全文获取类型
收费全文 | 32674篇 |
免费 | 457篇 |
国内免费 | 560篇 |
专业分类
化学 | 11509篇 |
晶体学 | 279篇 |
力学 | 1459篇 |
综合类 | 16篇 |
数学 | 9234篇 |
物理学 | 8716篇 |
无线电 | 2478篇 |
出版年
2023年 | 69篇 |
2022年 | 89篇 |
2021年 | 127篇 |
2020年 | 137篇 |
2019年 | 109篇 |
2018年 | 1290篇 |
2017年 | 1575篇 |
2016年 | 864篇 |
2015年 | 745篇 |
2014年 | 632篇 |
2013年 | 875篇 |
2012年 | 3427篇 |
2011年 | 2600篇 |
2010年 | 1934篇 |
2009年 | 1698篇 |
2008年 | 753篇 |
2007年 | 748篇 |
2006年 | 726篇 |
2005年 | 4900篇 |
2004年 | 4012篇 |
2003年 | 2360篇 |
2002年 | 556篇 |
2001年 | 377篇 |
2000年 | 159篇 |
1999年 | 222篇 |
1998年 | 156篇 |
1997年 | 110篇 |
1996年 | 94篇 |
1995年 | 89篇 |
1994年 | 86篇 |
1993年 | 55篇 |
1992年 | 198篇 |
1991年 | 194篇 |
1990年 | 184篇 |
1989年 | 141篇 |
1988年 | 132篇 |
1987年 | 103篇 |
1986年 | 86篇 |
1985年 | 78篇 |
1984年 | 62篇 |
1983年 | 53篇 |
1982年 | 46篇 |
1979年 | 45篇 |
1976年 | 88篇 |
1975年 | 48篇 |
1974年 | 48篇 |
1973年 | 61篇 |
1972年 | 47篇 |
1970年 | 48篇 |
1968年 | 45篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
891.
Effects of temperature and sodium carboxylate additives on mineralization of calcium oxalate in silica gel systems 总被引:5,自引:0,他引:5
Bernd Tieke 《中国科学B辑(英文版)》2004,47(4):311-319
Urolithiasis remains a major medical problem in China, especially in Guangdong Province in the southest of China[1]. A survey in Shenzhen city, the most southern city in China, showed the incidence of renal calculus was 4.87%, being 6.12% in the males and 4.07% in the females[2]. The prevalence of renal calculus has been more as the age advances and in the male population and so was in the less-educated population. The recurrence rate is more than 80%, with a moderate improvement by conventi… 相似文献
892.
893.
Werner Unterberger Bernd Jenewein Bernhard Kl?tzer Simon Penner Wolfgang Reichl Günther Rupprechter Di Wang Di Wang Robert Schl?gl Konrad Hayek 《Reaction Kinetics and Catalysis Letters》2006,87(2):215-234
Summary The effect of hydrogen reduction on the structure and catalytic properties of “thin film”and “inverse”model systems for supported
metal catalysts is discussed. Thin film model catalysts were obtained by epitaxial growth of Pt and Rh nanoparticles on NaCl(001),
which were coated with amorphous or crystalline supports of alumina, silica, titania, ceria and vanadia. Structural and morphological
changes upon hydrogen reduction between 473 and 973 K were examined by high resolution electron microscopy. Metal-oxide interaction
sets in at a specific reduction temperature and is characterized by an initial “wetting”stage, followed by alloy formation
at increasing temperature, in the order VOx< TiOx< SiO2< CeOx< Al2O3. “Inverse”model systems were prepared by deposition of oxides on a metal substrate, e.g. VOx/Rh and VOx/Pd. Reduction of inverse systems at elevated temperature induces subsurface alloy formation. In contrast to common bimetallic
surfaces, the stable subsurface alloys of V/Rh and V/Pd have a purely noble metal-terminated surface, with V positioned in
near-surface layers. The uniform composition of the metallic surface layer excludes catalytic ensemble effects in favor of
ligand effects. Activity and selectivity, e.g. for CO and CO2methanation and for partial oxidation of ethene, are mainly controlled by the temperature of annealing or reduction. Reduction
above 573 K turned out to be beneficial for the catalytic activity of the subsurface alloys, but not for the corresponding
thin film systems which tend to deactivate viaparticle encapsulation.</o:p> 相似文献
894.
