全文获取类型
收费全文 | 97156篇 |
免费 | 700篇 |
国内免费 | 883篇 |
专业分类
化学 | 64409篇 |
晶体学 | 24篇 |
力学 | 549篇 |
综合类 | 266篇 |
数学 | 851篇 |
物理学 | 25217篇 |
综合类 | 7423篇 |
出版年
2023年 | 107篇 |
2022年 | 129篇 |
2021年 | 128篇 |
2020年 | 108篇 |
2019年 | 120篇 |
2018年 | 141篇 |
2017年 | 90篇 |
2016年 | 169篇 |
2015年 | 152篇 |
2014年 | 326篇 |
2013年 | 281篇 |
2012年 | 8306篇 |
2011年 | 11752篇 |
2010年 | 2105篇 |
2009年 | 586篇 |
2008年 | 9180篇 |
2007年 | 9362篇 |
2006年 | 9414篇 |
2005年 | 9130篇 |
2004年 | 7186篇 |
2003年 | 5533篇 |
2002年 | 4782篇 |
2001年 | 3175篇 |
2000年 | 3927篇 |
1999年 | 919篇 |
1998年 | 332篇 |
1997年 | 262篇 |
1996年 | 1358篇 |
1995年 | 943篇 |
1994年 | 1190篇 |
1993年 | 1589篇 |
1992年 | 1402篇 |
1991年 | 576篇 |
1990年 | 560篇 |
1989年 | 436篇 |
1988年 | 385篇 |
1987年 | 378篇 |
1986年 | 411篇 |
1985年 | 355篇 |
1984年 | 87篇 |
1983年 | 79篇 |
1982年 | 60篇 |
1981年 | 68篇 |
1979年 | 55篇 |
1959年 | 76篇 |
1958年 | 144篇 |
1957年 | 82篇 |
1956年 | 65篇 |
1955年 | 60篇 |
1948年 | 74篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
951.
Lerbret A Bordat P Affouard F Descamps M Migliardo F 《The journal of physical chemistry. B》2005,109(21):11046-11057
The structural properties resulting from the reciprocal influence between water and three well-known homologous disaccharides, namely, trehalose, maltose, and sucrose, in aqueous solutions have been investigated in the 4-66 wt % concentration range by means of molecular dynamics computer simulations. Hydration numbers clearly show that trehalose binds to a larger number of water molecules than do maltose or sucrose, thus affecting the water structure to a deeper extent. Two-dimensional radial distribution functions of trehalose solutions definitely reveal that water is preferentially localized at the hydration sites found in the trehalose dihydrate crystal, this tendency being enhanced when increasing trehalose concentration. Over a rather wide concentration range (4-49 wt %), the fluctuations of the radius of gyration and of the glycosidic dihedral angles of trehalose indicate a higher flexibility with respect to maltose and sucrose. At sugar concentrations between 33 and 66 wt %, the mean sugar cluster size and the number of sugar-sugar hydrogen bonds formed within sugar clusters reveal that trehalose is able to form larger clusters than sucrose but smaller than maltose. These features suggest that trehalose-water mixtures would be more homogeneous than the two others, thus reducing both desiccation stresses and ice formation. 相似文献
952.
氯化钪-氯化钠-氯化钾熔盐制备新工艺研究 总被引:3,自引:1,他引:3
研究了以Sc2O3为原料,盐酸回流溶解后与NaCl,KCl,NH4Cl溶液混合,经蒸发浓缩、结晶、真空预脱水,再在氩气保护下分段升温脱水、升华除去过量NI-hCl后制备ScCl3-NaCl-KCl熔盐的新工艺。研究表明,添加NH4Cl后加热脱水时,NH4Cl分解产生的HCl气体能抑制ScCl3水合物加热过程中的水解,溶解产生的水不溶性钪,从而有效地防止了Sc2O3等水不溶化合物的生成。制备的ScCl3-NaCl-KCl熔盐脱水完全、水不溶性钪含量很低,能满足熔盐金属热还原法制备金属钪及铝钪中间合金对熔盐原料的要求。 相似文献
953.
Pizarro N Llebaria A Cano S Joglar J Farré M Segura J de la Torre R 《Rapid communications in mass spectrometry : RCM》2003,17(4):330-336
3,4-Methylenedioxymethamphetamine (MDMA, ecstasy) is consumed as the racemate but some metabolic steps are enantioselective. In addition, chiral properties are preserved during MDMA biotransformation. A quantitative analytical methodology using gas chromatography/mass spectrometry (GC/MS) to determine enantioselective disposition in the body of MDMA and its main metabolites including 3,4-methylenedioxyamphetamine (MDA), 4-hydroxy-3-methoxymethamphetamine (HMMA), and 4-hydroxy-3-methoxyamphetamine (HMA) was developed. Plasma and urine samples were collected from a male volunteer. The analysis of MDMA, MDA, and 4-hydroxy-3-methoxy metabolites by GC/MS required a two-step derivatization procedure. The first step consisted of derivatization of the amine with enantiomerically pure Mosher's reagent ((R)-MTPCl). Triethylamine was used as a base to neutralize hydrochloric acid formed during the reaction allowing quantitative derivatization, which resulted in a substantial improvement in the sensitivity of the method compared with other previously described techniques. Further treatment with ammonium hydroxide was required since both amine and hydroxyl groups underwent derivatization in the reaction. Ammonium hydroxide breaks bonds formed with hydroxyl groups without affecting amine derivatives. The second derivatization step using hexamethyldisilazane was needed for metabolites containing phenol residues. This derivatization method permitted the stereochemically specific study of MDMA and its main monohydroxylated metabolites by GC/MS. A detailed study of the chemical reactions involved in the derivatization steps was indispensable to develop a straightforward, sensitive, and reproducible method for the analysis of the parent drug compound and its metabolites. 相似文献
954.
