全文获取类型
收费全文 | 2557篇 |
免费 | 499篇 |
国内免费 | 280篇 |
专业分类
化学 | 1782篇 |
晶体学 | 29篇 |
力学 | 199篇 |
综合类 | 7篇 |
数学 | 240篇 |
物理学 | 1079篇 |
出版年
2024年 | 9篇 |
2023年 | 64篇 |
2022年 | 112篇 |
2021年 | 113篇 |
2020年 | 113篇 |
2019年 | 110篇 |
2018年 | 109篇 |
2017年 | 93篇 |
2016年 | 145篇 |
2015年 | 130篇 |
2014年 | 142篇 |
2013年 | 175篇 |
2012年 | 274篇 |
2011年 | 286篇 |
2010年 | 177篇 |
2009年 | 130篇 |
2008年 | 141篇 |
2007年 | 148篇 |
2006年 | 130篇 |
2005年 | 87篇 |
2004年 | 76篇 |
2003年 | 78篇 |
2002年 | 48篇 |
2001年 | 38篇 |
2000年 | 38篇 |
1999年 | 38篇 |
1998年 | 38篇 |
1997年 | 47篇 |
1996年 | 36篇 |
1995年 | 22篇 |
1994年 | 23篇 |
1993年 | 29篇 |
1992年 | 28篇 |
1991年 | 22篇 |
1990年 | 18篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1987年 | 5篇 |
1986年 | 16篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1973年 | 1篇 |
1970年 | 2篇 |
1957年 | 2篇 |
排序方式: 共有3336条查询结果,搜索用时 15 毫秒
141.
Fabrication and cytocompatibility evaluation for blood‐compatible polyethersulfone membrane modified by a synthesized poly (vinyl pyrrolidone)‐block‐poly (acrylate‐graft‐poly(methyl methacrylate))‐block‐poly‐(vinyl pyrrolidone) 下载免费PDF全文
Fen Ran Haiming Song Lang Ma Xiaoqin Niu Jiayu Wu Weijie Zhang Long Kang Changsheng Zhao 《先进技术聚合物》2016,27(5):591-596
Polyethersulfone (PES) membrane, one of the most important polymeric materials because of its good chemical resistance, thermal stability, mechanical, and film‐forming properties, has already been used in hemodialysis, tissue engineering, and artificial organs. In order to improve the blood compatibility of PES membrane, many amphiphilic block copolymers have been synthesized and used as additives for surface modification. The object of this study is to develop a hydrophilic PES membrane by blending a comblike amphiphilic block copolymer poly (vinyl pyrrolidone)‐block‐poly [acrylate‐graft‐poly (methyl methacrylate)]‐block‐poly‐(vinyl pyrrolidone) [PVP‐b‐P (AE‐g‐PMMA)‐b‐PVP] synthesized by RAFT polymerization. The cytocompatibility performance of PVP‐b‐P (AE‐g‐PMMA)‐b‐PVP modified PES membrane was evaluated, which showed better cytocompatibility compared with that of pristine PES membrane. Endothelial cells cultured on the modified membranes present improved growth in terms of scanning electron microscope observation, MTT assay, and confocal laser scanning microscope observation. These results indicate that the modified membrane has great potential application in blood‐contact fields such as hemodialysis and bio‐artificial liver supports. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
142.
以液体石蜡为介质,在合成甲醇催化剂与甲醇脱水催化剂比例为5、催化剂浓度为10 g/300 mL液体石蜡,温度为250℃~280℃,压力为3 MPa~5 MPa,气体空速为4 000 mL/(g(h)~7 000 mL/(g(h)的条件下,建立了浆态床合成气制二甲醚宏观动力学模型。甲醇合成反应和甲醇脱水反应的活化能分别为14.06 kJ/mol和23.53 kJ/mol。甲醇当量生成速率和二甲醚生成速率的计算值与实验值的相对误差在10%和20%以内。 相似文献
143.
