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951.
Burdzinski G Réhault J Wang J Platz MS 《The journal of physical chemistry. A》2008,112(41):10108-10112
The photochemistry of Diazo Meldrum's acid (DM) was investigated by fs time-resolved UV-vis and IR spectroscopic methods. UV (266 nm) excitation of DM pumps the molecule to the S 5 and S 7 excited states. After fast internal conversion (IC), the S 2 state is formed, which will undergo Wolff rearrangement to form vibrationally excited ketene, which relaxes in 9 ps. The S 2 state will also relax to the S 1 state, which isomerizes to diazirine, fragments to form carbene, and relaxes further to the ground state of DM. The singlet carbene absorbs at 305 nm, is formed within 300 fs of the laser pulse, and has a lifetime of 2.3 ps in acetonitrile. The lifetime of DM in the S 2 and S 1 states is less than 300 fs. The quantum efficiency of DM decomposition is approximately 50% in chloroform with 266 nm excitation. 相似文献
952.
Readily prepared beta-silyl substituted crotylzinc reagents undergo highly selective allylation of carbonyl compounds leading to syn-homoallylic alcohols. 相似文献
953.
Eveline Vriens Dr. Dries De Ruysscher Dr. Angus N. M. Weir Dr. Sofie Dekimpe Dr. Gert Steurs Ahmed Shemy Leentje Persoons Dr. Ana Rita Santos Dr. Christopher Williams Prof. Dirk Daelemans Prof. Matthew P. Crump Prof. Arnout Voet Prof. Wim De Borggraeve Prof. Eveline Lescrinier Prof. Joleen Masschelein 《Angewandte Chemie (International ed. in English)》2023,62(34):e202304476
Bacterial trans-acyltransferase polyketide synthases (trans-AT PKSs) are modular megaenzymes that employ unusual catalytic domains to assemble diverse bioactive natural products. One such PKS is responsible for the biosynthesis of the oximidine anticancer agents, oxime-substituted benzolactone enamides that inhibit vacuolar H+-ATPases. Here, we describe the identification of the oximidine gene cluster in Pseudomonas baetica and the characterization of four novel oximidine variants, including a structurally simpler intermediate that retains potent anticancer activity. Using a combination of in vivo, in vitro and computational approaches, we experimentally elucidate the oximidine biosynthetic pathway and reveal an unprecedented mechanism for O-methyloxime formation. We show that this process involves a specialized monooxygenase and methyltransferase domain and provide insight into their activity, mechanism and specificity. Our findings expand the catalytic capabilities of trans-AT PKSs and identify potential strategies for the production of novel oximidine analogues. 相似文献
954.
Hanna Morales Hernández Qiwei Sun Matthew Rosati Prof. Rebecca L. M. Gieseking Prof. Christopher J. Johnson 《Angewandte Chemie (International ed. in English)》2023,62(35):e202307723
The role of hydrogen atoms as surface ligands on metal nanoclusters is of profound importance but remains difficult to directly study. While hydrogen atoms often appear to be incorporated formally as hydrides, evidence suggests that they donate electrons to the cluster's delocalized superatomic orbitals and may consequently behave as acidic protons that play key roles in synthetic or catalytic mechanisms. Here we directly test this assertion for the prototypical Au9(PPh3)8H2+ nanocluster, formed by addition of a hydride to the well-characterized Au9(PPh3)83+. Using gas-phase infrared spectroscopy, we were able to unambiguously isolate Au9(PPh3)8H2+ and Au9(PPh3)8D2+, revealing an Au−H stretching mode at 1528 cm−1 that shifts to 1038 cm−1 upon deuteration. This shift is greater than the maximum expected for a typical harmonic potential, suggesting a potential governing cluster-H bonding that has some square-well character consistent with the hydrogen nucleus behaving as a metal atom in the cluster core. Complexing this cluster with very weak bases reveals a redshift of 37 cm−1 in the Au−H vibration, consistent with those typically seen for moderately acidic groups in gas phase molecules and providing an estimate of the acidity of Au9(PPh3)8H2+, at least with regard to its surface reactivity. 相似文献
955.
