全文获取类型
收费全文 | 19075篇 |
免费 | 3401篇 |
国内免费 | 3185篇 |
专业分类
化学 | 15042篇 |
晶体学 | 299篇 |
力学 | 954篇 |
综合类 | 259篇 |
数学 | 2226篇 |
物理学 | 6881篇 |
出版年
2024年 | 31篇 |
2023年 | 263篇 |
2022年 | 444篇 |
2021年 | 550篇 |
2020年 | 692篇 |
2019年 | 797篇 |
2018年 | 605篇 |
2017年 | 559篇 |
2016年 | 932篇 |
2015年 | 981篇 |
2014年 | 1204篇 |
2013年 | 1453篇 |
2012年 | 1701篇 |
2011年 | 1792篇 |
2010年 | 1404篇 |
2009年 | 1426篇 |
2008年 | 1605篇 |
2007年 | 1377篇 |
2006年 | 1232篇 |
2005年 | 979篇 |
2004年 | 878篇 |
2003年 | 679篇 |
2002年 | 803篇 |
2001年 | 644篇 |
2000年 | 507篇 |
1999年 | 367篇 |
1998年 | 261篇 |
1997年 | 202篇 |
1996年 | 229篇 |
1995年 | 190篇 |
1994年 | 161篇 |
1993年 | 151篇 |
1992年 | 105篇 |
1991年 | 89篇 |
1990年 | 65篇 |
1989年 | 47篇 |
1988年 | 55篇 |
1987年 | 37篇 |
1986年 | 32篇 |
1985年 | 38篇 |
1984年 | 18篇 |
1983年 | 21篇 |
1982年 | 6篇 |
1981年 | 13篇 |
1980年 | 5篇 |
1979年 | 10篇 |
1978年 | 6篇 |
1974年 | 3篇 |
1959年 | 2篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
Bridge‐Localized HOMO‐Binding Character of Divinylanthracene‐Bridged Dinuclear Ruthenium Carbonyl Complexes: Spectroscopic,Spectroelectrochemical, and Computational Studies
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Ya‐Ping Ou Jing Zhang Meng Xu Jianlong Xia Prof. František Hartl Prof. Dr. Jun Yin Prof. Dr. Guang‐Ao Yu Prof. Dr. Sheng Hua Liu 《化学:亚洲杂志》2014,9(4):1152-1160
The electronic properties of four divinylanthracene‐bridged diruthenium carbonyl complexes [{RuCl(CO)(PMe3)3}2(μ? CH?CHArCH?CH)] (Ar=9,10‐anthracene ( 1 ), 1,5‐anthracene ( 2 ), 2,6‐anthracene ( 3 ), 1,8‐anthracene ( 4 )) obtained by molecular spectroscopic methods (IR, UV/Vis/near‐IR, and EPR spectroscopy) and DFT calculations are reported. IR spectroelectrochemical studies have revealed that these complexes are first oxidized at the noninnocent bridging ligand, which is in line with the very small ν(C?O) wavenumber shift that accompanies this process and also supported by DFT calculations. Because of poor conjugation in complex 1 , except oxidized 1+ , the electronic absorption spectra of complexes 2+ , 3+ , and 4+ all display the characteristic near‐IR band envelopes that have been deconvoluted into three Gaussian sub‐bands. Two of the sub‐bands belong mainly to metal‐to‐ligand charge‐transfer (MLCT) transitions according to results from time‐dependent DFT calculations. EPR spectroscopy of chemically generated 1+ – 4+ proves largely ligand‐centered spin density, again in accordance with IR spectra and DFT calculations results. 相似文献
972.
