全文获取类型
收费全文 | 3980篇 |
免费 | 362篇 |
国内免费 | 1181篇 |
专业分类
化学 | 4559篇 |
晶体学 | 58篇 |
力学 | 123篇 |
综合类 | 32篇 |
数学 | 67篇 |
物理学 | 684篇 |
出版年
2024年 | 3篇 |
2023年 | 73篇 |
2022年 | 132篇 |
2021年 | 170篇 |
2020年 | 218篇 |
2019年 | 169篇 |
2018年 | 178篇 |
2017年 | 189篇 |
2016年 | 189篇 |
2015年 | 158篇 |
2014年 | 208篇 |
2013年 | 329篇 |
2012年 | 259篇 |
2011年 | 329篇 |
2010年 | 248篇 |
2009年 | 278篇 |
2008年 | 257篇 |
2007年 | 286篇 |
2006年 | 274篇 |
2005年 | 246篇 |
2004年 | 213篇 |
2003年 | 189篇 |
2002年 | 144篇 |
2001年 | 111篇 |
2000年 | 92篇 |
1999年 | 74篇 |
1998年 | 79篇 |
1997年 | 61篇 |
1996年 | 57篇 |
1995年 | 49篇 |
1994年 | 70篇 |
1993年 | 38篇 |
1992年 | 41篇 |
1991年 | 16篇 |
1990年 | 19篇 |
1989年 | 13篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1986年 | 7篇 |
1985年 | 10篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有5523条查询结果,搜索用时 15 毫秒
1.
近年来,设计和合成高性能非富勒烯受体(NFAs)材料已经成为太阳能电池研究领域的前沿课题。基于DA'D型稠环结构的NFAs由于具有吸光系数高、能级和带隙可调、结构易于修饰、分子可高效合成、光电学性能优异等优点而受到了越来越广泛的关注。在短短7年的时间里,能量转换效率(PCE)从3%~4%提高到18%。2019年初邹应萍等报道了一个优秀的受体分子Y6,与PM6共混制备单结电池,获得了15.7%的能量转换效率。Y6类受体材料的中心给电子单元为DA'D型稠环结构,缺电子单元(A')通过氮原子与两个给电子单元(D)并联形成稠环结构,这有助于降低前线分子轨道能级并增强吸收,同时与氮相连的两个烷基链和位于噻吩并噻吩β位的两个侧链则有助于提高溶解度及调节结晶性。自Y6问世以来,人们对分子的结构剪裁进行了深入的研究,并报道了数十种新的结构。在这些新的受体中,DA'D部分的结构裁剪对提高器件效率和太阳能电池的性能起着至关重要的作用。本文对A'、D单元和侧链结构修饰的研究进展进行了综述。通过选择几组受体,对最近报道的分子进行分类,并将它们的光学、电化学、电学和光电性质与精确的结构修饰相关联,从而对结构-性能关系进行全面概述。 相似文献
2.
Dr. Fa-Jie Chen Dr. Jianmin Gao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(66):e202201843
Cysteine bioconjugation serves as a powerful tool in biological research and has been widely used for chemical modification of proteins, constructing antibody-drug conjugates, and enabling cell imaging studies. Cysteine conjugation reactions with fast kinetics and exquisite selectivity have been under heavy pursuit as they would allow clean protein modification with just stoichiometric amounts of reagents, which minimizes side reactions, simplifies purification and broadens functional group tolerance. In this concept, we summarize the recent advances in fast cysteine bioconjugation, and discuss the mechanism and chemical principles that underlie the high efficiencies of the newly developed cysteine reactive reagents. 相似文献
3.
4.
