全文获取类型
收费全文 | 14866篇 |
免费 | 2164篇 |
国内免费 | 1334篇 |
专业分类
化学 | 10724篇 |
晶体学 | 179篇 |
力学 | 830篇 |
综合类 | 67篇 |
数学 | 1766篇 |
物理学 | 4798篇 |
出版年
2024年 | 50篇 |
2023年 | 323篇 |
2022年 | 561篇 |
2021年 | 592篇 |
2020年 | 673篇 |
2019年 | 579篇 |
2018年 | 506篇 |
2017年 | 440篇 |
2016年 | 699篇 |
2015年 | 729篇 |
2014年 | 752篇 |
2013年 | 1102篇 |
2012年 | 1257篇 |
2011年 | 1256篇 |
2010年 | 826篇 |
2009年 | 831篇 |
2008年 | 972篇 |
2007年 | 830篇 |
2006年 | 741篇 |
2005年 | 704篇 |
2004年 | 513篇 |
2003年 | 421篇 |
2002年 | 408篇 |
2001年 | 323篇 |
2000年 | 291篇 |
1999年 | 294篇 |
1998年 | 196篇 |
1997年 | 155篇 |
1996年 | 197篇 |
1995年 | 165篇 |
1994年 | 138篇 |
1993年 | 123篇 |
1992年 | 102篇 |
1991年 | 86篇 |
1990年 | 91篇 |
1989年 | 68篇 |
1988年 | 63篇 |
1987年 | 49篇 |
1986年 | 40篇 |
1985年 | 42篇 |
1984年 | 37篇 |
1983年 | 17篇 |
1982年 | 16篇 |
1981年 | 20篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1976年 | 10篇 |
1975年 | 11篇 |
1971年 | 7篇 |
1969年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
以纳米金溶胶(NGS)和多重壁碳纳米管(MWCNTs)的共混物(NGS/MWCNTs)作为固定漆酶的载体,研究了3种固定漆酶方法在酶固定量、比活力上的差异。 研究了不同的固定方法对固定酶热稳定性和重复使用性及纳米金溶胶颗粒粒径对酶固定量和固定酶动力学参数的影响。 实验结果表明,NGS/MWCNTs具有良好的固定漆酶能力和高固酶比活力,NGS/MWCNTs(NGS粒径37 nm)通过简单物理吸附法固定漆酶的量和固酶的比活力最高,分别可达33.80 mg/g和9.433 U/mg。 在NGS-MWCNTs上采用化学键合方法固定的漆酶在70 ℃放置2 h后仍然保持初始活力的75%,重复使用20次后仍保持初始活力的70%。 纳米金溶胶粒子越小(24 nm),底物和固定漆酶间亲和力越好(KM=0.027 mmol/L),表观速率常数越大。 相似文献
992.
气相色谱-正化学源-质谱联用技术测定葡萄和葡萄酒中多种唑类杀菌剂的残留量 总被引:3,自引:0,他引:3
建立了可用于葡萄和葡萄酒中20种唑类杀菌剂残留量的分散型固相萃取-气相色谱-正化学离子源质谱分析方法.葡萄和葡萄酒样品分别用乙腈(含1%冰醋酸)和乙酸乙酯提取,分散型固相萃取法净化,由气相色谱-正化学离子源质谱分时段选择离子监测技术进行测定与确证,外标法定量.20种农药在50~1000 μg/L范围内线性均良好; 所有农药的方法定量限(LOQ)均低于10 μg/kg;在3个添加水平(10, 20和40 μg/kg)下,所有农药的回收率均处于71.2%~102.2%之间, RSD≤10.6%. 相似文献
993.
The effects of molecular weight and concentration of poly (methyl methacrylate) (PMMA) homopolymer or symmetric short polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) diblock copolymer on the size of the nanostructures of its blends with symmetric long PS-b-PMMA diblock copolymer have been investigated by atomic force microscopy. By careful controlling of the film thickness, solvent selectivity, and annealing time, PMMA cylindrical microdomains oriented normal to the film surface were obtained in all thin films. With the addition of both low- and high-molecular-weight PMMA homopolymers, the cylindrical domain sizes increased although it was less obvious for the lower molecular weight homopolymer. In contrast to the homopolymer, adding the short chain diblock copolymer resulted in a decrease in the cylindrical domain size, which was ascribed to the reduction of the interfacial tension and increase in the stretching energy. 相似文献
994.
