全文获取类型
收费全文 | 68103篇 |
免费 | 1931篇 |
国内免费 | 24篇 |
专业分类
化学 | 41708篇 |
晶体学 | 394篇 |
力学 | 1231篇 |
综合类 | 1篇 |
数学 | 12101篇 |
物理学 | 14623篇 |
出版年
2023年 | 495篇 |
2022年 | 411篇 |
2021年 | 735篇 |
2020年 | 994篇 |
2019年 | 974篇 |
2018年 | 1412篇 |
2017年 | 1298篇 |
2016年 | 2489篇 |
2015年 | 2010篇 |
2014年 | 2017篇 |
2013年 | 4475篇 |
2012年 | 4320篇 |
2011年 | 4201篇 |
2010年 | 2709篇 |
2009年 | 2271篇 |
2008年 | 3760篇 |
2007年 | 3525篇 |
2006年 | 3152篇 |
2005年 | 2989篇 |
2004年 | 2502篇 |
2003年 | 2028篇 |
2002年 | 1795篇 |
2001年 | 1385篇 |
2000年 | 1358篇 |
1999年 | 961篇 |
1998年 | 725篇 |
1997年 | 619篇 |
1996年 | 810篇 |
1995年 | 572篇 |
1994年 | 651篇 |
1993年 | 643篇 |
1992年 | 633篇 |
1991年 | 503篇 |
1990年 | 544篇 |
1989年 | 446篇 |
1988年 | 465篇 |
1987年 | 412篇 |
1986年 | 404篇 |
1985年 | 580篇 |
1984年 | 535篇 |
1983年 | 419篇 |
1982年 | 404篇 |
1981年 | 411篇 |
1980年 | 363篇 |
1979年 | 354篇 |
1978年 | 352篇 |
1977年 | 349篇 |
1976年 | 356篇 |
1974年 | 324篇 |
1973年 | 334篇 |
排序方式: 共有10000条查询结果,搜索用时 9 毫秒
991.
T. Cserháti 《Fresenius' Journal of Analytical Chemistry》1993,345(7):541-544
Summary The interaction of the herbicides diquat and paraquat with humic acid and the influence of various salts and pH on the strength of interaction was studied by charge-transfer chromatography. Interactions between humic acids and both herbicides, probably by complex formation, were confirmed; they were stronger with paraquat than with diquat. The complex formation makes the herbicides more hydrophilic, facilitating their movement on cellulose surface. Salts in the environment significantly decreased the strength of interaction, indicating the hydrophilic character of the interactive forces. The charge of the cation also influenced the strength of interaction whereas the effect of ion radii was negligible. The effect of pH was lower than that of salt concentration. 相似文献
992.
Bromazepam, in the form of a cationic iron(II) chelate, can be determined spectrophotometrically at 588 nm with a limit of detection of ca. 10-6 M. When this chelate is ion-paired with perchlorate, it can be extracted into organic solvents such as 1,2-dichloroethane and 4-methyl-2-pentanone, and determined by atomic absorption spectrometry with a limit of detection of 1.5 × 10-5 M bromazepam at the iron resonance 248.3-nm line. Ion-pairs involving the Fe(II), Cu(II) and Co(II) chelates and perchlorate can be separated by h.p.l.c. using a C18 reverse-phase column and a mobile phase of 4:1 water—methanol, with a u.v. detector at 242 nm. This approach allowed for the determination of iron(II) ions in aqueous solution with a limit of detection of 10-8 M. The h.p.l.c. method could also be used to quantify bromazepam spiked in plasma in the concentration range 1–10 μg ml-1, following extraction of bromazepam from plasma and subsequent formation of the iron(II) ion-pair. Copper(II) forms a labile chelate with bromazepam in pH 4.8 acetate buffer which, when subjected to differential pulse voltammetry at the hanging mercury drop electrode, gives rise to a catalytic phenomenon which can be utilised for the determination of bromazepam in the concentration range 10-5–10-9 M. 相似文献
993.
