全文获取类型
收费全文 | 1417篇 |
免费 | 91篇 |
国内免费 | 2篇 |
专业分类
化学 | 1112篇 |
晶体学 | 12篇 |
力学 | 25篇 |
数学 | 204篇 |
物理学 | 157篇 |
出版年
2024年 | 1篇 |
2023年 | 11篇 |
2022年 | 11篇 |
2021年 | 22篇 |
2020年 | 49篇 |
2019年 | 36篇 |
2018年 | 42篇 |
2017年 | 22篇 |
2016年 | 52篇 |
2015年 | 54篇 |
2014年 | 53篇 |
2013年 | 93篇 |
2012年 | 122篇 |
2011年 | 133篇 |
2010年 | 60篇 |
2009年 | 63篇 |
2008年 | 113篇 |
2007年 | 96篇 |
2006年 | 85篇 |
2005年 | 93篇 |
2004年 | 67篇 |
2003年 | 55篇 |
2002年 | 48篇 |
2001年 | 15篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 10篇 |
1997年 | 7篇 |
1996年 | 19篇 |
1995年 | 4篇 |
1994年 | 8篇 |
1993年 | 4篇 |
1992年 | 9篇 |
1991年 | 3篇 |
1990年 | 6篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1976年 | 2篇 |
1963年 | 1篇 |
排序方式: 共有1510条查询结果,搜索用时 0 毫秒
61.
Fondo M García-Deibe AM Corbella M Ruiz E Tercero J Sanmartín J Bermejo MR 《Inorganic chemistry》2005,44(14):5011-5020
The new tetranuclear carbonate complex [Cu2L)2(CO3)] x 8H2O (1 x 8H2O) (H3L = (2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) has been obtained by two different synthetic routes and fully characterized. Recrystallization of 1 x 8H2O in methanol yields single crystals of {[(Cu2L)2(CO3)]}2 x 12H2O (1 x 6H2O), suitable for X-ray diffraction studies. The crystal structure of 1 x 6H2O shows two crystallographically different tetranuclear molecules in the asymmetric unit, 1a and 1b. Both molecules can be understood as self-assembled from two dinuclear [Cu2L]+ cations, joined by a mu4-eta(2):eta(1):eta(1) carbonate ligand. The copper atoms of each crystallographically different [(Cu2L)2(CO3)] molecule present miscellaneous coordination polyhedra: in both 1a and 1b, two metal centers are in square pyramidal environments, one displays a square planar chromophore and the other one has a geometry that can be considered as an intermediate between square pyramid and trigonal bipyramid. Magnetic studies reveal net intramolecular ferromagnetic coupling between the metal atoms. Density functional calculations allow the assignment of the different magnetic coupling constants and explain the unexpected ferromagnetic behavior, because of the presence of an unusual NCN bridging moiety and countercomplementarity of the phenoxo (or carbonate) and NCN bridges. 相似文献
62.
Kinzel D González-Vázquez J González L 《Physical chemistry chemical physics : PCCP》2012,14(18):6241-6249
Non-adiabatic molecular dynamics simulations have been performed in the fluoro-olefin (4-methylcyclohexylidene) fluoromethane (4MCF) using multiconfigurational CASSCF (complete active space self-consistent field) on-the-fly calculations. As an olefin containing a C[double bond, length as m-dash]C double bond, 4MCF is expected to undergo cis-trans isomerization after light irradiation. However, ab initio molecular dynamics shows that a preferential dissociation of atomic hydrogen is taking place after population transfer to the bright ππ* state. This state is strongly mixed with πσ* states allowing dissociation in the electronic excited state before deactivation to the ground state occurs. A minor amount of trajectories experiences F-dissociation, followed by pyramidalization at the sp(2) carbons and CHF dissociation. In contrast, the amount of trajectories undergoing torsion around the double bond, and therefore cis-trans isomerization, is marginal. The H-abstraction reaction is ultrafast, taking place in less than 60 fs. 相似文献
63.
el Hajjouji H Belmonte E García-López J Fernández I Iglesias MJ Roces L García-Granda S El Laghdach A López Ortiz F 《Organic & biomolecular chemistry》2012,10(29):5647-5658
ortho-Lithiation of N,N-diisopropyl-P,P-diphenylphosphinothioic amide using n-BuLi in the presence of TMEDA in diethyl ether followed by electrophilic trapping is described as an efficient method for the synthesis of ortho-functionalised derivatives in high yields. The structural modification of the phosphinothioic amide includes C-X (X = P, S, Si, Sn, I) and C-C bond forming reactions with a large variety of electrophiles. Additional applications based on functional group transformations are also reported. They include imine formation, desulfurization and Suzuki cross-coupling reactions on selected compounds. 相似文献
64.
