全文获取类型
收费全文 | 31733篇 |
免费 | 4733篇 |
国内免费 | 2945篇 |
专业分类
化学 | 19047篇 |
晶体学 | 535篇 |
力学 | 1199篇 |
综合类 | 212篇 |
数学 | 975篇 |
物理学 | 10090篇 |
无线电 | 7353篇 |
出版年
2024年 | 71篇 |
2023年 | 325篇 |
2022年 | 557篇 |
2021年 | 729篇 |
2020年 | 1009篇 |
2019年 | 881篇 |
2018年 | 899篇 |
2017年 | 1095篇 |
2016年 | 1379篇 |
2015年 | 1346篇 |
2014年 | 1524篇 |
2013年 | 2912篇 |
2012年 | 1965篇 |
2011年 | 1969篇 |
2010年 | 1625篇 |
2009年 | 1761篇 |
2008年 | 1837篇 |
2007年 | 1856篇 |
2006年 | 1804篇 |
2005年 | 1610篇 |
2004年 | 1521篇 |
2003年 | 1343篇 |
2002年 | 1336篇 |
2001年 | 968篇 |
2000年 | 1005篇 |
1999年 | 828篇 |
1998年 | 748篇 |
1997年 | 610篇 |
1996年 | 540篇 |
1995年 | 569篇 |
1994年 | 442篇 |
1993年 | 379篇 |
1992年 | 332篇 |
1991年 | 275篇 |
1990年 | 224篇 |
1989年 | 159篇 |
1988年 | 158篇 |
1987年 | 127篇 |
1986年 | 120篇 |
1985年 | 100篇 |
1984年 | 98篇 |
1983年 | 46篇 |
1982年 | 74篇 |
1981年 | 57篇 |
1980年 | 52篇 |
1979年 | 55篇 |
1978年 | 24篇 |
1977年 | 13篇 |
1976年 | 9篇 |
1973年 | 17篇 |
排序方式: 共有10000条查询结果,搜索用时 109 毫秒
991.
We describe a route for the polymer supported total synthesis of the cyclic bisbibenzyls of the isoplagiochin type found in liverworts. TentaGel® resins were used as solid support for a sequence involving Suzuki, Wittig and hydrogenation protocols. The polymer linked intermediates could be characterized by HR-MAS NMR. This route is to be extended to the synthesis of small libraries of differently halogenated derivatives. 相似文献
992.
The calix[4] open-chain crown ether, 5,11,17,23-tetra-tert-butyl-25,27-di(2-allyloxyethoxyl)-26,28-dihydroxycalix[4]arene was synthesized and used for preparation of solid-phase microextraction (SPME) fibers of enhanced extraction efficiency. The new SPME coating made from calix[4] open-chain crown ether and hydroxyl-terminated silicone oil was developed with the aid of vinyltriethoxylsilane as bridge using sol-gel method and cross-linking technology. The efficiency of the novel fiber in the extraction of polar aromatic and aliphatic compounds, such as phenols, alcohols, and volatile fatty acids, was also investigated. Due to the introduction of the polar open-chain crown ether in calix[4]arene molecules, the calix[4] open-chain crown ether fiber showed much better selectivity and sensitivity to these polar compounds in comparison with calix[4]arene fiber. It also had superior extraction efficiency when compared to commercial poly(dimethylsiloxane)-divinylbenzene and polyacrylate fibers. Parts per billion to parts per trillion level detection limits were achieved for most of the analytes through SPME in conjunction with GC and flame ionization detector. The linear ranges were two to four orders of magnitude, and the RSD values were below 7% for all analytes. The novel fiber was applied to determine volatile alcohols and fatty acids in wine samples. The volatile-free wine prepared in this work was used to assure similar chemical environment for analytes in both calibration solutions and in real wine samples, thus compensating for possible matrix interferences. The established internal standard method using 4-methyl-2-pentanol as internal standard showed satisfactory accuracy and precision. 相似文献
993.
Chiral separation method development is usually very time-consuming due to the diversity in chemical structures of pharmaceutical drug substances as well as the suitable separation conditions and the problem to choose the appropriate chiral selector. This paper shows capillary zone electrophoresis (CZE) which was developed for chiral separation of a basic compound - rivastigmine (RIV) using 30 cm × 50 μm i.d. polyacrylamide (PAA)-coated fused-silica capillary (effective length 20 cm), amine-modified phosphate buffer of pH 2.5 and sulfated-β-CD (S-β-CD) as chiral selector. Other selected native or derivatized cyclodextrins (CDs) were also tested: β-CD (5, 30 mM), carboxymethyl-β-CD (5, 30 mM), dimethyl-β-CD (15 mM), hydroxypropyl-β-CD (5, 30 mM), hydroxypropyl-α-CD (5, 30 mM) and hydroxypropyl-γ-CD (5, 30 mM). Complete enantiomeric separation of RIV was achieved at 20 kV, 18 °C and detection at 200 nm within 8 min with R.S.D. for the absolute migration time reproducibility of less than 2.1%. Rectilinear calibration range was 5.0-500.0 μM of each enantiomer (r = 0.9994-0.9995). The CZE method proposed was used for the control of chiral purity of pharmaceutically active S-RIV and for the analysis of Exelon caps preparation. 相似文献
994.
