全文获取类型
收费全文 | 76501篇 |
免费 | 20119篇 |
国内免费 | 333篇 |
专业分类
化学 | 71560篇 |
晶体学 | 310篇 |
力学 | 3679篇 |
综合类 | 12篇 |
数学 | 12114篇 |
物理学 | 9278篇 |
出版年
2024年 | 459篇 |
2023年 | 4758篇 |
2022年 | 1618篇 |
2021年 | 2809篇 |
2020年 | 5153篇 |
2019年 | 2554篇 |
2018年 | 3722篇 |
2017年 | 2101篇 |
2016年 | 6803篇 |
2015年 | 6636篇 |
2014年 | 5947篇 |
2013年 | 6316篇 |
2012年 | 6550篇 |
2011年 | 3396篇 |
2010年 | 5520篇 |
2009年 | 5216篇 |
2008年 | 1662篇 |
2007年 | 1381篇 |
2006年 | 693篇 |
2005年 | 4493篇 |
2004年 | 3951篇 |
2003年 | 2340篇 |
2002年 | 517篇 |
2001年 | 333篇 |
1999年 | 203篇 |
1997年 | 171篇 |
1995年 | 230篇 |
1994年 | 160篇 |
1993年 | 274篇 |
1992年 | 300篇 |
1991年 | 249篇 |
1990年 | 205篇 |
1989年 | 196篇 |
1988年 | 241篇 |
1987年 | 171篇 |
1982年 | 159篇 |
1981年 | 190篇 |
1980年 | 225篇 |
1979年 | 239篇 |
1978年 | 246篇 |
1977年 | 363篇 |
1976年 | 482篇 |
1975年 | 521篇 |
1974年 | 549篇 |
1973年 | 373篇 |
1972年 | 502篇 |
1971年 | 446篇 |
1970年 | 664篇 |
1969年 | 499篇 |
1968年 | 537篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
Koji Nakabayashi Masaki Kawano Prof. Dr. Tatsuhisa Kato Prof. Dr. Ko Furukawa Dr. Shin‐ichi Ohkoshi Prof. Dr. Toshiya Hozumi Dr. Makoto Fujita Prof. Dr. 《化学:亚洲杂志》2007,2(1):164-170
We show a new approach to manipulating the through‐space spin–spin interaction by utilizing the confined cavity of a self‐assembled M6L4 coordination cage. The coordination cage readily encapsulates stable organic radicals in solution, which brings the spin centers of the radicals closer to each other. In sharp contrast to the fact that the radical in solution in the absence of the cage is in a doublet state, in the presence of the cage through‐space spin–spin interaction is induced through cage‐encapsulation effects in solution as well as in the solid state, resulting in the triplet state of the complex. These results were confirmed by ESR spectroscopy and X‐ray crystallography. The quantity of triplet species generated by encapsulation in the cage increases with increasing affinity of the radicals to the cage. We estimated the affinity between several types of guests and the cage in solution by cyclic voltammetry. We also demonstrate that the through‐space interaction of organic radicals within the self‐assembled coordination cage can be controlled by external stimuli such as heat or pH. 相似文献
982.
A reversed-phase LC–MS method with quadrupole-time of flight (QTOF) detection has been developed for the determination of four dinitro-toluenesulfonic acids and two amino-nitro-toluenesulfonic acids in groundwater. The analytes were separated by HPLC with 0.1% (v/v) formic acid as mobile phase modifier compatible with mass spectrometric detection. QTOF-MS analysis with negative ion electrospray ionization afforded good selectivity and sensitivity for analysis of the dinitro- and amino-nitro-toluenesulfonic acids. Structure elucidation and confirmation were accomplished by tandem mass spectrometry. Characteristic ions resulting from the loss of NO, NO2, and SO2 from the [M–H]– ions were detected. An intense fragment ion at m/z 80 representing the [SO3]– ion was detected for all dinitro- and amino-nitro-toluenesulfonic acids. Solid-phase extraction using a co-polymer cartridge was developed for preconcentration of the analytes from water. Good recovery (>85%) was achieved when 0.1% formic acid was added into the water samples before extraction. Method detection limits ranged from 10 to 76 ng L–1 for the targeted compounds when 10 mL water was analyzed. Groundwater samples collected from wells close to a former ammunition plant in Stadtallendorf, Germany, were analyzed for the dinitro- and amino-nitro-toluenesulfonic acids. 相似文献
983.
