全文获取类型
收费全文 | 2805篇 |
免费 | 121篇 |
国内免费 | 7篇 |
专业分类
化学 | 2174篇 |
晶体学 | 9篇 |
力学 | 50篇 |
数学 | 405篇 |
物理学 | 295篇 |
出版年
2023年 | 22篇 |
2022年 | 57篇 |
2021年 | 95篇 |
2020年 | 74篇 |
2019年 | 79篇 |
2018年 | 40篇 |
2017年 | 43篇 |
2016年 | 116篇 |
2015年 | 99篇 |
2014年 | 104篇 |
2013年 | 178篇 |
2012年 | 208篇 |
2011年 | 205篇 |
2010年 | 157篇 |
2009年 | 121篇 |
2008年 | 172篇 |
2007年 | 157篇 |
2006年 | 149篇 |
2005年 | 141篇 |
2004年 | 133篇 |
2003年 | 108篇 |
2002年 | 105篇 |
2001年 | 37篇 |
2000年 | 42篇 |
1999年 | 32篇 |
1998年 | 25篇 |
1997年 | 26篇 |
1996年 | 30篇 |
1995年 | 21篇 |
1994年 | 22篇 |
1993年 | 18篇 |
1992年 | 21篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 10篇 |
1986年 | 8篇 |
1985年 | 9篇 |
1984年 | 3篇 |
1983年 | 6篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1977年 | 6篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1970年 | 2篇 |
排序方式: 共有2933条查询结果,搜索用时 62 毫秒
151.
Luís E. Sarto Iara M. R. Landre Gabriela F. Bozza Claudia Torres Eduardo T. de Almeida 《Transition Metal Chemistry》2014,39(5):495-500
Five new complexes of general formula [PdX2(p-diben)], where p-diben = N,N′-bis(4-dimethylaminobenzylidene)ethane-1,2-diamine) (1) and X = Cl (2), Br (3), I (4), N3 (5), or CNO (6), were synthesized and characterized by physicochemical and spectroscopic methods. The crystal structure of compound (5) was determined by single-crystal X-ray diffraction. Complexes 2–6 were characterized as N,N-chelated products. The crystal structure confirmed this formulation for [Pd(N3)2(p-diben)], besides showing the isomerism inversion of one of the C=N bonds, caused by Pd(II) coordination. 相似文献
152.
Oliver Mahony Sheng Yue Claudia Turdean-Ionescu John V. Hanna Mark E. Smith Peter D. Lee Julian R. Jones 《Journal of Sol-Gel Science and Technology》2014,69(2):288-298
Owing to their diverse range of highly tailorable material properties, inorganic/organic hybrids have the potential to meet the needs of biodegradable porous scaffolds across a range of tissue engineering applications. One such hybrid platform, the silica–gelatin sol–gel system, was examined and developed in this study. These hybrid scaffolds exhibit covalently linked interpenetrating networks of organic and inorganic components, which allows for independent control over their mechanical and degradation properties. A combination of the sol–gel foaming process and freeze drying was used to create an interconnected pore network. The synthesis and processing of the scaffolds has many variables that affect their structure and properties. The focus of this study was to develop a matrix tool that shows the inter-relationship between process variables by correlating the key hybrid material properties with the synthesis parameters that govern them. This was achieved by investigating the effect of the organic (gelatin) molecular weight and collating previously reported data. Control of molecular weight of the polymer is as an avenue that allows the modification of hybrid material properties without changing the surface chemistry of the material, which is a factor that governs the cell and tissue interaction with the scaffold. This presents a significant step forward in understanding the complete potential of the silica–gelatin hybrid system as a medical device. 相似文献
153.
Dr. Bidyut B. Sarma Jonglack Kim Jonas Amsler Dr. Giovanni Agostini Dr. Claudia Weidenthaler Norbert Pfänder Dr. Raul Arenal Dr. Patricia Concepción Dr. Philipp Plessow Prof. Dr. Felix Studt Dr. Gonzalo Prieto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5855-5864
Realizing the full potential of oxide-supported single-atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one-pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization-hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double-bond migration and anti-Markovnikov α-olefin hydrosilylation, respectively. First-principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single-pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio-selectivity (>95 %) even from industrially-relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide-supported single-atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. 相似文献
154.
