全文获取类型
收费全文 | 2404篇 |
免费 | 341篇 |
国内免费 | 390篇 |
专业分类
化学 | 2098篇 |
晶体学 | 68篇 |
力学 | 308篇 |
综合类 | 31篇 |
数学 | 17篇 |
物理学 | 613篇 |
出版年
2024年 | 7篇 |
2023年 | 25篇 |
2022年 | 74篇 |
2021年 | 88篇 |
2020年 | 120篇 |
2019年 | 93篇 |
2018年 | 71篇 |
2017年 | 79篇 |
2016年 | 118篇 |
2015年 | 113篇 |
2014年 | 125篇 |
2013年 | 219篇 |
2012年 | 145篇 |
2011年 | 146篇 |
2010年 | 141篇 |
2009年 | 132篇 |
2008年 | 145篇 |
2007年 | 149篇 |
2006年 | 145篇 |
2005年 | 133篇 |
2004年 | 139篇 |
2003年 | 122篇 |
2002年 | 129篇 |
2001年 | 76篇 |
2000年 | 77篇 |
1999年 | 40篇 |
1998年 | 52篇 |
1997年 | 45篇 |
1996年 | 46篇 |
1995年 | 31篇 |
1994年 | 26篇 |
1993年 | 18篇 |
1992年 | 14篇 |
1991年 | 16篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 8篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
排序方式: 共有3135条查询结果,搜索用时 15 毫秒
121.
122.
Dr. Yi Jiang Lei-Li Sun Guang-Zong Ren Xiang Niu Wen-zhou Hu Prof. Zhi-Qiang Hu 《ChemistryOpen》2015,4(3):378-382
The development of novel selective probes with high sensitivity for the detection of Al3+ is widely considered an important research goal due to the importance of such probes in medicine, living systems and the environment. Here, we describe a new fluorescent probe, N′-(4-diethylamino-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (1), for Al3+. Probe 1 was evaluated in a solution of acetonitrile/water (1:1 v/v). Compared with previously reported probes for Al3+, probe 1 can be synthesized easily and in high yield. A Job plot confirmed that probe 1 is able to complex Al3+ in a 1:1 ratio, and the binding constant was determined to be 4.25×108 m−1. Moreover, the detection limit was as low as 6.7×10−9 m, suggesting that probe 1 has a high sensitivity. Common coexistent metal ions, such as K+, Co2+, Ca2+, Ba2+, Ni2+, Pb2+, Hg2+, Ce2+, Zn2+, Cd2+, Fe3+, showed little or no interference in the detection of Al3+ in solution, demonstrating the high selectivity of the probe. Finally, the ability of probe 1 to act as a fluorescent probe for Al3+ in living systems was evaluated in Gram-negative bacteria, Escherichia coli, and confocal laser scanning microscopy confirmed its utility. The results of this study suggest that 1 has appropriate properties to be developed for application as a fluorescent probe of Al3+ for use in biological studies. 相似文献
123.
Chromate conversion coatings (CCCs) on AA7075‐T6 were characterized using scanning electron microscopy, focused ion beam sectioning and scanning transmission electron microscopy with nano‐electron dispersive spectroscopy line profiling. The thickness and composition of the CCC was different at different locations on the heterogeneous microstructure of AA7075‐T6. The coating formed on the matrix phase was much thicker than that formed on the coarse Al–Cu–Mg, Al–Fe–Cu and Mg–Si intermetallic particles. Nano‐electron dispersive spectroscopy line profiling indicated that the coating on the Al–Fe–Cu particles was similar to the CCC formed on the phase matrix, primarily a chromium oxide. However, the coatings on the Al–Cu–Mg and Mg–Si particles were mixed Al/Mg/Cr oxide and Mg oxide, respectively. The growth of CCC followed a linear‐logarithmic kinetic rate law. The observations of this study support the sol‐gel model of CCC formation. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
124.
