全文获取类型
收费全文 | 8004篇 |
免费 | 794篇 |
国内免费 | 536篇 |
专业分类
化学 | 5608篇 |
晶体学 | 96篇 |
力学 | 426篇 |
综合类 | 46篇 |
数学 | 697篇 |
物理学 | 2461篇 |
出版年
2024年 | 19篇 |
2023年 | 125篇 |
2022年 | 230篇 |
2021年 | 306篇 |
2020年 | 281篇 |
2019年 | 271篇 |
2018年 | 208篇 |
2017年 | 212篇 |
2016年 | 315篇 |
2015年 | 289篇 |
2014年 | 371篇 |
2013年 | 562篇 |
2012年 | 703篇 |
2011年 | 696篇 |
2010年 | 494篇 |
2009年 | 434篇 |
2008年 | 544篇 |
2007年 | 459篇 |
2006年 | 434篇 |
2005年 | 371篇 |
2004年 | 320篇 |
2003年 | 263篇 |
2002年 | 260篇 |
2001年 | 166篇 |
2000年 | 127篇 |
1999年 | 122篇 |
1998年 | 105篇 |
1997年 | 83篇 |
1996年 | 85篇 |
1995年 | 74篇 |
1994年 | 48篇 |
1993年 | 54篇 |
1992年 | 50篇 |
1991年 | 53篇 |
1990年 | 27篇 |
1989年 | 25篇 |
1988年 | 23篇 |
1987年 | 20篇 |
1986年 | 15篇 |
1985年 | 16篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1973年 | 4篇 |
1971年 | 6篇 |
1970年 | 6篇 |
排序方式: 共有9334条查询结果,搜索用时 15 毫秒
101.
Seung‐Chul Choi Jaejung Ko Sang Ook Kang Won‐Sik Han Ki‐Young Choi 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(3):m85-m87
The copper(II) ion in the syn–anti carboxylate‐bridged one‐dimensional zigzag chain title complex, {[Cu(C16H18N3O2)]ClO4}n, exhibits a distorted trigonal–bipyramidal environment. Two N atoms and one carboxylate O atom of the ligand form the basal plane, while the axial positions are filled by an N atom of the ligand and one O atom belonging to the carboxylate group of an adjacent molecule. The crystal packing is enhanced by C—H⋯O(perchlorate) hydrogen bonds. 相似文献
102.
Top layers of γ-Al2O3 composite membranes have been modified by the silane coupling technique using phenyltriethoxysilane for improving the separation factor of CO2 to N2. The separation efficiency of the modified membranes was strongly dependent upon the hydroxylation tendency of the support materials and the amount of the special functional group (i.e. phenyl radical) which was coupled onto a top layer. The separation factor through the TiO2 supported γ-Al2O3 membrane was found to be fairly enhanced by silane coupling, but in case of the -Al2O3 supported membrane was not. The CO2/N2 separation factor through the modified γ-Al2O3/TiO2 composite membrane is 1.7 at 90°C and ΔP = 2 × 105 Pa for the binary mixture containing 50 vol% CO2. The separation factor is proportional to the CO2 concentration in the gas mixture, and the modified membrane is stable up to 100°C. The main mechanism of the CO2 transport through the modified γ-Al2O3 layer is known to be a surface diffusion. 相似文献
103.
New (diamine)platinum(II) complexes A(2)PtX(2) (A(2) = trans-(+/-)-1,2-diaminocyclohexane (DACH), tetrahydro-4H-pyran-4,4-diylbis(methylamine)(THPDMA); X(2) = 9-fluorenylidenemalonate(FM), benzhydrylidenemalonate(BHM)) have been synthesized and characterized by means of multinuclear NMR spectroscopy and X-ray analysis. (DACH)Pt(FM) crystallizes in space group P2(1)/c with eight formula units in a cell of dimensions a = 20.071(7) ?, b = 12.717(3) ?, c = 24.512(6) ?, beta = 103.25(2) degrees, and V = 6090(3) ?.(3) (DACH)Pt(BHM) crystallizes in space group P&onemacr; with four molecular units in a cell of dimensions a = 11.048(3) ?, b = 13.639(3) ?, c = 14.043(6) ?, alpha = 90.17(3) degrees, beta = 91.31(4) degrees, gamma = 89.98(3) degrees, and V = 2116(1) ?(3). The platinum atom in both complexes adopts a typical square planar arrangement with two nitrogen atoms in cis position. The 9-fluorenylidene and benzhydrylidene groups of the amine ligands chelated to platinum are strikingly bent up by 88.8(3) and 80.8(2) degrees, respectively, from the platinum square plane in the solid state. Variable temperature (1)H NMR spectra of the title complexes in dimethyl sulfoxide solution reveals that the amine proton resonances are sensitive to the fluxional motion of the remote arylidene groups, and suggests that interconversion occurs between two "bent-up" and "bent-down" forms. The prominent difference between the FM and BHM complexes is observed in solution, due to the presence or absence of the angle constraint of the anionic coligands. 相似文献
104.
Aromatic molecular "clips" bearing two symmetrically bound platinum moieties have been prepared. The molecular "clip" 4 readily self-assembled with linear linkers such as 4,4'-bipyridyl, 1,4-bis[2-(4-isocyano-3,5-diisopropylphenyl)ethynyl]benzene, and nicotinic acid to form molecular rectangles. The overall dimensions of the rectangle 7 were 7.3 Angstroms x 15.3 Angstroms. The molecular "clip" also self-assembled with tritopic pyridyl and isocyanide ligands to form trigonal prismatic frameworks. The characterization of the supramolecules by multinuclear NMR, electrospray mass spectrometry, and X-ray crystal structures is also reported. 相似文献
105.
