全文获取类型
收费全文 | 3323篇 |
免费 | 232篇 |
国内免费 | 6篇 |
专业分类
化学 | 2415篇 |
晶体学 | 5篇 |
力学 | 75篇 |
数学 | 623篇 |
物理学 | 443篇 |
出版年
2023年 | 53篇 |
2022年 | 45篇 |
2021年 | 82篇 |
2020年 | 97篇 |
2019年 | 113篇 |
2018年 | 63篇 |
2017年 | 43篇 |
2016年 | 154篇 |
2015年 | 130篇 |
2014年 | 142篇 |
2013年 | 181篇 |
2012年 | 218篇 |
2011年 | 237篇 |
2010年 | 141篇 |
2009年 | 93篇 |
2008年 | 153篇 |
2007年 | 142篇 |
2006年 | 146篇 |
2005年 | 137篇 |
2004年 | 100篇 |
2003年 | 76篇 |
2002年 | 83篇 |
2001年 | 29篇 |
2000年 | 24篇 |
1999年 | 25篇 |
1998年 | 34篇 |
1997年 | 31篇 |
1996年 | 33篇 |
1995年 | 25篇 |
1994年 | 24篇 |
1993年 | 44篇 |
1992年 | 27篇 |
1991年 | 21篇 |
1990年 | 23篇 |
1989年 | 20篇 |
1988年 | 30篇 |
1987年 | 36篇 |
1986年 | 24篇 |
1985年 | 35篇 |
1984年 | 29篇 |
1983年 | 25篇 |
1982年 | 21篇 |
1981年 | 21篇 |
1980年 | 25篇 |
1979年 | 12篇 |
1978年 | 16篇 |
1976年 | 16篇 |
1974年 | 21篇 |
1966年 | 12篇 |
1909年 | 11篇 |
排序方式: 共有3561条查询结果,搜索用时 19 毫秒
91.
Matthias Treu Christian Hametner Johannes Frohlich Ulrich Jordis Kurt Mereiter 《Journal of heterocyclic chemistry》2002,39(6):1283-1288
The synthesis of a novel unnatural carbocyclic analog of the acetylcholine esterase inhibitor galanthamine with a K3[Fe(CN)6] promoted oxidative tandem cyclization as the key step is reported. 相似文献
92.
93.
René Csuk Johannes Haas Helmut Hönig Hans Weidmann 《Monatshefte für Chemie / Chemical Monthly》1981,112(6-7):879-882
A synthesis of new boron containingMannich bases of salicylamide by reaction of salicylamide, formaldehyde and boron-heterocycles is reported.
VIII. Mitteilung:Stump, R. K., Zimmerman jr., H. K., Schleppnik, A. A., Gutsche, C. D., Liebigs Ann. Chem.667, 18 (1963). 相似文献
94.
Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111) 总被引:2,自引:0,他引:2
Barth JV Weckesser J Trimarchi G Vladimirova M De Vita A Cai C Brune H Günter P Kern K 《Journal of the American Chemical Society》2002,124(27):7991-8000
We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems. 相似文献
95.
Chlorocarbenium salts
-
of the Vilsmeier-Arnold type react with the silylated isocyanuric acid
to give 1-oxa-3-azabutatrienium salts
under mild conditions. From reactions of diarylchloromethenium salts
-
with
and ketones or tertiary carboxamides high yields of 2-azaallenium salts
were obtained. A few chloro substituted 2-azaallenium salts
were prepared from
and carbonyl compounds. The mechanisms of the new reactions are discussed. 相似文献
96.
Molybdenum cofactor (Moco) deficiency (MoCD) is characterized by neonatal-onset myoclonic epileptic encephalopathy and dystonia with cerebral MRI changes similar to hypoxic–ischemic lesions. The molecular cause of the disease is the loss of sulfite oxidase (SOX) activity, one of four Moco-dependent enzymes in men. Accumulating toxic sulfite causes a secondary increase of metabolites such as S-sulfocysteine and thiosulfate as well as a decrease in cysteine and its oxidized form, cystine. Moco is synthesized by a three-step biosynthetic pathway that involves the gene products of MOCS1, MOCS2, MOCS3, and GPHN. Depending on which synthetic step is impaired, MoCD is classified as type A, B, or C. This distinction is relevant for patient management because the metabolic block in MoCD type A can be circumvented by administering cyclic pyranopterin monophosphate (cPMP). Substitution therapy with cPMP is highly effective in reducing sulfite toxicity and restoring biochemical homeostasis, while the clinical outcome critically depends on the degree of brain injury prior to the start of treatment. In the absence of a specific treatment for MoCD type B/C and SOX deficiency, we summarize recent progress in our understanding of the underlying metabolic changes in cysteine homeostasis and propose novel therapeutic interventions to circumvent those pathological changes. 相似文献
97.