Dr. Verena K. Gramm Daniel Smets Dr. Ireneus Grzesiak Theresa Block Prof. Dr. Rainer Pöttgen Dr. Markus Suta Prof. Dr. Claudia Wickleder Prof. Dr. Thomas Lorenz Prof. Dr. Uwe Ruschewitz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(12):2726-2734
Anhydrous EuII–acetylenedicarboxylate (EuADC; ADC2− = −O2C-C≡C-CO2−) was synthesized by reaction of EuBr2 with K2ADC or H2ADC in degassed water under oxygen-free conditions. EuADC crystallizes in the SrADC type structure (I41/amd, Z=4) forming a 3D coordination polymer with a diamond-like arrangement of Eu2+ nodes (msw topology including the connecting ADC2− linkers). Deep orange coloured EuADC is stable in air and starts decomposing upon heating in an argon atmosphere only at 440 °C. Measurements of the magnetic susceptibilities (μeff=7.76 μB) and 151Eu Mössbauer spectra (δ=−13.25 mm s−1 at 78 K) confirm the existence of Eu2+ cations. Diffuse reflectance spectra indicate a direct optical band gap of Eg=2.64 eV (470 nm), which is in accordance with the orange colour of the material. Surprisingly, EuADC does not show any photoluminescence under irradiation with UV light of different wavelengths. Similar to SrADC, EuADC exhibits a negative thermal volume expansion below room temperature with a volume expansion coefficient αV=−9.4(12)×10−6 K−1. 相似文献
155.
Apoorva D. Srivastava Dr. Luca Unione Dr. Margreet A. Wolfert Dr. Pablo Valverde Dr. Ana Ardá Prof. Dr. Jesús Jiménez-Barbero Prof. Dr. Geert-Jan Boons 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15605-15612
The parasitic worm, Schistosoma mansoni, expresses unusual fucosylated glycans in a stage-dependent manner that can be recognized by the human innate immune receptor DC-SIGN, thereby shaping host immune responses. We have developed a synthetic approach for mono- and bis-fucosylated LacdiNAc (LDN-F and LDN-DF, respectively), which are epitopes expressed on glycolipids and glycoproteins of S. mansoni. It is based on the use of monosaccharide building blocks having carefully selected amino-protecting groups, facilitating high yielding and stereoselective glycosylations. The molecular interaction between the synthetic glycans and DC-SIGN was studied by NMR and molecular modeling, which demonstrated that the α1,3-fucoside of LDN-F can coordinate with the Ca2+-ion of the canonical binding site of DC-SIGN allowing for additional interactions with the underlying LDN backbone. The 1,2-fucoside of LDN-DF can be complexed in a similar manner, however, in this binding mode GlcNAc and GalNAc of the LDN backbone are placed away from the protein surface resulting in a substantially lower binding affinity. Glycan microarray binding studies showed that the avidity and selectivity of binding is greatly enhanced when the glycans are presented multivalently, and in this format Lex and LDN-F gave strong responsiveness, whereas no binding was detected for LDN-DF. The data indicates that S. mansoni has developed a strategy to avoid detection by DC-SIGN in a stage-dependent manner by the addition of a fucoside to a number of its ligands. 相似文献
156.
Dr. Alessandro Presentato Dr. Antonino Scurria Dr. Lorenzo Albanese Dr. Claudia Lino Dr. Marzia Sciortino Dr. Mario Pagliaro Dr. Federica Zabini Dr. Francesco Meneguzzo Prof. Rosa Alduina Dr. Domenico Nuzzo Dr. Rosaria Ciriminna 《ChemistryOpen》2020,9(5):628-630
Pectin extracted via hydrodynamic cavitation in water only from waste lemon peel and further isolated via freeze drying displays significant antibacterial activity against Staphylococcus aureus, a Gram positive pathogen which easily contaminates food. The antibacterial effect of the new IntegroPectin is largely superior to that of commercial citrus pectin, opening the way to advanced applications of a new bioproduct now obtainable in large amounts and at low cost from citrus juice industry's waste. 相似文献
157.
