全文获取类型
收费全文 | 32747篇 |
免费 | 189篇 |
国内免费 | 272篇 |
专业分类
化学 | 12444篇 |
晶体学 | 352篇 |
力学 | 1443篇 |
综合类 | 12篇 |
数学 | 9591篇 |
物理学 | 9366篇 |
出版年
2021年 | 92篇 |
2018年 | 1228篇 |
2017年 | 1507篇 |
2016年 | 825篇 |
2015年 | 644篇 |
2014年 | 568篇 |
2013年 | 853篇 |
2012年 | 3241篇 |
2011年 | 2480篇 |
2010年 | 1878篇 |
2009年 | 1641篇 |
2008年 | 631篇 |
2007年 | 681篇 |
2006年 | 642篇 |
2005年 | 4481篇 |
2004年 | 3966篇 |
2003年 | 2350篇 |
2002年 | 540篇 |
2001年 | 335篇 |
2000年 | 155篇 |
1999年 | 239篇 |
1998年 | 172篇 |
1997年 | 125篇 |
1996年 | 112篇 |
1995年 | 99篇 |
1994年 | 99篇 |
1993年 | 87篇 |
1992年 | 222篇 |
1991年 | 206篇 |
1990年 | 197篇 |
1989年 | 165篇 |
1988年 | 146篇 |
1987年 | 127篇 |
1986年 | 80篇 |
1985年 | 97篇 |
1984年 | 92篇 |
1983年 | 88篇 |
1982年 | 84篇 |
1981年 | 78篇 |
1979年 | 93篇 |
1978年 | 80篇 |
1976年 | 135篇 |
1975年 | 96篇 |
1974年 | 86篇 |
1973年 | 89篇 |
1972年 | 79篇 |
1969年 | 81篇 |
1968年 | 79篇 |
1967年 | 71篇 |
1966年 | 87篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
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
992.
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
993.
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
994.
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
995.
Xia Y Wu J McLuckey SA Londry FA Hager JW 《Journal of the American Society for Mass Spectrometry》2005,16(1):71-81
Ion/ion proton transfer reactions involving mutual storage of both ion polarities in a linear ion trap (LIT) that comprises part of a hybrid triple quadrupole/linear ion trap mass spectrometer have been effected. Mutual ion storage in the x- and y-dimensions arises from the normal operation of the oscillating quadrupole field of the quadrupole array, while storage in the z-dimension is enabled by applying unbalanced radio-frequency amplitudes to opposing sets of rods of the array. Efficient trapping (>90%) is achieved for thermalized ions over periods of several seconds. Reactions were demonstrated for multiply charged protein/peptide cations formed by electrospray with anions derived from glow discharge ionization of perfluoro(methyldecalin) (PMD) introduced from the side of the LIT rod array. Doubly and singly charged protein ions are readily formed via ion/ion reactions. The parameters that affect ion/ion reactions are discussed, including the degree of RF unbalance on the LIT rods, vacuum pressure, nature of the buffer gas, reaction time, anion abundance, and the low mass cutoff for ion/ion reaction. The present system has a demonstrated upper mass-to-charge ratio limit of at least 33,000. The system also has high flexibility with respect to defining MS(n) experiments involving both collision-induced dissociation (CID) and ion/ion reactions. Experiments are demonstrated involving beam-type CID in the pressurized collision quadrupole (Q2) followed by ion/ion reactions involving the product ions in the LIT. Ion parking experiments are also demonstrated using the mutual storage ion/ion reaction mode in the LIT, with a parking efficiency over 60%. 相似文献
996.
Many aspects of the behavior of surfactants have not been well understood due to the coupling of many different mechanisms.
Computer simulation is, therefore, attractive in the sense that it can explore the effect of different mechanisms separately.
