全文获取类型
收费全文 | 156篇 |
免费 | 10篇 |
专业分类
化学 | 137篇 |
晶体学 | 1篇 |
数学 | 25篇 |
物理学 | 3篇 |
出版年
2022年 | 1篇 |
2021年 | 3篇 |
2020年 | 3篇 |
2019年 | 1篇 |
2018年 | 2篇 |
2017年 | 6篇 |
2016年 | 4篇 |
2015年 | 7篇 |
2014年 | 5篇 |
2013年 | 12篇 |
2012年 | 8篇 |
2011年 | 12篇 |
2010年 | 10篇 |
2009年 | 9篇 |
2008年 | 7篇 |
2007年 | 11篇 |
2006年 | 12篇 |
2005年 | 11篇 |
2004年 | 4篇 |
2003年 | 14篇 |
2002年 | 1篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1972年 | 1篇 |
1970年 | 1篇 |
1963年 | 1篇 |
排序方式: 共有166条查询结果,搜索用时 25 毫秒
51.
We analyze the deterministic infinite time horizon optimal control model aimed to determine optimal areas forested by particular tree species in Drahanska highlands in the Czech Republic. Facing the limitations in original data available we suggest a simulation technique to generate valid full scope data and to estimate correct underlaying functions. The simulation procedure, based on the experts suggestions and comments, is described in detail and the economic interpretations of the assumptions made are provided. Subsequently, we develop the optimal control model given the nonlinear cost and revenue functions and find its analytical solution. The results obtained are discussed with respect to forestry practice and further application of our model. The presented approach intends to be a valid basement for further thorough study of related dynamical decision problems in the Czech forestry business. 相似文献
52.
Martin Kubala Jan Vacek Marika Janovská Jitka Ulrichová Vilím Šimánek 《Journal of luminescence》2011,131(7):1340-1345
The fluorescence properties of protopine and allocryptopine in aqueous and organic environments are described for the first time. The fluorescence of alkaloids and their pH-dependent interconversion to cationic forms (transannular interaction) were studied using steady-state and time-resolved fluorescence techniques. For the analysis of tricyclic base and cis/trans tetracyclic cations of the alkaloids, NMR and X-ray crystallography were used. 相似文献
53.
Solutions of portfolio optimization problems are often influenced by a model misspecification or by errors due to approximation, estimation and incomplete information. The obtained results, recommendations for the risk and portfolio manager, should be then carefully analyzed. We shall deal with output analysis and stress testing with respect to uncertainty or perturbations of input data for static risk constrained portfolio optimization problems by means of the contamination technique. Dependence of the set of feasible solutions on the probability distribution rules out the straightforward construction of convexity-based global contamination bounds. Results obtained in our paper [Dupa?ová, J., & Kopa, M. (2012). Robustness in stochastic programs with risk constraints. Annals of Operations Research, 200, 55–74.] were derived for the risk and second order stochastic dominance constraints under suitable smoothness and/or convexity assumptions that are fulfilled, e.g. for the Markowitz mean–variance model. In this paper we relax these assumptions having in mind the first order stochastic dominance and probabilistic risk constraints. Local bounds for problems of a special structure are obtained. Under suitable conditions on the structure of the problem and for discrete distributions we shall exploit the contamination technique to derive a new robust first order stochastic dominance portfolio efficiency test. 相似文献
54.
