenase reactions, the Cu(II )–OOH complex, was prepared with the novel tripodal pyridylamine ligand, bis(6-pivalamide-2-pyridylmethyl)(2-pyridylmethyl)amine. The HOO⁻ moiety is stabilized by hydrogen bonding to two amine H atoms (see structure on the right).     

Molecular motion of ends of isolated poly(isobutylene) chains tethered on the poly(tetrafluoroethylene) surface in vacuo

Poly(isobutylene) (PIB) chains with a radical at the chain end were graft-copolymerized on the poly(tetrafluoroethylene) (PTFE) surface in vacuo at 77 K. The PIB chains tethered on the PTFE surface in vacuo were regarded as isolated chains from neighboring tethered PIB chains. The molecular motion of the ends of the isolated PIB chains was observed by an electron spin resonance (ESR) spectrometer in the temperature range from 3 to 125 K, which was lower than T_g of PIB, 200 K,¹ and two motion modes were found: One is a quantum tunneling of the methyl group located at the chain end at 3 K, and the other is an interconformation transition with freely rotating methyl group at the end at 77 K, where the transition rate was estimated to be 15 MHz at that temperature. The transition rate increased with an increase in temperature. The activation energy of the transition was estimated to be 370 J/mol. The high mobility and low activation energy was attributed to the isolation of PIB chains in vacuo. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2095–2102, 1998     

Rhodium-Catalyzed Intermolecular [4+2] Cycloaddition of Unactivated Substrates

No electron-withdrawing or electron-releasing substituents are necessary for the substrates in the rhodium-catalyzed [4+2] cycloaddition reaction between a vinylallene and an ordinary alkyne under mild conditions [Eq. (1)]. The use of the strongly electron-accepting P[OCH(CF₃)₂]₃ ligand affords the optimal rhodium catalyst. cod = 1,5-cyclooctadiene.