In this paper, the shapes, structures and sizes of sodium dodecylbenzenesulfonate (SDBS) micelles under different concentrations
in an oil/water mixture were studied via molecular dynamics (MD) simulations using a simplified atomistic model which basically
maintains the hydrophile and lipophile properties of the surfactant molecules. Above the critical micellar concentration (cmc),
surfactant molecules aggregate spontaneously to form a wide variety of assemblies, from spherical to rodlike, wormlike and
bilayer micelles. Changes in their ratios of the principle moments of inertia (g1/g3, g2/g3) indicated the transition of micelle shapes at different concentrations. The aggregation number of micelle is found to have
a power-law dependence on surfactant concentration. 相似文献
997.
Lucija Jukić Urška Bratušek Marko Škof Jurij Svete Branko Stanovnik 《Chemistry of Heterocyclic Compounds》1996,32(11-12):1295-1299
A novel approach to the synthesis of 3-acylindolizines and the transformations of some acids into tryptophane analogues are described. Reaction of ethyl 2-pyridinylacetate and methyl 2-quinolinylacetate with N-trifluoroacetyl-5-bromo-4-oxonorvaline methylester led to N-trifluoroacetyl-3-(1-ethoxycarbonylindolizinyl-2) alanine methyl ester and N-trifluoroacetyl-3-(3-methoxycarbonylpyrrolo [1,2-a]quinolinyl-2) alanine methyl ester, respectively. Treatment of ethyl 2-pyridinylacetate and 2-pyridinylacetonitrile, first with N,N-dimethylformamide dimethyl acetal (DMFDMA), followed by reaction with phenacyl bromide, gave the corresponding 3-benzoylindolizines, while the reaction of ethyl 2-pyridinylacetate and 2-pyridinylacetonitrile with DMFDMA, followed by treatment with (S)-N-trifluoroacetyl-5-bromo-4-oxonorvaline methyl ester, gave the corresponding N-trifluoroacetyl-4-oxo-4-(indolizinyl-3)homoalanine methyl esters. 相似文献
998.
E. Pollert J. Hejtmnek K. Kní
ek M. Mary
ko J. P. Doumerc J. C. Grenier J. Etourneau 《Journal of solid state chemistry》2003,170(2):368-373
The electric and magnetic properties of the perovskites Nd0.8Na0.2Mn(1−x)CoxO3 (0x0.2) prepared by the usual ceramic procedure were investigated. The insulator-to-metal-like (IM) transition, closely related to a ferromagnetic arrangement, was revealed for the composition of x=0.04 and a similar tendency was detected for x=0. The insulating behavior persists down to low temperatures for higher contents of cobalt ions in spite of the transition to the bulk ferromagnetism. The properties are interpreted in terms of the steric distortion, tilting of the Mn(Co)O6 octahedra and the double-exchange interactions of the type Mn3+–O2−–Mn4+and Mn3.5+δ–O2−–Co2+, respectively. Presence of antiferromagnetic domains in the ferromagnetic matrix for the most of cobalt-substituted samples is supposed. 相似文献
999.
Zinc(II) and mercury(II) complexes were prepared by reacting isatin-3-thiosemicarbazone (ISTSCH) with zinc(II) acetate or mercury(II) bromide. The complexes were characterized by IR, Raman, diffuse reflectance, 1H and 13C NMR spectra and elemental analysis. Tetrahedral structures for Zn(ISTSC)2 and Hg(ISTSCH)Br2 are suggested. 相似文献
1000.
Rakesh?Kumar?MahajanEmail author Jyoti?Chawla Mandeep?Singh?BakshiEmail author 《Colloid and polymer science》2004,282(10):1165-1168
Cloud point (CP) measurements of Tween 20 and Tween 80 were carried out in the presence of various glycol oligomers and triblock polymers (TBP). The cloud points of both Tween 20 and 80 decrease in the presence of both types of additives. Among the glycol oligomeric additives, ethylene glycol monobutyl ether was found to reduce the CP maximum. An increase in the repeating units of polymeric glycol additives leads to a decrease in CP. Reduction in the CP in the presence of TBP depends upon the increase in hydrophobic/hydrophilic ratio among the polypropylene to polyethylene units. 相似文献