全文获取类型
收费全文 | 25870篇 |
免费 | 3948篇 |
国内免费 | 2411篇 |
专业分类
化学 | 17974篇 |
晶体学 | 309篇 |
力学 | 1538篇 |
综合类 | 112篇 |
数学 | 2946篇 |
物理学 | 9350篇 |
出版年
2024年 | 70篇 |
2023年 | 526篇 |
2022年 | 949篇 |
2021年 | 963篇 |
2020年 | 1008篇 |
2019年 | 996篇 |
2018年 | 828篇 |
2017年 | 728篇 |
2016年 | 1204篇 |
2015年 | 1152篇 |
2014年 | 1346篇 |
2013年 | 1791篇 |
2012年 | 2402篇 |
2011年 | 2413篇 |
2010年 | 1578篇 |
2009年 | 1502篇 |
2008年 | 1646篇 |
2007年 | 1512篇 |
2006年 | 1362篇 |
2005年 | 1159篇 |
2004年 | 843篇 |
2003年 | 652篇 |
2002年 | 610篇 |
2001年 | 445篇 |
2000年 | 438篇 |
1999年 | 523篇 |
1998年 | 429篇 |
1997年 | 440篇 |
1996年 | 455篇 |
1995年 | 370篇 |
1994年 | 307篇 |
1993年 | 238篇 |
1992年 | 235篇 |
1991年 | 199篇 |
1990年 | 172篇 |
1989年 | 145篇 |
1988年 | 97篇 |
1987年 | 109篇 |
1986年 | 87篇 |
1985年 | 86篇 |
1984年 | 48篇 |
1983年 | 43篇 |
1982年 | 35篇 |
1981年 | 18篇 |
1980年 | 11篇 |
1979年 | 10篇 |
1978年 | 6篇 |
1976年 | 9篇 |
1975年 | 11篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
931.
Fourier transform infrared microspectroscopy is a powerful tool to obtain knowledge about the spatial and/or temporal distributions of the chemical compositions of plants for better understanding of their biological properties. However, the chemical morphologies of plant leaves in the plane of the blade are barely studied, because sections in this plane for mid-infrared transmission measurements are difficult to obtain. Besides, native compositions may be changed by chemical reagents used when plant samples are microtomed. To improve methods for direct infrared microspectroscopic imaging of plant leaves in the plane of the blade, the bulk and surface chemical morphologies of nonmicrotomed Ginkgo biloba leaves were characterized by near-infrared transmission and mid-infrared attenuated total reflection microspectroscopic imaging. A new self-modeling curve resolution procedure was proposed to extract the spectral and concentration information of pure compounds. Primary and secondary metabolites of secretory cavities, veins, and mesophylls of Ginkgo biloba leaf blades were analyzed, and the distributions of cuticle, protein, calcium oxalate, cellulose, and ginkgolic acids on the adaxial surface were determined. By the integration of multiple infrared microspectroscopic imaging and chemometrics methods, it is possible to analyze nonmicrotomed leaves and other plant samples directly to understand their native chemical morphologies in detail. Graphical abstract
Visible and infrared microspectroscopic images of a Ginkgo biloba leaf blade. PC-1 score image shows the physical morphology, while the positive and negative part of PC-2 score image shows the distribution of dichotomous branching veins and secretory cavities, respectively 相似文献
932.
Deqing Zhao Kefu Chen Fei Yang Guanglin Feng Yufeng Sun Ya Dai 《Cellulose (London, England)》2013,20(6):3205-3217
Accurate determination of the thermal properties of cellulose is of particular significance in studying the mechanism of cellulosic cigarette paper combustion. This paper probes into the influence of four kinds of potassium carboxylates on the thermal degradation kinetics and the heat properties of cigarette paper through simultaneous thermogravimetric analysis (TGA) coupled with differential scanning calorimetry (DSC) measurement under air atmosphere. Reduced mass loss and mass loss rate, and increased solid residue for samples containing four potassium salts implied that potassium carboxylates may retard the formation of levoglucosan and volatiles by inhibiting the depolymerization reaction and simultaneously accelerate char formation by catalyzing the dehydration reaction. Kinetic parameters were analyzed based on three non-isothermal models available in literature. The results indicated that three modeling methods exhibit good consistency. A global activation energy range of 106–155 kJ mol?1 was proposed for cigarette paper with potassium carboxylates. The four potassium salts studied considerably reduced the activation energy in the following descending order: potassium 1,2,3,4-butane tetracarboxylate (PBTCA) > citrate > gluconate > ascorbate. The heat properties of cigarette paper were also determined by integrating the DSC curves. The results demonstrated that both cellulose degradation and char oxidation have strong exothermic peaks. Cigarette paper samples with potassium salts have lower exothermic cellulose degradation process and higher exothermic char oxidation process, which were further confirmed by greater differences as the amounts of salt citrate or PBTCA increased. 相似文献
933.
