全文获取类型
收费全文 | 400篇 |
免费 | 9篇 |
国内免费 | 4篇 |
专业分类
化学 | 261篇 |
晶体学 | 3篇 |
力学 | 7篇 |
数学 | 24篇 |
物理学 | 118篇 |
出版年
2023年 | 3篇 |
2022年 | 2篇 |
2021年 | 7篇 |
2020年 | 5篇 |
2019年 | 4篇 |
2017年 | 5篇 |
2015年 | 5篇 |
2014年 | 8篇 |
2013年 | 15篇 |
2012年 | 12篇 |
2011年 | 23篇 |
2010年 | 15篇 |
2009年 | 10篇 |
2008年 | 14篇 |
2007年 | 22篇 |
2006年 | 19篇 |
2005年 | 20篇 |
2004年 | 12篇 |
2003年 | 14篇 |
2002年 | 17篇 |
2001年 | 12篇 |
2000年 | 15篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 13篇 |
1994年 | 4篇 |
1993年 | 9篇 |
1992年 | 10篇 |
1991年 | 8篇 |
1990年 | 10篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 7篇 |
1975年 | 5篇 |
1968年 | 2篇 |
1966年 | 2篇 |
1894年 | 2篇 |
1879年 | 1篇 |
排序方式: 共有413条查询结果,搜索用时 31 毫秒
71.
Remarkably strong binding of the new [5]polynorbornane based host to the terephthalate dianion is based on size complementarity of the preorganised binding cleft with the rigid dicarboxylate guest. 相似文献
72.
Burrows AD Dodds D Kirk AS Lowe JP Mahon MF Warren JE Whittlesey MK 《Dalton transactions (Cambridge, England : 2003)》2007,(5):570-580
Facile substitution reactions of the two water ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2)P{CH2N(CH2P(CH2OH)2)CH2}2P(CH2OH)}(H2O)2](SO4) (abbreviated to [Fe(L1)(H2O)2](SO4), 1) take place upon addition of Cl-, NCS-, N3(-), CO3(2-) and CO to give [Fe(L1)X2] (2, X = Cl; 4, X = NCS; 5, X=N3), [Fe(L1)(kappa2-O(2)CO)], 6 and [Fe(L1)(CO)2](SO4), 7. The unsymmetrical mono-substituted intermediates [Fe(L1)(H2O)(CO)](SO(4)) and [Fe(L(1))(CO)(kappa(1)-OSO(3))] (8/9) have been identified spectroscopically en-route to 7. Treatment of 1 with acetic anhydride affords the acylated derivative [Fe{(AcOCH2)P{CH2N(CH2P(CH2OAc)2)CH2}2P(CH2OAc)}(kappa2-O(2)SO2)] (abbreviated to [Fe(L2)(kappa2-O(2)SO2)], 10), which has increased solubility over 1 in both organic solvents and water. Treatment of 1 with glycine does not lead to functionalisation of L1, but substitution of the aqua ligands occurs to form [Fe(L(1))(NH(2)CH(2)CO(2)-kappa(2)N,O)](HSO(4)), 11. Compound 10 reacts with chloride to form [Fe(L(2))Cl(2)] 12, and 12 reacts with CO in the presence of NaBPh4 to form [Fe(L2)Cl(CO)](BPh4) 13b. Both of the chlorides in 12 are substituted on reaction with NCS- and N3(-) to form [Fe(L2)(NCS)2] 14 and [Fe(L2)(N3)2] 15, respectively. Complexes 2.H2O, 4.2H2O, 5.0.812H2O, 6.1.7H2O, 7.H2O, 10.1.3CH3C(O)CH3, 12 and 15.0.5H2O have all been crystallographically characterised. 相似文献
73.
Tucker DJ Southwell IA Lowe RF Russell MF Brereton IM 《Magnetic resonance in chemistry : MRC》2007,45(12):1081-1083
Lepidozenal and isobicyclogermacrenal were isolated from the leaves of Eucalyptus dawsonii and a complete assignment of their 1H and 13C NMR spectra was carried out using 2D NMR methods. 相似文献
74.
A Gd(III) complex bearing pendant acetoxymethyl esters is activated on exposure to porcine liver esterase; the 84% increase in relaxivity is a result of suppression of HCO(3)(-)/CO(3)(2-) binding by the resulting negative charge. 相似文献
75.
