全文获取类型
收费全文 | 21867篇 |
免费 | 3321篇 |
国内免费 | 2655篇 |
专业分类
化学 | 11433篇 |
晶体学 | 223篇 |
力学 | 1040篇 |
综合类 | 132篇 |
数学 | 1733篇 |
物理学 | 6046篇 |
无线电 | 7236篇 |
出版年
2024年 | 125篇 |
2023年 | 560篇 |
2022年 | 729篇 |
2021年 | 897篇 |
2020年 | 857篇 |
2019年 | 884篇 |
2018年 | 719篇 |
2017年 | 782篇 |
2016年 | 1023篇 |
2015年 | 1079篇 |
2014年 | 1262篇 |
2013年 | 1602篇 |
2012年 | 1795篇 |
2011年 | 1830篇 |
2010年 | 1397篇 |
2009年 | 1406篇 |
2008年 | 1484篇 |
2007年 | 1333篇 |
2006年 | 1236篇 |
2005年 | 957篇 |
2004年 | 764篇 |
2003年 | 627篇 |
2002年 | 643篇 |
2001年 | 509篇 |
2000年 | 487篇 |
1999年 | 482篇 |
1998年 | 363篇 |
1997年 | 273篇 |
1996年 | 305篇 |
1995年 | 246篇 |
1994年 | 187篇 |
1993年 | 179篇 |
1992年 | 167篇 |
1991年 | 131篇 |
1990年 | 123篇 |
1989年 | 93篇 |
1988年 | 60篇 |
1987年 | 45篇 |
1986年 | 41篇 |
1985年 | 43篇 |
1984年 | 31篇 |
1983年 | 19篇 |
1982年 | 16篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 7篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 10 毫秒
991.
Peripheral Templation‐Modulated Interconversion between an A4L6 Tetrahedral Anion Cage and A2L3 Triple Helicate with Guest Capture/Release 下载免费PDF全文
Xuemin Bai Prof. Chuandong Jia Prof. Yanxia Zhao Dr. Dong Yang Shi‐Cheng Wang Prof. Anyang Li Prof. Yi‐Tsu Chan Prof. Yao‐Yu Wang Prof. Xiao‐Juan Yang Prof. Biao Wu 《Angewandte Chemie (International ed. in English)》2018,57(7):1851-1855
An anion‐coordination‐based A4L6 (“A” denotes anion and “L” is ligand) tetrahedral cage was constructed by a C2‐symmetric bis‐bis(urea) ligand and phosphate anion, which showed reversible interconversion with the A2L3 triple helicate as a response to the template, concentration, or solvent. Notably, an unusual “peripheral” templation was found to be critical to stabilize the tetrahedral structure. This peripheral effect was utilized to assemble an “empty” A4L6 cage that allows the multi‐stimuli‐controlled capture/release of biologically important species such as choline and acetylcholine. 相似文献
992.
采用熔体快淬法制备了(Mg70.6 Ni29.4)90Nd10的非晶贮氢合金带,用X射线衍射仪和高分辨电镜对该合金在充放电循环过程中的组织结构演变进行了动态跟踪.结果表明:(Mg70.6Ni29.4)90Nd10贮氢合金在充放电循环过程中由非晶态慢慢晶化为纳米晶,初生相NdMg2 Ni9在循环过程中逐渐转化为Mg2 Ni,α-Mg和Nd2H5相.电化学性能测试表明,由于微观结构的变化对其放电容量的影响过程分为3个阶段:首先是前两个循环的活化过程,在第3个循环达到放电容量最高值(580.5 mAh·g-1);接下来是放电容量显著降低的4~10个循环阶段;最后是放电容量保持稳定的11 ~20个循环.研究发现NdMg2 Ni9相的存在和保持合金的非晶结构是提高镁基电极合金循环稳定性的重要因素. 相似文献
993.
