全文获取类型
收费全文 | 5185篇 |
免费 | 152篇 |
国内免费 | 15篇 |
专业分类
化学 | 3942篇 |
晶体学 | 103篇 |
力学 | 66篇 |
数学 | 211篇 |
物理学 | 1030篇 |
出版年
2023年 | 28篇 |
2022年 | 24篇 |
2021年 | 55篇 |
2020年 | 87篇 |
2019年 | 73篇 |
2018年 | 62篇 |
2017年 | 39篇 |
2016年 | 112篇 |
2015年 | 104篇 |
2014年 | 138篇 |
2013年 | 248篇 |
2012年 | 301篇 |
2011年 | 358篇 |
2010年 | 186篇 |
2009年 | 180篇 |
2008年 | 316篇 |
2007年 | 324篇 |
2006年 | 337篇 |
2005年 | 303篇 |
2004年 | 286篇 |
2003年 | 233篇 |
2002年 | 230篇 |
2001年 | 125篇 |
2000年 | 101篇 |
1999年 | 59篇 |
1998年 | 54篇 |
1997年 | 44篇 |
1996年 | 63篇 |
1995年 | 52篇 |
1994年 | 46篇 |
1993年 | 42篇 |
1992年 | 79篇 |
1991年 | 36篇 |
1990年 | 40篇 |
1989年 | 33篇 |
1988年 | 35篇 |
1987年 | 37篇 |
1986年 | 28篇 |
1985年 | 37篇 |
1984年 | 49篇 |
1983年 | 31篇 |
1982年 | 34篇 |
1981年 | 27篇 |
1980年 | 30篇 |
1979年 | 37篇 |
1978年 | 29篇 |
1977年 | 25篇 |
1976年 | 24篇 |
1975年 | 21篇 |
1974年 | 26篇 |
排序方式: 共有5352条查询结果,搜索用时 31 毫秒
81.
Yu Liu Bin Li Takehiko Wada Yoshihisa Inoue 《Journal of inclusion phenomena and macrocyclic chemistry》2000,36(3):311-325
The spectrophotometric titrations have beenperformed at 25–40 °C in aqueous solution to give the complexstability constants and the thermodynamic parametersfor the stoichiometric 1 : 1 inclusion complexation ofvarious aliphatic alcohols withmono[6-(phenylseleno)-6-deoxy]--cyclodextrin (2),mono[6-(o-, m-,p-tolylseleno)-6-deoxy]--cyclodextrin (3–5),mono[6-(p-chloro-phenyl-seleno)-6-deoxy]--cyclodextrin(6), mono[6-(benzylseleno)-6-deoxy]--cyclodextrin (7) and mono[6-(naphthaleneseleno)-6-deoxy]--cyclodextrin(8). On thebasis of the present and previous results, themolecular binding abilities and selectivities forguest aliphatic alcohols of the host -cyclodextrinderivatives (2–8) are discussed comparatively and globallyfrom the thermodynamic point of view. Thethermodynamic parameters obtained are criticalfunctions of the size/shape of aliphatic alcohols, andthe position and type of the substituent introduced tothe aromatic ring of -cyclodextrin's sidearm,which are elucidatedin terms of the conformational, electrostatic,hydrogen-bonding, and hydrophobic effects. 相似文献
82.
Tatsuro Ouchi Hirotoshi Fujie Satoshi Jokei Yoshiomi Sakamoto Hidenori Chikashita Takeshi Inoi Otto Vogl 《Journal of polymer science. Part A, Polymer chemistry》1986,24(9):2059-2074
Acryloyl-type polymer fixing 1-β-carbonylethyl-5-fluorouracil residues through D -glucofuranoses via ester bonds was synthesized by means of polymerization of the corresponding monomer and polymer reaction. In order to provide the water-soluble objective polymer, the copolymerization of the acryloyl-type monomer with acrylamide was carried out. The extent of release of 5-FU residues from the copolymer was investigated in the enzyme or nonenzyme system in vitro. Furthermore, the antitumor activities of the water-insoluble homopolymer and water-soluble copolymer obtained were tested in vivo. 相似文献
83.
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
84.
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
85.
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
86.
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
87.
Keivan Esfarjani Yuichi Hashi Satoshi Itoh Sigeo Ihara Yoshiyuki Kawazoe 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,41(1):73-76
To study the thermodynamic and mechanical stability of toroidal isomers of C 240, we use a semi-empirical tight-binding theory and calculate their electronic structure, cohesive energy and vibrational spectra within the harmonic approximation. From these, we deduce their free energy at temperatures up to 1500K. The results are also compared to the isomer with icosahedral symmetry. Finally, we discuss within this approach, their stability and abundance. 相似文献
88.
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
89.
Shimazaki Y Tashiro M Motoyama T Iwatsuki S Yajima T Nakabayashi Y Naruta Y Yamauchi O 《Inorganic chemistry》2005,44(17):6044-6051
Synthetic, structural, spectroscopic, and kinetic studies have been carried out on the Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-(N-2-pyridylmethyl-N-2-hydroxy-5-methoxybenzylamino)ethylindole (HMeO-iepp), 3-(N-2-pyridylmethyl-N-2-hydroxy-5-nitrobenzylamino)ethylindole (HNO2-iepp), and (N-2-pyridylmethyl-3-indolylethylamino)acetic acid (Hiepc) (H denotes a dissociable proton). [Pd(MeO-iepp)Cl] (2), [Pd(NO2-iepp)Cl] (3), and [Pd(iepc)Cl] (4) were prepared and revealed by X-ray analysis to have a pyridine nitrogen, an amine nitrogen, a phenolate or carboxylate oxygen, and a chloride ion in the coordination plane. UV absorption and 1H NMR spectral changes indicated that all the complexes could be converted to the indole-binding complexes where the O donor was replaced by the indole C2 atom by cyclopalladation in DMSO or DMF in the temperature range of 40-60 degrees C. Formation of the indole-binding complex species obeyed the first-order kinetics, from which the activation parameters were estimated. The formation rate was dependent on the properties of the O-donor group, a lower pKa value of its conjugate acid causing faster conversion to the indole-binding species in the order 2 (methoxyphenolate) < 3 (nitrophenolate) < 4 (carboxylate). On the other hand, the ratio of the indole-binding complex to the O-donor complex as a result of the conversion was greater for the complexes with a higher pKa value of the ligand OH group, the order being 2 > 3 > 4. 相似文献
90.
Characterization of the non-stoichiometric and isomorphic hydration and solvation in FK041 clathrate
Hisashi Mimura Satoshi Kitamura Teruyuki Kitagawa Shigetaka Kohda 《Colloids and surfaces. B, Biointerfaces》2002,26(4):397-406
FK041 crystallizes as a non-stoichiometric hydrate or as solvated hydrates which were characterized as isomorphic clathrates by powder X-ray diffractometry. Moisture and organic solvent vapor sorption studies, differential scanning calorimetry and thermogravimetric analysis revealed that FK041 monohydrate forms a physically stable host crystal, which has lattice channels for guest water and/or organic solvent molecules. The hydration state varies non-stoichiometrically between dihydrate and tetrahydrate depending on the relative humidity and the mol content of the co-existing organic solvent, that is 2-propanol, ethanol, or acetone. These organic solvents are thought to replace a part of originally present water with a mol ratio of 1:3. 2-Propanol exhibited the most stable solvation, indicating that the size and shape of 2-propanol are the most preferable to the lattice channels. 相似文献