Highly sensitive sensor for detection of NADH based on catalytic growth of Au nanoparticles on glassy carbon electrode 总被引:1,自引:0,他引:1
Lin Tang Guangming Zeng Guoli Shen Yi Zhang Yuanping Li Changzheng Fan Can Liu Chenggang Niu 《Analytical and bioanalytical chemistry》2009,393(6-7):1677-1684
In this work, an electrochemical dihydronicotinamide adenine dinucleotide (NADH) sensor based on the catalytic growth of Au nanoparticles (Au NPs) on glassy carbon electrode was developed. Catalyzed by Au NPs immobilized on pretreated glassy carbon electrode, the reduction of AuCl4 ? in the presence of hydroquinone and cetyltrimethyl ammonium chloride led to the formation of enlarged Au NPs on the electrode surface. Spectrophotometry and high-resolution scanning electronic microscope (SEM) analysis of the sensor morphologies before and after biocatalytic reaction revealed a diameter growth of the nanoparticles. The catalytic growth of Au NPs on electrode surface remarkably facilitated the electron transfer and improved the performance of the sensor. Under optimal conditions, NADH could be detected in the range from 1.25?×?10?6 to 3.08?×?10?4 M, and the detection limit was 2.5?×?10?7 M. The advantages of the proposed sensor, such as high precision and sensitivity, fast response, low cost, and good storage stability, made it suitable for on-line detection of NADH in complex biological systems and contaminant degradation processes. Figure
Schematic presentation of the bioelectrocatalytic sensing of NADH 相似文献
144.
Haijuan Li Xiaoqing Liu Wenxin Niu Shuyun Zhu Lishuang Fan Lihong Shi Guobao Xu 《Electrophoresis》2008,29(22):4475-4481
For the first time, CEC was coupled with tris(2,2‐bipyridyl) ruthenium(II) ( Ru(bpy) electrochemiluminescence detection. Efficient CEC separations of proline, putrescine, spermidine and spermine were achieved when the pH of the mobile phase is in the range of 3.5–7.0. The optimum mobile phase for CEC separation is much less acidic than that for CZE separation, which matches better with the optimum pH for Ru(bpy) electrochemiluminescence detection and dramatically shortens the analysis time because of larger EOF at higher pH. The time for CEC separation of the polyamines is less than 12.5 min, which is about half as much as the time needed for CZE. The detection limits were 1.7, 0.2, and 0.2 μM for putrescine, spermidine, and spermine, respectively. The RSD of retention time and peak height of these polyamines were less than 0.85 and 6.1%, respectively. The column showed good long‐term stability, and the RSD of retention time is below 5% for 150 runs over one‐month use. The method was successfully used for the determination of polyamines in urine samples. 相似文献
145.
Shuyan Gong Mingze Sun Yiyang Lee Nigel Becknell Jiangwei Zhang Zhongqi Wang Liang Zhang Zhiqiang Niu 《Angewandte Chemie (International ed. in English)》2023,62(4):e202214516
Single crystal surfaces with highly coordinated sites very often hold high specific activities toward oxygen reduction reaction (ORR) and others. Transposing their high specific activity to practical high-surface-area electrocatalysts remains challenging. Here, ultrathin Pt(100) alloy surface is constructed via epitaxial growth. The surface shows 3.1–6.9 % compressive strain and bulk-like characteristics as demonstrated by site-probe reactions and different spectroscopies. Its ORR activity exceeds that of bulk Pt3Ni(100) and Pt(111) and presents a 19-fold increase in specific activity and a 13-fold increase in mass activity relative to commercial Pt/C. Moreover, the electrochemically active surface area (ECSA) is increased by 4-fold compared to traditional thin films (e.g. NSTF), which makes the catalyst more tolerant to voltage loss at high current densities under fuel cell operation. This work broadens the family of extended surface catalysts and highlights the knowledge-driven approach in the development of advanced electrocatalysts. 相似文献
146.