This work utilizes on-column ligand synthesis and affinity capillary electrophoresis (ACE) to determine binding constants (Kb) of 9-flourenylmethyloxy carbonyl (Fmoc)-amino acid derivatives to the glycopeptide antibiotics ristocetin (Rist) and teicoplanin (Teic). In this technique, two separate plugs of sample are injected on to the capillary column and electrophoresed. The initial sample plug contains a d-Ala-d-Ala terminus peptide and either one or two non-interacting standard(s). The second plug contains a Fmoc-amino acid-N-hydroxysuccinimide (NHS) ester. The electrophoresis is then carried out with an increasing concentration of Rist or Teic in the running buffer. Upon electrophoresis the initial d-Ala-d-Ala peptide reacts with the Fmoc-amino acid yielding a new Fmoc-amino acid-d-Ala-d-Ala peptide derivative. Continued electrophoresis results in the binding of Rist or Teic to the Fmoc-amino acid-d-Ala-d-Ala peptide derivatives. Analysis of the change in the relative migration time ratio (RMTR) or electrophoretic mobility () of the Fmoc-amino acid-d-Ala-d-Ala peptide derivatives relative to the non-interacting standards, as a function of the concentration of Rist and Teic, yields a value for
Kb. These findings demonstrate the advantage of coupling on-column ligand synthesis to ACE for estimating binding parameters between antibiotics and ligands.Abbreviations Rist
Ristocetin
- Teic
Teicoplanin
- ACE
Affinity capillary electrophoresis
- RMTR
Relative migration time ratio 相似文献
984.
A simple and advantageous method for the determination of titanium using graphite furnace atomic absorption spectrometry with slurry sampling has been developed. Titanium is one of the refractory elements that form thermally stable carbides in the graphite tube, which leads to severe memory effects. Trifluoromethane (Freon-23) was applied in the purge gas during the atomization step or alternatively just prior to the atomization to successfully eliminate the problems of carbide formation and increase the lifetime of the furnace tube which could be used for more than 600 heating cycles. A flow rate of 40 mL min–1 (5% of Freon in argon) was used to obtain symmetrical peaks with no tailing. However, when the gas flow rate was too high (250 mL min–1) the peak-tailing and memory effects reappeared. Ti was determined in various materials covering a wide range of concentrations, from 2.8 g g–1 to 12% (m/m) Ti. The accuracy of the method was confirmed by analyzing certified reference materials (CRMs) or by comparing the results with those obtained using inductively coupled plasma–atomic emission spectrometry (ICP–AES) after decomposition of the samples. The materials analyzed were soil, plant, human hair, coal, urban particulate matters, toothpaste, and powdered paint. 相似文献
985.
Stefan?DiethelmEmail author Joseph?Sfeir Frank?Clemens Jan?Van herle Daniel?Favrat 《Journal of Solid State Electrochemistry》2004,8(9):611-617
Dense planar and tubular oxygen separation membranes of La0.6Ca0.4Fe0.75Co0.25O3– were investigated as reactors for the partial oxidation (POX) of methane to syngas. Their permeation properties were measured in an air/argon
pO2 gradient as a function of temperature. At 900 °C, the oxygen flux through a 1.26-mm-thick membrane was 0.075 mol/cm2·s and through a 0.25-mm-thick tube, 0.24 mol/cm2·s.For the POX measurements, a catalyst was added to the membrane and methane was introduced on the argon side. This resulted in a gradual increase of the oxygen flux with increasing concentration of methane, reaching 2 mol/cm2·s at 900 °C with pure methane. For the planar reactor, the CO selectivity reached 99% and the CH4 conversion 75% at 918 °C with pure methane. For the tubular reactor, the CO selectivity and CH4 conversion were 83 and 99%, respectively, under the same conditions. After 1,400 h of operation in a tubular POX reactor, the membrane was examined revealing phase demixing and local decomposition.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003 相似文献
986.