This paper presents a microsensor chip integrated with a gold nanoparticles‐modified ultramicroelectrode array (UMEA) as the working electrode for the detection of copper ions in water. The microsensor chip was fabricated with Micro‐Electromechanical System technique. Gold nanoparticles were electrodeposited onto the surface of UMEA at a constant potential of ?0.3 V. The ratio d/Rb of interelectrode spacing (d) over the individual electrode’s radius (Rb) was investigated to improve the electrochemical performance. The UMEA with a d/Rb of 20 showed the best hemispherical diffusion mode, resulted in fast response time and high current response. The gold nanoparticles increased the active surface area of UMEA by not changing the geometries of UMEA, and the current response was increased further. Incorporating the optimized characteristic of UMEA and gold nanoparticles, the microsensor showed a good linear range from 0.5 to 200 µg L?1 of copper ions in the acetate buffer solutions with the method of square wave stripping voltammetry. Compared with the gold nanoparticles‐modified disk electrode, the gold nanoparticles‐modified UMEA showed higher sensitivity (0.024 µA mm?2 µg?1 L) and lower limit of detection (0.2 µg L?1). Water samples from river water and tap water were analyzed by the microsensor chip with recovery ranging from 100.7 % to 107.8 %. 相似文献
934.
Wei Sun Yuanyuan Zhang Anhui Hu Yongxi Lu Fan Shi Bingxin Lei Zhenfan Sun 《Electroanalysis》2013,25(6):1417-1424
In this work a partially reduced graphene oxide (p‐RGO) modified carbon ionic liquid electrode (CILE) was prepared as the platform to fabricate an electrochemical DNA sensor, which was used for the sensitive detection of target ssDNA sequence related to transgenic soybean A2704‐12 sequence. The CILE was fabricated by using 1‐butylpyridinium hexafluorophosphate as the binder and then p‐RGO was deposited on the surface of CILE by controlling the electroreduction conditions. NH2 modified ssDNA probe sequences were immobilized on the electrode surface via covalent bonds between the unreduced oxygen groups on the p‐RGO surface and the amine group at the 5′‐end of ssDNA, which was denoted as ssDNA/p‐RGO/CILE and further used to hybridize with the target ssDNA sequence. Methylene blue (MB) was used as electrochemical indicator to monitor the DNA hybridization. The reduction peak current of MB after hybridization was proportional to the concentration of target A2704‐12 ssDNA sequences in the range from 1.0×10?12 to 1.0×10?6 mol/L with a detection limit of 2.9×10?13 mol/L (3σ). The electrochemical DNA biosensor was further used for the detection of PCR products of transgenic soybean with satisfactory results. 相似文献
935.
Yisheng Sun Zhao Zhao Qiangsheng Feng Qinqin Xu Longxian Lü Ji‐Kai Liu Ling Zhang Bin Wu Yong‐Quan Li 《Helvetica chimica acta》2013,96(1):76-84
Investigation of the cultured mycelia of Cordyceps ophioglossoides resulted in the isolation and characterization of three new unusual spiro[4.5]decane sesquiterpenes, cordycepol A ( 1 ), cordycepol B ( 2 ), and cordycepol C ( 3 ), and a new fumagillol analogue, cordycol ( 4 ). Their structures were established by spectroscopic means. The cytotoxic activities were also evaluated, compounds 3 and 4 showing their IC50 values in the range of 12–33 μg/ml against HeLa and HepG2 (Table 3). In addition, 3 and 4 were not obviously harmful towards normal liver cell lines LO2, showing IC50 values above 80 μg/ml. 相似文献
936.