The separation characteristics of alkylchloroformate-derivatised amino acids (AAs) by using comprehensive two-dimensional gas chromatography (GC×GC) is reported. The use of a low-polarity/polar column set did not provide as good a separation performance as that achieved with a polar/non-polar column set, where the latter appeared to provide less correlation over the separation space. The degree of component correlation in each column set was estimated by using the correlation coefficient (r2; for 1tR and 2tR data) with the low-polarity/polar and polar/low-polarity sets returning correlation coefficients of 0.86, and 0.00 respectively, under the respective conditions employed for the experiments. The 1.5-m non-polar 2D column (0.1-mm ID; 0.1-m film thickness) gave peak halfwidths of the order of 50–80 ms. Linearity of detection was good, over a three order of magnitude concentration range, with typical lower detection limit of ca. 0.01 mg L–1, compared with 0.5 mg L–1 for normal GC operation with splitless injection. The method was demonstrated for analysis of AAs in a range of food and beverage products, including wine, beer and honey. The major AA in these samples was proline. The Heineken beer sample had a relatively more complex and more abundant AA content compared with the other beer sample. The wine and honey samples also gave a range of AA compounds. Repetition of the sample preparation/analysis procedure for the honey sample gave acceptable reproducibility for individual AAs. 相似文献
895.
Arsenic-speciation analysis in marine samples was performed by high-pressure liquid chromatography (HPLC) with ICP–MS detection.
Separation of eight arsenic species—AsIII, MMA, DMA, AsV, AB, TMAO, AC and TeMAs+—was achieved on a C18 column with isocratic elution (pH 3.0), under which conditions AsIII and MMA co-eluted. The entire separation was accomplished in 15 min. The HPLC–ICP–MS detection limits for the eight arsenic
species were in the range 0.03–0.23 μg L−1 based on 3σ for the blank response (n=5). The precision was calculated to be 2.4–8.0% (RSD) for the eight species. The method was successfully applied to several
marine samples, e.g. oysters, fish, shrimps, and marine algae. Low-power microwave digestion was employed for extraction of
arsenic from seafood products; ultrasonic extraction was employed for the extraction of arsenic from seaweeds. Separation
of arsenosugars was achieved on an anion-exchange column. Concentrations of arsenosugars 2, 3, and 4 in marine algae were
in the range 0.18–9.59 μg g−1.
This paper was presented at the European Winter Conference 2005 相似文献
896.
A cylindrical chemosorptive denuder in series with a glass fibre filter has been evaluated for sampling toluene diisocyanate (TDI) aerosols. The sampler is designed for measuring personal exposure to diisocyanates. Several denuder coatings and derivatising reagents were investigated. Dimethylpolysiloxane (SE-30) and 5% phenyl dimethylpolysiloxane (SE-54) with either dibutylamine (DBA) or dipentylamine (DPeA) as derivatising reagents yielded the lowest vapour breakthrough (the amount (%) of the vapour that passes through the denuder), close to values predicted by theory. Immobilisation of the SE-30 denuder coating by in-situ cross-linking yielded comparable results. With an SE-30/DBA-coated denuder operating within an airflow range of 100–500 mL min–1, the phase separation was shown to be consistent with theoretical predictions derived by use of the Gormley–Kennedy equation. This provides a means of calculating the vapour breakthrough and correcting experimentally obtained values with regard to vapour–particulate phase distribution, suggesting that the denuder can provide accurate phase-distribution measurements. The SE-30/DBA denuder can be used over a concentration range spanning nearly six orders of magnitude. Its capacity is sufficient to perform 15-min exposure measurements of a TDI aerosol with air concentrations as high as 1,700 g m–3, 40 times higher than the Swedish occupational exposure limit (OEL). At the other end of the range, the estimated limit of detection (LOD) was less than 2 ng m–3 for both the vapour and the aerosol phases when LC–ESI–MS–MS was used for chemical analysis.Electronic Supplementary Material Supplementary material for this article is available at 相似文献
897.
