全文获取类型
收费全文 | 3504篇 |
免费 | 140篇 |
国内免费 | 26篇 |
专业分类
化学 | 2480篇 |
晶体学 | 19篇 |
力学 | 53篇 |
数学 | 549篇 |
物理学 | 569篇 |
出版年
2024年 | 5篇 |
2023年 | 19篇 |
2022年 | 65篇 |
2021年 | 96篇 |
2020年 | 86篇 |
2019年 | 106篇 |
2018年 | 118篇 |
2017年 | 80篇 |
2016年 | 136篇 |
2015年 | 128篇 |
2014年 | 145篇 |
2013年 | 200篇 |
2012年 | 239篇 |
2011年 | 259篇 |
2010年 | 172篇 |
2009年 | 113篇 |
2008年 | 242篇 |
2007年 | 241篇 |
2006年 | 217篇 |
2005年 | 189篇 |
2004年 | 148篇 |
2003年 | 119篇 |
2002年 | 100篇 |
2001年 | 44篇 |
2000年 | 30篇 |
1999年 | 36篇 |
1998年 | 34篇 |
1997年 | 21篇 |
1996年 | 31篇 |
1995年 | 23篇 |
1994年 | 29篇 |
1993年 | 15篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1989年 | 8篇 |
1988年 | 11篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1984年 | 9篇 |
1983年 | 9篇 |
1982年 | 10篇 |
1981年 | 6篇 |
1980年 | 9篇 |
1979年 | 8篇 |
1977年 | 5篇 |
1976年 | 12篇 |
1975年 | 11篇 |
1973年 | 7篇 |
1954年 | 5篇 |
排序方式: 共有3670条查询结果,搜索用时 265 毫秒
171.
Pavel F. Vlad Alexandru G. Ciocarlan Mihai N. Coltsa Alexandr V. Baranovsky Natalya B. Khripach 《合成通讯》2013,43(22):3960-3972
This article describes a new efficient synthesis of drim-7,9(11)-diene and its hydroxylated derivates from drim-8-en-7-one. Reduction of this ketone with NaBO4 in the presence of CeCl3 · 7H2O afforded regio- and stereoselectively drim-8-en-7β-ol in a high yield. Its dehydration with H2SO4 under mild conditions led to drim-7,9(11)-diene. Noncatalytic oxidation of drim-7,9(11)-diene with OsO4 and the catalytic oxidation with the pair OsO4–NMO gave, in a high yield, depending on conditions, driman-7β,8β,9α,11-tetraol or its mixture with drim-7-en-9α,11-diol and drim-9(11)-en-7α,8α-diol. Under optimal conditions the total yield of these diols reached 89%. The separate, noncatalytic oxidation of drim-7-en-9α,11-diol and of drim-9(11)-en-7α,8α-diol with OsO4 afforded driman-7α,8α,9α,11-tetraol. 相似文献
172.
Michaela Mačková Michal Himl Jan Budka Michaela Pojarová Ivana Císařová Václav Eigner Petra Cuřínová Hana Dvořáková Pavel Lhoták 《Tetrahedron》2013,69(4):1397-1402
Methylation of 5,11,17,23-tetranitrothiacalix[4]arene with diazomethane leads to the tetramethoxy derivative, which was studied using single-crystal X-ray crystallography. It revealed that this compound, albeit in the 1,3-alternate conformation, can form the inclusion complexes with various solvent molecules possessing acidic methyl groups (ethyl acetate, nitromethane, acetone, acetonitrile) and creates interesting infinite channels filled with solvent molecules. The subsequent transformation of nitro groups into the ureido moieties gave receptors capable of anion recognition even in a highly HB-competitive solvent like DMSO. 相似文献
173.
Nina K. Gusarova Pavel A. Volkov Nina I. Ivanova Boris G. Sukhov Ludmila I. Larina Olga N. Kazheva Grigorii G. Alexandrov Oleg A. D’yachenko Boris A. Trofimov 《Tetrahedron letters》2013
The oxidative cross-coupling between 4-hydroxy-6-methyl-2-pyrone or 3-hydroxy-2-methyl-4-pyrone and secondary phosphine chalcogenides proceeds in CCl4/Et3N under mild conditions (20–52 °С, 0.75–10 h) through the hydroxyl group to give O-(6-methyl-2-oxo-2H-pyran-4-yl) diorganylphosphinochalcogenoates or O-(2-methyl-4-oxo-4H-pyran-3-yl) diorganylphosphinochalcogenoates, in high yields. 相似文献
174.