Alejandro Valverde Amira ben Hassine Vernica Serafín Cristina Muoz‐San Martín María Pedrero María Garranzo‐Asensio Maria Gamella Noureddine Raouafi Rodrigo Barderas Paloma Yez‐Sedeo Susana Campuzano Jos M. Pingarrn 《Electroanalysis》2020,32(4):706-714
This paper reports the development of a dual immunosensor using magnetic microcarriers (MBs) and amperometric transduction at dual screen‐printed carbon electrodes (SPdCEs) for the simultaneous determination of two biomarkers: interleukin‐13 receptor α2 (IL‐13Rα2) and E‐cadherin (E‐CDH), with both extracellular and soluble fraction; oncogenic and tumor suppressor markers, respectively, of great relevance in metastatic processes. The implemented methodology involved the formation of sandwich‐type immunocomplexes using specific capture antibodies immobilized onto carboxylic acid magnetic microbeads (HOOC‐MBs), and biotinylated detector antibodies labeled with streptavidin?horseradish peroxidase conjugates (Strep‐HRP). The amperometric detection was performed by addition of hydrogen peroxide in the presence of hydroquinone (HQ) as the redox mediator. The dual immunosensing platform provided linear calibration ranges suitable for the determination of both biomarkers in liquid and solid clinical specimens as well as excellent selectivity against other cancer biomarkers. This simple handling dual bioplatform was applied to the determination of the soluble and extracellular fraction of the target biomarkers in serum and paraffined‐embedded tissues from colorectal cancer (CRC) patients diagnosed at different tumor grade. The obtained results reveal great potential of this configuration to improve the reliability in diagnosing metastatic CRC. 相似文献
158.
Santiago Pedro H. O. Fujimori Mahmi Chagas Marcio A. S. França Eduardo L. Honorio-França Adenilda C. Gatto Claudia C. 《Structural chemistry》2020,31(1):171-180
Structural Chemistry - Two novel Cu(I) complexes with the 2-acetylpyridine-N(4)-phenyl semicarbazone (HL) ligand, [CuCl (HL)(PPh3)]∙CH3CN (1) and [CuBr (HL)(PPh3)] (2), were investigated by... 相似文献
159.
Emanuela Colombo Rosaria Pascente Daniela Triolo Claudia Bassani Anthea De Angelis Francesca Ruffini Linda Ottoboni Giancarlo Comi Gianvito Martino Cinthia Farina 《Molecules (Basel, Switzerland)》2020,25(22)
Astrocytes greatly participate to inflammatory and neurotoxic reactions occurring in neurodegenerative diseases and are valuable pharmacological targets to support neuroprotection. Here we used human astrocytes generated from reprogrammed fibroblasts as a cellular model to study the effect of the compound Laquinimod and its active metabolite de-Laquinimod on astrocyte functions and the astrocyte–neuron interaction. We show that human iAstrocytes expressed the receptor for the inflammatory mediator IL1 and responded to it via nuclear translocation of NFκB, an event that did not occur if cells were treated with Laquinimod, indicating a direct anti-inflammatory activity of the drug on the human astrocyte. Similarly, while exposure to IL1 downregulated glial glutamate transporters GLAST and GLT1, treatment with Laquinimod supported maintenance of physiological levels of these proteins despite the inflammatory milieu. Laquinimod also induced nuclear translocation of the aryl hydrocarbon receptor (AHR), suggesting that drug action was mediated by activation of the AHR pathway. However, the drug was effective despite AHR inhibition via CH223191, indicating that AHR signaling in the astrocyte is dispensable for drug responses. Finally, in vitro experiments with rat spinal neurons showed that laquinimod did not exert neuroprotection directly on the neuron but dampened astrocyte-induced neurodegeneration. Our findings indicate that fibroblast-derived human astrocytes represent a suitable model to study astrocyte–neuron crosstalk and demonstrate indirect, partial neuroprotective efficacy for laquinimod. 相似文献
160.
Bidyut B. Sarma Jonglack Kim Jonas Amsler Giovanni Agostini Claudia Weidenthaler Norbert Pfnder Raul Arenal Patricia Concepcin Philipp Plessow Felix Studt Gonzalo Prieto 《Angewandte Chemie (International ed. in English)》2020,59(14):5806-5815
Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one‐pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization‐hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double‐bond migration and anti‐Markovnikov α‐olefin hydrosilylation, respectively. First‐principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single‐pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio‐selectivity (>95 %) even from industrially‐relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide‐supported single‐atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. 相似文献