全文获取类型
收费全文 | 88709篇 |
免费 | 1964篇 |
国内免费 | 1768篇 |
专业分类
化学 | 31927篇 |
晶体学 | 911篇 |
力学 | 7377篇 |
综合类 | 72篇 |
数学 | 33182篇 |
物理学 | 18972篇 |
出版年
2024年 | 57篇 |
2023年 | 288篇 |
2022年 | 438篇 |
2021年 | 448篇 |
2020年 | 475篇 |
2019年 | 499篇 |
2018年 | 10751篇 |
2017年 | 10569篇 |
2016年 | 6557篇 |
2015年 | 1388篇 |
2014年 | 915篇 |
2013年 | 1172篇 |
2012年 | 4713篇 |
2011年 | 11408篇 |
2010年 | 6266篇 |
2009年 | 6612篇 |
2008年 | 7310篇 |
2007年 | 9331篇 |
2006年 | 810篇 |
2005年 | 1713篇 |
2004年 | 1894篇 |
2003年 | 2244篇 |
2002年 | 1324篇 |
2001年 | 462篇 |
2000年 | 508篇 |
1999年 | 426篇 |
1998年 | 392篇 |
1997年 | 291篇 |
1996年 | 349篇 |
1995年 | 258篇 |
1994年 | 179篇 |
1993年 | 210篇 |
1992年 | 155篇 |
1991年 | 158篇 |
1990年 | 134篇 |
1989年 | 121篇 |
1988年 | 104篇 |
1987年 | 96篇 |
1986年 | 81篇 |
1985年 | 78篇 |
1984年 | 68篇 |
1983年 | 51篇 |
1982年 | 56篇 |
1981年 | 44篇 |
1980年 | 52篇 |
1979年 | 48篇 |
1914年 | 45篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 10 毫秒
971.
U. Ceren Başköse Sevgi Haman Bayarı Semran Sağlam Hacı Özışık 《Central European Journal of Chemistry》2012,10(2):395-406
The conformational analysis of rasagiline [N-propargyl-1(R)-aminoindan] was performed by the density functional theory (DFT) B3LYP method using the 6–31++G (d,p) basis set. A single
point energy calculations based on the B3LYP optimized geometries were also performed at MP2/6-31++G (d, p) level. The vibrational
frequencies of the most stable conformer of rasagiline was calculated at the B3LYP level and vibrational assignments were
made for normal modes on the basis of scaled quantum mechanical force field (SQM) method. The influence of mesylate and ethanedisulfonate
salts on the geometry of rasagiline free base and its normal modes are also discussed.
相似文献
972.
J. Steven Morris Vickie L. Spate Stacy B. Crane Alejandra Gudino 《Journal of Radioanalytical and Nuclear Chemistry》2012,291(2):409-414
Scalp hair is routinely used to assess exposure to toxic trace elements and nutritional status of some required trace elements.
The advantages and disadvantages of hair as a biologic monitor have been comprehensively discussed in the literature for many
years. Among the concerns is distinguishing between exogenous and endogenous contributions. Nested in this issue is the longitudinal
distribution of a trace element along the hair strand. The typical observation for many elements of interest is that the element
concentration increases from the root end to the distal end; and this is attributed to continuing contamination from exogenous
sources. In this study we used neutron activation analysis to measure 14 trace elements in 6 mm segments of full-length scalp
hair from three healthy members of the same household having light-urban environmental exposure. To extend the data set for
selenium, we included three adult female subjects with longer than average scalp hair. From these trace-element concentrations
we calculated the root-to-distal end ratios as a profile diagnostic of trace-element distributions. Ratios fall into three
diagnostic categories, >1, ≈1, and <1 corresponding to profiles having decreasing root-to-distal concentrations, unchanging
concentrations, and increasing concentrations, respectively. Of the 14 elements measured, only Se has R > 1, Zn and S have R ≈ 1, and the remaining 11 elements all have R < 1 in the order: As > I > Hg ≈ Au ≈ Mg ≈ Mn ≈ Sb ≈ Ca > Cu > Al ≈ Ag. R
Se is greater than 1 and increases with hair length (P = 0.02) corresponding to a continuous longitudinal loss of Se in stark and puzzling contrast to the other elements measured.
An analogous loss of Se in the nail monitor was not observed leading us to conclude that the nail is less prone to misclassification
of selenium status in epidemiological studies. 相似文献
973.