Pavel Andreevich Yunin Yurii Nikolaevich Drozdov Mikhail Nikolaevich Drozdov 《Surface and interface analysis : SIA》2013,45(8):1228-1232
We study the deconvolution of the secondary ion mass spectrometry (SIMS) depth profiles of silicon and gallium arsenide structures with doped thin layers. Special attention is paid to allowance for the instrumental shift of experimental SIMS depth profiles. This effect is taken into account by using Hofmann's mixing‐roughness‐information depth model to determine the depth resolution function. The ill‐posed inverse problem is solved in the Fourier space using the Tikhonov regularization method. The proposed deconvolution algorithm has been tested on various simulated and real structures. It is shown that the algorithm can improve the SIMS depth profiling relevancy and depth resolution. The implemented shift allowance method avoids significant systematic errors of determination of the near‐surface delta‐doped layer position. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
175.
Pavel ?iler Josef Kr��tky Iva Kol��?ov�� Jarom��r Havlica Ji?�� Brand?tetr 《Chemical Papers》2013,67(2):213-220
Possibilities of a multicell isoperibolic-semiadiabatic calorimeter application for the measurement of hydration heat and maximum temperature reached in mixtures of various compositions during their setting and early stages of hardening are presented. Measurements were aimed to determine the impact of selected components?? content on the course of ordinary Portland cement (OPC) hydration. The following components were selected for the determination of the hydration behaviour in mixtures: very finely ground granulated blast furnace slag (GBFS), silica fume (microsilica, SF), finely ground quartz sand (FGQ), and calcined bauxite (CB). A commercial polycarboxylate type superplasticizer was also added to the selected mixtures. All maximum temperatures measured for selected mineral components were lower than that reached for cement. The maximum temperature increased with the decreasing amount of components in the mixture for all components except for silica fume. For all components, except for CB, the values of total released heat were higher than those for pure Portland cement samples. 相似文献
176.
Emanuel Makrlík Pavel Selucký Petr Vaňura 《Journal of inclusion phenomena and macrocyclic chemistry》2013,76(1-2):13-17
From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M+ (aq) + 1·Cs+ (nb) ? 1·M+ (nb) + Cs+ (aq) taking place in the two-phase water–nitrobenzene system (M+ = Ag+, K+, Rb+, Tl+; 1 = 1,3-alternate-25,27-bis(1-octyloxy)calix[4]arene-crown-6; aq is aqueous phase, nb is nitrobenzene phase) were determined. Moreover, the stability constants of the 1·M+ complexes in water-saturated nitrobenzene were calculated; they were found to increase in the series of K+ < Rb+ < Ag+ < Tl+. 相似文献
177.
Prof. Pavel Anzenbacher Jr. Dr. Yuanli Liu Dr. Manuel A. Palacios Dr. Tsuyoshi Minami Dr. Zhuo Wang Dr. Ryuhei Nishiyabu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8497-8506
As the demand for probes suitable for sensor development increases, investigation of approaches that utilize known successful receptors gains in general importance. This study describes a two‐prong approach that can be used as a guide to developing sensors from known receptors. First, the conversion of a simple receptor, calix[4]pyrrole, into a fluorescent probe to establish a ratiometric signal is described. Secondly, the sensors that employ an output from a single ratiometric calix[4]pyrrole probe are fabricated by using poly(ether‐urethane) hydrogel copolymers. These hydrogels are designed to absorb, internalize and transport aqueous electrolytes. A sensor array of ten different poly(ether‐urethane) matrices with varying comonomer proportions were doped with a single probe and were exposed to eight different anions: acetate, benzoate, fluoride, chloride, phosphate, pyrophosphate, hydrogen sulfide, and cyanide, eight urine samples and anti‐inflammatory drugs (NSAIDs). The poly(ether‐urethane) matrices comprise different proportions of anion‐binding urethane moieties and different hydrophilicity given by the ratio between ethylene glycol ether and butylene glycol ether. This diversity in the hydration behavior provides different environment polarity, in which the recognition and self‐assembly processes display enough diverse behavior to allow for unique response of the probe to the analytes. Furthermore, a single probe is shown to recognize eight different aqueous anions and eight urine samples when embedded in ten different polyurethanes in an array that displays 100 % classification accuracy. To demonstrate the potential of the concept for quantitative studies, an estimation of non‐steroidal anti‐inflammatory drugs ibuprofen and diclofenac in water and in saliva was performed. A limit of detection of 0.1 ppm and a dynamic range of 0.1–0.6 and 0.05–60 ppm was observed, respectively. Given the general difficulty of chemosensors to recognize aqueous anions, the fact that one probe recognizes eight different analytes attests to an enormous effect of the polymer environment on the recognition process. This method could be used to generate a variety of sensor arrays for various analyses including species that are difficult to recognize, such as small‐molecule‐ and inorganic anions. 相似文献
178.