在管式反应器中采用苯甲酸、聚乙二醇、固体古马隆树脂(S)、液体古马隆树脂(L)为添加剂来降低煤沥青中有害物质苯并芘的含量,以期使得煤沥青可绿色化应用。采用紫外-可见分光光度计分析煤沥青中苯并芘含量。考察了反应温度、反应时间、添加剂添加量、催化剂等工艺条件对添加剂脱除煤沥青中苯并芘的影响。结果表明,不同工艺条件能降低煤沥青中苯并芘的含量。在优化条件下,不同添加剂对苯并芘脱除率由高到低依次为:液体古马隆树脂、聚乙二醇、苯甲酸和固体古马隆树脂。分析其反应机理,这与催化剂的酸性相关,发生亲电取代反应。结果表明,液体古马隆树脂(L)在催化剂存在下对煤沥青中苯并芘脱除率可达73.0%,显示了良好的应用前景。 相似文献
5.
Hendrik Schneider Lukas Deweid Thomas Pirzer Desislava Yanakieva Simon Englert Bastian Becker Dr. Olga Avrutina Prof. Dr. Harald Kolmar 《ChemistryOpen》2019,8(3):354-357
Antibody-drug conjugates (ADCs) are multicomponent biomolecules that have emerged as a powerful tool for targeted tumor therapy. Combining specific binding of an immunoglobulin with toxic properties of a payload, they however often suffer from poor hydrophilicity when loaded with a high amount of toxins. To address these issues simultaneously, we developed dextramabs, a novel class of hybrid antibody-drug conjugates. In these architectures, the therapeutic antibody trastuzumab is equipped with a multivalent dextran polysaccharide that enables efficient loading with a potent toxin in a controllable fashion. Our modular chemoenzymatic approach provides an access to synthetic dextramabs bearing monomethyl auristatin as releasable cytotoxic cargo. They possess high drug-to-antibody ratios, remarkable hydrophilicity, and high toxicity in vitro. 相似文献
6.
Sudipta Das Mischa Bonn Ellen H. G. Backus 《Angewandte Chemie (International ed. in English)》2019,58(44):15636-15639
The behavior of hydroxide and hydrated protons, the auto‐ionization products of water, at surfaces is important for a wide range of applications and disciplines. However, it is unknown at which bulk concentration these ions start to become surface active at the water–air interface. Here, we report changes in the D2O–air interface in the presence of excess D+hyd/OD?hyd determined using surface‐sensitive vibrational sum‐frequency generation (SFG) spectroscopy. The onset of the perturbation of the D2O surface occurs at a bulk concentration as low as 2.7±0.2 mm D+hyd. In contrast, a concentration of several hundred mm OD?hyd is required to change the D2O surface. The hydrated proton is thus orders of magnitude more surface‐active than hydroxide at the water–air interface. 相似文献
7.
This study presents a simple and green dispersive micro‐solid phase extraction method for preconcentration of acidic quinolones from honey prior to high performance liquid chromatography determination. A two‐dimensional nanostructured zinc‐aluminum layered double hydroxide was synthesized and used as the sorbent for dispersive micro‐solid phase extraction. Its different characteristics from conventional sorbents is that it is dissolvable in acidic solution (pH < 4). After the extraction, the analyte elution step was omitted and thus the use of organic solvents was avoided. The key parameters influencing the extraction efficiency such as the amount of sorbent, pH of sample solution, vortex time, type and volume of acidic solution were investigated and optimized. The method exhibited low limits of detection (3.0?5.0 ng/g), good linearity (10?2000 ng/g) with coefficients of determinations higher than 0.9991, acceptable precision (RSD<9.1%) and accuracy (RE<5.8%). The proposed method is fast, efficient, eco‐friendly, and suitable for the determination of acidic quinolones in honey samples. 相似文献
8.
Jun Ohata Samuel C. Martin Zachary T. Ball 《Angewandte Chemie (International ed. in English)》2019,58(19):6176-6199
Selective modification of natural proteins is a daunting methodological challenge and a stringent test of selectivity and reaction scope. There is a continued need for new reactivity and new selectivity concepts. Transition metals exhibit a wealth of unique reactivity that is orthogonal to biological reactions and processes. As such, metal‐based methods play an increasingly important role in bioconjugation. This Review examines metal‐based methods as well as their reactivity and selectivity for the functionalization of natural proteins and peptides. 相似文献
9.
10.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献