Phosphorescent Cyclometalated Iridium(III) Complexes That Contain Substituted 2‐Acetylbenzo[b]thiophen‐3‐olate Ligand for Red Organic Light‐Emitting Devices
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Chen Yang Dr. Shiu‐Lun Lai Dr. Sharon Lai‐Fung Chan Dr. Kam‐Hung Low Dr. Gang Cheng Kwan‐Ting Yeung Dr. Chi‐Chung Kwok Prof. Dr. Chi‐Ming Che 《化学:亚洲杂志》2014,9(12):3572-3585
We report the synthesis of a new class of thermally stable and strongly luminescent cyclometalated iridium(III) complexes 1 – 6 , which contain the 2‐acetylbenzo[b]thiophene‐3‐olate (bt) ligand, and their application in organic light‐emitting diodes (OLEDs). These heteroleptic iridium(III) complexes with bt as the ancillary ligand have a decomposition temperature that is 10–20 % higher and lower emission self‐quenching constants than those of their corresponding complexes with acetylacetonate (acac). The luminescent color of these iridium(III) complexes could be fine‐tuned from orange (e.g., 2‐phenyl‐6‐(trifluoromethyl)benzo[d]thiazole (cf3bta) for 4 ) to pure red (e.g., lpt (Hlpt=4‐methyl‐2‐(thiophen‐2‐yl)quinolone) for 6 ) by varying the cyclometalating ligands (C‐deprotonated C^N). In particular, highly efficient OLEDs based on 6 as dopant (emitter) and 1,3‐bis(carbazol‐9‐yl)benzene (mCP) as host that exhibit stable red emission over a wide range of brightness with CIE chromaticity coordinates of (0.67, 0.33) well matched to the National Television System Committee (NTSC) standard have been fabricated along with an external quantum efficiency (EQE) and current efficiency of 9 % and 10 cd A?1, respectively. A further 50 % increase in EQE (>13 %) by replacing mCP with bis[4‐(6H‐indolo[2,3‐b]quinoxalin‐6‐yl)phenyl]diphenylsilane (BIQS) as host for 6 in the red OLED is demonstrated. The performance of OLEDs fabricated with 6 (i.e., [(lpt)2Ir(bt)]) was comparable to that of the analogous iridium(III) complex that bore acac (i.e., [(lpt)2Ir(acac)]; 6 a in this work) [Adv. Mater. 2011 , 23, 2981] fabricated under similar conditions. By using ntt (Hnnt=3‐hydroxynaphtho[2,3‐b]thiophen‐2‐yl)(thiophen‐2‐yl)methanone) ligand, a substituted derivative of bt, the [(cf3bta)2Ir(ntt)] was prepared and found to display deep red emission at around 700 nm with a quantum yield of 12 % in mCP thin film. 相似文献
973.
Asymmetric Michael Addition/Intramolecular Cyclization Catalyzed by Bifunctional Tertiary Amine–Squaramides: Construction of Chiral 2‐Amino‐4H‐chromene‐3‐Carbonitrile Derivatives
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The efficient asymmetric Michael addition/intramolecular cyclization of malononitrile with dienones catalyzed by a chiral bifunctional tertiary amine–squaramide catalyst for the synthesis of chiral 2‐amino‐4H‐chromene‐3‐carbonitrile derivatives was developed. The corresponding products were obtained in good to excellent yields (up to 99 %) with excellent enantioselectivities (up to 98 % ee) for most of the bisarylidenecyclopentanones. 相似文献
974.
Guang‐Ming Liang Jing Shang Kun‐Guo Yang Kai Ma Qing‐Ling Ni 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(4):379-383
The title compounds, bis{μ‐N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine‐κ2N1:P}disilver bis(perchlorate) acetonitrile monosolvate, [Ag2(C18H17N2P)2](ClO4)2·CH3CN, (1), and bis{μ‐N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine‐κ2N1:P}bis[(nitrato‐κ2O,O)silver], [Ag2(C18H17N2P)2(NO3)2], (2), each contain disilver macrocyclic [Ag2(C18H17N2P)2]2+ cations lying about inversion centres. The cations are constructed by two N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine (DPP) ligands linking two Ag+ cations in a head‐to‐tail fashion. In (1), the unique Ag+ cation has a near‐linear coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands. Two ClO4− anions doubly bridge two metallomacrocycles through Ag...O and N—H...O weak interactions to form a chain extending in the c direction. The half‐occupancy acetonitrile molecule lies with its methyl C atom on a twofold axis and makes a weak N...Ag contact. In (2), there are two independent [Ag(C18H17N2P)]+ cations. The nitrate anions weakly chelate to each Ag+ cation, leading to each Ag+ cation having a distorted tetrahedral coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands, and two chelating nitrate O atoms. Each dinuclear [Ag2(C18H17N2P)2(NO3)2] molecule acts as a four‐node to bridge four adjacent equivalent molecules through N—H...O interactions, forming a two‐dimensional sheet parallel to the bc plane. Each sheet contains dinuclear molecules involving just Ag1 or Ag2 and these two types of sheet are stacked in an alternating fashion. The sheets containing Ag1 all lie near x = , , etc, while those containing Ag2 all lie near x = 0, 1, 2 etc. Thus, the two independent sheets are arranged in an alternating sequence at x = 0, , 1, etc. These two different supramolecular structures result from the different geometric conformations of the templating anions which direct the self‐assembly of the cations and anions. 相似文献
975.
Gui‐Xia Wang Li‐Li Shang Zhao‐Hao Li Bang‐Tun Zhao 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(7):715-717
A novel manganese coordination polymer, poly[(μ5‐thiophene‐3,4‐dicarboxylato)manganese(II)], [Mn(C6H2O4S)]n, was synthesized hydrothermally using 3,4‐thiophenedicarboxylate (3,4‐tdc2−) as the organic linker. The asymmetric unit of the complex contains an Mn2+ cation and one half of a deprotonated 3,4‐tdc2− anion, both residing on a twofold axis. Each Mn2+ centre is six‐coordinated by O atoms of bridging/chelating carboxylate groups from five 3,4‐tdc2− anions, forming a slightly distorted octahedron. The Mn2+ centres are bridged by 3,4‐tdc2− anions to give an infinite two‐dimensional layer which incorporates one‐dimensional Mn–O gridlike chains, and in which the 3,4‐tdc2− anion adopts a novel hexadentate chelating and μ5‐bridging coordination mode. The fully deprotonated 3,4‐tdc2− anion exhibits unexpected efficiency as a ligand towards the Mn2+ centres, which it coordinates through all of its carboxylate O atoms to provide the novel coordination mode. The IR spectrum of the complex is also reported. 相似文献
976.