A. Daoudi A. Anakkar J. -M. Buisine F. Bougrioua N. Isaert H. T. Nguyen 《Journal of Thermal Analysis and Calorimetry》1996,46(2):337-345
Effects of high pressures on phase sequences of the two homologousn=16 andn=18 of the (3-fluoro-4 ((R) or (S)-methylheptyloxy) 4, (4-fluoro benzoyloxy) tolans) series have been studied. Both compounds exhibit the new twisted Smectic A phase called Twist Grain Boundary TGBA phase. The high pressure experiments were performed by thermobarometric analysis. The order of the transitions (first or second) have been determined in respect to pressure and temperature. The pressure-temperature phase diagrams show that the TGBA phase is stabilized by increasing pressure; an inducedN
* phase appears under high pressure for n=18 leading to the observation of TGBA-N
*-I triple point. 相似文献
995.
CHU Yongbao GAO Baoyu YUE Qinyan WANG Yan & WANG Shuguang . School of Environmental Science Engineering Shandong University Jinan China . College of Material Environment Qingdao University of Science Technology Qingdao China 《中国科学B辑(英文版)》2006,(4)
Polyaluminum chloride (PAC) coagulant has been developed and widely used in water and wastewater treatment industry since the 1980s[1]. PAC is normally made by partial hydrolysis of acid aluminum chloride solution using slow alkaline titration method. However, this method would result in many different Al species. Among these Al species, it seems that tridecamer (Al13O4(OH) 724 , often denoted by Al13) is the most effective and stable polymeric Al species for water and wastewater treatme… 相似文献
996.
O. de la Iglesia M. Pedernera R. Mallada Z. Lin J. Rocha J. Coronas J. Santamaría 《Journal of membrane science》2006,280(1-2):867-875
MCM-48 membranes have been prepared on alumina supports of different pore sizes. A battery of characterization techniques has been used to study the physical properties and the quality of the membranes prepared. The highest quality membranes were prepared on supports with pore size of up to 60 nm. The MCM-48 membranes were tested in the separation of gas phase mixtures and a cyclohexane/O2 selectivity higher than 270 was obtained. The selective separation of organic compounds from inert components is a result of the cooperative effects of capillary condensation in MCM-48 pores and of the specific interactions of the permeating compounds and the membrane material. 相似文献
997.
In the present study a multi-residue analytical method was developed for monitoring some polar pesticides such as acephate,
methamidophos, carbofuran, isoproturon, dimethoate in water with SPE (solid-phase extraction) and LC–MS–MS. Acetochlor was
taken as surrogate, and alachlor as internal standard. SPE with different types of columns was compared with LLE (liquid-liquid
extraction). Further, the breakthrough volume for different pesticides was determined. The results showed that the selected
pesticides can be determined very sensitively with LC–MS–MS. The minimum detectable quantity (MDQ) for each pesticide was
about 1.0 ng. To date, SPE cartridge studies showed that the Oasis HLB cartridges were suitable for further studies. However,
for Oasis HLB cartridge, different pesticide showed different breakthrough volume. The results showed that for acephate and
methamidophos, the breakthrough volume was about 30 mL of water sample, much less than the breakthrough volume of other pesticides
studied. Because of the higher vapor pressure and higher Henry's constant of methamidophos, dimethoate and carbofuran, much
attention should be paid on their losses in the evaporation step of the experiment. This analytical method can be applied
to determine pesticide contamination in environmental water samples.
Revised: 12 September 2005 and 21 October 2005 相似文献
998.
As the relation of chirality and activities of drugs is researched deeply, people become to re-alize the clinic importance of chirality. The different enantiomers of a drug can have vastly differ-ent pharmacological activities, pharmacokinetic processes and toxicity[1,2]. The most well-docu- mented example is that of the drug substance thalidomide. Bitter lessons and scientific research promote the interest in single-enantiomer drugs, so the potential of the chiral drug market is enormous[3]. … 相似文献
999.
With the combination of the the stoichiometric displacement model for retention (SDM-R) in reversed phase liquid chromatography (RPLC) and the stoichiometric displacement model for adsorption (SDM-A) in physical chemistry,the total number of moles of the re-solvated methanol of stationary phase side.nr,and that of solute side in the mobile phase,q,corresponding the one mole of the desorbing solute,were separately determined and referred as the characterization parameters of the contributions of the adsorption mechanism and partition mechanism to the solute retention,respectively.A chromatographic system of insulin,using mobile phase consisting of the pseudo-homologue of alcohols(methanol,ethanol and 2-propanol)-water and trifluoroacetic acid was employed.The maximum number of the methanol layers on the stationary phase surface was found to be 10.6,only 3 of which being valid in usual RPLC,traditionally referred as a volume process in partition mechanism.However,it still follows the SDM-R.Both of q and nr of insulin were found not to be zero,indicating that the retention mechanism of insulin is a mixed mode of partition mechanism and adsorption mechanism.When methanol is used as the organic modifier,the ratio of q/nr was 1.13,indicating the contribution to insulin retention due to partition mechanism being a bit greater than that due to adsorption mechanism.A linear relationship between q,or nr and the carbon number of the pseudo-homologue in the mobile phase was also found.As a methodology for investigating the retention mechanism retention and behavior of biopolymers.a homologue of organic solvents as the organic modifier in mobile phase has also been explored. 相似文献
1000.
New uniform algorithm to predict reversed phase retention values under different gradient conditions
Wang Longxing 《Analytica chimica acta》2003,476(1):123-129
A new numerical emulation algorithm was established to calculate retention parameters in RP-HPLC with several retention times under different linear or nonlinear binary gradient elution conditions and further predict the retention time under any other binary gradient conditions. A program was written according to this algorithm and nine solutes were used to test the program. The prediction results were excellent. The maximum relative error of predicted retention time was less than 0.45%. 相似文献