Total selenium content and its distribution in the soluble and insoluble protein-bound fractions obtained after aqueous extraction of antarctic krill samples were determined. About 26% of the total selenium (2.4 g g–1 dry weight) was found in the supernatant; the rest was in the pellet. Isolation of low molecular selenium-containing fractions was also performed by enzymatic digestion of the protein, followed by size-exclusion chromatography in conjunction with atomic absorption spectrometry. From the applied various proteinases (pronase E, subtilisin Carlsberg, trypsin, chymotrypsin, proteinase and proteinase N from Bacillus subtilis and Novo 0.6 MPX enzyme), the treatment with pronase E led to best recovery of selenium. About 96% of the total Se was found in the hydrolysate, mainly in low molecular weight fractions. Eighty percent of the Se species were in fractions with molecular weights in the range of amino acids and short peptides. High-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC-ICP-MS) allowed the identification of selenomethionine and the assumption that selenocystine or its derivatives were the main species in these fractions. 相似文献
898.
Summary Atmospheric precipitation and aerosol samples are characterized by a complex mixture of several organic compounds. A simple method for the simultaneous determination of the main compound classes by GC/MS is presented. In detail, seasonal variations of C8–C32 fatty acids in precipitation in a semirural area have been studied. Total fatty acids concentrations of 7–53 g/l were detected. Summer rain is characterized by high amounts of fatty acids >C20 and lower amounts of C11–C20 species. Two effects may be responsible: larger emission rates of fatty acids during vegetation periods and an increased influence of vapour phase due to higher temperatures during summer. CPI values showed no general trend; lower CPI values for winter rain could not be observed. This would be expected if anthropogenic sources play an important role. Monounsaturated fatty acids (C16:1, C18:1) were more abundant during winter than in summer. High concentrations of polyunsaturated fatty acids (C18:x) could be detected during summer. High relative concentrations of the potential oxidation products of the unsaturated species, nonanedioic acid and w-oxononanoic acid, are associated with relatively low concentrations of their precursors. 相似文献
899.
Castellano PM Vignaduzzo SE Maggio RM Kaufman TS 《Analytical and bioanalytical chemistry》2005,382(7):1711-1714
A new, repeatable, and rapid method has been developed for resolution of binary mixtures of acetaminophen and diclofenac with minimum sample pretreatment and without separation of the analytes. The method, based on the PLS1 processing of absorbance data in the UV region, was successfully used for quantification of the drug content of three tablet preparations. The results obtained were in good agreement with HPLC recovery data. The method also enabled determination of drug-dissolution profiles of these commercial tablets, by simultaneous determination of both analytes during the dissolution test. 相似文献
900.
Zoya?Orekhova Yonit?SambiraEmail author Emanuel?Manzurola Alexander?Apelblat 《Journal of solution chemistry》2005,34(7):853-867
Conductivity measurements of DL-pyroglutamic acid and sodium pyroglutamate in dilute aqueous solutions were performed in the 288.15–323.15 K temperature range. The limiting molar conductances of pyroglutamate anion, λo(pGlu−, T) and the dissociation constants of pyroglutamic acid, K(T) were derived from the Onsager, and the Quint and Viallard conductivity equations. Densities of aqueous solutions with molalities lower than 0.5 mol-kg−1 were determined at 5 K intervals from T = 288.15 K to 333.15 K. Densities served to evaluate the apparent molar volumes, V2,φ(m, T), the cubic expansion coefficients, α (m,T) and the changes of the isobaric heat capacities with respect to pressure, (∂ CP/∂ P)T,m. They were correlated qualitatively with the changes in the structure of water when pyroglumatic acid is dissolved in it. 相似文献