977.
氧化还原与电解的相关知识是中学化学学习的重点内容。应用自主研制的MXLab21先进数字化实验系统电解Fe2(SO4)3溶液,用电解生成的Fe2+直接滴定KMnO4溶液以测定其浓度,再用返滴法测定消毒液中H2O2的含量。对恒电流电解的最佳条件如Fe2(SO4)3溶液浓度及电解电流大小进行了优化。该数字化实验系统相比较于常规数字化仪器(或手持技术)的优越性在于其自带电解、搅拌及控制系统,能在电解的同时利用电生物质实现对待测物质的准确测定,测定时间短(不超过4 min)。本实验采用预设终点电势值的方法自动估计滴定终点,不但便捷准确,且呈现出的实时直观的电势和电量随时间变化的动态曲线便于学生理解电解及氧化还原滴定反应的微观本质,对中学化学教学及化学学科核心素养的培养具有重要价值。 相似文献
978.
Microfluidic CE (MCE) is an effective solution for rapid and sensitive determination of multiple analytes. Herein, a dynamic coated cyclic olefin copolymer microchip was developed having an on-chip micropump for fluid velocity adjusting in electrophoretic separations. This micropump was fabricated by constructing a polyacrylamide gel membrane at one channel terminal. Once applying electric field across the membrane, a pressure-driven flow generated automatically to balance the electroosmotic flow (EOF) mismatch at the channel-membrane interface. The influence of gel precursor concentration and operating voltages on the fluid velocity was carefully evaluated. Moreover, the highly integration of injection, separation, and pumping units of the MCE system minimized the dead volume and provides satisfied column efficiency. Experiments showed that by adjusting of pumping voltage reduced the fluid velocity by a factor of 6, resulting six- and threefold resolving power enhancements of rhodamine dye mixture and amino acid mixture, respectively. Furthermore, the developed MCE method was applied for rhodamines and amino acids quantitation in food and cosmetics, with standard addition recoveries of 87.3–106.9% and 89.9–117.4%, respectively. These results were also confirmed by standard HPLC method, revealing the application potential in fast and onsite analysis of complex samples. 相似文献
979.
Current forensic DNA profiles are obtained based on analyses of PCR product sizes or DNA sequence polymorphisms. Sometimes routine forensic analysis using short tandem repeat (STR) generates unsuccessful DNA testing result if the biological sample encountered is excessively degraded and low-template DNA. Herein, a new six-color fluorescence labeling system, including 59 autosomal diallelic deletion or insertion polymorphisms (DIPs), 2 miniSTRs, 2 Y-chromosome DIPs, and 1 Amelogenin gene with the amplicon sizes of less than 200 bp, was self-developed. According to the validation guidelines for DNA analysis methods formulated by the Scientific Working Group on DNA Analysis Methods, the validation studies have also been carried out for the multiplex system. This novel panel possessed the features of strong stability, high sensitivity, and good specificity, which was especially suitable for the forensic degraded and mixed sample detections. The cumulative power of exclusion and cumulative matching probability of the system were 0.9999978 and 9.833E-28, respectively, in Han Chinese in Hunan, China. Moreover, this system will be an effective new tool that can be independently applied to forensic personal identification and paternity testing in the populations from the East Asia region, even from the South Asia, America, and Europe regions. The system can also contribute to population phylogenetic affinity and genetic structure analyses among different populations. 相似文献
980.
酶作为一种具有高度特异性和高效性的催化剂, 可在细胞器中通过复杂有序的生化反应调节细胞的代谢过程. 受细胞区隔化结构的启发, 仿生设计纳米酶催化体系、 构筑限域酶催化微环境从而提高酶催化活性的研究为酶催化应用开辟了新思路. 纳米催化体系保留了小尺寸、 大比表面积、 肿瘤部位选择性富集等优势, 在疾病的诊疗方面发挥了巨大的优势. 本文首先总结了天然酶、 模拟酶和级联酶体系的催化机理, 对仿生构筑的纳米酶催化材料的载体体系进行了概述, 介绍了纳米酶催化体系在生物成像方面的应用, 讨论了其在相关代谢类疾病的作用途径, 并对纳米酶催化体系用于生物诊疗的发展前景进行了展望. 相似文献