Prof. Dr. Andrei V. Malkov Dr. Sigitas Stončius Dr. Mark Bell Dr. Fabiomassimo Castelluzzo Dr. Pedro Ramírez‐López Dr. Lada Biedermannová Prof. Dr. Vratislav Langer Dr. Lubomír Rulíšek Prof. Dr. Pavel Kočovský 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(28):9167-9185
Detailed kinetic and computational investigation of the enantio‐ and diastereoselective allylation of aldehydes 1 with allyltrichlorosilanes 5 , employing the pyridine N‐oxides METHOX ( 9 ) and QUINOX ( 10 ) as chiral organocatalysts, indicate that the reaction can proceed through a dissociative (cationic) or associative (neutral) mechanism: METHOX apparently favors a pentacoordinate cationic transition state, while the less sterically demanding QUINOX is likely to operate via a hexacoordinate neutral complex. In both pathways, only one molecule of the catalyst is involved in the rate‐ and selectivity‐determining step, which is supported by both experimental and computational data. 相似文献
179.
Capillary electrophoresis for the analysis of paralytic shellfish poisoning toxins in shellfish: Comparison of detection methods 下载免费PDF全文
Aemi S. Abdul Keyon Rosanne M. Guijt Andras Gaspar Artaches A. Kazarian Pavel N. Nesterenko Christopher J. Bolch Michael C. Breadmore 《Electrophoresis》2014,35(10):1496-1503
Paralytic shellfish toxins (PSTs) are produced by marine and freshwater microalgae and accumulate in shellfish including mussels, oysters, and scallops, causing possible fatalities when inadvertently consumed. Monitoring of PST content of shellfish is therefore important for food safety, with currently approved methods based on HPLC, using pre‐ or postcolumn oxidation for fluorescence detection (HPLC‐FLD). CE is an attractive alternative for screening and detection of PSTs as it is compatible with miniaturization and could be implemented in portable instrumentation for on‐site monitoring. In this study, CE methods were developed for C4D, FLD, UV absorption detection, and MS—making this first report of C4D and FLD for PSTs detection. Because most oxidized toxins are neutral, MEKC was used in combination with FLD. The developed CZE‐UV and CZE‐C4D methods provide better resolution, selectivity, and separation efficiency compared to CZE‐MS and MEKC‐FLD. The sensitivity of the CZE‐C4D and MEKC‐FLD methods was superior to UV and MS, with LOD values ranging from 140 to 715 ng/mL for CZE‐C4D and 60.9 to 104 ng/mL for MEKC‐FLD. With the regulatory limit for shellfish samples of 800 ng/mL, the CZE‐C4D and MEKC‐FLD methods were evaluated for the screening and detection of PSTs in shellfish samples. While the CZE‐C4D method suffered from significant interferences from the shellfish matrix, MEKC‐FLD was successfully used for PST screening of a periodate‐oxidized mussel sample, with results confirmed by HPLC‐FLD. This confirms the potential of MEKC‐FLD for screening of PSTs in shellfish samples. 相似文献
180.
Filip Botha Jan Budka Václav Eigner Oldřich Hudeček Lukáš Vrzal Ivana Císařová Pavel Lhoták 《Tetrahedron》2014
A new type of calixarene-based receptor designed for the recognition of chiral anions was prepared by the introduction of (S)-2-methylbutan-1-ol moieties into the lower rim of calixarene. The immobilization of calixarene skeleton in the 1,3-alternate conformation enabled the construction of a cavity consisting of preorganised ureido functions and chiral substituents in close proximity. This cavity is capable of chiral discrimination of selected anions as demonstrated on d- and l-phenylalaninates. 相似文献