全文获取类型
收费全文 | 38203篇 |
免费 | 9431篇 |
国内免费 | 1409篇 |
专业分类
化学 | 42590篇 |
晶体学 | 346篇 |
力学 | 600篇 |
数学 | 2564篇 |
物理学 | 2943篇 |
出版年
2023年 | 42篇 |
2022年 | 181篇 |
2021年 | 294篇 |
2020年 | 1313篇 |
2019年 | 2665篇 |
2018年 | 1139篇 |
2017年 | 739篇 |
2016年 | 3519篇 |
2015年 | 3596篇 |
2014年 | 3578篇 |
2013年 | 4447篇 |
2012年 | 3083篇 |
2011年 | 2315篇 |
2010年 | 2953篇 |
2009年 | 2921篇 |
2008年 | 2441篇 |
2007年 | 1830篇 |
2006年 | 1509篇 |
2005年 | 1656篇 |
2004年 | 1452篇 |
2003年 | 1357篇 |
2002年 | 2040篇 |
2001年 | 1375篇 |
2000年 | 1323篇 |
1999年 | 395篇 |
1998年 | 78篇 |
1997年 | 71篇 |
1996年 | 43篇 |
1995年 | 41篇 |
1994年 | 38篇 |
1993年 | 40篇 |
1992年 | 40篇 |
1991年 | 33篇 |
1990年 | 24篇 |
1989年 | 33篇 |
1988年 | 31篇 |
1987年 | 31篇 |
1986年 | 28篇 |
1985年 | 34篇 |
1984年 | 31篇 |
1983年 | 27篇 |
1982年 | 26篇 |
1981年 | 32篇 |
1980年 | 23篇 |
1979年 | 18篇 |
1978年 | 21篇 |
1976年 | 16篇 |
1975年 | 17篇 |
1974年 | 10篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Relationships between structure,ionization profile and sensitivity of exogenous anabolic steroids under electrospray ionization and analysis in human urine using liquid chromatography–tandem mass spectrometry 下载免费PDF全文
Eunju Cha Sohee Kim Hee Won Kim Kang Mi Lee Ho Jun Kim Oh‐Seung Kwon Jaeick Lee 《Biomedical chromatography : BMC》2016,30(4):555-565
The relationships between the ionization profile, sensitivity, and structures of 64 exogenous anabolic steroids (groups I–IV) was investigated under electrospray ionization (ESI) conditions. The target analytes were ionized as [M + H]+ or [M + H–nH2O]+ in the positive mode, and these ions were used as precursor ions for selected reaction monitoring analysis. The collision energy and Q3 ions were optimized based on the sensitivity and selectivity. The limits of detection (LODs) were 0.05–20 ng/mL for the 64 steroids. The LODs for 38 compounds, 14 compounds and 12 compounds were in the range of 0.05–1, 2–5 and 10–20 ng/mL, respectively. Steroids including the conjugated keto‐functional group at C3 showed good proton affinity and stability, and generated the [M + H]+ ion as the most abundant precursor ion. In addition, the LODs of steroids using the [M + H]+ ion as the precursor ion were mostly distributed at low concentrations. In contrast, steroids containing conjugated/unconjugated hydroxyl functional groups at C3 generated [M + H ? H2O]+ or [M + H ? 2H2O]+ ions, and these steroids showed relatively high LODs owing to poor stability and multiple ion formation. An LC‐MS/MS method based on the present ionization profile was developed and validated for the determination of 78 steroids (groups I–V) in human urine. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
992.
An HPLC‐ECD method for monoamines and metabolites quantification in cuttlefish (cephalopod) brain tissue 下载免费PDF全文
Flavie Bidel Sophie Corvaisier Christelle Jozet‐Alves Ivannah Pottier François Dauphin Nadège Naud Cécile Bellanger 《Biomedical chromatography : BMC》2016,30(8):1175-1183
The cuttlefish belongs to the mollusk class Cephalopoda, considered as the most advanced marine invertebrates and thus widely used as models to study the biology of complex behaviors and cognition, as well as their related neurochemical mechanisms. Surprisingly, methods to quantify the biogenic monoamines and their metabolites in cuttlefish brain remain sparse and measure a limited number of analytes. This work aims to validate an HPLC‐ECD method for the simultaneous quantification of dopamine, serotonin, norepinephrine and their main metabolites in cuttlefish brain. In comparison and in order to develop a method suitable to answer both ecological and biomedical questions, the validation was also carried out on a phylogenetically remote species: mouse (mammals). The method was shown to be accurate, precise, selective, repeatable and sensitive over a wide range of concentrations for 5‐hydroxyindole‐3‐acetic acid, serotonin, dopamine, 3,4‐dihydroxyphenylacetic acid and norepinephrine in the both extracts of cuttlefish and mouse brain, though with low precision and recovery for 4‐hydroxy‐3‐methoxyphenylethylene glycol. Homovanillic acid, accurately studied in rodents, was not detectable in the brain of cuttlefish. Overall, we described here the first fully validated HPLC method for the routine measurement of both monoamines and metabolites in cuttlefish brain. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
993.