Schabas G Wang CW Oskooei A Yusuf H Moffitt MG Sinton D 《Langmuir : the ACS journal of surfaces and colloids》2008,24(19):10596-10603
The controlled self-assembly of polymer-stabilized quantum dots (QDs) into mesoscale aqueous spherical assemblies termed quantum dot compound micelles (QDCMs) using a two-phase gas-segmented microfluidic reactor is described. Self-assembly is initiated by the fast mixing of water (approximately 1 s) with a blend solution of polystyrene-coated QDs and amphiphilic polystyrene-block-poly(acrylic acid) stabilizing chains via chaotic advection within liquid plugs moving through a sinusoidal channel. Subsequent recirculating flow within a post-formation channel subjects the dynamic QDCMs to shear-induced processing, controlled via the flow rate and channel length, before a final quench into pure water. During processing, larger QDCMs within the initial population undergo breakup into smaller particles, resulting in smaller mean particle sizes, smaller relative standard deviations, and more skewed distribution shapes, as the overall shear exposure is increased. For these cases, shear-induced size reduction is sufficient to dominate surface tension-driven growth. 相似文献
956.
Jouzi M Kerby MB Tripathi A Xu J 《Langmuir : the ACS journal of surfaces and colloids》2008,24(19):10786-10790
We describe a new method for measuring the activity of protein in miniscule quantities using a carbon nanotube nanoneedle. The unique features of this new method are (a) the immobilization of a few molecules; (b) subsequent translocation and isolation of them near the tip of a position-actuated nanoneedle; and (c) a fixed, defined, and unhindered molecular position to allow rapid real-time sensing and monitoring. The kinetic bioactivity of immobilized alkaline phosphatase (AP) molecules was measured as test model. Results show no decrease in enzymatic activity compared to that of the solution-phase enzyme reaction, suggesting that the immobilization provided unhindered access for ligand binding and minimal conformational modulation caused by undesired surface interactions. 相似文献
957.
Schneider C Jusufi A Farina R Li F Pincus P Tirrell M Ballauff M 《Langmuir : the ACS journal of surfaces and colloids》2008,24(19):10612-10615
We propose a new way to determine weak repulsive forces operative between colloidal particles by measuring the rate of slow coagulation. The rate of slow coagulation is directly related to the competition of the repulsion with thermal motion. Since the thermal forces are weak, measurements of the coagulation rate can lead to precise information on repulsive potentials having a magnitude of just a few kT. We demonstrate this novel way by studying colloidal spherical polyelectrolyte brush (SPB) particles in aqueous solution containing trivalent La3+ counterions. The particles consist of a monodisperse polystyrene core of 121 nm radius from which linear sodium poly(styrenesulfonate) (PSS) chains are densely grafted (contour length 48 nm). We determine the rate of coagulation by time-resolved simultaneous static and dynamic light scattering in the presence of LaCl3 (0.2 to 150 mM). Direct measurements of the repulsive force between macroscopic brush layers demonstrate that the potential is decaying exponentially with distance. This is in good agreement with a simple theoretical treatment that furthermore leads to the effective surface potential Psi0. The good agreement of data obtained by the novel microscopic method with direct macroscopic measurements underscores the general validity of our approach. 相似文献
958.