Yanmin Hu Tingting Chao Yapeng Li Peigen Liu Tonghui Zhao Ge Yu Cai Chen Xiao Liang Huile Jin Shuwen Niu Wei Chen Dingsheng Wang Yadong Li 《Angewandte Chemie (International ed. in English)》2023,62(35):e202308800
Water electrolysis for H2 production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru1−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm−2, respectively. Inspiringly, two-electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record-high current density of 522 mA cm−2 at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru1−NiCoP optimize H* adsorption, and enhance adsorption of *N2H2 to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self-powered H2 production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h−1 m−2. 相似文献
147.
Jiakang Zhang Xueqing Niu Cheng Peng Haokun Jiang Le Yu Prof. Hong Zhou Prof. Zhongmin Zhou 《Angewandte Chemie (International ed. in English)》2023,62(50):e202314106
The migration of ions is known to be associated with various detrimental phenomena, including current density-voltage hysteresis, phase segregation, etc., which significantly limit the stability and performance of perovskite solar cells, impeding their progress toward commercial applications. To address these challenges, we propose incorporating a polymerizable organic small molecule monomer, N-carbamoyl-2-propan-2-ylpent-4-enamide (Apronal), into the perovskite film to form a crosslinked polymer (P-Apronal) through thermal crosslinking. The carbonyl and amino groups in Apronal effectively interact with shallow defects, such as uncoordinated Pb2+ and iodide vacancies, leading to the formation of high-quality films with enhanced crystallinity and reduced lattice strain. Furthermore, the introduction of P-Apronal improves energy level alignment, and facilitates charge carrier extraction and transport, resulting in a champion efficiency of 25.09 %. Importantly, P-Apronal can effectively suppress the migration of I− ions and improve the long-term stability of the devices. The present strategy sets forth a path to attain long-term stability and enhanced efficiency in perovskite solar cells. 相似文献
148.
Weidong Shang Sheng‐Nan Su Rong Shi Ze‐Dong Mou Guo‐Qiang Yu Xia Zhang Dawen Niu 《Angewandte Chemie (International ed. in English)》2021,60(1):385-390
We here report glycosyl sulfoxides appended with an aryl iodide moiety as readily available, air and moisture stable precursors to glycosyl radicals. These glycosyl sulfoxides could be converted to glycosyl radicals by way of a rapid and efficient intramolecular radical substitution event. The use of this type of precursors enabled the synthesis of various complex C‐linked glycoconjugates under mild conditions. This reaction could be performed in aqueous media and is amenable to the synthesis of glycopeptidomimetics and carbohydrate‐DNA conjugates. 相似文献
149.
Organotincompoundsareextensivelystudiedfortheirbiologicalactivity'.Organogermaniumisanotherkindofelementthathasawiderangeofbiologicalactivity=.Tolinkbiologicalactivepropertiesoforganotinandorganogermaniumcompounds.wehavepreviouslyreportedthebiologicalactivityoftrialkyltingermylpropionates'andanticanceractivityofdibutyltindigermylpropionates'.ItiswellknownthatTorque(his[tri(2-methyl-2-phenylpropyl)tin]oxide)iswidelyusedinagricultureasanacaricide.Inthispaper,asthecontinuationofourpreviouswork"'… 相似文献
150.
用CNBr-activated Sepharose4B和微囊藻毒素-LR的单克隆抗体制备了免疫亲和层析柱,测得抗体偶联率在75.7%~94.1%之间。制得的免疫亲和层析柱最大柱容量在76~95ng之间,柱空白为0,回收率在90.8%~105.1%之间。柱子再生重复使用6次后,回收率不低于75%。建立了免疫亲和层析柱-高效液相色谱测定水样中的微囊藻毒素-LR的方法。该法检出限为5ng/L;线性定量范围为10~500ng/L。实验结果显示,免疫亲和层析柱特异性好,一次净化能除去绝大部分干扰物,净化效果明显优于现有的固相萃取柱。 相似文献