全文获取类型
收费全文 | 1581篇 |
免费 | 36篇 |
国内免费 | 8篇 |
专业分类
化学 | 1076篇 |
晶体学 | 7篇 |
力学 | 43篇 |
数学 | 231篇 |
物理学 | 268篇 |
出版年
2023年 | 8篇 |
2022年 | 34篇 |
2021年 | 41篇 |
2020年 | 22篇 |
2019年 | 25篇 |
2018年 | 23篇 |
2017年 | 17篇 |
2016年 | 47篇 |
2015年 | 48篇 |
2014年 | 42篇 |
2013年 | 78篇 |
2012年 | 86篇 |
2011年 | 114篇 |
2010年 | 79篇 |
2009年 | 61篇 |
2008年 | 113篇 |
2007年 | 99篇 |
2006年 | 113篇 |
2005年 | 96篇 |
2004年 | 84篇 |
2003年 | 68篇 |
2002年 | 59篇 |
2001年 | 23篇 |
2000年 | 18篇 |
1999年 | 13篇 |
1998年 | 15篇 |
1997年 | 12篇 |
1996年 | 20篇 |
1995年 | 13篇 |
1994年 | 9篇 |
1993年 | 3篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 4篇 |
1989年 | 7篇 |
1988年 | 8篇 |
1987年 | 5篇 |
1986年 | 8篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 14篇 |
1981年 | 10篇 |
1980年 | 6篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1975年 | 7篇 |
1970年 | 5篇 |
1969年 | 3篇 |
排序方式: 共有1625条查询结果,搜索用时 15 毫秒
31.
[reaction: see text] Ketyl radicals with lignin related structures have been generated by means of radiation chemical and photochemical techniques. In the former studies ketyl radicals are produced by reaction of alpha-carbonyl-beta-aryl ether lignin models with the solvated electron produced by pulse radiolysis of an aqueous solution at pH 6.0. The UV-vis spectra of ketyl radicals are characterized by three main absorption bands. The shape and position of these bands slightly change when the spectra are recorded in alkaline solution (pH 11.0) being now assigned to the ketyl radical anions and a pKa = 9.5 is determined for the 1-(3,4,5-trimethoxyphenyl)-2-phenoxyethanol-1-yl radical. Decay rates of ketyl radicals are found to be dose dependent and, at low doses, lie in the range (1.7-2.7) x 10(3) s(-1). In the presence of oxygen a fast decay of the ketyl radicals is observed (k2 = 1.8-2.7 x 10(9) M(-1) s(-1)) that is accompanied by the formation of stable products, i.e., the starting ketones. In the photochemical studies ketyl radicals have been produced by charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methyl viologen (MV2+) with alpha-hydroxy-alpha-phenoxymethyl-aryl acetates. This process leads to the instantaneous formation of the reduced acceptor (methyl viologen radical cation, MV+*), as is clearly shown in a laser flash photolysis experiment by the two absorption bands centered at 390 and 605 nm, and an acyloxyl radical [ArC(CO2*))(OH)CH2(OC6H5)], which undergoes a very fast decarboxylation with formation of the ketyl radicals. Steady-state photoirradiation of the CT ion pairs indicates that 1-aryl-2-phenoxyethanones are formed as primary photoproducts by oxidation of ketyl radicals by MV2+ (under argon) or by molecular oxygen. Small amounts of acetophenones are formed by further photolysis of 1-aryl-2-phenoxyethanones and not by beta-fragmentation of the ketyl radicals. The high reactivity of ketyl radicals with oxygen coupled with the low rates of beta-fragmentation of the same species have an important bearing in the context of the photoyellowing of lignin containing pulps and papers. 相似文献
32.
(2S)- and (2R)-2-Amino-4-bromobutanoic acid were prepared starting from N-Boc-glutamic acid α tert-butyl ester. The double tert-butyl protection was necessary to prevent a partial racemisation during Barton’s radical decarboxylation used to transform the γ-carboxylic group into a bromide. This bromide reacted with different nitrogen, oxygen and sulphur nucleophiles to give nonnatural amino acids characterised by basic or heterocyclic side chains. The title compound was also used to prepare a conformationally constrained peptidomimetic. 相似文献
33.
The effect of energy exchange on the dynamics of the chemisorption of H2 on Pt (111) is studied within a LEPS potential quasi-classical trajectories treatment. The Einstein model is assumed for the solid. The rigidity of the surfaces is shown to be an acceptable approximation. 相似文献
34.
