全文获取类型
收费全文 | 1283篇 |
免费 | 61篇 |
国内免费 | 2篇 |
专业分类
化学 | 919篇 |
晶体学 | 16篇 |
力学 | 38篇 |
数学 | 91篇 |
物理学 | 282篇 |
出版年
2023年 | 7篇 |
2022年 | 24篇 |
2021年 | 25篇 |
2020年 | 32篇 |
2019年 | 28篇 |
2018年 | 33篇 |
2017年 | 34篇 |
2016年 | 57篇 |
2015年 | 47篇 |
2014年 | 59篇 |
2013年 | 95篇 |
2012年 | 117篇 |
2011年 | 84篇 |
2010年 | 47篇 |
2009年 | 47篇 |
2008年 | 96篇 |
2007年 | 58篇 |
2006年 | 51篇 |
2005年 | 44篇 |
2004年 | 43篇 |
2003年 | 28篇 |
2002年 | 33篇 |
2001年 | 8篇 |
2000年 | 6篇 |
1998年 | 7篇 |
1997年 | 8篇 |
1996年 | 13篇 |
1994年 | 4篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 6篇 |
1981年 | 11篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 16篇 |
1977年 | 5篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1969年 | 6篇 |
1968年 | 9篇 |
1964年 | 4篇 |
1963年 | 7篇 |
1962年 | 7篇 |
1961年 | 12篇 |
1958年 | 8篇 |
1955年 | 5篇 |
排序方式: 共有1346条查询结果,搜索用时 15 毫秒
51.
Abhishek Maurya Arun Kumar Mahato Nikita Chaudhary Neha Kesharwani Payal Kachhap Vivek Kumar Mishra Chanchal Haldar 《应用有机金属化学》2020,34(4):e5508
Two vanadium (IV) complexes [VIVO(Haeae-sal)(MeOH)]+ ( 1 ) and [VIVO(Haeae-hyap)(MeOH)]+ ( 2 ) were prepared by reacting [VO(acac)2] with ligands [H2aeae-sal] ( I ) and [H2aeae-hyap] ( II ) respectively. Condensation of 2-(2-aminoethylamino)ethanol with salicylaldehyde and 2-hydroxyacetophenone produces the ligands ( I ) and ( II ) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid-state. Single-crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid-state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion ( TOF value of 2.739 × 102 h−1) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 102 h−1) for the oxidative bromination of salicylaldehyde where 5-bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 104 h−1 whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 103 h−1 for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde. 相似文献
52.
53.
Allostatic load as a complex clinical construct: A case‐based computational modeling approach
下载免费PDF全文
![点击此处可从《Complexity》网站下载免费的PDF全文](/ch/ext_images/free.gif)
J. Galen Buckwalter Brian Castellani Bruce Mcewen Arun S. Karlamangla Albert A. Rizzo Bruce John Kyle O'donnell Teresa Seeman 《Complexity》2016,21(Z1):291-306
Allostatic load (AL) is a complex clinical construct, providing a unique window into the cumulative impact of stress. However, due to its inherent complexity, AL presents two major measurement challenges to conventional statistical modeling (the field's dominant methodology): it is comprised of a complex causal network of bioallostatic systems, represented by an even larger set of dynamic biomarkers; and, it is situated within a web of antecedent socioecological systems, linking AL to differences in health outcomes and disparities. To address these challenges, we employed case‐based computational modeling (CBM), which allowed us to make four advances: (1) we developed a multisystem, 7‐factor (20 biomarker) model of AL's network of allostatic systems; (2) used it to create a catalog of nine different clinical AL profiles (causal pathways); (3) linked each clinical profile to a typology of 23 health outcomes; and (4) explored our results (post hoc) as a function of gender, a key socioecological factor. In terms of highlights, (a) the Healthy clinical profile had few health risks; (b) the pro‐inflammatory profile linked to high blood pressure and diabetes; (c) Low Stress Hormones linked to heart disease, TIA/Stroke, diabetes, and circulation problems; and (d) high stress hormones linked to heart disease and high blood pressure. Post hoc analyses also found that males were overrepresented on the High Blood Pressure (61.2%), Metabolic Syndrome (63.2%), High Stress Hormones (66.4%), and High Blood Sugar (57.1%); while females were overrepresented on the Healthy (81.9%), Low Stress Hormones (66.3%), and Low Stress Antagonists (stress buffers) (95.4%) profiles. © 2015 Wiley Periodicals, Inc. Complexity 21: 291–306, 2016 相似文献
54.
