全文获取类型
收费全文 | 1753篇 |
免费 | 102篇 |
国内免费 | 28篇 |
专业分类
化学 | 1201篇 |
晶体学 | 11篇 |
力学 | 70篇 |
综合类 | 2篇 |
数学 | 292篇 |
物理学 | 307篇 |
出版年
2023年 | 12篇 |
2022年 | 35篇 |
2021年 | 37篇 |
2020年 | 48篇 |
2019年 | 44篇 |
2018年 | 32篇 |
2017年 | 28篇 |
2016年 | 83篇 |
2015年 | 57篇 |
2014年 | 79篇 |
2013年 | 111篇 |
2012年 | 120篇 |
2011年 | 140篇 |
2010年 | 73篇 |
2009年 | 96篇 |
2008年 | 102篇 |
2007年 | 87篇 |
2006年 | 65篇 |
2005年 | 76篇 |
2004年 | 71篇 |
2003年 | 71篇 |
2002年 | 61篇 |
2001年 | 17篇 |
2000年 | 32篇 |
1999年 | 14篇 |
1998年 | 10篇 |
1997年 | 16篇 |
1996年 | 19篇 |
1995年 | 19篇 |
1994年 | 17篇 |
1993年 | 12篇 |
1992年 | 10篇 |
1991年 | 15篇 |
1990年 | 14篇 |
1989年 | 4篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 20篇 |
1982年 | 10篇 |
1981年 | 6篇 |
1980年 | 11篇 |
1979年 | 6篇 |
1978年 | 12篇 |
1977年 | 13篇 |
1976年 | 13篇 |
1974年 | 10篇 |
1973年 | 6篇 |
1972年 | 5篇 |
排序方式: 共有1883条查询结果,搜索用时 15 毫秒
71.
Aleksandra Holownia Chieh‐Hung Tien Diego B. Diaz Reed T. Larson Andrei K. Yudin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(42):15292-15297
The synthesis and applications of carboxy‐MIDA‐boronate, a novel C1 building block, are described. This molecule is accessible via a ruthenium tetraoxide‐mediated cleavage of commercially available ethynyl‐MIDA‐boronate. In the course of this study, carboxy‐MIDA‐boronate was found to possess ambident reactivity towards nucleophiles. Carboxylic acid derivatization produces a broad range of previously unknown carbamoyl‐, oxycarbo‐ and thiocarboboronates. Carboxy‐MIDA‐boronate and its derivatives undergo condensations to access borylated heterocycles with boron at positions that are difficult to access using alternate methods. The resulting heterocycles participate in the Suzuki–Miyaura cross‐coupling reaction, enabling entry into diverse bis(heteroaryl) motifs. The carbon monoxide‐releasing capacity of carboxy‐MIDA‐boronate was also examined and applied in palladium‐catalyzed carbonylation. 相似文献
72.
A new chiral aminophosphine ligand 6,6′-dimethoxy-2,2′-bis(diphenylphosphinoamino)biphenyl(DMBDPPABP) was prepared and its rhodium complex was found to be an effective catalyst for the asymmetric hydrogenation of amidoacrylic acid and its dervatives.The effects of solvent and reaction temperature on enantioselectivity were also studied. 相似文献
73.
Protonation and bromination of an osmabenzyne: reactions leading to the formation of new metallabenzynes 总被引:1,自引:0,他引:1
Wen TB Ng SM Hung WY Zhou ZY Lo MF Shek LY Williams ID Lin Z Jia G 《Journal of the American Chemical Society》2003,125(4):884-885
The reactivities of benzynes and metal-carbyne complexes are normally associated with the triple bond units. However, we have now found that electrophiles do not attack the formal osmium-carbon triple bond of osmabenzyne complex 1. Instead, 1 undergoes electrophilic substitution reactions-the typical reactions of aromatic systems. 相似文献
74.
Guang‐Tao Xu Liang‐Liang Wu Xiao‐Yong Chang Tim Wai Hung Ang Wai‐Yeung Wong Jie‐Sheng Huang Chi‐Ming Che 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(45):16443-16452
Supramolecular ensembles adopting ring‐in‐ring structures are less developed compared with catenanes featuring interlocked rings. While catenanes with inter‐ring closed‐shell metallophilic interactions, such as d10–d10 AuI–AuI interactions, have been well‐documented, the ring‐in‐ring complexes featuring such metallophilic interactions remain underdeveloped. Herein is described an unprecedented ring‐in‐ring structure of a AuI‐thiolate Au12 cluster formed by recrystallization of a AuI‐thiolate Au10 [2]catenane from alkane solvents such as hexane, with use of a bulky dibutylfluorene‐2‐thiolate ligand. The ring‐in‐ring AuI‐thiolate Au12 cluster features inter‐ring AuI–AuI interactions and underwent cluster core change to form the thermodynamically more stable Au10 [2]catenane structure upon dissolving in, or recrystallization from, other solvents such as CH2Cl2, CHCl3, and CH2Cl2/MeCN. The cluster‐to‐cluster transformation process was monitored by 1H NMR and ESI‐MS measurements. Density functional theory (DFT) calculations were performed to provide insight into the mechanism of the “ring‐in‐ring? [2]catenane” interconversions. 相似文献
75.
Huatian Shi Jianhui Xie William W. Y. Lam Wai-Lun Man Chi-Keung Mak Shek-Man Yiu Hung Kay Lee Tai-Chu Lau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12895-12899
The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [MnV(TAML)(N-Mes)]− ( 1 ), are reported. Compound 1 is oxidized by [(p-BrC6H4)3N ]+.[SbCl6]− and the resulting MnVI species readily undergoes H-atom transfer and nitrene transfer reactions. 相似文献
76.