A novel algorithm for modeling the influence of the host lattice flexibility in molecular dynamics simulations is extended to chain-like molecules and mixtures. This technique, based on a Lowe-Andersen thermostat, maintains the advantages of both simplicity and efficiency. The same diffusivities and other properties of the flexible framework system are reproduced. Advantageously, the computationally demanding flexible host lattice simulations can be avoided. Using this methodology we study the influence of flexibility on diffusion of n-alkanes inside single-walled carbon nanotubes. Furthermore, results are shown for diffusion of two mixtures (methane-helium and ethane-butane). Using these results we investigate the accuracy of theories describing diffusion in the Knudsen regime. For the dynamics in carbon nanotubes the Knudsen diffusivities are much too low. The Smoluchowski model gives better results. Interestingly, the extended Smoluchowski model can reproduce our simulation results obtained with a rigid host lattice. We modify this model to also treat collisions with a flexible interface correctly. As the tangential momentum accommodation coefficient is needed for the theoretical models, we introduce a simple concept to calculate it. 相似文献
76.
Miles A. Dunbar Shawna L. Balof Lawrence J. LaBeaud Bing Yu Dr. Andrew B. Lowe Dr. Edward J. Valente Dr. Hans‐Jörg Schanz Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(45):12435-12446
The effect of the addition of H3PO4 on the ROMP activity of cyclooctene (COE) with first‐ [Cl2(PCy3)2Ru?CHPh] and second‐generation [(H2IMes)Cl2(PCy3)Ru?CHPh] Grubbs’ catalysts 1 and 4 (Cy=cyclohexyl, Ph=phenyl, Mes=2,4,6‐trimethylphenyl (mesityl)), their inhibited mixtures with 1‐methylimidazole (MIM), as well as their isolated bis‐N,N′‐dimethylaminopyridine (DMAP) derivatives [Cl2(PCy3)(DMAP)2Ru?CHPh)] ( 5 b ) and [Cl2(H2IMes)(DMAP)2Ru?CHPh] ( 7 b ) (DMAP=dimethylaminopyridine), a novel catalyst, has been investigated. The studies include the determination of their initiation rates, as well as a determination of the molecular weights and molecular weight distributions of the polymers obtained with these catalysts and catalyst mixtures from the exo‐7‐oxanorbornene derivative 11 . The structure of catalyst 7 b was confirmed by means of X‐ray diffraction. All N‐donor‐bearing catalysts or N‐donor‐containing catalyst mixtures not only exhibited elevated activity in the presence of acid, but also increased initiation rates. Using the reversible inhibition/activation protocol with MIM and H3PO4 enabled us to conduct controlled ROMP with catalyst 4 producing the isolated exo‐7‐oxanorbornene‐based polymer 12 with predetermined molecular weights and narrow molecular weight distributions. This effect was based on fast and efficient catalyst initiation in contrast to the parent catalyst 4 . Hexacoordinate complex 5 b also experienced a dramatic increase in initiation rates upon acid‐addition and the ROMP reactions became well‐controlled in contrast to the acid‐free reaction. In contrast, complex 7 b performs well‐controlled ROMP in the absence of acid, whereas the polymerization of the same monomer becomes less controlled in the presence of H3PO4. The closer evaluation of catalysts 5 b and 7 b demonstrated that their initiation rates exhibit a linear dependency on the substrate concentration in contrast to catalysts 1 and 4 . As a consequence, their initiation rates are determined by an associative step, not a dissociative step as seen for catalysts 1 and 4 . A feasible associative metathesis initiation mechanism is proposed. 相似文献
77.
Troy A. Lowe Gordon G. Wallace Aaron K. Neufeld 《Journal of Solid State Electrochemistry》2009,13(4):619-631
Electrochemical polarisation experiments have shown that anodic dissolution processes on Al–40% Zn alloys are significantly
enhanced in chloride compared to sulfate-based electrolytes. The aluminium content of the alloys allowed passive behaviour
to be observed in sulfate electrolyte even in the presence of zinc-rich precipitates on the surface. Electrolyte pH affected
cathodic processes, which was attributed to the rate of proton reduction and the passivity of the surface. Monitoring the
OCP of the alloy band during polarisation of neighbouring zinc electrodes in band microelectrode (BME) arrays showed that
generation of alkaline pH at the zinc electrodes affected the OCP of the alloy when the inter-electrode spacing was 10, 50,
and 200 μm. Where elements of a BME array were close enough to interact via mass transport, the overall galvanic behaviour
of the cell was found to be anodic or cathodic, whereas the alloy was consistently cathodic with respect to zinc in galvanic
cells at larger separations.
Dedicated to the 80th birthday of Keith B. Oldham. 相似文献
78.