Toward the Design of a Catalytic Metallodrug: Selective Cleavage of G‐Quadruplex Telomeric DNA by an Anticancer Copper–Acridine–ATCUN Complex 下载免费PDF全文
Zhen Yu Menglu Han Dr. James A. Cowan 《Angewandte Chemie (International ed. in English)》2015,54(6):1901-1905
Telomeric DNA represents a novel target for the development of anticancer drugs. By application of a catalytic metallodrug strategy, a copper–acridine–ATCUN complex (CuGGHK‐Acr) has been designed that targets G‐quadruplex telomeric DNA. Both fluorescence solution assays and gel sequencing demonstrate the CuGGHK‐Acr catalyst to selectively bind and cleave the G‐quadruplex telomere sequence. The cleavage pathway has been mapped by matrix assisted laser desorption ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) experiments. CuGGHK‐Acr promotes significant inhibition of cancer cell proliferation and shortening of telomere length. Both senescence and apoptosis are induced in the breast cancer cell line MCF7. 相似文献
995.
High‐Contrast Red–Green–Blue Tricolor Fluorescence Switching in Bicomponent Molecular Film 下载免费PDF全文
Hyeong‐Ju Kim Dr. Dong Ryeol Whang Chong Han Lee Prof. Soo Young Park 《Angewandte Chemie (International ed. in English)》2015,54(14):4330-4333
Highly efficient red–green–blue (RGB) tricolor luminescence switching was demonstrated in a bicomponent solid film consisting of (2Z,2′Z)‐2,2′‐(1,4‐phenylene)bis(3‐(4‐butoxyphenyl)acrylonitrile) (DBDCS) and (2Z,2′Z)‐3,3′‐(2,5‐bis(6‐(9H‐carbazol‐9‐yl)hexyloxy)‐1,4‐phenylene)bis(2‐(3,5‐bis(trifluoromethyl)phenyl)acrylonitrile) (m‐BHCDCS). Reversible RGB luminescence switching with a high ratiometric color contrast (λem=594, 527, 458 nm for red, green, and blue, respectively) was realized by different external stimuli such as heat, solvent vapor exposure, and mechanical force. It was shown that Förster resonance energy transfer in the bicomponent mixture could be efficiently switched on and off through supramolecular control. 相似文献
996.
Fangyi Cheng Qing Zhao Xiaopeng Han Jun Chen 《Angewandte Chemie (International ed. in English)》2015,54(14):4338-4343
The ever‐increasing consumption of a huge quantity of lithium batteries, for example, Li–MnO2 cells, raises critical concern about their recycling. We demonstrate herein that decayed Li–MnO2 cells can be further utilized as rechargeable lithium–air cells with admitted oxygen. We further investigated the effects of lithiated manganese dioxide on the electrocatalytic properties of oxygen‐reduction and oxygen‐evolution reactions (ORR/OER). The catalytic activity was found to be correlated with the composition of LixMnO2 electrodes (0<x<1) generated in situ in aprotic Li–MnO2 cells owing to tuning of the Mn valence and electronic structure. In particular, modestly lithiated Li0.50MnO2 exhibited superior performance with enhanced round‐trip efficiency (ca. 76 %), high cycling ability (190 cycles), and high discharge capacity (10 823 mA h gcarbon?1). The results indicate that the use of depleted Li–MnO2 batteries can be prolonged by their application as rechargeable lithium–air batteries. 相似文献
997.
Improved Efficiency and Stability of Flexible Dye Sensitized Solar Cells on ITO/PEN Substrates Using an Ionic Liquid Electrolyte 下载免费PDF全文
Flexible dye‐sensitized solar cells (DSSCs) built on plastic substrates have attracted great interest as they are lightweight and can be roll‐to‐roll printed to accelerate production and reduce cost. However, plastic substrates such as PEN and PET are permeable to water, oxygen and volatile electrolyte solvents, which is detrimental to the cell stability. Therefore, to address this problem, in this work, an ionic liquid (IL) electrolyte is used to replace the volatile solvent electrolyte. The initial IL‐based devices only achieved around 50% of the photovoltaic conversion efficiency of the cells using the solvent electrolyte. Current‐voltage and electrochemical impedance spectroscopy (EIS) analysis of the cells in the dark indicated that this lower efficiency mainly originated from (i) a lack of blocking layer to reduce recombination, and (ii) a lower charge collection efficiency. To combat these problems, cells were developed using a 12 nm thick blocking layer, produced by atomic layer deposition, and 1 μm thick P25 TiO2 film sensitized with the hydrophobic MK‐2 dye. These flexible DSSCs utilizing an IL electrolyte exhibit significantly improved efficiencies and a <10% drop in performance after 1000 h aging at 60°C under continuous light illumination. 相似文献
998.