Dr. Albert Ferrer‐Ugalde Dr. Arántzazu González‐Campo Prof. Dr. Clara Viñas Dr. Jesús Rodríguez‐Romero Dr. Rosa Santillan Dr. Norberto Farfán Prof. Dr. Reijo Sillanpää Dr. Antonio Sousa‐Pedrares Dr. Rosario Núñez Prof. Dr. Francesc Teixidor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):9940-9951
Two sets of o‐carborane derivatives incorporating fluorene and anthracene fragments as fluorophore groups have been successfully synthesized and characterized, and their photophysical properties studied. The first set, comprising fluorene‐containing carboranes 6 – 9 , was prepared by catalyzed hydrosilylation reactions of ethynylfluorene with appropriate carboranylsilanes. The compound 1‐[(9,9‐dioctyl‐fluorene‐2‐yl)ethynyl]carborane ( 11 ) was synthesized by the reaction of 9,9‐dioctyl‐2‐ethynylfluorene and decaborane (B10H14). Furthermore, reactions of the lithium salt of 11 with 1 equivalent of 4‐(chloromethyl)styrene or 9‐(chloromethyl)anthracene yielded compounds 12 and 13 . Members of the second set of derivatives, comprising anthracene‐containing carboranes, were synthesized by reactions of monolithium or dilithium salts of 1‐Me‐1,2‐C2B10H11, 1‐Ph‐1,2‐C2B10H11, and 1,2‐C2B10H12 with 1 or 2 equivalents of 9‐(chloromethyl)anthracene, respectively, to produce compounds 14 – 16 . In addition, 2 equivalents of the monolithium salts of 1‐Me‐1,2‐C2B10H11 (Me‐o‐carborane) and 1‐Ph‐1,2‐C2B10H11 (Ph‐o‐carborane) were reacted with 9,10‐bis(chloromethyl)anthracene to produce compounds 17 and 18 , respectively. Fluorene derivatives 6 – 9 exhibit moderate fluorescence quantum yields (32–44 %), whereas 11 – 13 , in which the fluorophore is bonded to the Ccluster (Cc), show very low emission intensity (6 %) or complete fluorescence quenching. The anthracenyl derivatives containing the Me‐o‐carborane moiety exhibit notably high fluorescence emissions, with ?F=82 and 94 %, whereas their Ph‐o‐carborane analogues are not fluorescent at all. For these compounds, we have observed a correlation between the Cc?Cc bond length and the fluorescence intensity in CH2Cl2 solution, comparable to that observed for previously reported styrene‐containing carboranes. Thus, our hypothesis is that for systems of this type the fluorescence may be tuned and even predicted by changing the substituent on the adjacent Cc. 相似文献
65.
Highly Stable Water‐Soluble Platinum Nanoparticles Stabilized by Hydrophilic N‐Heterocyclic Carbenes 下载免费PDF全文
Edwin A. Baquero Dr. Simon Tricard Dr. Juan Carlos Flores Prof. Dr. Ernesto de Jesús Prof. Dr. Bruno Chaudret 《Angewandte Chemie (International ed. in English)》2014,53(48):13220-13224
Controlling the synthesis of stable metal nanoparticles in water is a current challenge in nanochemistry. The strategy presented herein uses sulfonated N‐heterocyclic carbene (NHC) ligands to stabilize platinum nanoparticles (PtNPs) in water, under air, for an indefinite time period. The particles were prepared by thermal decomposition of a preformed molecular Pt complex containing the NHC ligand and were then purified by dialysis and characterized by TEM, high‐resolution TEM, and spectroscopic techniques. Solid‐state NMR studies showed coordination of the carbene ligands to the nanoparticle surface and allowed the determination of a 13C–195Pt coupling constant for the first time in a nanosystem (940 Hz). Additionally, in one case a novel structure was formed in which platinum(II) NHC complexes form a second coordination sphere around the nanoparticle. 相似文献
66.
A Carbene‐Rich but Carbonyl‐Poor [Ir6(IMe)8(CO)2H14]2+ Polyhydride Cluster as a Deactivation Product from Catalytic Glycerol Dehydrogenation 下载免费PDF全文
Jesús Campos Liam S. Sharninghausen Prof. Robert H. Crabtree Dr. David Balcells 《Angewandte Chemie (International ed. in English)》2014,53(47):12808-12811
The title cluster, a deactivation product in the catalytic dehydrogenation of glycerol, was characterized by XRD, DFT calculations, HRMS, FTIR spectroscopy, and NMR spectroscopy. Experimental/computational studies located the 14 H ligands, and all 1H and 13C{1H} NMR resonances were assigned. The structure contains an unprecedented Ir6H14 core with two CO and eight IMe ligands. 相似文献
67.