955.
Bringmann G Pfeifer RM Rummey C Hartner K Breuning M 《The Journal of organic chemistry》2003,68(18):6859-6863
The enantioselective synthesis of a novel-type C(3)-symmetric tripodal ligand that is composed of a central mesitylene-derived core and three functionalized, axially chiral biaryl subunits is described. The triol (M,M,M)-3 is a suitable catalyst for the enantioselective addition of dialkylzinc to various aromatic aldehydes with asymmetric inductions of up to 98% ee. 相似文献
956.
A novel pulse sequence improving the efficiency for electron capture dissociation (ECD) of an unmodified Fourier transform ion cyclotron resonance (FTICR) mass spectrometer by more than an order of magnitude is presented. Commercially available FTICR instruments are usually equipped with a filament-based electron source producing an electron beam that has a rather small cross section. An ideal overlap between the rotating ion cloud and the electron beam appears to be a prerequisite for a high ECD efficiency. A reduced interception of the ion cloud and the electron beam is probably due to the contribution of the magnetron motion to the trajectory of the ions, resulting in a precession about the z-axis of the instrument. By increasing the kinetic energy and therefore increasing the cyclotron radii of the precursor ions by resonant excitation, the overlap of the rotating ion cloud with the electron beam is improved. By use of this protocol the efficiency of electron capture is substantially increased and consequently the acquisition time of ECD spectra is reduced significantly. The capability of resonant excitation of the precursor ions during the irradiation with electrons is demonstrated for standard peptides. This approach is particularly valuable for analysis and characterization of O-glycosylated peptides. In addition to amino acid sequence information, the attachment site of the labile glycan moiety is determined, and also radical-site-induced fragmentations of the glycosidic bonds are observed. 相似文献
957.
Bolm C Verrucci M Simic O Cozzi PG Raabe G Okamura H 《Chemical communications (Cambridge, England)》2003,(22):2826-2827
Quinoline-based C1-symmetric sulfoximines have been used as chiral ligands in copper-catalyzed asymmetric hetero Diels-Alder reactions leading to cycloadducts with up to 96% ee. 相似文献
958.
Volonterio A Bellosta S Bravin F Bellucci MC Bruché L Colombo G Malpezzi L Mazzini S Meille SV Meli M Ramírez De Arellano C Zanda M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4510-4522
Partially modified retro- (PMR) and retro-inverso (PMRI) psi[NHCH(CF(3))]Gly peptides, a conceptually new class of peptidomimetics, have been synthesized in wide structural diversity and variable length by aza-Michael reaction of enantiomerically pure alpha-amino esters and peptides with enantiomerically and geometrically pure N-4,4,4-trifluorocrotonoyl-oxazolidin-2-ones. The factors underlying the observed moderate to good diastereocontrol have been investigated. The conformations of model PMR-psi[NHCH(CF(3))]Gly tripeptides have been studied in solution by (1)H NMR spectroscopy supported by MD calculations, as well as in the solid-state by X-ray diffraction. Remarkable stability of turn-like conformations, comparable to that of parent malonyl-based retropeptides, was evidenced, as a likely consequence of two main factors: 1) severe torsional restrictions about sp(3) bonds in the [CO-CH(2)-CH(CF(3))-NH-CH(R)-CO] module, which is biased by the stereoelectronically demanding CF(3) group and the R side chain; 2) formation of nine-membered intramolecularly hydrogen-bonded rings, which have been clearly detected both in CHCl(3) solution and in some crystal structures. The former factor seems to be more important, as turn-like conformations were found in the solid-state even in the absence of intramolecular hydrogen bonding. The relative configuration of the -C*H(CF(3))NHC*H(R)- stereogenic centers has a major effect on the stability of the turn-like conformation, which seems to require a syn stereochemistry. X-ray diffraction and ab initio computational studies showed that the [-CH(CF(3))NH-] group can be seen as a sort of hybrid between a peptide bond mimic and a proteolytic transition state analogue, as it combines some of the properties of a peptidyl -CONH- group (low NH basicity, CH(CF(3))-NH-CH backbone angle close to 120 degrees, C-CF(3) bond substantially isopolar with the C=O) with some others of the tetrahedral intermediate [-C(OX)(O(-))NH-] involved in the protease-mediated hydrolysis reaction of a peptide bond (high electron density on the CF(3) group, tetrahedral backbone carbon). 相似文献
959.
Berger A Djukic JP Pfeffer M de Cian A Kyritsakas-Gruber N Lacour J Vial L 《Chemical communications (Cambridge, England)》2003,(5):658-659
In the presence of large amounts of [Me4N]Cl, the reaction of ortho-chloromercurated 2-[(eta6-phenyl)tricarbonylchromium]pyridine with mu-chloro cyclopalladated aromatic compounds yields a series of new heteroleptic heterodinuclear cis-(C--N)2Pd(II) complexes, which are valuable precursors of planar chiral cyclopalladated (eta6-arene)Cr(CO)3 complexes. 相似文献
960.
In peptide synthesis, hydrazides are important intermediates for the azide coupling method. A hydrazide is converted to the corresponding azide in the presence of an acid and a nitrite. When acetic acid (or formic acid) is used as the acid, partial acetylation (or formylation) of the hydrazide occurs as a side reaction. Formylation of the hydrazide is much faster than acetylation. Removal of the formyl group on the hydrazide with hydrazine and hydroxylamine was studied. The rate of deformylation with hydrazine treatment is faster than that with hydroxylamine treatment. 相似文献