Lorenzo Estivi Luisa Pellegrino Johannes A. Hogenboom Andrea Brandolini Alyssa Hidalgo 《Molecules (Basel, Switzerland)》2022,27(21)
A viable approach to improve the nutritional quality of cereal-based foods is their enrichment with pseudocereals. The aim of this research was to evaluate the antioxidant properties of amaranth, quinoa and buckwheat, and the heat damage of water biscuits (WB) produced from either wholemeal or refined flour of einkorn and enriched with 50% buckwheat, amaranth or quinoa wholemeal. Buckwheat had the highest tocols content (86.2 mg/kg), and einkorn the most carotenoids (5.6 mg/kg). Conjugated phenolics concentration was highest in buckwheat (230.2 mg/kg) and quinoa (218.6 mg/kg), while bound phenolics content was greatest in einkorn (712.5 mg/kg) and bread wheat (675.7 mg/kg). The all-wholemeal WB had greater heat damage than those containing refined flour (furosine: 251.5 vs. 235.8 mg/100 g protein; glucosylisomaltol: 1.0 vs. 0.6 mg/kg DM; hydroxymethylfurfural: 4.3 vs. 2.8 mg/kg DM; furfural: 8.6 vs. 4.8 mg/kg DM). The 100% bread wheat and einkorn wholemeal WB showed greater heat damage than the WB with pseudocereals (furfural, 9.2 vs. 5.1 mg/kg; glucosylisomaltol 1.1 vs. 0.7 mg/kg). Despite a superior lysine loss, the amino-acid profile of the pseudocereals-enriched WB remained more balanced compared to that of the wheats WB. 相似文献
98.
Johannes Krebs Alena Hfner Sonja Fuchs Xueying Guo Florian Rauch Antonius Eichhorn Ivo Krummenacher Alexandra Friedrich Lei Ji Maik Finze Zhenyang Lin Holger Braunschweig Todd B. Marder 《Chemical science》2022,13(47):14165
The choice of backbone linker for two ortho-bis-(9-borafluorene)s has a great influence on the LUMO located at the boron centers and, therefore, the reactivity of the respective compounds. Herein, we report the room temperature rearrangement of 1,2-bis-(9-borafluorenyl)-ortho-carborane, C2B10H10-1,2-[B(C12H8)]2 ([2a]) featuring o-carborane as the inorganic three-dimensional backbone and the synthesis of 1,2-bis-(9-borafluorenyl)benzene, C6H4-1,2-[B(C12H8)]2 (2b), its phenylene analog. DFT calculations on the transition state for the rearrangement support an intramolecular C–H bond activation process via an SEAr-like mechanism in [2a], and predicted that the same rearrangement would take place in 2b, but at elevated temperatures, which indeed proved to be the case. The rearrangement gives access to 3a and 3b as dibora-benzo[a]fluoroanthene isomers, a form of diboron polycyclic aromatic hydrocarbon (PAH) that had yet to be explored. The isolated compounds 2b, 3a, and 3b were fully characterized by NMR, HRMS, cyclic voltammetry (CV), single-crystal X-ray diffraction analysis, and photophysical measurements, supported by DFT and TD-DFT calculations.The backbone linker for two ortho-bis-(9-borafluorene)s influences the LUMO at the boron centers and the reactivity of the respective compounds. 相似文献
99.
Johannes Karthuser Vladimirs Biziks Carsten Mai Holger Militz 《Molecules (Basel, Switzerland)》2021,26(9)
Improving the environmental performance of resins in wood treatment by using renewable chemicals has been a topic of interest for a long time. At the same time, lignin, the second most abundant biomass on earth, is produced in large scale as a side product and mainly used energetically. The use of lignin in wood adhesives or for wood modification has received a lot of scientific attention. Despite this, there are only few lignin-derived wood products commercially available. This review provides a summary of the research on lignin application in wood adhesives, as well as for wood modification. The research on the use of uncleaved lignin and of cleavage products of lignin is reviewed. Finally, the current state of the art of commercialization of lignin-derived wood products is presented. 相似文献
100.
Carsten Jaeschke Marta Padilla Johannes Glckler Inese Polaka Martins Leja Viktors Veliks Jan Mitrovics Marcis Leja Boris Mizaikoff 《Molecules (Basel, Switzerland)》2021,26(12)
Exhaled breath analysis for early disease detection may provide a convenient method for painless and non-invasive diagnosis. In this work, a novel, compact and easy-to-use breath analyzer platform with a modular sensing chamber and direct breath sampling unit is presented. The developed analyzer system comprises a compact, low volume, temperature-controlled sensing chamber in three modules that can host any type of resistive gas sensor arrays. Furthermore, in this study three modular breath analyzers are explicitly tested for reproducibility in a real-life breath analysis experiment with several calibration transfer (CT) techniques using transfer samples from the experiment. The experiment consists of classifying breath samples from 15 subjects before and after eating a specific meal using three instruments. We investigate the possibility to transfer calibration models across instruments using transfer samples from the experiment under study, since representative samples of human breath at some conditions are difficult to simulate in a laboratory. For example, exhaled breath from subjects suffering from a disease for which the biomarkers are mostly unknown. Results show that many transfer samples of all the classes under study (in our case meal/no meal) are needed, although some CT methods present reasonably good results with only one class. 相似文献