E. I. Klimova E. A. Vazquez Lopez T. Klimova M. Martinez Garcia Ortega S. Hernandez L. Ruiz Ramirez 《Russian Journal of General Chemistry》2004,74(11):1757-1762
Ferrocenyltetrahydropyrimidin-2-ones were prepared by reactions of linear and cyclic ,-unsaturated ketones of the ferrocene series with urea in i-PrOH in the presence of t-BuOK. The structures of the compounds prepared were studied by 1H and 13C NMR and IR spectroscopy, and also by single crystal X-ray diffraction.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1887–1893.Original Russian Text Copyright © 2004 by E. Klimova, Lorez, T. Klimova, Garcia, Hernandez, Ramirez.This revised version was published online in April 2005 with a corrected cover date. 相似文献
974.
975.
Ielpo P Cassano D Lopez A Pappagallo G Uricchio VF De Napoli PA 《Chemistry Central journal》2012,6(Z2):S5
Background
Ground waters are an important resource of water supply for human health and activities. Groundwater uses and applications are often related to its composition, which is increasingly influenced by human activities.In fact the water quality of groundwater is affected by many factors including precipitation, surface runoff, groundwater flow, and the characteristics of the catchment area. During the years 2004-2007 the Agricultural and Food Authority of Apulia Region has implemented the project “Expansion of regional agro-meteorological network” in order to assess, monitor and manage of regional groundwater quality. The total wells monitored during this activity amounted to 473, and the water samples analyzed were 1021. This resulted in a huge and complex data matrix comprised of a large number of physical-chemical parameters, which are often difficult to interpret and draw meaningful conclusions. The application of different multivariate statistical techniques such as Cluster Analysis (CA), Principal Component Analysis (PCA), Absolute Principal Component Scores (APCS) for interpretation of the complex databases offers a better understanding of water quality in the study region.Results
Form results obtained by Principal Component and Cluster Analysis applied to data set of Foggia province it’s evident that some sampling sites investigated show dissimilarities, mostly due to the location of the site, the land use and management techniques and groundwater overuse. By APCS method it’s been possible to identify three pollutant sources: Agricultural pollution 1 due to fertilizer applications, Agricultural pollution 2 due to microelements for agriculture and groundwater overuse and a third source that can be identified as soil run off and rock tracer mining.Conclusions
Multivariate statistical methods represent a valid tool to understand complex nature of groundwater quality issues, determine priorities in the use of ground waters as irrigation water and suggest interactions between land use and irrigation water quality.976.
Whitehurst CE Yao Z Murphy D Zhang M Taremi S Wojcik L Strizki JM Bracken JD Cheng CC Yang X Shipps GW Ziebell M Nickbarg E 《Combinatorial chemistry & high throughput screening》2012,15(6):473-485
Affinity selection-mass spectrometry (AS-MS) is a sensitive technology for identifying small molecules that bind to target proteins, and assays enabled by AS-MS can be used to delineate relative binding affinities of ligands for proteins. 'Indirect' AS-MS assays employ size-exclusion techniques to separate target-ligand complexes from unbound ligands, and target-associated ligands are then specifically detected by liquid chromatography mass spectrometry. We report how indirect AS-MS binding assays with known reference control compounds were used as guideposts for development of an optimized purification method for CXCR4, a G-protein coupled chemokine receptor, for which we sought novel antagonists. The CXCR4 purification method that was developed was amenable to scale-up and enabled the screening of purified recombinant human CXCR4 against a large combinatorial library of small molecules by high throughput indirect AS-MS. The screen resulted in the discovery of new ligands that competed off binding of reference compounds to CXCR4 in AS-MS binding assays and that antagonized SDF1α-triggered responses and CXCR4-mediated HIV1 viral uptake in cell-based assays. This report provides a methodological paradigm whereby indirect AS-MS-based ligand binding assays may be used to guide optimal integral membrane protein purification methods that enable downstream affinity selection-based applications such as high throughput AS-MS screens. 相似文献
977.
