首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1064篇
  免费   33篇
  国内免费   12篇
化学   681篇
晶体学   11篇
力学   35篇
数学   243篇
物理学   139篇
  2023年   3篇
  2022年   20篇
  2021年   47篇
  2020年   36篇
  2019年   20篇
  2018年   31篇
  2017年   22篇
  2016年   54篇
  2015年   33篇
  2014年   43篇
  2013年   84篇
  2012年   76篇
  2011年   71篇
  2010年   61篇
  2009年   54篇
  2008年   55篇
  2007年   64篇
  2006年   43篇
  2005年   41篇
  2004年   49篇
  2003年   28篇
  2002年   35篇
  2001年   13篇
  2000年   11篇
  1999年   12篇
  1998年   9篇
  1997年   11篇
  1996年   15篇
  1995年   6篇
  1994年   9篇
  1993年   6篇
  1992年   5篇
  1991年   6篇
  1990年   3篇
  1989年   6篇
  1988年   4篇
  1987年   2篇
  1986年   1篇
  1985年   3篇
  1984年   5篇
  1982年   3篇
  1981年   2篇
  1980年   1篇
  1979年   1篇
  1978年   1篇
  1977年   4篇
排序方式: 共有1109条查询结果,搜索用时 31 毫秒
61.
Volatile organic compounds (VOCs) exiting in urine are potential biomarkers of chronic kidney diseases. Headspace solid phase microextraction (HS-SPME) was applied for extraction VOCs over the urine samples. Volatile metabolites were separated and identified by means of two-dimensional gas chromatography and time of flight mass spectrometry (GC × GC TOF MS). Patients with glomerular diseases (n = 27) and healthy controls (n = 20) were recruited in the study. Different VOCs profiles were obtained from patients and control. Developed methodology offers the opportunity to examine the metabolic profile associated with glomerulopathy. Four compounds found in elevated amounts in the patients group, i.e., methyl hexadecanoate; 9-hexadecen-1-ol; 6,10-dimethyl-5,9-undecadien-2-one and 2-pentanone were proposed as markers of glomerular diseases.  相似文献   
62.
Phytoestrogens are naturally occurring non-steroidal phenolic plant compounds. Their structure is similar to 17-β-estradiol, the main female sex hormone. This review offers a concise summary of the current literature on several potential health benefits of phytoestrogens, mainly their neuroprotective effect. Phytoestrogens lower the risk of menopausal symptoms and osteoporosis, as well as cardiovascular disease. They also reduce the risk of brain disease. The effects of phytoestrogens and their derivatives on cancer are mainly due to the inhibition of estrogen synthesis and metabolism, leading to antiangiogenic, antimetastatic, and epigenetic effects. The brain controls the secretion of estrogen (hypothalamus-pituitary-gonads axis). However, it has not been unequivocally established whether estrogen therapy has a neuroprotective effect on brain function. The neuroprotective effects of phytoestrogens seem to be related to both their antioxidant properties and interaction with the estrogen receptor. The possible effects of phytoestrogens on the thyroid cause some concern; nevertheless, generally, no serious side effects have been reported, and these compounds can be recommended as health-promoting food components or supplements.  相似文献   
63.
Sulphur isotope compositions were determined in two different Polish coals (hard coal and lignite) and by-products originating from their combustion. The desulphurization process was also investigated. It was demonstrated that desulphurization changes the isotopic composition of sulphur emitted in the form of SO(2) to the atmosphere even if the process is conducted in a different way (wet lime technology and electron beam method). This fact has to be considered in the studies regarding anthropogenic sulphur genesis and its fate in the environment.  相似文献   
64.
Generation of scratches on surface of m‐plane GaN substrates due to polishing was studied by atomic force microscopy (AFM). For epi‐ready substrates AFM images confirm a flat surface with the atomic step roughness while a lot of scratches are visible in AFM images for partially polished GaN substrates. The Fourier analysis of AFM images show that scratches propagate easier along {c‐plane} and {a‐plane} directions on m‐plane GaN surface. This observation is an evidence of anisotropy of mechanical properties of GaN crystals in the micro‐scale. This anisotropy is directly correlated with the symmetry and atomic arrangement of m‐plane GaN.  相似文献   
65.
X‐ray photoelectron spectroscopy (XPS) is an indispensable technique in modern materials science for the determination of chemical bonding as evidenced by more than 10 000 XPS papers published annually. A literature survey reveals that in the vast majority of cases an incorrect referencing of the binding energy scale is used, neglecting warnings that have been formulated from the early days of the technique. Consequences for the data reliability are disastrous and decades of XPS work require revisiting. The purpose of this Viewpoint is to highlight the existing problems, review the criticism and suggest ways forward.  相似文献   
66.