Kurkuri MD Nussio MR Deslandes A Voelcker NH 《Langmuir : the ACS journal of surfaces and colloids》2008,24(8):4238-4244
Expanded cross-linked copolymers of poly(N-isopropylacrylamide) (PNiPAAm) and poly(acrylic acid) (PAAc) of varying monomer ratios were grafted from a crystalline silicon surface. Surface-tethered polymerization was performed at a slightly basic pH, where electrostatic repulsion among acrylic acid monomer units forces the network into an expanded polymer conformation. The influence of this expanded conformation on switchability between a hydrophilic and a hydrophobic state was investigated. Characterization of the copolymer coating was carried out by means of X-ray photoelectron spectroscopy (XPS) ellipsometry, and diffuse reflectance IR. Lower critical solution temperatures (LCSTs) of the copolymer grafts on the silicon surfaces were determined by spectrophotometry. Temperature-induced wettability changes were studied using sessile drop contact angle measurements. The surface topography was investigated by atomic force microscopy (AFM) in Milli-Q water at 25 and 40 degrees C. The reversible attachment of a fluorescently labeled model protein was studied as a function of temperature using a fluorescence microscope and a fluorescence spectrometer. Maximum switching in terms of the contact angle change around the LCST was observed at a ratio of 36:1 PNiPAAm to PAAc. The enhanced control of biointerfaces achieved by these coatings may find applications in biomaterials, biochips, drug delivery, and microfluidics. 相似文献
959.
Alex S. Ionkin William J. Marshall Douglas J. Adelman Barbara Bobik Fones Brian M. Fish Matthew F. Schiffhauer Paul D. Soper Robert L. Waterland Rupert E. Spence Tuyu Xie 《Journal of polymer science. Part A, Polymer chemistry》2008,46(2):585-611
Series of Fe(II) and Fe(III) tridentate bis(imino)pyridine complexes without nitrilo groups 2–6 and with nitrilo groups 7–13 were synthesized. According to X‐ray analysis, the introduction of nitrilo groups in para‐ and ortho‐positions tends to result in shorter axial Fe? N bonds. Both types of complexes, 2–6 and 9–13 , afforded very productive catalysts for the production of α‐olefins with higher K values and better linearity of Schultz–Flory distribution α‐olefins than the parent methyl substituted Fe(II) complex 1 . Noticeably, the complexes functionalized with a para‐nitrilo group 9–13 tend to make α‐olefins with higher K values of the Schultz–Flory distribution, more ideal distributions, and less of the heavier insoluble fractions of α‐olefins than corresponding nonsymmetrically substituted complexes without para‐nitrilo groups 2–6 . Statistically significant correlations were obtained between % solids of total α‐olefins and the blocked solid angle fraction in the +z hemisphere ( = 51.3%, p = 0.012) and between catalyst productivity and total blocked solid angle fraction ( = 43.5%, p = 0.023). The modest values of show that, while steric effects are significant, they are not the sole factor determining catalyst performance. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 585–611, 2008 相似文献
960.
Haggenmueller R Rahatekar SS Fagan JA Chun J Becker ML Naik RR Krauss T Carlson L Kadla JF Trulove PC Fox DF Delong HC Fang Z Kelley SO Gilman JW 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):5070-5078
The use of single wall carbon nanotubes (SWCNTs) in current and future applications depends on the ability to process SWCNTs in a solvent to yield high-quality dispersions characterized by individual SWCNTs and possessing a minimum of SWCNT bundles. Many approaches for the dispersion of SWCNTs have been reported. However, there is no general assessment which compares the relative quality and dispersion efficiency of the respective methods. Herein we report a quantitative comparison of the relative ability of "wrapping polymers" including oligonucleotides, peptides, lignin, chitosan, and cellulose and surfactants such as cholates, ionic liquids, and organosulfates to disperse SWCNTs in water. Optical absorption and fluorescence spectroscopy provide quantitative characterization (amount of SWCNTs that can be suspended by a given surfactant and its ability to debundle SWCNTs) of these suspensions. Sodium deoxy cholate (SDOCO), oligonucleotides (GT)(15), (GT)(10), (AC)(15), (AC)(10), C(10-30), and carboxymethylcellulose (CBMC-250K) exhibited the highest quality suspensions of the various systems studied in this work. The information presented here provides a good framework for further study of SWCNT purification and applications. 相似文献