To improve the efficiency of the use of nuclease P1, enzyme immobilization technology was applied using nuclease P1. Characterization
of immobilized nuclease P1 on different supports was studied. The results showed that the optimum pH and temperature of nuclease
P1 immobilized via different supports were enhanced. The immobilized enzyme was obviously stable when stored for long periods
and was reusable. The best results were obtained when nuclease P1 was immobilized on chitosan nanoparticles. The nanoparticles
were applied to protect the activity of nuclease P1 and improved enzyme activity by 13.17% over that of free nuclease P1 at
the same conditions. The Michaelis constant Km and V
max were determined for free and immobilized enzyme as well. 相似文献
978.
Zhao RS Cheng CG Yuan JP Jiang T Wang X Lin JM 《Analytical and bioanalytical chemistry》2007,387(2):687-694
A novel purge-and-trap method coupled with gas chromatography-mass spectrometry (GC-MS) is developed for the analysis of trace
and ultratrace phenols based on their derivatization with acetic anhydride. Parameters affecting the extraction efficiency,
such as purge temperature, concentration of sodium chloride, purge time, and volume of derivatization reagent, were investigated.
The optimized conditions were addition of 150 μL acetic anhydride, purge time of 25 min at the purge temperature of 60 °C
with 30% NaCl. The linear range was 0.2–100 μg L−1 for phenols. The limits of detection (LODs) ranged from 0.08 to 0.15 μg L−1 and the relative standard deviations (RSDs) for most of the phenols at the 10 μg L−1level were below 10%. Natural water samples collected from a pool were successfully analyzed using the proposed method. The
recovery of spiked water samples was 72.9–84.2%. 相似文献
979.
Schmitt-Jansen M Bartels P Adler N Altenburger R 《Analytical and bioanalytical chemistry》2007,387(4):1389-1396
The occurrence of pharmaceuticals in the environment is an emerging issue. Several studies observed that the non-steroidal
anti-inflammatory drug diclofenac is ubiquitously present in most of the surveyed surface waters, worldwide. Phototransformation
of diclofenac was reported from laboratory assays as well as in natural water systems, raising the question of possible adverse
effects of the phototransformation products of diclofenac to aquatic organisms. In this study the phytotoxicity of diclofenac
exposed to natural sunlight was evaluated using synchronized cultures of the unicellular chlorophyte Scenedesmus vacuolatus. Diclofenac dissolved in ultra-pure water at 50 mg L−1 was exposed to natural midsummer sunlight for a maximum of 145 h. Twice a day subsamples were taken for chromatography and
parallel phytotoxicity assessment. Inhibition of algal reproduction of the initial diclofenac solution was in the mg L−1 range indicating no specific toxicity of diclofenac towards S. vacuolatus. Fast degradation of diclofenac was observed with half lives between 3.3 and 6.4 h during the first and the third day of
exposure, respectively. Phytotoxicity increased after 3.5 h of exposure of diclofenac to sunlight and showed a maximum of
sixfold enhanced toxicity after 53 h of exposure to sunlight. Several phototransformation products were found during the experiment.
The time courses of the relative concentration of three transformation products significantly correlated with enhanced phytotoxicity
during the experiment. This indicates a high toxicity potential of phototransformation products of diclofenac at concentration
levels that may come close to environmental concentrations of residual diclofenac after degradation. We conclude that toxicity
assessment of phototransformation products should be included in the risk assessment of pharmaceuticals in the environment. 相似文献
980.
Contribution of UV light to the decomposition of toluene in dielectric barrier discharge plasma/photocatalysis system 总被引:1,自引:0,他引:1
Hai Bao Huang Dai Qi Ye Ming Li Fu Fa Da Feng 《Plasma Chemistry and Plasma Processing》2007,27(5):577-588
The contribution of UV light from plasma and an external UV lamp to the decomposition of toluene in a dielectric barrier discharge
(DBD) plasma/UV system, as well as in a plasma/photocatalysis system was investigated. It was found that UV light from the
DBD reactor was very weak. Its contribution to the removal of toluene in the plasma/photocatalysis system could be ignored.
Whereas, the introduction of external UV light to the plasma significantly improves the removal efficiency of toluene by 20%.
The removal efficiency of toluene in the plasma/photocatalysis system increased about 22% and 16% when compared with a plasma
only system and plasma driven photocatalyst system, respectively. The increased toluene removal efficiency was mostly attributed
to the contribution of the synergy between plasma and UV light, but not to the synergy between plasma and photocatalysis.
The synergetic effect between plasma and photocatalysis was not significant. 相似文献