Dr. Yao Zhao Dr. Julie A. Woods Dr. Nicola J. Farrer Kim S. Robinson Jitka Pracharova Dr. Jana Kasparkova Olga Novakova Huilin Li Dr. Luca Salassa Dr. Ana M. Pizarro Dr. Guy J. Clarkson Dr. Lijiang Song Prof. Dr. Viktor Brabec Prof. Dr. Peter J. Sadler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(29):9578-9591
Platinum diam(m)ine complexes, such as cisplatin, are successful anticancer drugs, but suffer from problems of resistance and side‐effects. Photoactivatable PtIV prodrugs offer the potential of targeted drug release and new mechanisms of action. We report the synthesis, X‐ray crystallographic and spectroscopic properties of photoactivatable diazido complexes trans,trans,trans‐[Pt(N3)2(OH)2(MA)(Py)] ( 1 ; MA=methylamine, Py=pyridine) and trans,trans,trans‐[Pt(N3)2(OH)2(MA)(Tz)] ( 2 ; Tz=thiazole), and interpret their photophysical properties by TD‐DFT modelling. The orientation of the azido groups is highly dependent on H bonding and crystal packing, as shown by polymorphs 1 p and 1 q . Complexes 1 and 2 are stable in the dark towards hydrolysis and glutathione reduction, but undergo rapid photoreduction with UVA or blue light with minimal amine photodissociation. They are over an order of magnitude more potent towards HaCaT keratinocytes, A2780 ovarian, and OE19 oesophageal carcinoma cells than cisplatin and show particular potency towards cisplatin‐resistant human ovarian cancer cells (A2780cis). Analysis of binding to calf‐thymus (CT), plasmids, oligonucleotide DNA and individual nucleotides reveals that photoactivated 1 and 2 form both mono‐ and bifunctional DNA lesions, with preference for G and C, similar to transplatin, but with significantly larger unwinding angles and a higher percentage of interstrand cross‐links, with evidence for DNA strand cross‐linking further supported by a comet assay. DNA lesions of 1 and 2 on a 50 bp duplex were not recognised by HMGB1 protein, in contrast to cisplatin‐type lesions. The photo‐induced platination reactions of DNA by 1 and 2 show similarities with the products of the dark reactions of the PtII compounds trans‐[PtCl2(MA)(Py)] ( 5 ) and trans‐[PtCl2(MA)(Tz)] ( 6 ). Following photoactivation, complex 2 reacted most rapidly with CT DNA, followed by 1 , whereas the dark reactions of 5 and 6 with DNA were comparatively slow. Complexes 1 and 2 can therefore give rapid potent photocytotoxicity and novel DNA lesions in cancer cells, with no activity in the absence of irradiation. 相似文献
55.
Determination of genetic transferrin variants in human serum by high‐resolution capillary zone electrophoresis† 下载免费PDF全文
Jitka Caslavska Jeannine Joneli Ursula Wanzenried Jeannette Schiess Christian Lanz Wolfgang Thormann 《Journal of separation science》2014,37(13):1663-1670
High‐resolution capillary zone electrophoresis in the routine arena with stringent quality assurance is employed for the determination of carbohydrate‐deficient transferrin in human serum. The assay comprises mixing of human serum with a FeIII‐containing solution prior to analysis of the iron‐saturated mixture in a dynamically double‐coated capillary using a commercial buffer at alkaline pH. In contrast to other assays, it provides sufficient resolution for proper recognition of genetic transferrin variants. Analysis of 7290 patient sera revealed 166 isoform patterns that could be assigned to genetic variants, namely, 109 BC, 53 CD, one BD and three CC variants. Several subtypes of transferrin D can be distinguished as they have large enough differences in pI values. Subtypes of transferrin C and B cannot be resolved. However, analysis of the detection time ratios of tetrasialo isoforms of transferrin BC and transferrin CD variants revealed multimodal frequency histograms, indicating the presence of subtypes of transferrin C, B and D. The data gathered over 11 years demonstrate the robustness of the high‐resolution capillary zone electrophoresis assay. This is the first account of a capillary zone electrophoresis based carbohydrate‐deficient transferrin assay with a broad overview on transferrin isoform patterns associated with genetic transferrin variants. 相似文献
56.
Trouillas P Marsal P Svobodová A Vostálová J Gazák R Hrbác J Sedmera P Kren V Lazzaroni R Duroux JL Walterová D 《The journal of physical chemistry. A》2008,112(5):1054-1063
Flavonolignans from silymarin, the standardized plant extract obtained from thistle, exhibit various antioxidant activities, which correlate with the other biological and therapeutic properties of that extract. To highlight the mode of action of flavonolignans as free radical scavengers and antioxidants, 10 flavonolignans, selectively methylated at different positions, were tested in vitro for their capacity to scavenge radicals (DPPH and superoxide) and to inhibit the lipid peroxidation induced on microsome membranes. The results are rationalized on the basis of (i) the oxidation potentials experimentally obtained by cyclic voltammetry and (ii) the theoretical redox properties obtained by quantum-chemical calculations (using a polarizable continuum model (PCM)-density functional theory (DFT) approach) of the ionization potentials and the O-H bond dissociation enthalpies (BDEs) of each OH group of the 10 compounds. We clearly establish the importance of the 3-OH and 20-OH groups as H donors, in the presence of the 2,3 double bond and the catechol moiety in the E-ring, respectively. For silybin derivatives (i.e., in the absence of the 2,3 double bond), secondary mechanisms (i.e., electron transfer (ET) mechanism and adduct formation with radicals) could become more important (or predominant) as the active sites for H atom transfer (HAT) mechanism are much less effective (high BDEs). 相似文献
57.