Arun Kumar Bar Dr. Srinivasarao Raghothama Dr. Dohyun Moon Prof. Partha Sarathi Mukherjee 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(11):3199-3209
Template‐assisted formation of multicomponent Pd6 coordination prisms and formation of their self‐templated triply interlocked Pd12 analogues in the absence of an external template have been established in a single step through Pd? N/Pd? O coordination. Treatment of cis‐[Pd(en)(NO3)2] with K3tma and linear pillar 4,4′‐bpy (en=ethylenediamine, H3tma=benzene‐1,3,5‐tricarboxylic acid, 4,4′‐bpy=4,4′‐bipyridine) gave intercalated coordination cage [{Pd(en)}6(bpy)3(tma)2]2[NO3]12 ( 1 ) exclusively, whereas the same reaction in the presence of H3tma as an aromatic guest gave a H3tma‐encapsulating non‐interlocked discrete Pd6 molecular prism [{Pd(en)}6(bpy)3(tma)2(H3tma)2][NO3]6 ( 2 ). Though the same reaction using cis‐[Pd(NO3)2(pn)] (pn=propane‐1,2‐diamine) instead of cis‐[Pd(en)(NO3)2] gave triply interlocked coordination cage [{Pd(pn)}6(bpy)3(tma)2]2[NO3]12 ( 3 ) along with non‐interlocked Pd6 analogue [{Pd(pn)}6(bpy)3(tma)2](NO3)6 ( 3′ ), and the presence of H3tma as a guest gave H3tma‐encapsulating molecular prism [{Pd(pn)}6(bpy)3(tma)2(H3tma)2][NO3]6 ( 4 ) exclusively. In solution, the amount of 3′ decreases as the temperature is decreased, and in the solid state 3 is the sole product. Notably, an analogous reaction using the relatively short pillar pz (pz=pyrazine) instead of 4,4′‐bpy gave triply interlocked coordination cage [{Pd(pn)}6(pz)3(tma)2]2[NO3]12 ( 5 ) as the single product. Interestingly, the same reaction using slightly more bulky cis‐[Pd(NO3)2(tmen)] (tmen=N,N,N′,N′‐tetramethylethylene diamine) instead of cis‐[Pd(NO3)2(pn)] gave non‐interlocked [{Pd(tmen)}6(pz)3(tma)2][NO3]6 ( 6 ) exclusively. Complexes 1 , 3 , and 5 represent the first examples of template‐free triply interlocked molecular prisms obtained through multicomponent self‐assembly. Formation of the complexes was supported by IR and multinuclear NMR (1H and 13C) spectroscopy. Formation of guest‐encapsulating complexes ( 2 and 4 ) was confirmed by 2D DOSY and ROESY NMR spectroscopic analyses, whereas for complexes 1 , 3 , 5 , and 6 single‐crystal X‐ray diffraction techniques unambiguously confirmed their formation. The gross geometries of H3tma‐encapsulating complexes 2 and 4 were obtained by universal force field (UFF) simulations. 相似文献
55.
Saroha Rakesh Panwar Amrish K. Gaur Anurag Sharma Yogesh Kumar Vinay Tyagi Pawan K. 《Journal of Solid State Electrochemistry》2018,22(8):2507-2513
Journal of Solid State Electrochemistry - In the present work, olivine-layered composites, i.e., LiFePO4-Li2MnO3, are successfully synthesized in the form of a single monolithic electrode and layer... 相似文献
56.
57.
Relationships between molecular structure and thermomechanical properties of bio‐based thermosetting polymers
下载免费PDF全文
![点击此处可从《Journal of Polymer Science.Polymer Physics》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Jung Ho Yang Arun Srikanth Changwoon Jang Cameron F. Abrams 《Journal of Polymer Science.Polymer Physics》2017,55(3):285-292
Molecular dynamics simulations are used to study highly cross‐linked epoxy networks comprised of furanyl epoxy monomer, 2,5‐bis[(2‐oxiranylmethoxy)methyl]‐furan (BOF), that is cross‐linked by two furanyl amine hardeners, 5,5'‐methylenedifurfurylamine (DFDA) and 5,5'‐ethylidenedifurfirylamine (CH3‐DFDA). Important properties of these fully furan‐based systems, including room temperature density, glass transition temperature, and Young's modulus are found to agree with previous experimental results. We also compare the simulated and experimental values of four fully furan‐based thermosetting materials to those using the conventional resin diglycidyl ether of bisphenol A (DGEBA) cured with the two furanyl hardeners. Our simulation results predict a slight decrease in density and Young's modulus, but no impact on the glass transition temperature, upon adding the methyl group in DFDA. Detailed analyses of the MD trajectories reveal the underlying mechanisms responsible for the observed structure/property relations, which center on the lack of collinear covalent bonds in the BOF molecular structure. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 285–292 相似文献
58.
Journal of Cluster Science - Zinc oxide nanoparticles were synthesized through sol–gel technique using Azadirachta indica leaves extract. The formation of structure, crystallite parameters,... 相似文献
59.
Impact of APCI ionization source in liquid chromatography tandem mass spectrometry based tissue distribution studies
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Laxman Khatal Ashwani Gaur Ashish Naphade Vishwottam Kandikere Kasim Mookhtiar 《Biomedical chromatography : BMC》2016,30(10):1676-1685
Measurement of test article concentration in tissue samples has been an important part of pharmacokinetic study and has helped to co‐relate pharmacokinetic/pharmacodynamic relationships since the 1950s. Bioanalysis of tissue samples using LC–MS/MS comes with unique challenges in terms of sample handling and inconsistent analyte response owing to nonvolatile matrix components. Matrix effect is a phenomenon where the target analyte response is either suppressed or enhanced in the presence of matrix components. Based on previous reports electrospray ionization (ESI) mode of ionization is believed to be more affected by matrix components than atmospheric pressure chemical ionization (APCI) or atmospheric pressure photoionization. To explore the impact of ionization source with respect to bioanalysis of tissue samples, five structurally diverse compounds – atenolol, verapamil, diclofenac, propranolol and flufenamic acid – were selected. Quality control standards were spiked into 10 different biological matrices like whole blood, liver, heart, brain, spleen, kidney, skeletal muscle, eye and skin tissue and were quantified against calibration standards prepared in rat plasma. Quantitative bioanalysis was performed utilizing both APCI and ESI mode and results were compared. Quality control standards when analyzed with APCI mode were found to be more consistent in terms of accuracy and precision as compared with ESI mode. Additionally, for some instances, up to 20‐fold broader dynamic linearity range was observed with APCI mode as compared with ESI mode. As phospholid interferences have poor response in APCI mode, protein precipitation extraction technique can be used for multimatrix quantitation, which is more amenable to automation. The approach of multiple biological matrix quantitation against a single calibration curve helps bioanalysts to reduce turnaround time. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
60.