The synthesis of a novel class of functionalized benzophanes in which a (2′-hydroxy)ethoxy pendant arm is attached to the phenyl ring is reported. The reported approach, utilizes simple starting materials, and skillful organization of the synthetic steps allows for simultaneous transforms of the macrocyclic ring and the pendant arm. Binding studies of these systems with Pd2+ and Cd2+ cations is described. A chromatographic stationary phase containing the benzodiazacoronand moiety was also synthesized, and found to interact specifically with isomeric nitrobenzene derivatives. 相似文献
987.
Rafa? Bogel-?ukasik 《Monatshefte für Chemie / Chemical Monthly》2007,2(3):1137-1144
Secondary chiral alcohols are very attractive intermediates in organic synthesis of pharmaceutical and the fine-chemical industries.
The processes employing ionic liquids to obtain enantiomers of secondary alcohols have become sustainable. Furthermore, physico-chemical
properties of ionic liquids opened new possibilities to design “solvent free” processes for the resolution of racemic secondary
alcohols. This review is aimed to highlight some of the most important achievements in resolution of secondary alcohols. 相似文献
988.
Organic and inorganic anions are analyzed using capillary zone electrophoresis with indirect fluorescence detection. As electrolyte 2,5-dihydroxybenzoic acid is used. By adding Pb2+ to the electrolyte the migration time of SO4(2-) can be selectively influenced and the separation of Cl- and SO4(2-) considerably improved. The fluorescence intensity of 2,5-dihydroxybenzoic acid increases in the presence of Pb2+ up to a concentration of 6*10(-4) mol/L Pb2+. Limits of detection in the lower mumol/L range were obtained. 相似文献
989.
Summary Shearing at constant gradient of polyisobutylene (PIB) solutions in viscous polybutene oils results in time dependent changes
of their viscosities. Two PIB fractions (M=8·106 and 3.8·106) have been studied in a variety of solvents, covering the viscosity range from 5 to 0.5·10−2 poise. The overall phenomenon is similar to that already observed for polymethylmethacrylate, polystyrene, and polyethylene
oxide solutions in Aroclor.
Results have been discussed in terms of polymer molecular weight and concentration, solvent viscosity and gradient. The systems
investigated are free from strong polar interactions and tendency toward molecular aggregation; time dependent changes of
viscosity are therefore observable also for true molecularly dispersed solutions.
Zusammenfassung Scherung mit konstantem Geschwindigkeitsgradienten von Polyisobutylen (PIB)-L?sungen in viskosen Polybuten-?len ergibt zeitabh?ngige ?nderungen ihrer Viskosit?ten. Zwei PIB-Fraktionen (M=8·106 und 3,8·106) wurden in einer Vielzahl von L?sungsmitteln untersucht, die den Viskosit?tsbereich von 5 bis 0,5·10−2 Poise überdeckten. Das ph?nomenologische Erscheinungsbild ist ?hnlich dem schon beobachteten für Polymethylmethacrylat, Polystyrol und Poly?thylenoxid-L?sungen in Aroclor. Die Ergebnisse wurden hinsichtlich des Polymer-Molekulargewichts und der Konzentration, der L?sungsmittelviskosit?t und des Gradienten diskutiert. Die untersuchten Systeme sind frei von starken polaren Wechselwirkungen und von Tendenzen in Richtung auf molekulare Aggregation. Zeitabh?ngige ?nderungen der Viskosit?t sind deshalb auch für wahre molekulardisperse L?sungen beobachtbar.相似文献
990.
Zusammenfassung Es werden Verbesserungen von Nachweisen von Alkoholen, Chloral, Salicylalkohol, Salicin, Sulfoxylatverbindungen und bestimmten reduzierenden organischen Verbindungen beschrieben, durch die man zu mikroanalytischer Empfindlichkeit und zum Teil auch zu erhöhter Selektivität gelangt.
Summary Improvements of tests for alcohols, chloral, salicylalcohol, salicine, sulfoxylate compounds and certain reducing organic compounds are described, which lead to microanalytical sensibility and sometimes also to enhanced selectivity.
Résumé On décrit des améliorations des méthodes d'identification des alcools, du chloral, de l'alcool salicylique, de la salicine, de composés sulfoxyliques et de combinaisons organiques réductrices définies. Elles atteignent une sensibilité microanalytique et leur sélectivité est parfois accrue.相似文献