全文获取类型
收费全文 | 23117篇 |
免费 | 1114篇 |
国内免费 | 832篇 |
专业分类
化学 | 14395篇 |
晶体学 | 207篇 |
力学 | 882篇 |
综合类 | 74篇 |
数学 | 2919篇 |
物理学 | 6586篇 |
出版年
2023年 | 151篇 |
2022年 | 273篇 |
2021年 | 291篇 |
2020年 | 389篇 |
2019年 | 358篇 |
2018年 | 286篇 |
2017年 | 263篇 |
2016年 | 536篇 |
2015年 | 573篇 |
2014年 | 633篇 |
2013年 | 1084篇 |
2012年 | 1154篇 |
2011年 | 1296篇 |
2010年 | 903篇 |
2009年 | 760篇 |
2008年 | 1187篇 |
2007年 | 1168篇 |
2006年 | 1109篇 |
2005年 | 1117篇 |
2004年 | 924篇 |
2003年 | 762篇 |
2002年 | 685篇 |
2001年 | 656篇 |
2000年 | 573篇 |
1999年 | 367篇 |
1998年 | 302篇 |
1997年 | 284篇 |
1996年 | 346篇 |
1995年 | 319篇 |
1994年 | 291篇 |
1993年 | 341篇 |
1992年 | 333篇 |
1991年 | 298篇 |
1990年 | 234篇 |
1989年 | 221篇 |
1988年 | 249篇 |
1987年 | 226篇 |
1986年 | 193篇 |
1985年 | 253篇 |
1984年 | 221篇 |
1983年 | 177篇 |
1982年 | 212篇 |
1981年 | 186篇 |
1980年 | 191篇 |
1979年 | 191篇 |
1978年 | 188篇 |
1977年 | 160篇 |
1976年 | 167篇 |
1974年 | 153篇 |
1973年 | 132篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
11.
Willem A.L. van Otterlo 《Tetrahedron letters》2004,45(26):5091-5094
Contrary to literature reports, bromination of 3-hydroxybenzaldehyde can afford both 2-bromo-5-hydroxybenzaldehyde and 2-bromo-3-hydroxybenzaldehyde, but 4-bromo-3-hydroxybenzaldehyde was not detected. 2-Bromo-3-hydroxybenzaldehyde was converted into 2-(benzyloxy)-1-bromo-5-methoxy-7-methylnaphthalene. X-ray crystallographic analysis supports the identity of 2-bromo-3-hydroxybenzaldehyde. 相似文献
12.
13.
W M Niessen M A de Kraa E R Verheij P J Bergers G F La Vos U R Tjaden J van der Greef 《Rapid communications in mass spectrometry : RCM》1989,3(1):1-4
On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL. 相似文献
14.
激光晶体YAG中Er3+的辐射跃迁 总被引:2,自引:0,他引:2
本文讨论和分析了激光晶体YAG中Er3+离子的激光上能级的4S3/2、4I11/2和4I13/2辐射跃迁的有关因素。 相似文献
15.
16.
Leif Schrder Christian Schmitz Peter Bachert 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):87
Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl-l-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct 1H–1H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized 1H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD0 (S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 (δ = 8 ppm) and H4 (δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD0 from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution 1H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D0 (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 − 3) × 10−4 indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 − 137) × 10−4. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, 1H NMR experiments on aqueous model solutions of histidine and N-acetyl-l-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo 1H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle (θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids. 相似文献
17.
Xin‐Gui Li Run‐Feng Chen Mei‐Rong Huang Mei‐Fang Zhu Qun Chen 《Journal of polymer science. Part A, Polymer chemistry》2004,42(9):2073-2092
A new series of copolymers was synthesized through the oxidative polymerization of pyrrole (PY) and o‐phenetidine (PHT) with inorganic oxidants in acidic media. The polymerization parameters including the mixing method of the oxidant with the comonomer, the comonomer ratio, the time, the temperature, the oxidant, the organic medium, and the acid were systematically optimized for the synthesis of copolymers with high yields, intrinsic viscosities, and solubility. The resultant copolymers were characterized by elemental analysis, infrared, ultraviolet–visible, solution high‐resolution 1H NMR and solid‐state high‐resolution 13C NMR, circular dichroism spectroscopy, and cyclic voltammetry. The results showed that the PY observed content in the copolymers was much higher than the PY feed content. The regular variation of the polymerization yield, intrinsic viscosity, solubility, macromolecular structure, and electroactivity of the resulting polymers with the comonomer ratio, together with the complete solubility of a PY/PHT (10/90) polymer in highly polar solvents, indicated the formation of real random copolymers containing both PY and PHT units rather than a mixture of two homopolymers. However, the polymers containing more than 59 mol % PY were not homogeneous copolymers consisting of soluble and insoluble parts. A semiquantitative relationship between the polymerization yield or solubility of the copolymers and the polarity index of the organic solvents was examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2073–2092, 2004 相似文献
18.
Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (Ea) of the segmental chain motion was lowest for dimeric maltose (Ea = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (Ea = 60.8 ± 1.8 kJ/mol). Subsequently, Ea leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the Ea dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher Ea values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004 相似文献
19.
Nelly A. Kachurovskaya Georgii M. Zhidomirov Rutger A. van Santen 《Research on Chemical Intermediates》2004,30(1):99-103
Periodical calculations of Zn(II) metal cation stabilization in cationic positions with distantly placed aluminium ions has been performed for high-silica ferrierite. It was found that decrease of the stabilization energy at large distances between Al ions (more than 10 Å) is about of 2 eV in comparison with nearest possible position of two Al ions in the zeolite lattice and weekly depended on following increase of the Al-Al distance. Main changes in stabilization energy occured within a 3-Å interval of these distances. Only for the localizations of both Al ions in one zeolite ring zinc cationic form is more stable than hydrogen form. 相似文献
20.
Qing An WU Zhen Yuan XU Mei ZHENG Dan Qian XU Jun XU Yin Chu SHENCollege of Chemical Engineering Materials Zhejiang University of Technology Hangzhou 《中国化学快报》2004,(7)
Six new 13-O-acylavermectin Bl aglycones(3-8) were synthesized from avermectin B1 aglycone and their bioactivities were evaluated against Spodoptera exigua, Spodoptera eridania, Tetranychus urticae and Aphis fabae. 相似文献