全文获取类型
收费全文 | 1098篇 |
免费 | 41篇 |
国内免费 | 6篇 |
专业分类
化学 | 714篇 |
晶体学 | 7篇 |
力学 | 20篇 |
数学 | 178篇 |
物理学 | 195篇 |
无线电 | 31篇 |
出版年
2023年 | 5篇 |
2022年 | 24篇 |
2021年 | 23篇 |
2020年 | 22篇 |
2019年 | 26篇 |
2018年 | 22篇 |
2017年 | 21篇 |
2016年 | 40篇 |
2015年 | 32篇 |
2014年 | 33篇 |
2013年 | 68篇 |
2012年 | 84篇 |
2011年 | 85篇 |
2010年 | 55篇 |
2009年 | 44篇 |
2008年 | 74篇 |
2007年 | 62篇 |
2006年 | 62篇 |
2005年 | 48篇 |
2004年 | 58篇 |
2003年 | 29篇 |
2002年 | 33篇 |
2001年 | 25篇 |
2000年 | 12篇 |
1999年 | 17篇 |
1998年 | 8篇 |
1997年 | 13篇 |
1996年 | 20篇 |
1995年 | 8篇 |
1994年 | 10篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1958年 | 2篇 |
1957年 | 6篇 |
1956年 | 6篇 |
1954年 | 10篇 |
排序方式: 共有1145条查询结果,搜索用时 15 毫秒
51.
Stanislav Kozin Vladimir Skrebitsky Rodion Kondratenko Alexander Kravtsov Elena Butina Arkady Moiseev Vadim Malyshko Mikhail Baryshev Anna Elkina Stepan Dzhimak 《Molecules (Basel, Switzerland)》2021,26(7)
The deuterium content modification in an organism has a neuroprotective effect during the hypoxia model, affecting anxiety, memory and stress resistance. The aim of this work was to elucidate the possible mechanisms of the medium D/H composition modification on nerve cells. We studied the effect of an incubation medium with a 50 ppm deuterium content compared to a medium with 150 ppm on: (1) the activity of Wistar rats’ hippocampus CA1 field neurons, (2) the level of cultured cerebellar neuron death during glucose deprivation and temperature stress, (3) mitochondrial membrane potential (MMP) and the generation of reactive oxygen species in cultures of cerebellar neurons. The results of the analysis showed that the incubation of hippocampal sections in a medium with a 50 ppm deuterium reduced the amplitude of the pop-spike. The restoration of neuron activity was observed when sections were returned to the incubation medium with a 150 ppm deuterium content. An environment with a 50 ppm deuterium did not significantly affect the level of reactive oxygen species in neuron cultures, while MMP decreased by 16–20%. In experiments with glucose deprivation and temperature stress, the medium with 50 ppm increased the death of neurons. Thus, a short exposure of nerve cells in the medium with 50 ppm deuterium acts as an additional stressful factor, which is possibly associated with the violation of the cell energy balance. The decrease in the mitochondrial membrane potential, which is known to be associated with ATP synthesis, indicates that this effect may be associated with the cell energy imbalance. The decrease in the activity of the CA1 field hippocampal neurons may reflect reversible adaptive changes in the operation of fast-reacting ion channels. 相似文献
52.
Synthesis and Biochemical Evaluation of Warhead-Decorated Psoralens as (Immuno)Proteasome Inhibitors
Eva Shannon Schiffrer Matic Proj Martina Gobec Luka Rejc Andrej terman Janez Mravljak Stanislav Gobec Izidor Sosi
《Molecules (Basel, Switzerland)》2021,26(2)
The immunoproteasome is a multicatalytic protease that is predominantly expressed in cells of hematopoietic origin. Its elevated expression has been associated with autoimmune diseases, various types of cancer, and inflammatory diseases. Selective inhibition of its catalytic activities is therefore a viable approach for the treatment of these diseases. However, the development of immunoproteasome-selective inhibitors with non-peptidic scaffolds remains a challenging task. We previously reported 7H-furo[3,2-g]chromen-7-one (psoralen)-based compounds with an oxathiazolone warhead as selective inhibitors of the chymotrypsin-like (β5i) subunit of immunoproteasome. Here, we describe the influence of the electrophilic warhead variations at position 3 of the psoralen core on the inhibitory potencies. Despite mapping the chemical space with different warheads, all compounds showed decreased inhibition of the β5i subunit of immunoproteasome in comparison to the parent oxathiazolone-based compound. Although suboptimal, these results provide crucial information about structure–activity relationships that will serve as guidance for the further design of (immuno)proteasome inhibitors. 相似文献
53.
