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101.
Shultz CS Dreher SD Ikemoto N Williams JM Grabowski EJ Krska SW Sun Y Dormer PG Dimichele L 《Organic letters》2005,7(16):3405-3408
A novel and highly enantioselective Ru-catalyzed hydrogenation of N-sulfonylated-alpha-dehydroamino acids has been discovered and demonstrated in the synthesis of an anthrax lethal factor inhibitor (LFI). Herein, this methodology is used to prepare N-sulfonylated amino acids in up to 98% ee. This unprecedented hydrogenation uses a chiral Ru catalyst rather than Rh as typical for acylated dehydroamino acids and esters, and this work reports the first asymmetric hydrogenation of a tetrasubstituted dehydroamino acid derivative using a Ru catalyst. [reaction: see text] 相似文献
102.
Brustolon M Barbon A Bortolus M Maniero AL Sozzani P Comotti A Simonutti R 《Journal of the American Chemical Society》2004,126(47):15512-15519
Two oligothiophenes, 4,4'-dipentoxy-2,2'-dithiophene and 4,4"-dipentoxy-2,2':5',2":5",2' '-tetrathiophene, have been included in the nanochannels of the autoassembling host TPP (tris-o-phenylenedioxycyclotriphosphazene). The effect of the confinement on the structure and properties of the two dyes, as conformational arrangements, dynamics, and photophysical behavior, was addressed by the combination of high spinning speed solid-state NMR and time-resolved EPR spectroscopy. We compared the conformations of the dyes in their ground and photoexcited triplet states and described in detail the dynamics of the supramolecular adducts from 4 K to room temperature. Above 200 K surprisingly fast spinning rates of the dithiophene core were discovered, while the side chains show far slower reorientation motion, being in bulky gauche-rich conformations. These lateral plugs keep the planar core as appended in the space like a nanoscale gyroscope, allowing a reorientation in the motion regime of liquids and a long triplet lifetime at unusually high temperature. The nuclear magnetic properties of the guest dyes are also largely affected by the aromatic rings of the neighboring host, imparting an impressive magnetic susceptibility effect (2 ppm proton shift). The high mobility is due to the formation of a nanocage in a channel where aliphatic and aromatic functions isolate the thiophene moieties. Instead, two conformers of the tetrathiophene twisted on the central bond are stabilized by interaction with the host. They interconvert fast enough to be averaged in the NMR time scale. 相似文献
103.
Inorganic anion retention on a porous graphitic carbon (PGC) stationary phase is investigated by electrochemically modulated liquid chromatography (EMLC). Through various combinations of the potential applied (Eapp) to the PGC packing and/or changes in the composition (sodium salts of tetrafluoroborate, sulfate, and fluoride) and concentration (10, 25, and 50 mM) of an aqueous mobile phase, conditions for the separation of two different inorganic anion mixtures (iodate, bromide, nitrite, and nitrate or iodate, bromate, and chlorate) are developed. Results show that retention was affected by both variables, with the analyte retention factor, k', changing in a few cases by as much as a factor of ca. six. Moreover, plots of In k' are linearly dependent on both Eapp and In [SE], where [SE] is the supporting electrolyte concentration. Based on these findings, insights into the retention mechanism are briefly discussed by drawing on the theory for ion exchange chromatography. 相似文献
104.
Application of adaptive matched field processing to the problem of detecting quiet targets in shallow water is complicated by source motion, both the motion of the target and the motion of discrete interferers. Target motion causes spreading of the target peak, thereby reducing output signal power. Interferer motion increases the dimensionality of the interference subspace, reducing adaptive interference suppression. This paper presents three techniques that mitigate source motion problems in adaptive matched field processing. The first involves rank reduction, which enables adaptive weight computation over short observation intervals where motion effects are less pronounced. The other two techniques specifically compensate for source motion. Explicit target motion compensation reduces target motion mismatch by focusing snapshots according to a target velocity hypothesis. And time-varying interference filtering places time-varying nulls on moving interferers not otherwise suppressed by adaptive weights. The three techniques are applied to volumetric array data from the Santa Barbara Channel Experiment and are shown to improve output signal-to-background-plus-noise ratio by more than 3 dB over the standard minimum-variance, distortionless response adaptive beam-former. Application of the techniques in some cases proves to be the difference between detecting and not detecting the target. 相似文献
105.
106.
Lowe LB Brewer SH Krämer S Fuierer RR Qian G Agbasi-Porter CO Moses S Franzen S Feldheim DL 《Journal of the American Chemical Society》2003,125(47):14258-14259
Laser-induced temperature jumps (LITJs) at gold nanoparticle-coated indium tin oxide (ITO) electrodes in contact with electrolyte solutions have been measured using temperature-sensitive redox probes and an infrared charge-coupled device. Upon irradiation with 532 nm light, interfacial temperature changes of ca. 20 degrees C were recorded for particle coverages of ca. 1 x 1010 cm-2. In the presence of a redox molecule, LITJ yields open-circuit photovoltages and photocurrents that are proportional to the number of particles on the surface. When ssDNA was used to chemisorb nanoparticles to the ITO surface, solution concentrations as low as 100 fM of target ssDNA-modified nanoparticles could be detected at the electrode surface. 相似文献
107.
