全文获取类型
收费全文 | 9109篇 |
免费 | 823篇 |
国内免费 | 704篇 |
专业分类
化学 | 2703篇 |
晶体学 | 10篇 |
力学 | 802篇 |
综合类 | 154篇 |
数学 | 3565篇 |
物理学 | 3402篇 |
出版年
2024年 | 9篇 |
2023年 | 75篇 |
2022年 | 155篇 |
2021年 | 118篇 |
2020年 | 224篇 |
2019年 | 225篇 |
2018年 | 242篇 |
2017年 | 296篇 |
2016年 | 321篇 |
2015年 | 238篇 |
2014年 | 455篇 |
2013年 | 522篇 |
2012年 | 409篇 |
2011年 | 533篇 |
2010年 | 425篇 |
2009年 | 583篇 |
2008年 | 634篇 |
2007年 | 651篇 |
2006年 | 559篇 |
2005年 | 524篇 |
2004年 | 492篇 |
2003年 | 382篇 |
2002年 | 352篇 |
2001年 | 266篇 |
2000年 | 305篇 |
1999年 | 247篇 |
1998年 | 222篇 |
1997年 | 199篇 |
1996年 | 134篇 |
1995年 | 126篇 |
1994年 | 104篇 |
1993年 | 56篇 |
1992年 | 57篇 |
1991年 | 58篇 |
1990年 | 46篇 |
1989年 | 41篇 |
1988年 | 58篇 |
1987年 | 47篇 |
1986年 | 26篇 |
1985年 | 38篇 |
1984年 | 34篇 |
1983年 | 22篇 |
1982年 | 26篇 |
1981年 | 32篇 |
1980年 | 13篇 |
1979年 | 15篇 |
1978年 | 7篇 |
1977年 | 11篇 |
1976年 | 5篇 |
1975年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
121.
V. I. Kovalenko L. I. Maklakov E. I. Borisoglebskaya L. I. Potapova E. A. Shokova I. M. Vatsouro V. V. Kovalev 《Russian Chemical Bulletin》2007,56(6):1103-1109
Based on the Fourier transform IR spectroscopy together with the published NMR and X-ray data, it was shown that cyclic co-operative
intramolecular hydrogen bond in calix[n]arene (n = 4, 6, 8) molecules is mainly responsible for their conformational state irrespective of the presence or absence of bulky
substituents at the upper rim of the molecules. In accordance with the size of a macrocycle (n = 4, 6, 8), the stable conformation, secured by such a hydrogen bond, constitutes a cone, a pinched cone, and a pleated loop, respectively. The new, potentially competing system of hydrogen bonds in calix[6]arenes with 3-carboxymethyl-1-adamantyl
substituents does not affect the conformational state of the macrocycle and its H-bonding. Six carboxy groups at the upper
rim form in pairs three cyclic dimers, which does not disturb the hydrogen bonds of the hydroxy groups and the conformation
of the macrocycle. In addition, the cavity of the molecule is considerably enlarged. The removal or rearrangement of the guest
molecules in the solid calixarene by heating up to 180 °C only slightly affects the conformational state of macrocycles bearing
bulky substituents, whereas in calixarenes devoid of such substituents, the similar procedure leads to somewhat of a distortion
of the macrocycles (judging from the IR spectral indications of hydrogen bonding).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1062–1068, June, 2007. 相似文献
122.
Traditionally, the application of supercritical fluid chromatography has been limited to compounds of relatively low polarity.
Thus, we report here that one secondary amine and two quaternary amine salts were successfully eluted from a Deltabond Cyano-bonded
silica column with the addition of sodium alkylsulfonate to the methanol-modified, carbon dioxide-based mobile phase. A possible
ion-pairing interaction between the positively charged analytes and the anionic part of the sulfonate additive has been proposed.