Zusammenfassung Die früher beschriebene Halbmikromethode zur Bestimmung von Isonitrosogruppen in organischen Verbindungen wurde in den Mikromaßstab übergeführt. Sie beruht auf der Reaktion der Substanz mit Eisen(III)-sulfat in verd. Schwefelsäure. Dabei wird der Oximstickstoff als Distickstoffoxid frei, das mit Kupfer zu elementarem Stickstoff reduziert und im Mikroazotometer gemessen wird. Für die Berechnung des Oximstickstoffgehaltes aus den abgelesenen Gasvolumina wurden Werte für die konstante und proportionale Volumenkorrektur mit Hilfe der Methode der Regressionsgeraden experimentell festgestellt. Beide Werte sind den bei der N-N-Gruppenbestimmung benützten Volumenkorrekturen fast gleich. Die Bestimmung von Oximgruppen ist durch die Anwesenheit von Nitro- oder Aminogruppen nicht gestört. Diese Gruppen können aus derselben Einwaage durch nachfolgende Oxydation mit Chromsäure bestimmt werden.
XXII. Mitteilung s.1. 相似文献
Analytical aspects of the oxidation of organic nitrogen compounds with chromic acid. XXIII
Summary The semimicro method previously described for the determination of isonitroso groups in organic compounds has been converted to the microscale. It is based on the reaction of the material with iron(III)-sulfate in dilute sulfuric acid. The oxime nitrogen is thus liberated as dinitrogen oxide, which is reduced to elementary nitrogen by copper and measured in the mieroazotometer. To calculate the oxime nitrogen content from the read-off gas volume, values for the constant and proportional volume correction with the aid of the regression lines were established experimentally. Both values are almost equal in the case of the determination of the volume corrections employed in the determination of the N-N-groups. The presence of nitro-or amino groups does not interfere with the determination of oxime groups. These groups may be determined from the same sample by subsequent oxidation with chromic acid.
XXII. Mitteilung s.1. 相似文献
994.
F. Pérez-Giménez G. M. Antón-Fos F. J. García-March M. T. Salabert-Salvador R. A. Cercós-del-Pozo J. Jaén-Oltra 《Chromatographia》1995,41(3-4):167-174
Summary The possible relation existing between RF values obtained by thin-layer chromatography for a group of anilines with connectivity indices proposed by Kier and Hall has been studied. Using multivariable regression the corresponding connectivity functions, selected for their respective correlation coefficients, standard deviations, Snedecor's F and Student's t were obtained. Regression analysis of the connectivity functions gives a correct prediction of the experimental elution sequence for this group of substances on silica gel stationary phases and various mobile phases of different polarity. The corresponding random and stability studies of the different prediction models selected were carried out, showing good stability and null randomness in all cases. 相似文献
995.
P. Podhájecký P. Beneš A. Gosman 《Journal of Radioanalytical and Nuclear Chemistry》1979,51(2):315-324
Theoretical and experimental analysis of the open-ended capillary diffusion method for study of the state of trace elements
in aqueous solutions is presented. It is shown by theoretical considerations that the use of the discontinuous capillary method
of diffusion and the evaluation of single measurements using the classical Anderson-Saddington equation yields incorrect diffusion
coefficients if two or more forms of the trace element with significantly different diffusion characteristics are simultaneously
present in the solution. A new method for the evaluation of diffusion is suggested, which enables calculation of the abundance
of two different forms of a trace element. The method employs a continuous measurement of diffusion combined with computer
analysis of the data obtained. Verification of the method is carried out for a particular case using trace radiocerium. The
effect of adsorption on the diffusion measurement and interpretation is discussed. 相似文献
996.
α-(1-adamantyl)-β-diketones are now accessible by the alkylation of Co(II) complexes of β-diketones with 1-bromoadamantane. The intermediacy of adamantyl cation is proposed. Co(II), Co(III) and Zn(II) complexes of pentane-2,4-dione react with alkyl halides precursors of stabilized carbenium ions, to give 3-alkylpentane-2,4-diones. 相似文献
997.