Wang JY Jin Y Xie R Liu JY Ju XJ Meng T Chu LY 《Journal of colloid and interface science》2011,353(1):61-68
Novel calcium-alginate (Ca-alginate) capsules with aqueous core and thermo-responsive membrane are successfully prepared by introducing a co-extrusion minifluidic approach, and the thermo-responsive gating characteristics of Ca-alginate capsule membranes embedded with poly(N-isopropylacrylamide) (PNIPAM) microspheres are investigated systematically. The experimental results show that the prepared Ca-alginate capsules are highly monodisperse, and the average diameter and membrane thickness of Ca-alginate capsules are about 2.96 mm and 0.11 mm respectively. The Ca-alginate capsule membranes exhibit desired thermo-responsive gating property. With increasing the content of PNIPAM microspheres embedded in the Ca-alginate capsule membranes, the thermo-responsive gating coefficient of the capsule membranes increases simply. When solute molecules diffuse through the capsule membrane, the thermo-responsive gating coefficient is significantly affected by the molecular weight of solute molecules. 相似文献
994.
Two new guaiane-type sesquiterpenoid glucosides (1 and 2) were isolated from the fruit of Gardenia jasminoides Ellis. Their structures were elucidated to be (1R,7R,10S)-11-O-β-D-glucopyranosyl-4-guaien-3-one (1) and (1R,7R,10S)-7-hydroxy-11-O-β-D-glucopyranosyl-4-guaien-3-one (2) by one- and two-dimensional NMR techniques ((1)H NMR, (13)C NMR, HSQC, HMBC and NOESY), MS, CD spectrometry and chemical methods. 相似文献
995.
Yu TH Sha Y Liu WG Merinov BV Shirvanian P Goddard WA 《Journal of the American Chemical Society》2011,133(49):19857-19863
We report results of quantum mechanics (QM) mechanistic studies of Nafion membrane degradation in a polymer electrolyte membrane (PEM) fuel cell. Experiments suggest that Nafion degradation is caused by generation of trace radical species (such as OH(●), H(●)) only when in the presence of H(2), O(2), and Pt. We use density functional theory (DFT) to construct the potential energy surfaces for various plausible reactions involving intermediates that might be formed when Nafion is exposed to H(2) (or H(+)) and O(2) in the presence of the Pt catalyst. We find a barrier of 0.53 eV for OH radical formation from HOOH chemisorbed on Pt(111) and of 0.76 eV from chemisorbed OOH(ad), suggesting that OH might be present during the ORR, particularly when the fuel cell is turned on and off. Based on the QM, we propose two chemical mechanisms for OH radical attack on the Nafion polymer: (1) OH attack on the S-C bond to form H(2)SO(4) plus a carbon radical (barrier: 0.96 eV) followed by decomposition of the carbon radical to form an epoxide (barrier: 1.40 eV). (2) OH attack on H(2) crossover gas to form hydrogen radical (barrier: 0.04 eV), which subsequently attacks a C-F bond to form HF plus carbon radicals (barrier as low as 1.00 eV). This carbon radical can then decompose to form a ketone plus a carbon radical with a barrier of 0.86 eV. The products (HF, OCF(2), SCF(2)) of these proposed mechanisms have all been observed by F NMR in the fuel cell exit gases along with the decrease in pH expected from our mechanism. 相似文献
996.
Introducing various pendant functional groups and building blocks of interest to polypeptides in a highly efficient, controlled manner is crucial to access polypeptide materials with desired structures and functions. In this study, we synthesized γ-(4-vinylbenzyl)-(L)-glutamate N-carboxyanhydride (VB-Glu-NCA), which was readily obtained and purified in large quantity. VB-Glu-NCA monomer was subsequently used for the synthesis of polypeptides containing conjugation-amenable, pendant vinyl functional groups. Controlled, living polymerizations of VB-Glu-NCA were achieved by using hexamethyldisilazane (HMDS) as the initiator, catalytic amounts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the co-catalyst, and nitrobenzene as the inhibitor of radical-induced side reactions on the vinyl group of VB-Glu-NCA. The resulting poly(γ-(4-vinylbenzyl)-(L)-glutamate) (PVBLG) gave rise to polypeptides containing pendant functional groups or moieties through various vinyl chemistries. 相似文献
997.
