全文获取类型
收费全文 | 7601篇 |
免费 | 142篇 |
国内免费 | 575篇 |
专业分类
化学 | 7112篇 |
晶体学 | 577篇 |
力学 | 30篇 |
综合类 | 15篇 |
数学 | 142篇 |
物理学 | 442篇 |
出版年
2024年 | 7篇 |
2023年 | 61篇 |
2022年 | 125篇 |
2021年 | 106篇 |
2020年 | 179篇 |
2019年 | 212篇 |
2018年 | 198篇 |
2017年 | 264篇 |
2016年 | 238篇 |
2015年 | 135篇 |
2014年 | 211篇 |
2013年 | 390篇 |
2012年 | 1339篇 |
2011年 | 361篇 |
2010年 | 363篇 |
2009年 | 405篇 |
2008年 | 470篇 |
2007年 | 515篇 |
2006年 | 393篇 |
2005年 | 373篇 |
2004年 | 296篇 |
2003年 | 243篇 |
2002年 | 190篇 |
2001年 | 151篇 |
2000年 | 128篇 |
1999年 | 138篇 |
1998年 | 105篇 |
1997年 | 88篇 |
1996年 | 78篇 |
1995年 | 79篇 |
1994年 | 67篇 |
1993年 | 59篇 |
1992年 | 56篇 |
1991年 | 44篇 |
1990年 | 35篇 |
1989年 | 21篇 |
1988年 | 10篇 |
1987年 | 18篇 |
1986年 | 20篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1982年 | 8篇 |
1981年 | 12篇 |
1980年 | 16篇 |
1979年 | 19篇 |
1978年 | 11篇 |
1977年 | 18篇 |
1976年 | 15篇 |
1974年 | 6篇 |
1973年 | 9篇 |
排序方式: 共有8318条查询结果,搜索用时 0 毫秒
31.
Chen-Xi Zhang Zhi-Liang Liu Dai-Zheng Liao Zong-Hui Jiang Shi-Ping Yan 《Journal of Molecular Structure》2003,650(1-3):21-26
A novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H2O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H2O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py. 相似文献
32.
Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pKa1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pKa2 and pKa3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group. 相似文献
33.
IntroductionInthepastseveralyears ,considerableprogresshasbeenachievedincontrollingtheassemblyofindividualbuildingblocksintostructureswithspecifictopologiesandinterestingpropertiessuchasmolecularrecognition ,ionexchangeandselectiveguestinclusion .1 3 Itis… 相似文献
34.
The thermal decomposition studies for two palladium(II) complexes Pd(apyr)2Cl2 and Pd(pmpa)Cl2 (apyr=1–aminopyrene and pmpa=N–(2–pyridylmethylene)–1–pyrenylamine) were carried out in pure nitrogen using TG-DTG techniques. The non-isothermal kinetic parameters for the two complexes were evaluated employing the method suggested by Málek, esták, Koga et al. Based on the above results, thermal behaviour of the complexes were carefully discussed, which showed that not only the parameters value, but also the decomposition pattern and mechanism for complex 1 are different from complex 2.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
35.
Philip Wormald Kristina Wickholm Per Tomas Larsson Tommy Iversen 《Cellulose (London, England)》1996,3(1):141-152
An investigation into the effects of mechanical treatment and hydration on the order of cellulose substrates (microcrystalline cellulose and Cladophora cellulose) was performed by the use of ball milling followed by cyclic wetting and drying. The results, monitored by13C-CP/MAS NMR-spectroscopy, were evaluated by calculation of the crystallinity indices and principal component analysis of the NMR data acquired. The results showed that a large part of the disorder induced by the mechanical treatment of cellulose by ball milling is reversible and reordering upon hydration leads to the cellulose I form initially present. The C4 signals corresponding to the reversibly disordered cellulose chains are observed in the amorphous region between 79 and 86 ppm in the13C-CP/MAS NMR-spectra together with signals from cellulose chains on the surface of ordered regions. The peak cluster which contains the C2, C3 and C5 ring carbons can be divided into two specific spectral regions; one between 74 and 77 ppm largely originates from ring carbons within disordered cellulose structures, and one between 70 and 74 ppm contains larger contributions from ordered cellulose. The behaviour of the celluloses upon milling is in accordance with a concept of ordered cellulose fibrils containing amorphous cellulose mainly as surface layers and induced reversible lattice distortions. 相似文献
36.
