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91.
Barbara Franczuk Witold Danikiewicz 《Journal of the American Society for Mass Spectrometry》2018,29(3):588-599
Ion-molecule reactions of Me2S2 with a wide range of aliphatic carbanions differing by structure and proton affinity values have been studied in the gas phase using mass spectrometry techniques and DFT calculations. The analysis of the spectra shows a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. Product ions of thiophilic reaction (m/z 47), SN2 (m/z 79), and E2 elimination – addition sequence of reactions (m/z 93) can be observed. Primary products of thiophilic reaction can undergo subsequent SN2 and proton transfer reactions. Gibbs free energy profiles calculated for experimentally observed reactions using PBE0/6-311+G(2d,p) method show good agreement with experimental results. 相似文献
92.
Witold Marciszewski Jan Pelant 《Transactions of the American Mathematical Society》1997,349(9):3585-3596
An internal characterization of metric spaces which are absolute Borel sets of multiplicative classes is given. This characterization uses complete sequences of covers, a notion introduced by Frolík for characterizing Cech-complete spaces. We also show that the absolute Borel class of is determined by the uniform structure of the space of continuous functions ; however the case of absolute metric spaces is still open. More precisely, we prove that, for metrizable spaces and , if is a uniformly continuous surjection and is an absolute Borel set of multiplicative (resp., additive) class , , then is also an absolute Borel set of the same class. This result is new even if is a linear homeomorphism, and extends a result of Baars, de Groot, and Pelant which shows that the \v{C}ech-completeness of a metric space is determined by the linear structure of .
93.
A novel algorithmic scheme for numerical solution of the 3D Poisson-Nernst-Planck model is proposed. The algorithmic improvements are universal and independent of the detailed physical model. They include three major steps: an adjustable gradient-based step value, an adjustable relaxation coefficient, and an optimized segmentation of the modeled space. The enhanced algorithm significantly accelerates the speed of computation and reduces the computational demands. The theoretical model was tested on a regular artificial channel and validated on a real protein channel-alpha-hemolysin, proving its efficiency. 相似文献
94.
JPC – Journal of Planar Chromatography – Modern TLC - A simple and convenient thin-layer chromatography (TLC) method combined with image analysis technique was developed to determine... 相似文献
95.
Antagonistic Effects of Endogenous Nitric Oxide in a Glioblastoma Photodynamic Therapy Model 下载免费PDF全文
Jonathan M. Fahey Joseph V. Emmer Witold Korytowski Neil Hogg Albert W. Girotti 《Photochemistry and photobiology》2016,92(6):842-853
Gliomas are aggressive brain tumors that are resistant to conventional chemotherapy and radiotherapy. Much of this resistance is attributed to endogenous nitric oxide (NO). Recent studies revealed that 5‐aminolevulinic acid (ALA)‐based photodynamic therapy (PDT) has advantages over conventional treatments for glioblastoma. In this study, we used an in vitro model to assess whether NO from glioblastoma cells can interfere with ALA‐PDT. Human U87 and U251 cells expressed significant basal levels of neuronal NO synthase (nNOS) and its inducible counterpart (iNOS). After an ALA/light challenge, iNOS level increased three‐ to fourfold over 24 h, whereas nNOS remained unchanged. Elevated iNOS resulted in a large increase in intracellular NO. Extent of ALA/light‐induced apoptosis increased substantially when an iNOS inhibitor or NO scavenger was present, implying that iNOS/NO was acting cytoprotectively. Moreover, cells surviving a photochallenge exhibited a striking increase in proliferation, migration and invasion rates, iNOS/NO again playing a dominant role. Also observed was a large iNOS/NO‐dependent increase in matrix metalloproteinase‐9 activity, decrease in tissue inhibitor of metalloproteinase‐1 expression and increase in survivin and S100A4 expression, each effect being consistent with accelerated migration/invasion as a prelude to metastasis. Our findings suggest introduction of iNOS inhibitors as pharmacologic adjuvants for glioblastoma PDT. 相似文献
96.
97.