Triazolo‐fused 2′,3′‐cyclic nucleoside analogs were synthesized by an intramolecular 1,3‐dipolar cycloaddition of nucleoside‐derived azido alkynes in a regio‐ and stereospecific manner. The uracil base in these target compounds was successfully transformed to the corresponding cytosine. The synthesized compounds were examined in a MAGI assay for their anti‐HIV activities, and in a H9 T lymphocytes assay for their cell toxicities. 相似文献
937.
Yutong Zhao Fu Kit Sheong Jian Sun Pedro Sander Xuhui Huang 《Journal of computational chemistry》2013,34(2):95-104
We implemented a GPU‐powered parallel k‐centers algorithm to perform clustering on the conformations of molecular dynamics (MD) simulations. The algorithm is up to two orders of magnitude faster than the CPU implementation. We tested our algorithm on four protein MD simulation datasets ranging from the small Alanine Dipeptide to a 370‐residue Maltose Binding Protein (MBP). It is capable of grouping 250,000 conformations of the MBP into 4000 clusters within 40 seconds. To achieve this, we effectively parallelized the code on the GPU and utilize the triangle inequality of metric spaces. Furthermore, the algorithm's running time is linear with respect to the number of cluster centers. In addition, we found the triangle inequality to be less effective in higher dimensions and provide a mathematical rationale. Finally, using Alanine Dipeptide as an example, we show a strong correlation between cluster populations resulting from the k‐centers algorithm and the underlying density. © 2012 Wiley Periodicals, Inc. 相似文献
938.
Yongqing Li Jiuchuang Yuan Maodu Chen Fengcai Ma Mengtao Sun 《Journal of computational chemistry》2013,34(19):1686-1696
An accurate single‐sheeted double many‐body expansion potential energy surface is reported for the title system. A switching function formalism has been used to warrant the correct behavior at the and dissociation channels involving nitrogen in the ground and first excited states. The topographical features of the novel global potential energy surface are examined in detail, and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. The novel surface can be using to treat well the Renner–Teller degeneracy of the and states of . Such a work can both be recommended for dynamics studies of the reaction and as building blocks for constructing the double many‐body expansion potential energy surface of larger nitrogen/hydrogen‐containing systems. In turn, a test theoretical study of the reaction has been carried out with the method of quantum wave packet on the new potential energy surface. Reaction probabilities, integral cross sections, and differential cross sections have been calculated. Threshold exists because of the energy barrier (68.5 meV) along the minimum energy path. On the curve of reaction probability for total angular momentum J = 0, there are two sharp peaks just above threshold. The value of integral cross section increases quickly from zero to maximum with the increase of collision energy, and then stays stable with small oscillations. The differential cross section result shows that the reaction is a typical forward and backward scatter in agreement with experimental measurement result. © 2013 Wiley Periodicals, Inc. 相似文献
939.
A chiral coordination compound {(Δ)[Fe(II)(phen)3][(Δ)Fe(III)(C2O4)3](NH4)(H2O)3(DMF)}n (phen = 1,10‐phenanthroline), (DMF = N,N'‐Dimethylformamide), has been synthesized, and the structure has been revealed by infrared spectroscopy and X‐ray single‐crystal diffraction. The framework consists of two chiral subunits. One subunit (Δ)[(Fe(III)(C2O4)3]3? which as host anion forms a chiral porous three‐dimensional supermolecular network with lattice water, lattice DMF and lattice ammonium cation through hydrogen bonds. And then the other is Δ[Fe(II)(phen)3]2+ which as guest cation fills in the chiral cavity located in the previously mentioned host porous network. 相似文献
940.
Zymogen granule (ZG) constituents play important roles in pancreatic injury and disease. In previous studies, proteomic analyses with rat zymogen granules were separated by two‐dimensional gel electrophoresis or one‐dimensional SDS–PAGE, followed by in‐gel tryptic digestion. In order to overcome the disadvantage of in‐gel digestion and to carry out further in‐depth proteomic analysis of the zymogen granules, in this study, by combining a filter‐aided sample preparation method and fully automated 2D‐LC‐MS/MS technique, 800 ZG proteins were identified with at least two unique peptides for each protein, 75% of which have not been previously reported. The identified proteins revealed broad diversity in protein identity and function. This is the largest dataset of ZG proteome, and also the first dataset of the mouse ZG proteome, which may help elucidate on the molecular architecture of ZGs and their functions. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献