In another set of experiments, the three amine salts readily eluted from both Ethyl-pyridine-bonded silica and Amino-bonded
silica phases without the need of additive although the peak shapes were less than desirable. The addition of sulfonate salt
to the mobile phase again sharpened the peaks. In the presence of a mixture of methanol and CO2, we suggest that these stationary phases are positively charged. We describe here also for the first time the employment
of a strong silica-based anion exchange (SAX) column for supercritical fluid separation of cationic species. Two elution mechanisms
were proposed for the three amine salts depending upon whether the ionic additive was incorporated into the mobile phase.
Separation as the ion-pair was proposed with an ionic additive in the mobile phase; whereas separation of the intact amine
salt from the positively charged basic stationary phases was suggested to be operational without the ionic additive. 相似文献
123.
In this work, a flow analysis system with hydride generation and Fourier transform infrared (FTIR) spectrometric detection has been developed for the determination of antimony in pharmaceuticals. The method is based on the on-line mineralization/oxidation of the organic antimonials present in the sample and pre-reduction of Sb(V) to Sb(III) with K2S2O8 and KI, respectively; prior to the stibine generation. The gaseous SbH3 is separated from the solution in a gas phase separator, and transported by means of a nitrogen carrier into a short pathway (10 cm) IR gas cell, where the corresponding FTIR spectrum is acquired by accumulating 3 scans in a continuous mode. The 1893 cm−1 band was used for the quantification of the antimony. The procedure is carried out in a closed system, which reduces sample handling and makes possible the complete automation of the antimony determination. The figures of merit of the proposed method (linear range: 0-600 mg l−1, limit of detection (3σ)=0.9 mg l−1, limit of quantification (10σ)=3 mg Sb l−1, precision (R.S.D.) less than 1% and sample frequency=28 h−1), are appropriate for the designed application. Furthermore, precise and accurate results were found for the analysis of different antimonial pharmaceutical samples, indicating that the methodology developed represents a valid alternative for the determination of antimony in pharmaceuticals, which could be suitable for the routine control analysis. 相似文献
124.
萘普生是一种消炎镇痛药 ,其 S对映体的抗炎作用是 R构型的 2 8倍 ,萘普生及其衍生物的拆分具有重要意义 .手性固定相 HPLC直接拆分 [1~ 4 ] 是最简便的分析方法 .氧化锆是近年来备受关注的色谱载体 [5,6 ] .Carr等 [7] 对碱性药物快速拆分表明氧化锆在手性分离Scheme1 Structuresof chiral naproxen and its derivatives中的独特选择性 .萘普生及其衍生物在锆基手性固定相上的分离未见文献报道 .本组利用自制的球形氧化锆制备了涂敷型纤维素 -三 ( 3,5 -二甲基苯基氨基甲酸酯 ) -Zr O2 手性固定相 ( CDMPC- Zr O2 - CSP) ,在正… 相似文献
125.
Roberto Dallocchio Barbara Sechi Alessandro Dessì Bezhan Chankvetadze Sergio Cossu Victor Mamane Robin Weiss Patrick Pale Paola Peluso 《Electrophoresis》2021,42(17-18):1853-1863
2’-(4-Pyridyl)- and 2’-(4-hydroxyphenyl)-TCIBPs (TCIBP = 3,3’,5,5’-tetrachloro-2-iodo-4,4’-bipyridyl) are chiral compounds that showed interesting inhibition activity against transthyretin fibrillation in vitro. We became interested in their enantioseparation since we noticed that the M-stereoisomer is more effective than the P-enantiomer. Based thereon, we recently reported the enantioseparation of 2’-substituted TCIBP derivatives with amylose-based chiral columns. Following this study, herein we describe the comparative enantioseparation of both 2’-(4-pyridyl)- and 2’-(4-hydroxyphenyl)-TCIBPs on four cellulose phenylcarbamate-based chiral columns aiming to explore the effect of the polymer backbone, as well as the nature and position of substituents on the side groups on the enantioseparability of these compounds. In the frame of this project, the impact of subtle variations of analyte and polysaccharide structures, and mobile phase (MP) polarity on retention and selectivity was evaluated. The effect of temperature on retention and selectivity was also considered, and overall thermodynamic parameters associated with the analyte adsorption onto the CSP surface were derived from van ’t Hoff plots. Interesting cases of enantiomer elution order (EEO) reversal were observed. In particular, the EEO was shown to be dependent on polysaccharide backbone, the elution sequence of the two analytes being P-M and M-P on cellulose and amylose tris(3,5-dimethylphenylcarbamate), respectively. In this regard, a theoretical investigation based on molecular dynamics (MD) simulations was performed by using amylose and cellulose tris(3,5-dimethylphenylcarbamate) nonamers as virtual models of the polysaccharide-based selectors. This exploration at the molecular level shed light on the origin of the enantiodiscrimination processes. 相似文献
126.