The intermolecular interactions in the structures of a series of Schiff base ligands have been thoroughly studied. These ligands can be obtained in different forms, namely, as the free base 2‐[(2E)‐2‐(1H‐imidazol‐4‐ylmethylidene)‐1‐methylhydrazinyl]pyridine, C10H11N5, 1 , the hydrates 2‐[(2E)‐2‐(1H‐imidazol‐2‐ylmethylidene)‐1‐methylhydrazinyl]‐1H‐benzimidazole monohydrate, C12H12N6·H2O, 2 , and 2‐{(2E)‐1‐methyl‐2‐[(1‐methyl‐1H‐imidazol‐2‐yl)methylidene]hydrazinyl}‐1H‐benzimidazole 1.25‐hydrate, C13H14N6·1.25H2O, 3 , the monocationic hydrate 5‐{(1E)‐[2‐(1H‐1,3‐benzodiazol‐2‐yl)‐2‐methylhydrazinylidene]methyl}‐1H‐imidazol‐3‐ium trifluoromethanesulfonate monohydrate, C12H13N6+·CF3O3S?·H2O, 5 , and the dicationic 2‐{(2E)‐1‐methyl‐2‐[(1H‐imidazol‐3‐ium‐2‐yl)methylidene]hydrazinyl}pyridinium bis(trifluoromethanesulfonate), C10H13N52+·2CF3O3S?, 6 . The connection between the forms and the preferred intermolecular interactions is described and further studied by means of the calculation of the interaction energies between the neutral and charged components of the crystal structures. These studies show that, in general, the most important contribution to the stabilization energy of the crystal is provided by π–π interactions, especially between charged ligands, while the details of the crystal architecture are influenced by directional interactions, especially relatively strong hydrogen bonds. In one of the structures, a very interesting example of the nontypical F…O interaction was found and its length, 2.859 (2) Å, is one of the shortest ever reported.  相似文献   
67.
The mechanism of polymerization is discussed, in which cyclic esters of phosphoric acid, and related compounds are converted into linear macromolecules, modelling nucleic and teichoic acid backbones. Structures like deoxyribose polyphosphate and glycerol polyphosphate were prepared from the corresponding cyclic compounds. These polymerizations involve heterolytic breaking of the P-O bond in the cyclic monomer and proceed by ionic mechanism. Both 5- and 6-membered monomers have been polymerized. The thermodynamic parameters of the ring-chain interconversion were determined; the 5-membered rings polymerization is driven by the exothermicity of the ring-opening, whereas polymerization of several 6-membered rings is endothermic and allowed because of the positive change of entropy. Anionic polymerization, and particularly the pseudo(coordinate)anionic polymerization provides, in contrast to the cationic process, high-molecular-weight polymers with more uniform structure. Anionic polymerization proceeds mostly (at the applied conditions) on the macroion – -pairs. The elementary reactions consist of the nucleophilic attack of the paired macroanions on the phosphorus atom in the cyclic monomer molecule. Rate constants of the elementary reactions for the model monomers will be presented. Stereochemistry of the propagation steps is shown to be governed by the statistical ring-opening, leading to the three kinds of polymer units (head-to-tail and two symmetrical units). Apart from the ring-opening, the polyaddition of diepoxides to phosphorous and phosphoric acids is described. Finally, a few examples of preparation of models of biopolymers are given, namely poly(deoxyribose phosphate) and poly(glycerol phosphate).  相似文献   
68.
New functionalization methods of meta- and para-aramid fabrics with silver nanowires (AgNWs) and two silanes (3-aminopropyltriethoxysilane (APTES)) and diethoxydimethylsilane (DEDMS) were developed: a one-step method (mixture) with AgNWs dispersed in the silane mixture and a two-step method (layer-by-layer) in which the silanes mixture was applied to the previously deposited AgNWs layer. The fabrics were pre-treated in a low-pressure air radio frequency (RF) plasma and subsequently coated with polydopamine. The modified fabrics acquired hydrophobic properties (contact angle ΘW of 112–125°). The surface free energy for both modified fabrics was approximately 29 mJ/m2, while for reference, meta- and para-aramid fabrics have a free energy of 53 mJ/m2 and 40 mJ/m2, respectively. The electrical surface resistance (Rs) was on the order of 102 Ω and 104 Ω for the two-step and one-step method, respectively. The electrical volume resistance (Rv) for both modified fabrics was on the order of 102 Ω. After UV irradiation, the Rs did not change for the two-step method, and for the one-step method, it increased to the order of 1010 Ω. The specific strength values were higher by 71% and 63% for the meta-aramid fabric and by 102% and 110% for the para-aramid fabric for the two-step and one-step method, respectively, compared to the unmodified fabrics after UV radiation.  相似文献   
69.
The European Physical Journal A - The transverse momentum ($$p_{T}$$) distribution of strange hadrons ($$K_{S}^{0}$$ and $$\varLambda $$) and multi-strange hadrons( $$\varXi $$ and $$\varOmega $$)...  相似文献   
70.
Measurements of stable carbon isotopic composition (delta13C) of carbonates or carbonate-rich soils are seldom performed in a continuous-flow isotope ratio mass spectrometer (IRMS) using an elemental analyzer (EA) as an online sample preparation device. Such analyses are routinely carried out with an external precision better than 0.1 per thousand using a GasBench II (GB) sample preparation device coupled online with a continuous-flow IRMS. In this paper, we report and compare delta13C analyses (86 total analyses) of calcium carbonates obtained by using both the GB and the EA. Using both techniques, the delta13C compositions of two in-house carbonate standards (MERCK carbonate and NR calcite) and ten selected carbonate-rich paleosol samples (of variable CaCO3 content) were analyzed, and data are reported in the VPDB scale calibrated against international standards, NBS 18 and 19. For the in-house standards analyzed by both techniques, a precision better than 0.08 per thousand is achieved. The analytical errors (1sigma) computed from multiple analyses of the delta13C of both the MERCK and NR obtained by the above two techniques are nearly identical. In general, the 1sigma (internal error) of paleosol analyses obtained in the GB is better than 0.06 per thousand, whereas that for the analyses in the EA (three repetitive analyses of the same sample) varies in the range 0.05-0.21 per thousand. However, for paleosols having more than 85% CaCO3, 1sigma is better than 0.15 per thousand (similar to the instrument precision), and in this case the delta13C(VPDB) of samples obtained by the GB is similar to that obtained by the EA. Our results suggest that the delta13C of pure calcium carbonate samples can also be analyzed using the EA technique.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号