Adrian W. Markwell-Heys Michael Roemelt Ashley D. Slattery Oliver M. Linder-Patton Witold M. Bloch 《Chemical science》2021,13(1):68
Using metal–organic cages (MOCs) as preformed supermolecular building-blocks (SBBs) is a powerful strategy to design functional metal–organic frameworks (MOFs) with control over the pore architecture and connectivity. However, introducing chemical complexity into the network via this route is limited as most methodologies focus on only one type of MOC as the building-block. Herein we present the pairwise linking of MOCs as a design approach to introduce defined chemical complexity into porous materials. Our methodology exploits preferential Rh-aniline coordination and stoichiometric control to rationally link Cu4L4 and Rh4L4 MOCs into chemically complex, yet extremely well-defined crystalline solids. This strategy is expected to open up significant new possibilities to design bespoke multi-functional materials with atomistic control over the location and ordering of chemical functionalities.A new strategy to design atomically precise multivariate metal–organic frameworks is presented. This is achieved by linking two preformed metal–organic cages via a precisely tuned Rh–aniline interaction. 相似文献
98.
Witold Brostow Samir Majumdar Ram Prakash Singh 《Macromolecular rapid communications》1999,20(3):144-147
A model is described which explains drag reduction (DR) in dilute polymer solutions in terms of solvation of macromolecular chains and formation of relatively stable domains. The domains partly suppress the vortex formation, act as energy sinks, and also play a role in mechanical degradation in flow (MDF). We report ultrasonically determined solvation numbers for a series of copolymers with the same chemical structure but differing widely in their intrinsic viscosities. The solvation numbers confirm the model. Thus, we have a criterion for selection of DR agents with low MDF for: oil well operations; crude oil transport; fire fighting; high sewer throughput; irrigation; hydrotransport of solids; marine applications; and biomedical applications including the arteriosclerosis prevention. 相似文献
99.
Steven M. Pylecor L. Donnelly Betowski Alvin B. Marcus Witold Winnik Robert D. Brittain 《Journal of the American Society for Mass Spectrometry》1997,8(2):183-190
An ion-trap mass spectrometer with a wave board and tandem mass spectrometry software was used to analyze gas chromatographically separated polycyclic aromatic hydrocarbons (PAHs) by using collision-induced dissociation (CID). The nonresonant (multiple collision) mode was used to determine the conditions for CID ionization of 18 PAHs. Unlike in electron impact (EI) analysis, the relative abundances of progeny ions of isomers were statistically different (using Student’s t-test) in CID analysis, thus making isomer identification by CID possible. For comparison, CID and EI were applied to the analysis of used motor oil. CID analysis was shown to be more sensitive than EI analysis of the used motor oil. Precision at the 10-ppb level for EI and CID showed relative standard deviations of 5. 2 and 7. 7%, respectively. 相似文献
100.
Rafal Nowaczynski Marcin Gajc Hancza B. Surma Pawel Osewski Adam Strzep Witold Ryba‐Romanowski Dorota A. Pawlak 《Particle & Particle Systems Characterization》2019,36(1)
Quantum dot (QD)‐based light‐emitting materials are gaining increased attention because of their easily tunable optical properties desired for various applications in biology, optoelectronics, and photonics. However, few methods can be used to manufacture volumetric materials doped with more than one type of QD other than QD‐polymer hybrids, and they often require complicated preparation processes and are prone to luminescence quenching by QD aggregation and separation from the matrix. Here, simultaneous doping of a volumetric glass‐based nanocomposite with two types of QDs is demonstrated for the first time in a single‐step process using the nanoparticle direct doping method. Glass rods doped with CdTe, CdSe/ZnS, or co‐doped with both QDs, are obtained. Photoluminescence and lifetime experiments confirm temperature‐dependent double emission with maxima at 596 and 720 nm with mean lifetimes up to 16 ns, as well as radiative energy transfer from the short wavelength–emitting QDs to the long wavelength–emitting QDs. This approach may enable the simple and cost‐efficient manufacturing of bulk materials that produce multicolor luminescence with cascade excitation pumping. Applications that could benefit from this include broadband optical fiber amplifiers, backlight systems in LCD screens, high‐power LEDs, or down‐converting solar concentrators used to increase the efficiency of solar panels. 相似文献