全文获取类型
收费全文 | 1753篇 |
免费 | 30篇 |
国内免费 | 4篇 |
专业分类
化学 | 922篇 |
晶体学 | 9篇 |
力学 | 45篇 |
数学 | 201篇 |
物理学 | 610篇 |
出版年
2021年 | 13篇 |
2020年 | 12篇 |
2019年 | 18篇 |
2017年 | 14篇 |
2016年 | 27篇 |
2015年 | 15篇 |
2014年 | 27篇 |
2013年 | 88篇 |
2012年 | 57篇 |
2011年 | 82篇 |
2010年 | 58篇 |
2009年 | 29篇 |
2008年 | 78篇 |
2007年 | 98篇 |
2006年 | 67篇 |
2005年 | 58篇 |
2004年 | 60篇 |
2003年 | 29篇 |
2002年 | 59篇 |
2001年 | 45篇 |
2000年 | 39篇 |
1999年 | 18篇 |
1998年 | 23篇 |
1997年 | 19篇 |
1996年 | 18篇 |
1995年 | 31篇 |
1994年 | 36篇 |
1993年 | 39篇 |
1992年 | 32篇 |
1991年 | 26篇 |
1990年 | 21篇 |
1989年 | 16篇 |
1988年 | 28篇 |
1987年 | 14篇 |
1986年 | 19篇 |
1985年 | 32篇 |
1984年 | 17篇 |
1983年 | 17篇 |
1982年 | 24篇 |
1981年 | 20篇 |
1980年 | 27篇 |
1979年 | 24篇 |
1978年 | 31篇 |
1977年 | 21篇 |
1976年 | 32篇 |
1975年 | 34篇 |
1974年 | 20篇 |
1973年 | 33篇 |
1972年 | 14篇 |
1971年 | 15篇 |
排序方式: 共有1787条查询结果,搜索用时 15 毫秒
81.
The selectivity of mass traces obtained by monitoring liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was compared. A number of blank extracts (fish, pork kidney, pork liver and honey) were separated by ultra performance liquid chromatography (UPLC). Detected were some 100 dummy transitions respectively dummy exact masses (traces). These dummy masses were the product of a random generator. The range of the permitted masses corresponded to those which are typical for analytes (e.g. veterinary drugs). The large number of monitored dummy traces ensured that endogenous compounds present in the matrix extract, produced a significant number of detectable chromatographic peaks. All obtained chromatographic peaks were integrated and standardized. Standardisation was done by dividing these absolute peak areas by the average response of a set of 7 different veterinary drugs. This permitted a direct comparison between the LC-HRMS and LC-MS/MS data. The data indicated that the selectivity of LC-HRMS exceeds LC-MS/MS, if high resolution mass spectrometry (HRMS) data is recorded with a resolution of 50,000 full width at half maximum (FWHM) and a corresponding mass window. This conclusion was further supported by experimental data (MS/MS based trace analysis), where a false positive finding was observed. An endogenous matrix compound present in honey matrix behaved like a banned nitroimidazole drug. This included identical retention time and two MRM traces, producing an MRM ratio between them, which perfectly matched the ratio observed in the external standard. HRMS measurement clearly resolved the interfering matrix compound and unmasked the false positive MS/MS finding. 相似文献
82.
Evans DR Macniven RP Labanca M Walker J Notarnicola SM 《Journal of chromatography. A》2008,1177(2):265-271
An hydrophobic interaction chromatography step was developed for the large-scale production of an Fc-fusion biologic. Two abundant product-related impurities were separated from the active monomer using a Butyl resin and a simple step-wash and step-elution strategy. Capacity and resolution of the HIC step was optimal when sodium sulfate was employed as the lyotropic salt and pore size of the Butyl resin was 750A. Factorial analysis identified critical parameters for the Butyl chromatography and an operating window capable of delivering high product quality and yield over a broad column loading range. 相似文献
83.
84.
The properties of the symmetric group are used to deduce matrix elements of one and two-electron operators between molecular states. It is shown that these techniques can be applied to any point group as long as no irreducible representation is more than doubly degenerate. 相似文献
85.