McCarroll AJ Sandham DA Titcomb LR Lewis AK Cloke FG Davies BP de Santana AP Hiller W Caddick S 《Molecular diversity》2003,7(2-4):115-123
The palladium catalysed coupling of aryl chlorides and amines can be readily achieved with short reaction times when carried out at high temperatures under thermal or microwave conditions. These coupling protocols are successful using two co-ordinate palladium-N-heterocyclic carbene complexes, or imidazolium salt protocols. 相似文献
108.
Chung P Ajitanand NN Alexander JM Anderson M Best D Brady FP Case T Caskey W Cebra D Chance JL Cole B Crowe K Das A Draper JE Gilkes ML Gushue S Heffner M Hirsch AS Hjort EL Huo L Justice M Kaplan M Keane D Kintner JC Klay J Krofcheck D Lacey RA Lauret J Lisa MA Liu H Liu YM McGrath R Milosevich Z Odyniec G Olson DL Panitkin SY Pinkenburg C Porile NT Rai G Ritter HG Romero JL Scharenberg R Schroeder L Srivastava B Stone NT Symons TJ Wienold T Witt R Whitfield J Wood L Zhang WN;E Collaboration 《Physical review letters》2001,86(12):2533-2536
Directed flow measurements for Lambda hyperons are presented and compared to those for protons produced in the same Au+Au collisions (2A, 4A, and 6A GeV; b<5-6 fm). The measurements indicate that Lambda hyperons flow consistently in the same direction but with smaller magnitudes. A strong positive flow [for Lambdas] has been predicted in calculations which include the influence of the Lambda-nucleon potential. The experimental flow ratio Lambda/p is in qualitative agreement with expectations (approximately 2/3) from the quark counting rule at 2A GeV but is found to decrease with increasing beam energy. 相似文献
109.
Gary Chartrand Lisa Hansen Reza Rashidi Naveed Sherwani 《Czechoslovak Mathematical Journal》2000,50(1):35-46
A graph G is stratified if its vertex set is partitioned into classes, called strata. If there are k strata, then G is k-stratified. These graphs were introduced to study problems in VLSI design. The strata in a stratified graph are also referred to as color classes. For a color X in a stratified graph G, the X-eccentricity e
X(v) of a vertex v of G is the distance between v and an X-colored vertex furthest from v. The minimum X-eccentricity among the vertices of G is the X-radius radX
G of G and the maximum X-eccentricity is the X-diameter diamX
G. It is shown that for every three positive integers a, b and k with ab, there exist a k-stratified graph G with radX
G = a and diamX
G = b. The number s
X denotes the minimum X-eccetricity among the X-colored vertices of G. It is shown that for every integer t with radX
G t diamX
G, there exist at least one vertex v with e
X(v) = t; while if radX
G t s
X, then there are at least two such vertices. The X-center C
X(G) is the subgraph induced by those vertices v with e
X(v) = radX
G and the X-periphery P
X (G) is the subgraph induced by those vertices v with e
X(G) = diamX
G. It is shown that for k-stratified graphs H
1, H
2,..., H
k with colors X
1, X
2,..., X
k and a positive integer n, there exists a k-stratified graph G such that C
X
i(G) H
i (1 ; i
; k1) and
for i j. Those k-stratified graphs that are peripheries of k-stratified graphs are characterized. Other distance-related topics in stratified graphs are also discussed. 相似文献
110.
Wen Zhang Jing Jiang Chunhua Qin Lisa M. Pérez Alan R. Parrish Stephen H. Safe 《Supramolecular chemistry》2013,25(7-8):607-616
Three criteria are evaluated to assess the potential of a dendrimer based on triazines, 1, for use as a vehicle for drug delivery. These criteria are: (1) its ability to solubilize small hydrophobic guests as measured spectrophotometrically; (2) its ability to deliver a drug in vitro as evaluated using a gene reporter assay; and (3) its in vivo toxicity in mice as determined by autopsy and screens of liver and kidney function. Vehicle 1 solubilizes pyrene to a similar extent to dendrimers based on poly(arylether)s, 4, encapsulating approximately 0.2 molecules of pyrene per dendrimer. This activity is approximately 10-fold greater than that of the more polar poly(propyleneimine) and poly(amidoamine) dendrimers, 2 and 3. Gas-phase computational models reveal that both 1 and 4 have cores that are accessible to solvent, suggesting that these dendrimers can occupy much greater volumes than 2 and 3 whose cores are confined toward the interior of the structure. Electrostatic potential maps can be used to rationalize differences in solubilization between 1 and 4. Precipitation results from mixing cationic 1 with the anionic indomethacin, but not with methotrexate, suggesting that the composition of the drug may dictate the scope of delivery applications. Dendrimer 1 solubilizes 10-hydroxycamptothecin and a novel bisindolemethane; approximately four and five molecules of drug per dendrimer are solubilized, respectively. In cell-culture experiments using a luciferase reporter gene assay, the dendrimer:bisindolemethane conjugate shows comparable activity to the bisindolemethane delivered in aqueous DMSO, suggesting that the dendrimer does not preclude delivery of the molecule to an intracellular target. Preliminary toxicology studies of 1 in mice show that this molecule has no adverse toxicity to the kidneys or the liver in single doses delivered intraperitoneally up to 10?mg/kg. 相似文献