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1.
Silver-mediated α-dC–Ag+–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong Tm increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag+–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology.  相似文献   
2.
The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence.  相似文献   
3.
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield.  相似文献   
4.
2,5-Disubstituted oxazoles were prepared conveniently by treatment of aromatic α-methyl ketones and nitriles with poly[styrene(iodosodiacetate)] in one-pot process.  相似文献   
5.
Numerical methods for solving constrained optimization problems need to incorporate the constraints in a manner that satisfies essentially competing interests; the incorporation needs to be simple enough that the solution method is tractable, yet complex enough to ensure the validity of the ultimate solution. We introduce a framework for constraint incorporation that identifies a minimal acceptable level of complexity and defines two basic types of constraint incorporation which (with combinations) cover nearly all popular numerical methods for constrained optimization, including trust region methods, penalty methods, barrier methods, penalty-multiplier methods, and sequential quadratic programming methods. The broad application of our framework relies on addition and chain rules for constraint incorporation which we develop here.  相似文献   
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7.
The feature selection consists of obtaining a subset of these features to optimally realize the task without the irrelevant ones. Since it can provide faster and cost-effective learning machines and also improve the prediction performance of the predictors, it is a crucial step in machine learning. The feature selection methods using support machines have obtained satisfactory results, but the noises and outliers often reduce the performance. In this paper, we propose a feature selection approach using fuzzy support vector machines and compare it with the previous work, the results of experiments on the UCI data sets show that feature selection using fuzzy SVM obtains better results than using SVM.  相似文献   
8.
刘文安  聂赞坎 《应用数学》2004,17(3):405-409
本文通过建立简洁而有效的搜索方法 ,证明了对于无穷多个n来说 ,三个目标的最优搜索问题的最小试验次数等于信息论下界 .同时也研究了上述问题的修正情形 ,证明了对于所有整数n来说 ,对应的最小试验次数或者等于信息论下界或者超过信息论下界 1次并且对于无穷多个区间 ,信息论下界均是可以达到的 .  相似文献   
9.
该文通过构造特殊形式的有效集来逼近KKT点处的有效集,给出了一个任意初始点下的序列线性方程组新算法,并证明了该算法在没有严格互补松驰条件的情况下具有全局收敛性和一步超线性收敛性。   相似文献   
10.
概率罐子模型中一种最优设计   总被引:3,自引:0,他引:3       下载免费PDF全文
基于错误概率达到最小的原则,该文在罐子模型序贯试验中构造了一种渐近最优设计。在这种设计下,不仅能使病员以较多机会分配到较好的处理,而且能使估计量的统计效率在一定意义下达到最优。  相似文献   
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