The determination of acceptable mass error tolerances for high‐resolution mass spectrometry based signals has been evaluated in a comprehensive way. This was achieved by using a technical approach which is based on the post‐column infusion of an analyte containing solution. This well‐known experimental setup was not used to spot signal suppression regions of a particular analyte, but to spot regions of the chromatogram where a systematic mass drift of the analyte ion can be observed (isobaric interference plot). Not the changing signal intensity but the stability of the measured analyte mass was observed. A wide range of different analytes in combinations with potentially interfering matrices has been evaluated. Furthermore, different mass resolving power settings were evaluated. Isobaric interferences between matrix compounds and analytes were common at mass resolving powers <50 000 full width at half maximum. The proposed post‐column infusion technique is a useful tool for the determination of the assay and matrix‐specific mass error tolerances. It aims to ensure the highest possible selectivity, at the same time preventing the encounter of detrimental mass error related peak deformations as well as false negative findings. Unlike conventional matrix spiking approaches, isobaric interference plots provide information of potential interferences across the whole chromatographic time range. This becomes relevant when there is a relative retention time shift between the analyte and potential interfering matrix compounds. Furthermore, the described setup can be used to study how the mass accuracy of any mass spectrometer is affected by a widely varying total ion current. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
86.
Reflections from geometric discontinuities can be used with ultrasonic energy to predict the temperature of an interface where classical temperature measurement techniques are impractical because of physical access limitations or harsh environmental conditions. Additionally, these same ultrasonic measurements can be used with inversion methods commonly applied to ill-posed heat transfer problems to increase the accuracy of the measurement of surface temperature or heat flux at the surface of interest. Both methods for determining surface temperature are presented, along with a comparison of results both from a verification example and using data gathered in a field test of the methods. The results obtained with these two methods are shown to be in good agreement with an empirical relationship used in the design of large caliber guns. 相似文献
87.
The effective diffusion coefficient that gives a steady-state xenon concentration of 0.2-0.3wt% in the recrystallised grains of high burn-up UO 2 fuel is calculated to lie in the range 10 m 24 to 10 m 22 m 2 s m 1 . These values are one to three orders of magnitude lower than the value currently accepted for the radiation-enhanced diffusion coefficient. The time required to reach the steady-state concentration depends on the local fission rate, the grain size distribution and the precise magnitude of the radiation-enhanced diffusion coefficient, and can take from 2 to 10 years. Additional calculations reveal that substantially less than 10% of the fission gas inventory is released from the original UO 2 grains in the outer region of the fuel prior to recrystallisation. In contrast, with a diffusion coefficient of 10 m 22 m 2 s m 1 more than 80% of the fission gas is released from the recrystallised grains of the high burn-up structure in one year. 相似文献
88.
89.
90.
Bharathi Avula Babu L. Tekwani Narayan D. Chaurasiya NP Dhammika Nanayakkara Yan‐Hong Wang Shabana I. Khan Vijender R. Adelli Rajnish Sahu Mahmoud A. Elsohly James D. McChesney Ikhlas A. Khan Larry A. Walker 《Journal of mass spectrometry : JMS》2013,48(2):276-285
Therapeutic efficiency and hemolytic toxicity of primaquine (PQ), the only drug available for radical cure of relapsing vivax malaria are believed to be mediated by its metabolites. However, identification of these metabolites has remained a major challenge apparently due to low quantities and their reactive nature. Drug candidates labeled with stable isotopes afford convenient tools for tracking drug‐derived metabolites in complex matrices by liquid chromatography‐tandem mass spectrometry (LC‐MS‐MS) and filtering for masses with twin peaks attributable to the label. This study was undertaken to identify metabolites of PQ from an in vitro incubation of a 1:1 w/w mixture of 13C6‐PQ/PQ with primary human hepatocytes. Acquity ultra‐performance LC (UHPLC) was integrated with QTOF‐MS to combine the efficiency of separation with high sensitivity, selectivity of detection and accurate mass determination. UHPLC retention time, twin mass peaks with difference of 6 (originating from 13C6‐PQ/PQ), and MS‐MS fragmentation pattern were used for phenotyping. Besides carboxy‐PQ (cPQ), formed by oxidative deamination of PQ to an aldehyde and subsequent oxidation, several other metabolites were identified: including PQ alcohol, predictably generated by oxidative deamination of PQ to an aldehyde and subsequent reduction, its acetate and the alcohol's glucuronide conjugate. Trace amounts of quinone‐imine metabolites of PQ and cPQ were also detected which may be generated by hydroxylation of the PQ/cPQ quinoline ring at the 5‐position and subsequent oxidation. These findings shed additional light on the human hepatic metabolism of PQ, and the method can be applied for identification of reactive PQ metabolites generated in vivo in preclinical and clinical studies. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献