全文获取类型
收费全文 | 3925篇 |
免费 | 119篇 |
国内免费 | 14篇 |
专业分类
化学 | 3071篇 |
晶体学 | 90篇 |
力学 | 59篇 |
数学 | 133篇 |
物理学 | 705篇 |
出版年
2022年 | 25篇 |
2021年 | 32篇 |
2020年 | 40篇 |
2019年 | 60篇 |
2018年 | 31篇 |
2017年 | 18篇 |
2016年 | 74篇 |
2015年 | 71篇 |
2014年 | 97篇 |
2013年 | 176篇 |
2012年 | 195篇 |
2011年 | 215篇 |
2010年 | 136篇 |
2009年 | 116篇 |
2008年 | 217篇 |
2007年 | 237篇 |
2006年 | 242篇 |
2005年 | 241篇 |
2004年 | 220篇 |
2003年 | 184篇 |
2002年 | 155篇 |
2001年 | 101篇 |
2000年 | 86篇 |
1999年 | 55篇 |
1998年 | 50篇 |
1997年 | 41篇 |
1996年 | 49篇 |
1995年 | 44篇 |
1994年 | 37篇 |
1993年 | 35篇 |
1992年 | 79篇 |
1991年 | 37篇 |
1990年 | 34篇 |
1989年 | 29篇 |
1988年 | 35篇 |
1987年 | 33篇 |
1986年 | 34篇 |
1985年 | 44篇 |
1984年 | 50篇 |
1983年 | 27篇 |
1982年 | 33篇 |
1981年 | 37篇 |
1980年 | 29篇 |
1979年 | 48篇 |
1978年 | 31篇 |
1977年 | 26篇 |
1976年 | 28篇 |
1975年 | 20篇 |
1974年 | 30篇 |
1973年 | 22篇 |
排序方式: 共有4058条查询结果,搜索用时 15 毫秒
71.
Liquid chromatographic-mass spectrometric analysis for screening of patients with cystinuria, and identification of cystine stone. 总被引:1,自引:0,他引:1
Analyses of amino acids in the urine of a normal human and of patients with heterozygous and homozygous cystinuria have been carried out, using liquid chromatography-mass spectrometry with an atmospheric pressure ionization interface system. A kidney cystine stone was also analysed by this system. Very intense quasi-molecular ions ([M + H]+) of standard cystine, arginine, lysine and ornithine were observed on mass chromatograms as base peaks. Mass chromatograms of the urine samples from a normal human and from patients with heterozygous and homozygous cystinuria were easily distinguishable. The retention times in the mass chromatogram and mass spectrum of kidney stone cystine was almost the same as that of authentic cystine. 相似文献
72.
A convenient and sensitive ion chromatographic (IC) method for the analysis of ethylenediaminetetraacetic acid (EDTA) in water
samples was proposed. Using a fast reversible reaction of free EDTA and metal–EDTA complexes into Fe(III)–EDTA complex in
the presence of Fe(III) ions, sample solutions were applied to an ion-exchange column using a mobile phase (pH 2.3), which
was composed of 100 μM Fe(III) chloride and 5 mM methanesulfonic acid. The addition of Fe(III) solution (100 μL) containing
10 mM Fe(III) chloride and 0.5 M methanesulfonic acid to the sample solution (10 mL) permitted the injection of a large volume
(400 μL) of sample, which allowed for greater sensitivity. The proposed IC method gave a highly linear (r
2 > 0.999) calibration curve ranging 0.005–1.0 μM EDTA and had a limit of detection of 1.5 nM. High repeatability (RSD < 2.1%)
and recoveries (88–108%) were also obtained. With this method, total EDTA level in raw and drinking waters were analyzed successfully. 相似文献
73.
Thermal nitrogen extrusion of 2-methylene-6,7-diazabicyclo[3.2.2]non-6-enes and 6,7- diazabicyclo[3.2.2]nona-2,6-diene,6 proceeded easily to give closure and cleavage products the corresponding 5-methylene-1,4-cycloheptylenes and 4-cyclohepten-1,3-ylenes, respectively. 相似文献
74.
Improved separation of alpha chains of collagen type I (alpha 1 [I]2 alpha 2[I]), type III(alpha 1[III]3), and type V (alpha 1[V]alpha 3[V])was achieved by noninterrupted sodium dodecyl sulfate-polyacrylamide gel electrophoresis with a negatively charged reducer, thioglycolic acid. The thioglycolic acid, added to the running buffer of the cathodic reservoir, in the middle of electrophoresis quickly migrated in the gel anode, reducing interchain disulfide linkages in collagen type III and dissociating it into its alpha chain monomer, alpha 1[III], without an interruption of electrophoresis. The alpha chain, alpha 1[III], migrated more slowly than the alpha 1 [I] and alpha 2[I] chains of collagen type I, resulting in an excellent separation of alpha 1[III] from alpha 1[I]. The mobility of alpha 1[III] could be controlled by varying the time of thioglycolic acid addition to the running buffer. This enabled us not only to separate alpha 1[III] from alpha 1[I] and alpha 1[V], but also to precisely quantitate these alpha chains, even at low protein loading of mixed samples. 相似文献
75.
Inoue M 《Organic & biomolecular chemistry》2004,2(13):1811-1817
One of the most characteristic and spectacular class of compounds isolated from marine sources is the polycyclic ethers. Following the initial report of the structural determination of brevetoxin B, a variety of novel polycyclic ethers have begun to surface. These natural products include ciguatoxins, gambierol, gambieric acids, yessotoxins and gymnocins, each of which exhibit distinct biological properties such as cytotoxicity and neurotoxicity, as well as antiviral and antifungal activities. Because of these intriguing biological activities and their complex molecular architecture, the total synthesis of these compounds has been pursued by many laboratories over two decades. In particular, the development of novel convergent strategies to assemble the structural fragments is crucial for the successful construction of these nano-scale molecules. This Perspective will focus on a recent convergent methodology using an acetal-linkage as a key motif. Application of this methodology culminated in the total syntheses of gambierol and ciguatoxin CTX3C. 相似文献
76.