Ruiz-Angel MJ Caballero RD Simó-Alfonso EF García-Alvarez-Coque MC 《Journal of chromatography. A》2002,947(1):31-45
The screening capability of micellar liquid chromatography (MLC) is discussed using the reported chromatographic data of several sets of compounds (amino acids, beta-blockers, diuretics, phenethylamines, phenols, polynuclear aromatic hydrocarbons, steroids and sulfonamides) and new results (sulfonamides and steroids). The chromatographic data are treated with an interpretive optimisation resolution procedure to obtain the best separation conditions. Usually, the pH and the concentration of surfactant (sodium dodecyl sulfate, SDS, or cetyltrimethylammonium bromide) for the optimal mobile phase were 2.5-3 and < 0.12 M, respectively. The nature and concentration of organic solvent depended on the polarity of the eluted compounds: a low volume fraction of propanol (approximately 1%, v/v) was useful to separate the amino acids, with log P(o/w) < -1 (where P(o/w) is the octanol-water partition coefficient). A greater concentration of this solvent (approximately 5-7%) was needed for compounds in the range -1 < log P(o/w) < 2, as with the studied diuretics and sulfonamides, and a high concentration of propanol (approximately 15%) or a low concentration of butanol (< 10%) had to be used for less polar compounds with 1 < log P(o/w) < 3, such as the beta-blockers. Pentanol (< 6%) was more suitable for the even less polar compounds with log P(o/w) > 3, such as the steroids. For basic drugs such as the phenethylamines (0 < log P(o/w) < 1.7), eluted with a micellar eluent of anionic SDS, propanol was too weak. A study is also shown for mixtures of sulfonamides (log P(o/w) = -1.2 to 1.7) and steroids (log P(o/w) = 3.0-8.1) eluted from conventional C18 columns with SDS mobile phases containing acetonitrile and 1-pentanol, respectively, which are compared with classical acetonitrile-water and methanol-water mixtures. The results complement a previous study on beta-blockers (log P(o/w) = -0.03 to 2.8) and reveal that MLC is a very competitive technique for the screening of compounds against conventional RPLC, due to its peculiar behaviour with regard to the selectivity and elution strength. The concentration of organic solvent needed to obtain sufficiently low retention times (even for highly hydrophobic steroids with log P(o/w) = 7-8) is also appreciably smaller for MLC, which reduces the environmental impact of the mobile phases. 相似文献
998.
Wagner?M.?Teles Flávia?C.?Machado Carlos?A.?Montanari Carlos?A.?L.?FilgueirasEmail author Terence?C.?Jenkins 《Transition Metal Chemistry》2005,30(6):733-737
The mesoionic compound, 1,4,5-triazole-2-thiolate, is a versatile ligand, capable of binding metal centres in different ways. The present study shows how it reacts with the bridging platinum(II) complex μ-dichlorobis[(chlorotriethylphosphineplatinum(II)], [Pt2(PEt3)2Cl4], originating a bimetallic complex. Both the sulphur atom and nitrogen 3 behave as basic sites, coordinating different platinum centres. An interesting isomerization process, shown by 31P{1H} n.m.r. spectroscopy, occurs at the S-bonded platinum moiety, resulting in a fluxional behaviour of the complex. It is also shown to target CT-DNA with moderate binding affinity.To the memory of Dr. Wagner M. Teles (1971–2004). 相似文献
999.
A solution of a Zn-complex of recombinant mouse MT-1 isoform (Zn(7)-MT-1) was prepared and titrated with Cd(2+) ions. A method based on the coupling of capillary zone electrophoresis (CZE) with electrospray MS detection was developed for the analysis of the stoichiometry of the species formed during the titration. The method offered the possibility of the on-line removal of up to 100 mM Tris or phosphate buffer solutions that would otherwise suppress the electrospray signal. By allowing the determination of the metal stoichiometry of the complex species present in solution the method was shown to be complementary to circular dichroism and UV-VIS spectrophotometry conventionally used for similar studies. The titration of the Zn(7)-MT complex with Cd(II) showed the sequential displacement of the Zn by Cd. The unusually high stability of the Cd(6)Zn(1)-MT species was observed which suggests a structural role of the remaining Zn(II) ion. 相似文献
1000.
V. Spěvá?ková J. Jhn M. Pra?ská 《Journal of Radioanalytical and Nuclear Chemistry》1983,80(1-2):115-120
The determination of uranium in natural waters by XRF analysis after its preconcentration with some organic precipitants is described.109Cd source is used for the excitation of L-series X-rays of uranium. Separation yield, kinetics of coprecipitation and the possibility of preparing thin-layer samples for XRF analysis were studied in detail for uranium concentration with α-nitroso-β-naphtol, methylene blue with ammonium thiocyanate, tannin with urotropine and other precipitants. A procedure using coprecipitation of uranium with α-nitroso-β-naphtol from 500 ml samples of surface or waste, waters is proposed. 相似文献