An amperometric sensor for the detection of ethanol has been designed. The sensing layer consists of alcohol dehydrogenase (ADH), NADH oxidase and NAD+-dextran, entrapped together in a matrix of poly(vinyl alcohol) bearing styrylpyridinium groups (PVA-SbQ). Measurements have been carried out at a low oxidizing potential (equivalent to 250 mV vs. SCE) to detect hexacyanoferrate(II), thus avoiding interferences due to presence of oxidizable compounds in real samples. The influence of the amount of polymer, enzymes and coenzyme in the sensing layer on the sensor sensitivity, linear range and operational stability has been studied. The sensitivity was close to 2 mA 1 mol−1, with a linear range 3 × 10−7 −2 × 10−4M and a response time <2 min. Good operational stability was observed, allowing more than 40 reproducible assays without NAD+ addition. Alcoholic beverages were analysed with the use of sensor and the results showed good correlation with those obtained using a standard spectrophotometric procedure. 相似文献
37.
Ho-Shen Lin Ashraff A. Rampersaud Karen Zimmerman Mitchell I. Steinberg Donald B. Boyd 《中国化学会会志》1993,40(3):273-282
A series of nonpeptide angiotensin II receptor antagonists was synthesized via palladium-assisted cross coupling of aryl stannane and cycloalkenyl triflates and subsequent alkylation of silyl-protected imidazole. Our compounds, which have a terminal five- to seven-membered cycloalkenyl ring, are compared to DuPont EXP7711, an N-[(2′-carboxybiphenylyl)methyl]imidazole, which has a terminal phenyl moiety. Physicochemical properties of the compounds, such as lipophilicity, steric bulk, conformation, and the relative spatial proximity of the 2-carboxyl and the middle phenyl, are quantitated by computational chemistry. Potency in terms of binding affinity to AT1 receptors in rat adrenal glomerulosa and rabbit aorta is maximized when the terminal ring is aromatic. 相似文献
38.
Single Crystal Investigations on Fluoroperovskites MPdF3 (M = Rb, K) and PdF2 Single crystal investigations on PdF2 (violet) confirm the tetragonale rutile structure [1, 2] with a = 495.44(3) pm, c = 338.48(3) pm, Z = 2, space group P42/mnm-D (No. 136) (xF = 0.3058(8)). RbPdF3 and KPdF3 have been obtained. RbPdF3 and KPdF3 both ruby-red single crystals crystallize cubic (perovskite-structure), space group Pm3m-O (No. 221) with a = 429.41(8) pm (RbPdF3) respectively a = 424.30(4) pm (KPdF3). 相似文献
39.
Kamal M. Dawood 《Tetrahedron》2007,63(39):9642-9651
The catalytic activity of benzothiazole-based Pd(II)-complexes was evaluated in Suzuki-Miyaura and Heck-Mizoroki C-C cross-coupling reactions of aryl chlorides and bromides with olefins and arylboronic acids both under thermal as well as microwave irradiation conditions in water. The factors affecting the optimization of such reactions as well as the reusability of the Pd-precatalysts are studied. 相似文献
40.
Solution equilibrium studies on Cu(II)-, Ni(II)- and Zn(II)-N-Me-β-Alaninehydroxamic acid (N-Me-β-Alaha), -N-Me-α-alaninehydroxamic acid (N-Me-α-Alaha), -Imidazole-4-carbohydroxamic acid (Im-4-Cha), -N-Me-imidazole-4-carbohydroxamic acid (N-Me-Im-4-Cha) and -Imidazole-4-acetohydroxamic acid (Im-4-Aha) systems have been performed by pH-potentiometry, UV–Vis spectrophotometry, EPR, CD, ESI-MS and 1H NMR methods. According to the results: (i) the amino-N atoms are more basic in N-Me-α-Alaha and N-Me-β-Alaha than the hydroxamate function, but the trend is just the opposite between the imidazole-N(3) and hydroxamate. (ii) The metal ion anchor is always the hydroxamate part in the amino acid derivatives, while it is always the imidazole-N(3) in the studied imidazolehydroxamic acids. (iii) The three studied N-Me derivatives do not form metallacrowns. Only hydroxamate type chelate is formed with N-Me-β-Alaha, but with N-Me-α-Alaha a new type of coordination mode (via amino-N and hydroxamate-O) also exists. N-Me-Im-4-Cha also forms a dinuclear complex, [M2L3], with Cu(II) and Ni(II) (but not with Zn(II)). In this complex, one of the three ligands might bridge the two metal ions (five-membered hydroxamate-(O,O) plus five-membered (Nim, Ocarb) bridging bis-chelating mode), while each of the additional two ligands binds to one metal. (iv) The two studied N–H derivatives, having dissociable proton on the hydroxamic-N, are able to form metallacrown species. A pentanuclear complex, [M5L4H−4], is exclusively formed above pH 4 between Cu(II) and Im-4-Aha. Interestingly, this 12-metallacrown-4 type complex, although together with various mononuclear binding isomers, appears also with Ni(II) and Zn(II). Unfortunately, the complexes of Im-4-Cha are not soluble in water at physiological pH at all. 相似文献