[structure: see text] The first total synthesis of gambierol, a marine polycyclic ether toxin, has been achieved. The synthesis features the Pd(PPh3)4/CuCl/LiCl-promoted Stille coupling for the stereoselective construction of the sensitive triene side chain that includes a conjugated (Z,Z)-diene moiety. 相似文献
77.
Katsuma Hiraki Takeo Inoue Hidefumi Hirai 《Journal of polymer science. Part A, Polymer chemistry》1970,8(9):2543-2554
ESR spectra of homogeneous catalyst derived from tris(acetylacetonato)titanium(III) and triethylaluminum were observed at several temperatures from ?78°C, to +25°C, at molar ratios of aluminum to titanium of 1–108. At ?78°C, this catalyst yields a violet complex which shows an ESR signal with a g value of 1.959 and is associated with the first intermediate. At ?40°C to ?30°C, this signal decreases, and two signals with g values of 1.947 and 1.960 are observed. The latter two signals diminish at ?5°C to +10°C, while two kinds of new signals with g values of 1.965 and 1.969 appear overlapping each other. The structures of the species corresponding to these five signals are discussed on the basis of the ESR spectra, the intensity change, and the unpaired spin distribution. A new signal with a g value of 1.978 is found in the presence of butadiene at 25°C at Al/Ti > 8 and is assigned to a growing end of polybutadiene with this catalyst. The polymer yield increases remarkedly at Al/Ti molar ratios greater than 10. The microstructure of the resulting polymer consists almost completely of 1,2 units. The structure of the growing end is proposed to be a titanium (III) species containing two 1-substituted allyl groups, by comparison with the structure ascribed to the growing end of polybutadiene with n-butyl titanate-triethylaluminum catalyst. 相似文献
78.
Summary A porous polymer resin loaded with hydrous zirconium oxide (Zr-gel) was evaluated as a stationary phase for the liquid chromatographic separation of disubstituted aromatic compounds. The prepared Zr-gel was used to separate disubstituted phenols andortho-substituted benzoic acid derivatives in reversed-phase mode. The retention time of catechol was greater than those of other disubstituted phenols; this implies that the Zr-gel has specificity for the phenolic hydroxyl group. The retention behavior ofortho-substituted benzoic acid derivatives on the Zr-gel was also evaluated in reversedphase mode using buffer. Phthalic acid was specifically retained in the vicinity of pH 6.0, which has been regarded as the equal adsorbic point. Similar behavior was also observed for salicylic acid, although the retention time of salicylic acid was less than that of phthalic acid. It seems that the specific retention behavior of hydrous zirconium oxide is a result of complexation with ligands such as hydroxyl and carboxyl groups. The results of this study have revealed that the retention mechanism of hydrous zirconium oxide is a combination of ion exchange and interaction based on complexation with ligands. 相似文献
79.
Morikawa T Sun B Matsuda H Wu LJ Harima S Yoshikawa M 《Chemical & pharmaceutical bulletin》2004,52(10):1194-1199
A new beta-carboline-type alkaloidal glycoside, glucodichotomine B, four new neolignan glycosides, dichotomosides A, B, C, and D, and a new phenylpropanoid glycoside, dichotomoside E, were isolated from a Chinese natural medicine, the roots of Stellaria dichotoma L. var. lanceolata. The structures of the new glycosides were determined on the basis of chemical and physicochemical evidence. Among them, dichotomoside D inhibited the release of beta-hexosaminidase (IC(50)=64 microM) as well as tumor necrosis factor-alpha and interleukin-4 (IC(50)=16, 34 microM) in RBL-2H3 cells. These findings suggest that dichotomoside D is more effective against the late-phase reactions in type I allergy than in the immediate phase. 相似文献
80.
K. Osaki T. Inoue T. Uematsu Y. Yamashita 《Journal of Polymer Science.Polymer Physics》2002,40(10):1038-1045
Linear viscoelasticity behavior is described with the sum of two terms for polystyrene solutions in tricresyl phosphate around the coil overlapping concentration (K. Osaki, T. Inoue, & T. Uematsu, J Polym Sci Part B: Polym Phys 2001, 39, 211). One is a Rouse–Zimm (RZ) term represented by the Zimm theory with arbitrarily chosen values of the hydrodynamic interaction parameter and the longest relaxation time (τRZ). The other (the L term) consists of a relaxation mode with a single relaxation time (τL > τRZ) and a high‐frequency limiting modulus proportional to the square of the concentration. In this study, we describe the viscosity (η) and first normal stress coefficient (Ψ1) in steady shear with simple formulas. The stress due to the L term is assumed to be given by a Kaye, Bernstein, Kearsley, and Zapas (K‐BKZ) equation with the damping function h(γ) = (1 + 0.2γ2)?1/2, where γ is the magnitude of shear. Contributions to η and Ψ1 from the RZ term are derived from the RZ model, in which the relaxation time in steady flow is given by τst = τ + (τRZ ? τ)/(1 + 0.35τRZ γ˙) instead of τRZ. Here, γ˙ is the rate of shear, and τ is the τRZ value at the infinite dilution limit. η and Ψ1 at various concentrations for two polystyrene samples (with molecular weights of 2890 and 8420 kg mol?1) are well described with parameters derived from dynamic viscoelasticity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1038–1045, 2002 相似文献