Dmitriy S. Yambulatov Stanislav A. Nikolaevskii Mikhail A. Kiskin Kirill V. Kholin Mikhail N. Khrizanforov Yulia G. Budnikova Konstantin A. Babeshkin Nikolay N. Efimov Alexander S. Goloveshkin Vladimir K. Imshennik Yurii V. Maksimov Evgeny M. Kadilenko Nina P. Gritsan Igor L. Eremenko 《Molecules (Basel, Switzerland)》2021,26(10)
The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeIII2] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2–300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively. The neutral character of dpp-BIAN in 1 was confirmed by IR and UV spectroscopy. The electrochemistry of 1 was studied in solution and solid state using cyclic voltammetry. The generation of the radical anion form of the dpp-BIAN ligand upon reduction of 1 in a CH2Cl2 solution was monitored by EPR spectroscopy. 相似文献
54.
We present a novel approach to the nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) analysis of complex samples with nontrivial distribution of longitudinal relaxation rate R(1). Parametrically enabled relaxation filters with double and multiple inversion (PERFIDI) aim to separate signals arising from components with different R(1) values prior to actual data acquisition. Given any standard NMR/MRI pulse sequence, which, by itself, is insensitive to differences in R(1) values, it can be combined with a PERFIDI preamble, which functions as a preliminary R(1) filter and confers on the original technique sensitivity to the dimension R(1). This article states the principles of the approach, including the way to account for instrumental imperfections, and shows how PERFIDI with specific filter profile functions can be built. Using terms borrowed from electronics, these filters are classified as low-pass, high-pass and band-pass types. Also included are an experimental verification example and a discussion of potential applications of PERFIDI in various NMR areas. 相似文献
55.
56.
Taye B. Demissie Nataliya Kostenko Stanislav Komorovsky Michal Repisky Johan Isaksson Annette Bayer Kenneth Ruud 《Journal of Physical Organic Chemistry》2015,28(12):723-731
We present a theoretical and experimental study of the structure and nuclear magnetic resonance (NMR) parameters of the pentacarbonyltungsten complexes of η1‐2‐(trimethylstannyl)‐4,5‐dimethylphosphinine, η2‐norbornene, and imidazolidine‐2‐thione. The three complexes have a pseudo‐octahedral molecular structure with the six ligands bonded to the tungsten atom. The η1‐2‐(trimethylstannyl)‐4,5‐dimethylphosphinine‐pentacarbonyl tungsten complex was synthesized for the first time. For all compounds, we present four‐component relativistic calculations of the NMR parameters at the Dirac–Kohn–Sham density functional level of theory using hybrid functionals. These large‐scale relativistic calculations of NMR chemical shifts and spin–spin coupling constants were compared with available experimental data, either taken from the literature or measured in this work. The inclusion of solvent effects modeled using a conductor‐like screening model was found to improve agreement between the calculated and experimental NMR parameters, and our best estimates for the NMR parameters are generally in good agreement with available experimental results. The present work demonstrates that four‐component relativistic theory has reached a level of maturity that makes it a convenient and accurate tool for modeling and understanding chemical shifts and indirect spin–spin coupling constants of organometallic compounds containing heavy elements, for which conventional non‐relativistic theory breaks down. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
57.