In recent years, Mitogen-Activated Protein Kinase (MAPK) pathways have emerged as major regulators of cellular physiology. In the fungal pathogen Candida albicans, three different MAPK pathways have been characterized in the last years. The HOG pathway is mainly a stress response pathway that is activated in response to osmotic and oxidative stress and also participates regulating other pathways. The SVG pathway (or mediated by the Cek1 MAPK) is involved in cell wall formation under vegetative and filamentous growth, while the Mkc1-mediated pathway is involved in cell wall integrity. Oxidative stress is one of the types of stress that every fungal cell has to face during colonization of the host, where the cell encounters both hypoxia niches (i.e. gut) and high concentrations of reactive oxygen species (upon challenge with immune cells). Two pathways have been shown to be activated in response to oxidative stress: the HOG pathway and the MKC1-mediated pathway while the third, the Cek1 pathway is deactivated. The timing, kinetics, stimuli and functional responses generated upon oxidative stress differ among them; however, they have essential functional consequences that severely influence pathogenesis. MAPK pathways are, therefore, valuable targets to be explored in antifungal research. 相似文献
68.
Garbiñe Álvarez Francisco Alcaide Oscar Miguel Laura Calvillo María Jesús Lázaro Jacob J. Quintana Juan Carlos Calderón Elena Pastor 《Journal of Solid State Electrochemistry》2010,14(6):1027-1034
This paper presents the behavior of ordered mesoporous carbon (OMC)-supported catalysts as anodes for direct methanol fuel
cells (DMFC), fed with an aqueous methanol solution. OMC samples were prepared by the nanocasting method from a polymerized
furan resin using mesoporous silica as a template. Pt and PtRu nanoparticles were supported on OMC with high dispersion, the
particle size being 2.4 nm at PtRu loading of 15 wt.%. The resulting catalysts were analyzed using carbon monoxide stripping
voltammetry, cyclic voltammetry, and chronoamperometry in three-electrode experiments and recording cell voltage vs. current
density curves in practical DMFC. It was found that PtRu-catalyzed technical electrodes exhibited good activity towards methanol
electrooxidation in half-cell experiments under fuel-cell-relevant conditions. Specifically, Pt85Ru15/OMC catalyst showed the highest catalytic enhancement compared to Pt/OMC for the steady-state electrooxidation of methanol
at 60 °C and 0.5 V, by a factor of 22 in 2-M MeOH solution. DMFC single cells yielded an open-circuit voltage of 0.625 V at
60 °C. Polarization curves indicate that DMFC with OMC-supported Pt85Ru15 catalyst at the anode exhibited the best performance. 相似文献
69.
Estefanía Gioria Dr. Juan del Pozo Dr. Jesús M. Martínez‐Ilarduya Prof. Dr. Pablo Espinet 《Angewandte Chemie (International ed. in English)》2016,55(42):13276-13280
A Pd complex, cis‐[Pd(C6F5)2(THF)2] ( 1 ), is proposed as a useful touchstone for direct and simple experimental measurement of the relative ability of ancillary ligands to induce C?C coupling. Interestingly, 1 is also a good alternative to other precatalysts used to produce Pd0L. Complex 1 ranks the coupling ability of some popular ligands in the order PtBu3>o‐TolPEWO‐F≈tBuXPhos>P(C6F5)3≈PhPEWO‐F>P(o‐Tol)3≈THF≈tBuBrettPhos?Xantphos≈PhPEWO‐H?PPh3 according to their initial coupling rates, whereas their efficiency, depending on competitive hydrolysis, is ranked tBuXPhos≈PtBu3≈o‐TolPEWO‐F>PhPEWO‐F>P(C6F5)3?tBuBrettPhos>THF≈P(o‐Tol)3>Xantphos>PhPEWO‐H?PPh3. This “meter” also detects some other possible virtues or complications of ligands such as tBuXPhos or tBuBrettPhos. 相似文献
70.
A rapid and reliable capillary zone electrophoresis method for the determination of inorganic cations was developed. The complete separation of K+, Ba2+, Ca2+, Na+, Mg2+, Mn2+, Ni2+, Cd2+, Li+ and Cu2+ can be achieved in 4 min with a simple electrolyte composed by 10 mM imidazole as the carrier buffer and background absorbance provider and acetic acid as the complexing agent (pH 3.60). Injection was performed hydrostatically by elevating the sample at 10 cm for 30 s. The running voltage was +25 kV at room temperature. Indirect UV-absorption detection was achieved at 185 nm. The detection limit was in the range between 0.06 mg/l (Mg2+) and 0.57 mg/l (K+) and the quantification limits ranged from 0.10 mg/l (Ni2+) to 0.80 mg/l (Cu2+). The calibration graphs were linear in the concentration range from the quantification limit till at least 1 g/l in K+, 10 mg/l in Ba2+, Ca2+, Mg2+, Mn2+, Ni2+ and Cd2+, 40 mg/l in Na+ and 12 mg/l in Li+ and Cu2+. The repeatability, intraday and interday analysis were ≤1.55% and ≤3.64% for migration time and ≤3.38% and ≤3.63% for peak area. The method developed has been applied to several beverage samples with only a simple dilution and filtration treatment of the sample. The proposed method is simple, fast, cheap and it is achieved with common products in either laboratory. For these reasons, it is a very useful method for routine analysis. 相似文献