Arjomandi J Shah AU Bilal S Van Hoang H Holze R 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(1):1-6
Polypyrrole (PPy) and poly(pyrrole-2,6-dimethyl-β-cyclodextrin) [P(Py-β-DMCD)] films prepared by potential cycling in aqueous acidic solutions on indium tin oxide (ITO)-coated glass and gold electrodes were studied by in situ UV-vis and Raman spectroscopy. Characteristic UV-vis and Raman bands were identified and their dependencies on the electrode potential have been discussed. Spectroelectrochemical results reveal differences both in the position of the spectral bands and their potential dependence for PPy and P(Py-β-DMCD) films indicating interactions between polymer chains and CDs during electropolymerization process. The films were also characterized by cyclic voltammetry and FT-IR spectroscopy. 相似文献
77.
The aim of this research was to investigate new bulky electron donors (EDs) generating hindered active species in the cationic polymerization of 1,3-pentadiene initiated by AlCl3 in pentane, in order to avoid or strongly reduce the reaction between the active species and the double bonds of the polymer which are responsible for side reactions. At room temperature, the polymerization in the presence of new ED, such as OPh2, N(PhBr)3, NPh3 and SPh2, allowed to obtain higher conversions and lower insoluble fractions than without electron donor. The formation of a complex ED/AlCl3 was shown for each electron donor. However, in the case of NPh3 and SPh2, variations of the polymer microstructure demonstrated an interaction between active species and these EDs. Similar results were obtained at lower temperature (−10 °C). The beneficial effect of the presence of electron donors such as NPh3 and SPh2 demonstrated the validity of the concept of sterically hindered active species, but the polymerization was still uncontrolled. 相似文献
78.
Hung‐Chuan Cheng Li‐Tang Wang Ashraf Taha Khalil Yao‐To Chang Yu‐Chi Lin Ya‐Ching Shen 《中国化学会会志》2004,51(2):431-435
Phytochemical investigation of the stem bark of Calophyllum inophyllum resulted in the isolation of a new dipyrenoxanthone, calophinone ( 1 ), together with four related xanthones ( 2–5 ). Identification of the isolated compounds was achieved through intensive studies of their spectral data, especially 2D NMR. 相似文献
79.
Chen-I Yang Kai-Hung ChengShao-Po Hung Motohiro NakanoHui-Lien Tsai 《Polyhedron》2011,30(18):3272-3278
The reactions of 2-hydroxyphenylethanone oxime (Me-H2salox) and (2-hydroxy-phenyl)-phenyl-methanone oxime (Ph-H2salox) with Mn(ClO4)2·6H2O in MeOH afford trinuclear manganese complexes of [Mn3O(Me-salox)3(MeOH)3(ClO4)]·MeOH (1·MeOH) and [Mn3O(Ph-salox)3(MeOH)3(ClO4)]·2MeOH (2·2MeOH), respectively. X-ray analysis shows that both complexes contain a manganese triangle core, [MnIII3O]7+. The structural distortion from the twisting of the oxime ligands dominates the ferromagnetic interactions within the three Mn ions in both compounds and results in an S = 6 ground state. The frequency dependence of out-of-phase signals in the alternating current (AC) magnetic susceptibility measurements and the temperature-dependent and sweep-rate-dependent hysteresis loops are indicative of single-molecule magnet behavior. Moreover, both complexes show step-wise magnetization, indicating the occurrence of quantum tunneling of magnetization (QTM). Interestingly, a tail to tail arrangement in the crystal packing of complex 1·MeOH results in strong intermolecular H-bonding interactions and leads to the exchange-bias effect from the antiferromagnetic interaction between the adjacent Mn3 molecules. In contract, QTM steps of complex 2·2MeOH show an absence of the exchange-bias effect due to a weak intermolecular interaction from a head to tail arrangement. 相似文献
80.
Simokaitiene J Stanislovaityte E Grazulevicius JV Jankauskas V Gu R Dehaen W Hung YC Hsu CP 《The Journal of organic chemistry》2012,77(11):4924-4931
The synthesis and full characterization of new derivatives of indolo[3,2-b]carbazole with differently substituted phenyl groups at nitrogen atoms is reported. Comparative study on their thermal, optical electrochemical, and photoelectrical properties is presented. The synthesized compounds are electrochemically stable. Their highest occupied molecular orbital energy values range from -5.14 to -5.07 eV. The electron photoemission spectra of the films of synthesized materials revealed the ionization potentials of 5.31-5.47 eV. Hole drift mobility of the amorphous film of 5,11-bis(3-methoxyphenyl)-6-pentyl-5,11-dihydroindolo[3,2-b]carbazole exceed 10(-3) cm(2)/V·s at high electric fields, as it was established by xerographic time-of-flight technique. In contrast to diphenylamino substituted derivatives of carbazole, no effect of the position of methoxy groups on the photoelectrical properties was observed for the synthesized methoxyphenyl-substituted derivatives of indolo[3,2-b]carbazole. The indolo[3,2-b]carbazole core has a larger resonance structure that includes 3 phenyl rings, and thus the energy gap of the HOMO and LUMO π orbitals is lower as compared to that of carbazoles. With a larger energy difference between the phenyl substituents and the core moiety, the indolo[3,2-b]carbazole derivatives studied all have a weaker coupling between the phenyl group and a much weaker dependence of the molecular properties on the position of substituents on the phenyl groups as compared to those observed in substituted carbazoles. 相似文献