994.
Determination and validation of chikusetsusaponin IVa in rat plasma by UPLC‐MS/MS and its application to pharmacokinetic study 下载免费PDF全文
A novel, sensitive and rapid ultra‐performance liquid chromatography–tandem mass spectrometric method for the quantification of chikusetsusaponin IVa (CHS‐IVa) in rat plasma was established and validated. Plasma samples were pre‐treated by precipitation of protein with acetonitrile and chromatographed on a Waters Symmetry C18 analytical column (4.6 × 50 mm, i.d., 3.5 μm) using a mobile phase consisting of methanol and water containing 0.05% formic acid (55:45, v/v) at a flow rate of 0.4 mL/min. The deprotonated molecular ions [M ? H]– were employed in electrospray negative ionization mode and selected reaction monitoring transitions were performed for detection. The calibration curves exhibited good linearity (r > 0.99) over the range of 0.5–1000 ng/mL for CHS‐IVa. The recoveries of CHS‐IVa were >92.5% and exhibited no severe matrix effect. This method was successfully applied in the pharmacokinetic study of CHS‐IVa in rats. For oral administration, the plasma concentrations of CHS‐IVa increased to a peak value at 0.35 ± 0.14 h, followed by a gradual decrease to the lower limit of quantitation in 24 h. For intravenous administration, the plasma concentrations of CHS‐IVa decreased quickly (t1/2, 1.59 ± 0.25 h). The absolute bioavailability of CHS‐IVa in rats was 8.63%. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
995.
Pharmacokinetic comparison of five tanshinones in normal and arthritic rats after oral administration of Huo Luo Xiao Ling Dan or its single herb extract by UPLC‐MS/MS 下载免费PDF全文
Wen Ma Yan Peng Weihui Wang Qiaoxia Bian Nannan Wang David Y.‐W. Lee Ronghua Dai 《Biomedical chromatography : BMC》2016,30(10):1573-1581
A fast, sensitive and reliable ultra performance liquid chromatography–tandem mass spectrometry (UPLC‐MS/MS) method has been developed and validated for simultaneous quantitation and pharmacokinetic study of five tanshinones (tanshinone I, tanshinone IIA, tanshinone IIB, dihydrotanshinone I, cryptotanshinone), the bio‐active ingredients of Huo Luo Xiao Ling Dan (HLXLD) in rat plasma. After liquid–liquid extraction, chromatographic separation was accomplished on a Shim‐pack XR‐ODS column (75 × 3.0 mm, 2.2 µm particles) and eluted with a mobile phase consisting of acetonitrile–0.05% formic acid aqueous solution (80:20, v/v) at a flow rate of 0.4 mL/min, and the total run time was 7.0 min. The detection was performed on a triple quadrupole tandem mass spectrometry equipped with an electrospray ionization source in positive ionization and multiple reaction monitoring mode. The lower limits of quantification were 0.050–0.400 ng/mL for all the analytes. Linearity, precision and accuracy, the mean extraction recoveries and matrix effects all satisfied criteria for acceptance. This validated method was successfully applied to a comparative pharmacokinetic study of five bio‐active components in rat plasma after oral administration of HLXLD or Salvia miltiorrhiza extract in normal and arthritic rats. The results showed that there were different pharmacokinetic characteristics among different groups. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
996.
Alberto Hernn‐Gmez Emma Herd Eva Hevia Alan R. Kennedy Paul Knochel Konrad Koszinowski Sophia M. Manolikakes Robert E. Mulvey Christoph Schnegelsberg 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(10):2744-2748
The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D8]THF solution these reagents exist as separated Me(p‐C6H4)ZnCl and Mg(OPiv)2 species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)2 enhances the air stability of aryl zinc species by sequestering H2O contaminants. Coupling reactions of Me(p‐C6H4)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)2. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)2Li2(Cl)2(OPiv)2Zn]. 相似文献
997.
