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排序方式: 共有265条查询结果,搜索用时 15 毫秒
101.
Exceedingly Facile PhX Activation (X=Cl,Br, I) with Ruthenium(II): Arresting Kinetics,Autocatalysis, and Mechanisms 下载免费PDF全文
Dr. Fedor M. Miloserdov Dr. David McKay Dr. Bianca K. Muñoz Dr. Hamidreza Samouei Prof. Stuart A. Macgregor Prof. Vladimir V. Grushin 《Angewandte Chemie (International ed. in English)》2015,54(29):8466-8470
[(Ph3P)3Ru(L)(H)2] (where L=H2 ( 1 ) in the presence of styrene, Ph3P ( 3 ), and N2 ( 4 )) cleave the Ph? X bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] ( 2 ) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4 . The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2 , originating from the initial PhI activation with 3 , is roughly as reactive toward PhI as 3 itself; and 2) the Ph? I bond cleavage with the just‐produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still‐present 3 to recover 2 . Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2‐PhI intermediate, and Ph? I oxidative addition. 相似文献
102.
Kennedy DC McKay CS Tay LL Rouleau Y Pezacki JP 《Chemical communications (Cambridge, England)》2011,47(11):3156-3158
Silver nanoparticles bonded to terminal alkynes form stable particles in aqueous solution, produce strong SERS signals for molecular imaging that arise from the carbon-metal bond, and expand the scope of molecules that can be used to stably functionalize plasmonic particles for mammalian cell imaging applications. β-Lactams represent a class of biologically important molecules that can be adapted to SERS studies in this manner. 相似文献
103.
Investigations of Scope and Mechanism of Nickel‐Catalyzed Transformations of Glycosyl Trichloroacetimidates to Glycosyl Trichloroacetamides and Subsequent,Atom‐Economical,One‐Step Conversion to α‐Urea‐Glycosides 下载免费PDF全文
Dr. Matthew J. McKay Nathaniel H. Park Prof. Dr. Hien M. Nguyen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(28):8691-8701
The development and mechanistic investigation of a highly stereoselective methodology for preparing α‐linked‐urea neo‐glycoconjugates and pseudo‐oligosaccharides is described. This two‐step procedure begins with the selective nickel‐catalyzed conversion of glycosyl trichloroacetimidates to the corresponding α‐trichloroacetamides. The α‐selective nature of the conversion is controlled with a cationic nickel(II) catalyst, [Ni(dppe)(OTf)2] (dppe=1,2‐bis(diphenylphosphino)ethane, OTf=triflate). Mechanistic studies have identified the coordination of the nickel catalyst with the equatorial C2‐ether functionality of the α‐glycosyl trichloroacetimidate to be paramount for achieving an α‐stereoselective transformation. A cross‐over experiment has indicated that the reaction does not proceed in an exclusively intramolecular fashion. The second step in this sequence is the direct conversion of α‐glycosyl trichloroacetamide products into the corresponding α‐urea glycosides by reacting them with a wide variety of amine nucleophiles in presence of cesium carbonate. Only α‐urea‐product formation is observed, as the reaction proceeds with complete retention of stereochemical integrity at the anomeric C?N bond. 相似文献
104.
A McAnaw M Elena Lopez G Scott D Ellis D McKay GM Rosair AJ Welch 《Dalton transactions (Cambridge, England : 2003)》2012,41(36):10957-10969
Reduction of the tethered carborane 1,2-μ-(CH(2)SiMe(2)CH(2))-1,2-closo-C(2)B(10)H(10) followed by metallation with {CpCo} or {(p-cymene)Ru} fragments affords both C,C'-dimethyl 4,1,2-MC(2)B(10) and 4,1,6-MC(2)B(10) species. DFT calculations indicate that the barriers to isomerisation of both 4-Cp-4,1,2-closo-CoC(2)B(10)H(12) and 4-(η-C(6)H(6))-4,1,2-closo-RuC(2)B(10)H(12) to their respective 4,1,6-isomers are too high for this to be the origin of the unexpected formation of 4,1,6-MC(2)B(10) products (in marked contrast to the related isomerisation of 1,2-closo-C(2)B(11)H(13) to 1,6-closo-C(2)B(11)H(13)), and, indeed, the 4,1,2-species are recovered unchanged from refluxing toluene. Equally, the DFT-calculated profile for the isomerisation of [7,8-nido-C(2)B(10)H(12)](2-) to [7,9-nido-C(2)B(10)H(12)](2-) suggests that the unexpected formation of 4,1,6-metallacarboranes is unlikely to result from isomerisation of a reduced (nido) carborane following desilylation. Instead, the source of the 4,1,6-MC(2)B(10) compounds is traced to desilylation of 1,2-μ-(CH(2)SiMe(2)CH(2))-1,2-closo-C(2)B(10)H(10) by Li or Na prior to reduction. The supraicosahedral metallacarboranes 1,8-Me(2)-4-Cp-4,1,8-closo-CoC(2)B(10)H(10), 1,12-Me(2)-4-Cp-4,1,12-closo-CoC(2)B(10)H(10) and 1,12-Me(2)-4-(p-cymene)-4,1,12-closo-RuC(2)B(10)H(10) are also reported with all new species characterised both spectroscopically and crystallographically. 相似文献
105.