Yang X Lee MC Sartain F Pan X Lowe CR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(33):8491-8497
In this study, 2-acrylamidophenylboronate (2-APB) was synthesised and its ability to bind with glucose was investigated both in solution and when integrated into a holographic sensor. Multiple forms of 2-APB, resulting from the neighbouring effect of the amido group with the boronic acid through an intramolecular B--O-coordinated interaction, were shown to exist in solution by using multinuclear NMR spectrometry. It was found that 2-APB predominantly adopts a zwitterionic tetrahedral form at physiological pH values. The complex formation of 2-APB with glucose and lactate was investigated in DMSO; 2-APB favours binding with glucose rather than lactate and generates a five-membered-ring complex. Furthermore, a 2-APB-based holographic sensor displayed a significant response to glucose with little interference from lactate, and with no dependence on pH in the physiological pH range. These features suggest that the new ligand 2-APB is a potential candidate for the development of glucose-selective sensors. 相似文献
79.
Gao J Lowe MA Conte S Burkhardt SE Abruña HD 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8521-8526
Organosulfur compounds with multiple thiol groups are promising for high gravimetric energy density electrochemical energy storage. We have synthesized a poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT)/poly(3,4-ethylenedioxythiophene) (PEDOT) composite cathode for lithium-ion batteries with a new method and investigated its electrochemical behavior by charge/discharge cycles and cyclic voltammetry (CV) in an ether-based electrolyte. Based on a comparison of the electrochemical performance with a carbonate-based electrolyte, we found a much higher discharge capacity, but also a very attractive cycling performance of PDMcT by using a tetra(ethylene glycol) dimethyl ether (TEGDME)-based electrolyte. The first discharge capacity of the as-synthesized PDMcT/PEDOT composite approached 210 mAh g(-1) in the TEGDME-based electrolyte. CV results clearly show that the redox reactions of PDMcT are highly reversible in this TEGDME-based electrolyte. The reversible capacity remained around 120 mAh g(-1) after 20 charge/discharge cycles. With improved cycling performance and very low cost, PDMcT could become a very promising cathode material when combined with a TEGDME-based electrolyte. The poor capacity in the carbonate-based electrolyte is a consequence of the irreversible reaction of the DMcT monomer and dimer with the solvent, emphasizing the importance of electrolyte chemistry when studying molecular-based battery materials. 相似文献
80.
Willcocks AM Robinson TP Roche C Pugh T Richards SP Kingsley AJ Lowe JP Johnson AL 《Inorganic chemistry》2012,51(1):246-257
A series of multinuclear Copper(I) guanidinate complexes have been synthesized in a succession of reactions between CuCl and the lithium guanidinate systems Li{L} (L = Me(2)NC((i)PrN)(2) (1a), Me(2)NC(CyN)(2) (1b), Me(2)NC((t)BuN)(2)(1c), and Me(2)NC(DipN)(2) (2d) ((i)Pr = iso-propyl, Cy = cyclohexyl, (t)Bu = tert-butyl, and Dip = 2,6-disopropylphenyl) made in situ, and structurally characterized. The di-copper guanidinates systems with the general formula [Cu(2){L}(2)] (L = {Me(2)NC((i)PrN)(2)} (2a), {Me(2)NC(CyN)(2)} (2b), and {Me(2)NC(DipN)(2)} (2d) differed significantly from related amidinate complexes because of a large torsion of the dimer ring, which in turn is a result of transannular repulsion between adjacent guanidinate substituents. Attempts to synthesis the tert-butyl derivative [Cu(2){Me(2)NC((t)BuN)(2)}(2)] result in the separate formation and isolation of the tri-copper complexes [Cu(3){Me(2)NC((t)BuN)(2)}(2)(μ-NMe(2))] (3c) and [Cu(3){Me(2)NC((t)BuN)(2)}(2)(μ-Cl)] (4c), both of which have been unambiguously characterized by single crystal X-ray diffraction. Closer inspection of the solution state behavior of the lithium salt 1c reveals a previously unobserved equilibrium between 1c and its starting materials, LiNMe(2) and N,N'-di-tert-butyl-carbodiimide, for which activation enthalpy and entropy values of ΔH(?) = 48.2 ± 18 kJ mol(-1) and ΔS(?) = 70.6 ± 6 J/K mol have been calculated using 1D-EXSY NMR spectroscopy to establish temperature dependent rates of exchange between the species in solution. The molecular structures of the lithium complexes 1c and 1d have also been determined and shown to form tetrameric and dimeric complexes respectively held together by Li-N and agostic Li···H-C interactions. The thermal chemistry of the copper complexes have also been assessed by thermogravimetric analysis. 相似文献