Paecilomycines A and B,Novel Diterpenoids,Isolated from Insect‐Pathogenic Fungi Paecilomyces sp. ACCC 37762 下载免费PDF全文
Kun Zhou Xiao‐Ling Zhao Li‐Ping Han Meng‐Meng Cao Chuan Chen Bao‐Zhong Shi Du‐Qiang Luo 《Helvetica chimica acta》2015,98(5):642-649
Two new diterpenoids, named paecilomycine A ( 1 ) and paecilomycine B ( 2 ), including a novel skeleton with a five‐membered lactone ring, together with three known labdane diterpenoids, rel‐(1R,3S,4aS,5R,8aS)‐5‐[(3E)‐4‐carboxy‐3‐methylbut‐3‐en‐1‐yl]decahydro‐3‐hydroxy‐1,4a‐dimethyl‐6‐methylidenenaphthalene‐1‐carboxylic acid ( 3 ), botryosphaerin E ( 4 ), and agathic acid ( 5 ), were isolated from solid culture of the insect pathogenic fungi strain Paecilomyces sp. The structures of all compounds were established on the basis of comprehensive spectroscopic studies. The relative configurations of 1 and 2 were determined by single‐crystal X‐ray diffraction analyses. 相似文献
999.
Wen‐Hao Chen Chang‐Ri Han Yang Hui Da‐Shuai Zhang Xin‐Ming Song Guang‐Ying Chen Xiao‐Ping Song 《Helvetica chimica acta》2015,98(5):724-730
Two new eremophilane‐type sesquiterpenoids, 1α‐hydroxyeremophila‐6,9,11‐trien‐8‐one ( 1 ), 4α‐hydroxyeremophila‐1,9‐diene‐3,8‐dione ( 2 ), and a new friedelane‐type triterpenoid, friedelane‐3α,16β‐diol ( 4 ), along with six known terpenoids, 3 and 5 – 9 , have been isolated from the stems of Drypetes congestiflora. Their structures and relative configurations were elucidated on the basis of detailed spectroscopic analyses and by comparison of their NMR data with those reported in the literature. All of the compounds, 1 – 9 , were isolated for the first time from this species. Compound 3 exhibited moderate cytotoxic activities against the A549 and B16F10 cell lines. 相似文献
1000.
Stochastic/Controlled Symmetry Breaking of the T8‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks 下载免费PDF全文
Xiao‐Man Wang Qing‐Yun Guo Shuai‐Yuan Han Jing‐Yi Wang Di Han Prof. Qiang Fu Prof. Wen‐Bin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15246-15255
Precise synthesis of nanobuilding blocks with accurately positioned functional groups presents a daunting challenge. Herein, a practical synthesis and thorough characterization of a series of T8‐polyhedral oligomeric silsesquioxane (POSS) di‐ and triadducts is reported. Upon addition of triflic acid across the double bonds in octavinylPOSS (V8T8) followed by hydrolysis, the cubic symmetry of the T8‐POSS cage (Oh) is broken into C2v (ortho‐), C2v (meta‐), and D3d (para‐) for diadducts and further to Cs (oom‐), Cs (omp‐), and C3v (mmm‐) for triadducts in a stochastic fashion. Their structures and regioconfigurations have been unambiguously demonstrated by 1H, 13C, and 29Si NMR spectroscopy, as well as MALDI‐TOF mass spectrometry. The assignment of the diadducts was further corroborated by converting each individual diadduct into triadduct(s), the structure of which is controlled by the symmetry of the precursor. Except for the C3v triadduct, they can all be prepared in synthetically useful quantities. The presence of two types of highly reactive and mutually orthogonal functional groups facilitates further modification into complex nanostructures and composite materials. These unique regioisomers provide a versatile platform for constructing giant molecules and Janus silsesquioxanes. 相似文献