Single and multicomponent equilibrium studies for the adsorption of acidic dyes on carbon from effluents 总被引:2,自引:0,他引:2
Choy KK Porter JF McKay G 《Langmuir : the ACS journal of surfaces and colloids》2004,20(22):9646-9656
The ability of activated carbon to adsorb three acidic dyes, namely, Acid Blue 80 (AB80), Acid Red 114 (AR114), and Acid Yellow (AY117), from wastewater has been studied at 20 degrees C. The three single-component systems and the three binary equilibrium systems have been measured experimentally. The three single-component isotherms were analyzed using the Langmuir, Freundlich, Redlich-Peterson, and Sips equations. The Redlich-Peterson equation gave the lowest errors using the sum of the squares of the errors closely followed by the Sips and Langmuir equations; the Freundlich fits were significantly worse. The three bisolute experimental equilibrium sets of data were analyzed by incorporating the previous four single-component isotherm equations into the ideal adsorbed solution theory (IAST). The solution methods for each of the four isotherm equations are presented in the paper, and the predicted results for the three bisolute systems, using the four isotherm equations, are compared. For the three bisolute systems (AB80 + AR114, AB80 + AY117, and AR114 + AY117), the Redlich-Peterson isotherm gives the best correlation with the experimental isotherm data. 相似文献
106.
Conditions are found under which the expected number of automorphisms of a large random labelled graph with a given degree
sequence is close to 1. These conditions involve the probability that such a graph has a given subgraph. One implication is
that the probability that a random unlabelledk-regular simple graph onn vertices has only the trivial group of automorphisms is asymptotic to 1 asn → ∞ with 3≦k=O(n
1/2−c). In combination with previously known results, this produces an asymptotic formula for the number of unlabelledk-regular simple graphs onn vertices, as well as various asymptotic results on the probable connectivity and girth of such graphs. Corresponding results
for graphs with more arbitrary degree sequences are obtained. The main results apply equally well to graphs in which multiple
edges and loops are permitted, and also to bicoloured graphs.
Research of the second author supported by U. S. National Science Foundation Grant MCS-8101555, and by the Australian Department
of Science and Technology under the Queen Elizabeth II Fellowships Scheme. Current address: Mathematics Department, University
of Auckland, Auckland, New Zealand. 相似文献
107.
DC magnetization, neutron depolarization and neutron diffraction (with both polarized and unpolarized neutrons) measurements
have been reported for the Co1.1−x
Zn
x
Ge0.1Fe1.2O1 spinels with x=0.5, 0.6 and 0.7. Neutron depolarization and neutron diffraction measurements confirm the presence of a long range ferrimagnetic
ordering of the local canted spins in these ferrite samples. The observed features of low field magnetization have been explained
under the framework of thermally activated domain wall movement of ferrimagnetic arrangement of local canted spins. An important
role of magnetic anisotropy (due to the presence of Co2+ ions) in establishing the magnetic ordering and domain kinetics in these ferrites has been observed. 相似文献
108.
G. McKay 《Continuum Mechanics and Thermodynamics》1998,10(4):241-251
The stability of a fluid saturated, horizontal porous layer in the presence of a solute concentration gradient and time-periodic
thermal gradient is examined. The modulated gradient is the result of a sinusoidal upper surface temperature which models
the effect of variable solar radiation heating of the layer. Darcy's law and the Boussinesq approximation are employed, and
we assume an equation of state linear in temperature and concentration. A linear stability analysis is carried out to obtain
predictions for the onset of convection and critical wavenumbers for the system. The critical conditions are obtained via
the Galerkin method and Floquet theory. The effects of variable concentration gradient, temperature modulation amplitude and
frequency are examined, and compared with the results obtained analytically from the corresponding unmodulated problem. It
is shown that instabilities can occur as convective motions which are synchronous or subharmonic with the surface heating,
or can be identified via complex conjugate Floquet exponents. The neutral stability curves at the transitions between instabilities
are found to be bimodal when the temperature is time-periodic, and are characterized by jumps in the critical wavenumbers.
Received February 5, 1998 相似文献
109.
Archiv der Mathematik - 相似文献
110.
Darshan C Kundaliya Reeta Vij AA Tulapurkar U Vaidya R Pinto RG Kulkarni 《Pramana》2002,58(5-6):1041-1044
Electrical resistance (R) measurements of a bulk La0.33Nd0.33Ca0.33MnO3 perovskite in magnetic fields up to 40 kOe have revealed anomalous temperature hysteretic effects both in 0 Oe and 20 kOe
magnetic fields. The sharp peak observed in the R vs. T plot indicates the occurrence of metal-to-insulator (M-I) transition at a temperature of T
MI=110 K and 140 K, for cooling and warming paths, respectively. An applied magnetic field of 20 kOe reduces the resistance
and shifts T
MI to 160 K and 185 K for cooling and warming, respectively. We have observed a much higher resistance in the cooling path than
in the warming path leading to the hysteretic resistance ratio (R
cool/R
warm) of 200 at 110 K and 1.8 at 160 K for 0 Oe and 20 kOe, respectively. Record values of colossal magnetoresistance (CMR) have
been achieved. The CMR value reaches nearly 99% in the temperature ranges of 90 K to 140 K and 90 K to 170 K for 20 kOe and
40 kOe magnetic fields in the cooling mode, respectively. The observed unusual behavior is attributed to the co-existence
of La-rich and Nd-rich domains assumed to be distributed randomly in the compound. 相似文献