Hong‐Ze Gao Zhong‐Min Su Chun‐Sheng Qin Ri‐Gen Mo Yu‐He Kan 《International journal of quantum chemistry》2004,97(6):992-1001
Bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex (AlMq2OH) is used in organic light‐emitting diodes (OLEDs) as an electron transport material and emitting layer. By means of ab initio Hartree–Fock (HF) and density functional theory (DFT) B3LYP methods, the structure of AlMq2OH was optimized. The frontier molecular orbital characteristics and energy levels of AlMq2OH have been analyzed systematically to study the electronic transition mechanism in AlMq2OH. For comparison and calibration, bis(8‐quinolinolato)aluminum(III) hydroxide complex (Alq2OH) has also been examined with these methods using the same basis sets. The lowest singlet excited state (S1) of AlMq2OH has been studied by the singles configuration interaction (CIS) method and time‐dependent DFT (TD‐DFT) using a hybrid functional, B3‐LYP, and the 6‐31G* basis set. The lowest singlet electronic transition (S0 → S1) of AlMq2OH is π → π* electronic transitions and primarily localized on the different quinolate ligands. The emission of AlMq2OH is due to the electron transitions from a phenoxide donor to a pyridyl acceptor from another quinolate ligand including C → C and O → N transference. Two possible electron transfer pathways are presented, one by carbon, oxygen, and nitrogen atoms and the other via metal cation Al3+. The comparison between the CIS‐optimized excited‐state structure with the HF ground‐state structure indicates that the geometric shift is mainly confined to the one quinolate and these changes can be easily understood in terms of the nodal patterns of the highest occupied and lowest unoccupied molecular orbitals. On the basis of the CIS‐optimized structure of the excited state, TD‐B3‐LYP calculations predict an emission wavelength of 499.78 nm. An absorption wavelength at 380.79 nm on the optimized structure of B3LYP/6‐31G* was predicted. They are comparable to AlMq2OH 485 and 390 nm observed experimentally for photoluminescence and UV‐vis absorption spectra of AlMq2OH solid thin film on quartz, respectively. Lending theoretical corroboration to recent experimental observations and supposition, the reasons for the blue‐shift of AlMq2OH were revealed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004 相似文献
125.
E. D. Matveeva T. A. Podrugina M. V. Prisyazhnoi I. N. Rusetskaya N. S. Zefirov 《Russian Chemical Bulletin》2007,56(4):798-805
Interaction of aliphatic and aromatic aldehydes and ketones with optically active L-α-amino acids or their esters in the three-component catalytic one-pot synthesis of α-aminophosphonates was studied. The
corresponding α-amino phosphonates are formed in high yields as mixtures of diastereomers.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 768–774, April, 2007. 相似文献
126.
Qing Wang Mingxing Fu Xiaojun Li Runfeng Huang Rainer E. Glaser Lili Zhao 《Journal of computational chemistry》2019,40(16):1599-1608
Density functional theory calculations were performed to understand the detailed reaction mechanism of aluminum alkoxy-catalyzed conversion of glucose to 5-hydroxymethylfurfural (HMF) using Al(OMe)3 as catalyst. Potential energy surfaces were studied for aggregates formed between the organic compounds and Al(OMe)3 and effects of the medium were considered via continuum solvent models. The reaction takes place via two stages: isomerization from glucose to fructose (stage I) and transformation of fructose to HMF (stage II). Stage II includes three successive dehydrations, which begins with a 1,2-elimination to form an enolate (i.e., B), continues with the formation of the acrolein moiety (i.e., D), and ends with the formation of the furan ring (i.e., HMF). All of these steps are facilitated by aluminum alkoxy catalysis. The highest barriers for stage I and stage II are 23.9 and 31.2 kcal/mol, respectively, and the overall catalytic reaction is highly exothermic. The energetic and geometric results indicate that the catalyzed reaction path has feasible kinetics and thermodynamics and is consistent with the experimental process under high temperature (i.e., 120 °C). Remarkably, the released water molecules in stage II act as the product, reactant, proton shuttle, as well as stabilizer in the conversion of fructose to HMF. The metal–ligand functionality of the Al(OMe)3 catalyst, which combines cooperative Lewis acid and Lewis base properties and thereby enables proton shuttling, plays a crucial role in the overall catalysis and is responsible for the high reactivity. © 2019 Wiley Periodicals, Inc. 相似文献
127.