Two nanosized hexameric polyoxometalate-based solid state assemblies (H(2)en)(6)Na(15)K(9)[Dy(6)Fe(6)(H(2)O)(12)(SiW(10)O(38))(6)]·34H(2)O (1) and K(13)Na(17)[H(2)en](3)[Tb(6)Fe(6)(H(2)O)(12)(SiW(10)O(38))(6)]·40H(2)O (2) (en = 1,2-ethylenediamine), decorated by six [Ln-(μ(3)-O)(3)-Fe] 3d-4f heterometallic clusters, have been synthesized by the hydrothermal method, and characterized by IR, element analysis, magnetic studies and the single-crystal X-ray analyses. The detailed study of the synthetic conditions reveals that the use of the organic ligands, pH value and the reaction temperature all play important roles in the synthesis of the 3d-4f heterometallic POMs. Magnetic study suggests the presence of antiferromagnetic interactions in these two compounds. 相似文献
998.
Tsai YT Choi CH Gao N Yang EH 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):4249-4256
This paper presents the experimental results and analyses on a controlled manipulation of liquid droplets upon local reduction and oxidation (redox) of a smart polymer-dodecylbenzenesulfonate doped polypyrrole (PPy(DBS)). The electrochemically tunable wetting property of PPy(DBS) permitted liquid droplet manipulation at very low voltages (-0.9 to 0.6 V). A dichloromethane (DCM) droplet was flattened upon PPy(DBS) reduction. It was found that the surface tension gradient across the droplet contact line induced Marangoni stress, which caused this deformation. Further observation of PPy(DBS)'s color change upon the redox process confirmed that the surface tension gradient was the driving force for the droplet shape change. 相似文献
999.
采用二甲亚砜水溶液为反应介质, 在常压和108 ℃条件下, 经短时间的液相反应直接制备出橄榄石结构的纳米级LiFePO4. IR分析表明, 液相法直接制得的LiFePO4晶体结构中含有少量的Fe3+. 将液相直接制备的样品与少量葡萄糖混合后在600 ℃下焙烧3 h得到类球形的LiFePO4/C材料. 电化学测试结果表明, 这种纳米级LiFePO4/C材料在0.2 C 倍率下放电容量达到157.2 mAh/g, 并且具有较好的放电平台. 5 C和10 C放电容量仍能达到126.1和103.4 mAh/g, 且循环200次后容量没有明显衰减, 表现出优异的倍率放电特性和循环性能. 相似文献
1000.
Jiang X Zhang T Xu L Wang C Zhou X Gu N 《Langmuir : the ACS journal of surfaces and colloids》2011,27(9):5410-5419
Breath figure (BF) process is a facile method to prepare honeycomb structures by dynamic movements of condensed micrometer-sized water droplets at the interface of volatile fluid. Here, we aim to find answers to understand how the BF process occurs on micropipettes with curvature gradient and to understand the role of the surfactant in obtaining honeycomb patterns. Poly (L-lactic acid) (PLLA) chloroform solution with dioleoylphosphatidylethanolamine (DOPE) as surfactant was utilized. It is found that the honeycomb structure formed on the micropipettes changes remarkably with the gradually increased surface curvature. The variation trends of the arrangement and diameter of pores on the micropipettes with the increasing curvature are similar to the different time stages of BF process: smaller and sparse pores formed at higher curvature are similar to those formed at early stage of BF; regular honeycomb patterns formed at lower curvature are similar to those formed at the late stage of BF. Especially, the "semi-coalescence" hemispherical pores strings are found at high curvatures on PLLA-DOPE films, indicating the surfactant-induced coalescence of water droplets in BF process. The differences of drying speed of polymer solvent on micropipette with gradually increased curvatures make the printing of the pores at different BF stages on polymer film possible. These findings not only strongly support the mechanism of BF array formation, but also elucidate the surfactant-induced coalescence. 相似文献