P. Perez‐Tejeda A. Jimenez‐Ruiz E. M. Grueso R. Prado‐Gotor C. Carrasco A. Pastor N. Alvarez M. Garcia‐Lora M. Garcia‐Pageo 《国际化学动力学杂志》2013,45(12):780-786
The electron transfer reaction between [Ru(NH3)5pz]2+ and [Co(C2O4)3]3? was studied in the presence of monomers and aggregates of bile salts (sodium deoxycholate, sodium taurodeoxycholate, and sodium glycocholate) at 298.2 ± 0.1 K. The results show a decreasing rate constant with the successive addition of bile salts. To rationalize the trends of the reaction rate on the [bile salts], two models were used. One of them takes into account the aggregation feature by considering a stepwise self‐association between monomers, whereas the other assumes the formation of a critical micellar concentration. Binding constants between [Ru(NH3)5pz]2+ species and deoxycholate or taurodeoxycholate aggregates were higher than that for glycocholate aggregates. These results are consistent with the way in which the monomers are added to form the bile anion aggregates. 相似文献
998.
Xudong Yao Craig Bunt Jillian Cornish Siew‐Young Quek Jingyuan Wen 《Biomedical chromatography : BMC》2013,27(2):197-202
The objective of this study was to qualitatively and quantitatively evaluate bovine lactoferrin (bLf) and its stability using a rapid RP‐HPLC method. bLf could be rapidly detected within 20 min and quantitated at levels down to 5 µg/mL, and the equation of linearity was y = 86.10x + 178.31 with the correlation coefficient (r2) 0.9997. Quantitative data obtained in the present study proved the improved RP‐HPLC method to be a sensitive and accurate analytical tool for bLf determination. The proteolytic cleavage of bLf in simulated human gastrointestinal fluids was further analyzed by RP‐HPLC, and found to follow pseudo‐first‐order kinetics. The typical equation obtained by pepsin was log10 [At]/[A0] = ?0.03x (r2 = 0.85), and log10 [At]/[A0] = ?0.01x (r2 = 0.81) for trypsin and chymotrypsin combination. Pepsinolysis of bLf in simulated gastric fluid was relatively fast with the half‐life t1/2 23.1 min. The digestion of bLf in simulated intestinal fluid was slower with about a 3‐fold increase in half‐life (69.3 min). After the complete proteolysis of bLf, small cleaved peptide fragments were fully separated and identified by RP‐HPLC. The proteolytic study indicated that this validated RP‐HPLC was able to evaluate bLf stability though monitoring the derivatization products. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
999.
Xiao‐Lan Wei Rong Han Xiao Hu Li‐Hui Quan Chun‐Yu Liu Qi Chang Yong‐Hong Liao 《Biomedical chromatography : BMC》2013,27(5):636-640
Six esterase inhibitors, namely EDTA·2Na+, NaF, phenylmethanesulfonyl fluoride, dichlorvos, bis‐nitrophenyl phosphate (BNPP) and thenoyltrifluoroacetone, and the mixture of NaF and BNPP, were evaluated for the stabilization of labile benzoate containing zeylenone in rat plasma. The mixture appeared to exhibit the most effectively stabilizing effect with the degraded content of zeylenone decreasing from >60% (in the absence of inhibitors) to <6%. Following the stabilization by the addition of NaF (5 mm ) and BNPP (5 mm ), the analytes in rat plasma were acidified by formic acid and extracted into ethyl acetate at 0°C. After chromatographic separation, the detection of zeylenone was performed on a 3200 Q‐Trap with positive ion electrospray mode, monitoring the ion transition m/z 383.2 → 105.0. The method was validated over the range from 2.68 to 1340 ng/mL with inter‐ and intra‐run precision for the quality control samples being less than 6.8%. The assay accuracy was within 100 ± 7.0%. The validated method was successfully applied to a pharmacokinetic study in rats after the intratracheal administration of zeylenone in free drug or polymeric micellar solutions. The results showed that the pulmonary absorption of zeylenone loaded in micelles was significantly retarded compared with that of free drug solutions. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
1000.
Dr. Alexander Hoffmann Cooper Citek Dr. Stephan Binder Arne Goos Prof. Dr. Michael Rübhausen Oliver Troeppner Prof. Dr. Ivana Ivanović‐Burmazović Prof. Dr. Erik C. Wasinger Prof. Dr. T. Daniel P. Stack Prof. Dr. Sonja Herres‐Pawlis 《Angewandte Chemie (International ed. in English)》2013,52(20):5398-5401