The use of capillary zone electrophoresis (CZE) with indirect absorbance detection for the analysis of ethyl sulfate (EtS) in serum and urine was investigated. EtS is a direct metabolite of ethanol employed as marker for recent alcohol consumption. Fused-silica capillaries of 60 cm total length were either coated with cetyltrimethylammonium bromide (CTAB, 50 microm I.D. capillary) or poly(diallyldimethylammonium chloride) (PDADMAC, 100 microm I.D. capillary) to allow CZE analyses to be performed with reversed polarity. At pH 2.2 with a maleic acid/phthalic acid background electrolyte, both approaches provided reliable EtS serum levels down to 0.2 mg L(-1) (1.6 microM) for the analysis of solid-phase extracts that were prepared after chloride precipitation. Analysis of urines diluted to a conductivity of 5 S m(-1) and analyzed in the two capillary formats resulted in limits of quantification (LOQs) of 2 and 1 mg L(-1), respectively. With urines adjusted to 10 S m(-1) via dilution or condensation, an LOQ of 0.6 mg L(-1) (4.8 microM) was obtained in the CTAB coated capillary whereas in the PDADMAC-coated capillary of equal length not all matrix components were resolved from EtS. The developed assays are robust and suitable to monitor EtS in samples of individuals who consumed as little as one standard drink of an alcoholic beverage containing about 14 g of ethanol. 相似文献
58.
Azidopropylvinylsulfonamide as a New Bifunctional Click Reagent for Bioorthogonal Conjugations: Application for DNA–Protein Cross‐Linking 下载免费PDF全文
Jitka Dadová Dr. Milan Vrábel Matej Adámik Dr. Marie Brázdová Dr. Radek Pohl Prof. Dr. Miroslav Fojta Prof. Dr. Michal Hocek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):16091-16102
N‐(3‐Azidopropyl)vinylsulfonamide was developed as a new bifunctional bioconjugation reagent suitable for the cross‐linking of biomolecules through copper(I)‐catalyzed azide–alkyne cycloaddition and thiol Michael addition reactions under biorthogonal conditions. The reagent is easily clicked to an acetylene‐containing DNA or protein and then reacts with cysteine‐containing peptides or proteins to form covalent cross‐links. Several examples of bioconjugations of ethynyl‐ or octadiynyl‐modified DNA with peptides, p53 protein, or alkyne‐modified human carbonic anhydrase with peptides are given. 相似文献
59.
During the past two decades, chiral capillary electrophoresis (CE) emerged as a promising, effective and economic approach for the enantioselective determination of drugs and their metabolites in body fluids, tissues and in vitro preparations. This review discusses the principles and important aspects of CE-based chiral bioassays, provides a survey of the assays developed during the past 10 years and presents an overview of the key achievements encountered in that time period. Applications discussed encompass the pharmacokinetics of drug enantiomers in vivo and in vitro, the elucidation of the stereoselectivity of drug metabolism in vivo and in vitro, and bioanalysis of drug enantiomers of toxicological, forensic and doping interest. Chiral CE was extensively employed for research purposes to investigate the stereoselectivity associated with hydroxylation, dealkylation, carboxylation, sulfoxidation, N-oxidation and ketoreduction of drugs and metabolites. Enantioselective CE played a pivotal role in many biomedical studies, thereby providing new insights into the stereoselective metabolism of drugs in different species which might eventually lead to new strategies for optimization of pharmacotherapy in clinical practice. 相似文献
60.
A novel long drop time mercury electrode has been constructed from common fused-silica capillary (50 μm I.D., 360 μm E.D.). Proposed device provides reproducible mercury drops with typical lifetime 40-120 s. The electrode was used for a set of electrocapillary measurements aimed at determination of critical micelle concentration of anionic surfactants by a convection controlled drop-time technique. A critical micelle concentration of sodium dodecyl sulfate 5.6 ± 0.4 mmol L−1 and 4.3 ± 0.4 mmol L−1 were obtained in 1 mmol L−1 and 5 mmol L−1 phosphate buffer (pH 7.0), respectively. The values were comparable to those obtained from conductometric measurements under the same conditions (7.0 ± 0.1 mmol L−1 and 5.2 ± 0.1 mmol L−1, respectively) and the difference was explained in accordance with theory of hemi-micelle formation. 相似文献