碳十八键合锆胶固定相的制备与色谱性能评价 总被引:5,自引:0,他引:5
用诱导聚合胶体凝聚法(PICA)制得的二氧化锆微球与碳十八三乙氧基硅烷反应制备了碳十八键合锆胶固定相(ODZ),评价了该柱填料的色谱性能,并用此固定相分离了中性和碱性化合物。 相似文献
127.
A Background and noise elimination method for quantitative calibration of near infrared spectra 总被引:1,自引:0,他引:1
Da Chen 《Analytica chimica acta》2004,511(1):37-45
A new hybrid algorithm is proposed to eliminate the varying background and noise simultaneously for multivariate calibration of near infrared (NIR) spectral signals. The method is based on the use of multi-resolution, which is one of the main advantages provided by wavelet transform. The signals are firstly split into different frequency components, which keep the same data points of the original signals. In conjunction with a modified uninformative variable elimination (mUVE) criterion, the new method can be used to remove the low-frequency varying background and the high-frequency noise simultaneously. The method is successfully applied to simulated spectral data set and experimental NIR spectral data, resulting in more parsimonious multivariate models with higher precision. In addition, the proposed strategy can be applied to other spectral signals as well. 相似文献
128.
Two ligand exchange chiral stationary phases (CSPs) based on (S)-leucinol derivative, sodium N-((S)-1-hydroxymethyl-3-methylbutyl)-N-undecylaminoacetate, and (R)-phenylglycinol derivative, sodium N-((R)-2-hydroxy-1-phenylethyl)-N-undecylaminoacetate, covalently bonded to silica gel have been successfully applied in the resolution of nine -hydroxycarboxylic acids. The latter was more effective than the former, the separation factors () being 1.05 to 2.12 while the resolution factors (RS) varying from 0.18 to 5.29 on the latter. The chromatographic resolution behaviors were dependent on the type and the content of organic modifier and the content of CuSO4 in aqueous mobile phase and the column temperature. A possible chiral recognition mechanism was also proposed based on the chromatographic resolution behaviors. 相似文献
129.
玉米叶片残体腐解过程的傅里叶变换红外光谱研究 总被引:10,自引:2,他引:10
采用傅里叶变换红外光谱对玉米植株叶片残体腐解过程进行了研究。结果表明,随着玉米叶片残体腐解的进行,羟基,酮碳基,甲基,在和次甲基的含量逐渐降收据 的含量增加。 相似文献
130.
Summary The theory of the evaporation of the liquid stationary phase is elaborated and experimentally verified. On the basis of this theory the role played by the losses in the amount of liquid phase present is quantitatively determined. General techniques are examined which minimize the losses; these techniques are based on saturating the incoming carrier gas with liquid phase vapours and raising the pressure of the carrier gas in the column, e.g. by connecting a capillary to the column outlet in order to offer resistance to the gas flow. The application of these techniques ensures stable performance of the gas chromatographic columns using a volatile liquid phase. 相似文献