Shady Farah Oren Aviv Natalia Laout Stanislav Ratner Nurit Beyth Abraham J. Domb 《先进技术聚合物》2014,25(6):689-692
Silica particles functionalized with quaternary ammonium groups were prepared by interpenetrating polyethylenimine (PEI) into silica particles and crosslinking with diiodopentane, followed by octyliodide alkylation and methyliodide quaternarization (S‐QA‐PEI). The synthesized S‐QA‐PEI particles were identified with a slight particle size increase of 2–3 µm. Different ratios of PEI:silica particles were prepared and analyzed. While silica particles are negatively charged, ?16.7 ± 5.11 mV, the prepared S‐QA‐PEI particles are positively charged, +50–60 mV. These particles were embedded in poly(ethylene vinyl acetate) and poly(ethylene methacrylic acid) coatings which exhibited strong antibacterial activity. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
58.
Eric J. Lanni Sage J. B. Dunham Peter Nemes Stanislav S. Rubakhin Jonathan V. Sweedler 《Journal of the American Society for Mass Spectrometry》2014,25(11):1897-1907
We describe a hybrid MALDI/C60-SIMS Q-TOF mass spectrometer and corresponding sample preparation protocols to image intact biomolecules and their fragments in mammalian spinal cord, individual invertebrate neurons, and cultured neuronal networks. A lateral spatial resolution of 10 μm was demonstrated, with further improvement feasible to 1 μm, sufficient to resolve cell outgrowth and interconnections in neuronal networks. The high mass resolution (>13,000 FWHM) and tandem mass spectrometry capability of this hybrid instrument enabled the confident identification of cellular metabolites. Sublimation of a suitable matrix, 2,5-dihydroxybenzoic acid, significantly enhanced the ion signal intensity for intact glycerophospholipid ions from mammalian nervous tissue, facilitating the acquisition of high-quality ion images for low-abundance biomolecules. These results illustrate that the combination of C60-SIMS and MALDI mass spectrometry offers particular benefits for studies that require the imaging of intact biomolecules with high spatial and mass resolution, such as investigations of single cells, subcellular organelles, and communities of cells. Graphical Abstract
? 相似文献
59.
Mitja Krnel Primož Koželj Stanislav Vrtnik Andreja Jelen Magdalena Wencka Peter Gille Janez Dolinšek 《无机化学与普通化学杂志》2020,646(14):1099-1104
We present the anisotropic electrical and thermal transport coefficients (electrical resistivity, magnetoresistance, thermoelectric power, thermal conductivity), the magnetic properties, the specific heat and the electronic density of states of a monocrystalline In3Ni2 intermetallic compound, representing a precious-metal-free (and noble-metal-free) intermetallic catalyst for the selective hydrogenation of α,β-unsaturated aldehydes. The investigated physical parameters were determined along three orthogonal crystal-symmetry directions of the trigonal structure, the twofold axis, the 3 axis and within the mirror plane. All the investigated tensorial and vectorial quantities show the same anisotropy, with the quantities being isotropic for the twofold direction and in the mirror plane, whereas there is small, though still significant anisotropy to the 3 direction. The In3Ni2 crystal conducts the electricity and heat somewhat less efficiently along the 3 direction than along the twofold direction and in the mirror plane, but the differences are not large, of about 20 %. In3Ni2 is a diamagnetic intermetallic compound, with a presumably simple Fermi surface and electrons as the majority charge carriers. 相似文献
60.
Dmitri O. Charkin Stanislav I. Bezzubov Oleg I. Siidra Artem S. Borisov Stepan N. Kalmykov 《无机化学与普通化学杂志》2020,646(11-12):540-543
Crystals of a new uranyl sulfate (C2N4H8S2)[UO2(SO4)2] · 0.3H2O ( 1 ) templated by a relatively rare bis-isothiouronium cation, were formed upon evaporation of aqueous solutions containing uranyl acetate, thiourea, and excess sulfuric acid. The new compound is orthorhombic, P212121, a = 6.928(2) Å, b = 13.398(3) Å, c = 15.225(3) Å, Z = 2. Its crystal structure is comprised of [UO2(SO4)2] moieties linked by hydrogen bonds formed between the template cations and terminal oxygen atoms of the sulfate tetrahedra. The C2N4H8S22+ template is most likely formed in situ during a redox reaction between uranyl cation and thiourea in a strongly acidic medium, with UO22+ partially reduced to U4+. 相似文献