The flame‐retardant microcapsules were successfully fabricated with an aluminum hypophosphite (AHP) core. Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS) were used to verify that AHP was encapsulated in the microcapsules, and thermogravimetry analysis showed that microencapsulated AHP (MAHP) possessed higher thermal stability than that of AHP. Then, a flame‐retardant and smoke suppression system for silicone foams (SiFs) was obtained through a synergistic effect of MAHP and zinc borate (2ZnO·3B2O3·3.5H2O). The mechanical properties, flame retardance, and smoke suppression of SiFs with MAHP and zinc borate were tested using the tensile test, limiting oxygen index (LOI) test, UL‐94 test, and cone calorimeter test. The mechanical properties indicated that the tensile strength and elongation at break of SiFs could evidently improve with the incorporation of MAHP. Compared with pure SiF, SiF8 with 4.5‐wt% MAHP and 1.5‐wt% zinc borate could achieve an LOI value of 30.7 vol% and an UL‐94 V‐0 rating, the time to ignition amplified almost six times, the peak heat release rate and total heat release were 51.10% and 46.00% less than that of pure SiF, respectively, the fire performance index increased nearly 13 times, and the fire growth index value was only 13.18% of pure SiF. Moreover, the partial substitution of zinc borate imparted a substantial improvement in both flame retardancy and smoke suppression. Especially, the peak smoke production rate and total smoke production of SiF8 were merely 38.46% and 38.84% of pure SiF. 相似文献
128.
涂碳铝箔对磷酸铁锂电池性能影响研究 总被引:1,自引:0,他引:1
本文研究了使用涂碳铝箔作为正极集流体磷酸铁锂电池的性能。研究对比了使用普通铝箔和涂层铝箔的10 Ah软包磷酸铁锂电池的主要性能。研究表明:使用涂层铝箔不但可以提高磷酸铁锂材料的粘结性,而且使用导电涂层可以有效降低正极材料和集流体的接触内阻,从而减小电池内阻,提高电池倍率性能。与使用普通铝箔作为集流体相比,通过使用涂碳铝箔可以使得电池的内阻降低65%左右,但是,磷酸铁锂正极材料的克容量却偏低约5~10 mAh·g-1,首次效率也偏低4%左右;在快速放电15C倍率下,使用涂碳铝箔的电芯比使用普通铝箔容量提高约15%左右,10C放电倍率下,平台增加0.3~0.4 V;使用涂碳铝箔电芯的常温自放电率较高,但容量恢复率也较高;550周循环下,使用涂碳铝箔可以使得电池的循环性能提高约1%。而在电池低温性能方面,使用涂碳铝箔对低温性能并无改善。 相似文献
129.
Dr. Koichi Nagata Takahiro Murosaki Prof. Dr. Tomohiro Agou Prof. Dr. Takahiro Sasamori Prof. Dr. Tsukasa Matsuo Prof. Dr. Norihiro Tokitoh 《Angewandte Chemie (International ed. in English)》2016,55(41):12877-12880
Activation of dihydrogen by masked dialumenes (Al=Al doubly bonded species) is reported. Reactions of barrelene‐type dialumanes, which have the reactivity as masked equivalents of 1,2‐diaryldialumenes ArAl=AlAr, with H2 afforded dihydroalumanes ArAlH2 at room temperature (Ar: bulky aryl groups). These dihydroalumanes form hydrogen‐bridged dimers [ArHAl(μ‐H)]2 in the crystalline state, while a monomer–dimer equilibrium was suggested in solution. The 1,2‐diaryldialumenes generated from the barrelene‐type dialumanes are the putative active species in the cleavage of H2. 相似文献
130.