JiChengCHU HongShengGUO JunBiaoCHANG KangZHAO 《中国化学快报》2004,15(7):785-786
The synthesis of novel nucleoside analog (3R)-2,3-dideoxy-3-(N-hydroxy-N-methylamino)-L-arabinofuranosyl uracil was studied. A twelve-step synthetic route, started from L-ascorbic acid, was designed, and the final product was obtained in 20.8% yield. 相似文献
106.
The pretreatment of waste-activated sludge (WAS) by electron beam irradiation was studied in order to improve anaerobic sludge
digestion. The irradiation dose of the electron beam was varied from 0.5 to 10 kGy. Batch and continuous-flow stirred tank
reactors (CFSTRs) were operated to evaluate the effect of the electron beam pretreatment on anaerobic sludge digestion. Approximately
30–52% of the total chemical oxygen demand (COD) content of the WAS was solubilized within 24 h after electron beam irradiation.
A large quantity of soluble COD, protein, and carbohydrates leached out from cell ruptures caused by the electron beam irradiation.
Volatile fatty acids production from the irradiated sludge was approx 90% higher than that of the unirradiated sludge. The
degradation of irradiated sewage sludge was described by two distinct first-order decay rates (k
1 and k
2). Most initial decay reaction accelerated within 10 d, with an average k
1 of 0.06/d for sewage sludge irradiated at all dosages. The mean values for the long-term batch first-order decay coefficient
(k
2) were 0.025/d for irradiated sewage sludge and 0.007/d for unirradiated sludge. Volatile solids removal efficiency of the
control reactor fed with unirradiated sewage sludge at a hydraulic retention time (HRT) of 20 d was almost the same as that
of the CFSTRs fed with irradiated sludge at an HRT of 10 d. Therefore, disintegration of sewage sludge cells using electron
beam pretreatment could reduce the reactor solid retention time by half. 相似文献
107.
A novel chemical cyclization method using BBr3 has been successfully developed to prepare ladder-type conjugated systems. The cyclized ladder compounds revealed an extended conjugation due to planarization of the structures. The extended ladder polymer can also be easily prepared by our chemical cyclization method using a soluble precursor. 相似文献
108.
Zi-Shu Yang Yuhang Yao Adam C. Sedgwick Cuicui Li Ye Xia Yan Wang Lei Kang Hongmei Su Bing-Wu Wang Song Gao Jonathan L. Sessler Jun-Long Zhang 《Chemical science》2020,11(31):8204
We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as “all-in-one” phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd3+ and Lu3+. The net result led to a metalloporphodilactol system, Gd-trans-2, with seemingly optimal ISC efficiency, photothermal conversion efficiency and fluorescence properties, as well as good chemical stability. Encapsulation of Gd-trans-2 within mesoporous silica nanoparticles (MSN) allowed its evaluation for tumour diagnosis and therapy. It was found to be effective as an “all-in-one” phototheranostic that allowed for NIR fluorescence/photoacoustic dual-modal imaging while providing an excellent combined PTT/PDT therapeutic efficacy in vitro and in vivo in 4T1-tumour-bearing mice.We report here porphodilactol derivatives and their corresponding metal complexes as “all-in-one” phototheranostics by controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. 相似文献
109.
Jun Dai Liqiang Xu Zengli Fang Daopeng Sheng Qingfeng Guo Zeyu Ren Kang Wang Yitai Qian 《Chemical physics letters》2007,440(4-6):253-258
Straight boron nitride nanotubes (BNNTs) with pure hexagonal phase were conveniently prepared by heating the mixture of Mg(BO2)2 · H2O, NH4Cl, NaN3 and Mg powder in an autoclave at 600 °C for 20–60 h. These BNNTs had diameters mainly ranging 30–300 nm and lengths up to 5 μm, and a majority of them had at least one closed end. Besides the traditional end tips, additional cone-like tips were frequently found to be attached on the BNNTs. The effects of temperature, reactants and the possible mechanism of the catalytic formation of the BNNTs are discussed. 相似文献
110.
Efforts were made to assess the efficiency of an anaerobic filter packed with porous floating ceramic media and to identify
the optimum operational condition of anaerobic filter as a pretreatment of swine wastewater for the subsequent biological
removal of nitrogen and phosphorus. A stepwise decrease in hydraulic retention time (HRT) and an increase in organic loading
rate (OLR) were utilized in an anaerobic filter reactor at mesophilic temperature (35°C). The optimum operating condition
of the anaerobic filter was found to be at an HRT of 1 d. A soluble chemical oxygen demand (COD) removal efficiency of 62%
and a total suspended solids removal efficiency of 39% at an HRT of 1 d were achieved with an OLR of 16.0 kg total COD/(m3·d), respectively. The maximum methane production rate approached 1.70 vol of biogas produced per volume of reactor per day
at an HRT of 1 d. It was likely that the effluent COD/total Kjeldahl nitrogen ratio, of 22, the COD/total phosphorous ratio
of 47, and the high effluent alkalinity >2500 mg/L as CaCO3 of the anaerobic filter operated at an HRT of 1 d was adequate for the subsequent biological removal of nitrogen and phosphorus. 相似文献