Norberto Masciocchi Vincenzo Mirco Abbinante Marco Zambra Giuseppe Barreca Massimo Zampieri 《Molecules (Basel, Switzerland)》2022,27(21)
Tafamidis, chemical formula C14H7Cl2NO3, is a drug used to delay disease progression in adults suffering from transthyretin amyloidosis, and is marketed worldwide under different tradenames as a free acid or in the form of its meglumine salt. The free acid (CAS no. 594839-88-0) is reported to crystallize as distinct (polymorphic) crystal forms, the thermal stability and structural features of which remained thus far undisclosed. In this paper, we present—by selectively isolating highly pure batches of Tafamidis Form 1 and Tafamidis Form 4—the full characterization of these solids, in terms of crystal structures (determined using state-of-the-art structural powder diffraction methods) and spectroscopic and thermal properties. Beyond conventional thermogravimetric and calorimetric analyses, variable-temperature X-ray diffraction was employed to measure the highly anisotropic response of these (poly)crystalline materials to thermal stimuli and enabled the determination of the linear and volumetric thermal expansion coefficients and of the related indicatrix. Both crystal phases are monoclinic and contain substantially flat and π-π stacked Tafamidis molecules, arranged as centrosymmetric dimers by strong O-H···O bonds; weaker C-H···N contacts give rise, in both polymorphs, to infinite ribbons, which guarantee the substantial stiffness of the crystals in the direction of their elongation. Complete knowledge of the structural models will foster the usage of full-pattern quantitative phase analyses of Tafamidis in drug and polymorphic mixtures, an important aspect in both the forensic and the industrial sectors. 相似文献
35.
Elisabetta Marini Marco Marino Giulia Gionfriddo Federica Maione Marta Pandini Daniele Oddo Marta Giorgis Barbara Rolando Federica Blua Simone Gastaldi Serena Marchi Sandra Kovachka Francesca Spyrakis Eleonora Gianquinto Federica Di Nicolantonio Massimo Bertinaria 《Molecules (Basel, Switzerland)》2022,27(23)
BRAF is a serine/threonine kinase frequently mutated in human cancers. BRAFV600E mutated protein is targeted through the use of kinase inhibitors which are approved for the treatment of melanoma; however, their long-term efficacy is hampered by resistance mechanisms. The PROTAC-induced degradation of BRAFV600E has been proposed as an alternative strategy to avoid the onset of resistance. In this study, we designed a series of compounds where the BRAF kinase inhibitor encorafenib was conjugated to pomalidomide through different linkers. The synthesized compounds maintained their ability to inhibit the kinase activity of mutated BRAF with IC50 values in the 40–88 nM range. Selected compounds inhibited BRAFV600E signaling and cellular proliferation of A375 and Colo205 tumor cell lines. Compounds 10 and 11, the most active of the series, were not able to induce degradation of mutated BRAF. Docking and molecular dynamic studies, conducted in comparison with the efficient BRAF degrader P5B, suggest that a different orientation of the linker bearing the pomalidomide substructure, together with a decreased mobility of the solvent-exposed part of the conjugates, could explain this behavior. 相似文献
36.
Gourab Chatterjee Ajay Jha Alejandro Blanco-Gonzalez Vandana Tiwari Madushanka Manathunga Hong-Guang Duan Friedjof Tellkamp Valentyn I. Prokhorenko Nicolas Ferr Jyotishman Dasgupta Massimo Olivucci R. J. Dwayne Miller 《Chemical science》2022,13(32):9392
The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Here, we demonstrate that out-of-plane torsional deformation and vibrational excitation of stretching motions in the electronic ground state modulate the charge-density distribution in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change, visualised by transient absorption spectroscopy with a mid-infrared pump and a visible probe, is mechanistically resolved by ab initio molecular dynamics simulations. Mapping the potential energy landscape attributes the observed charge-coupled coherent nuclear motions to the population of the initial segment of a double-bond isomerization channel, also seen in biological molecules. Our results illustrate the pivotal role of pre-twisted molecular geometries in enhancing the transfer of vibrational energy to specific molecular modes, prior to thermal redistribution. This motivates the search for synthetic strategies towards achieving potentially new infrared-mediated chemistry.Channelling vibrational excitation energy to achieve ground-state charge-transfer (CT)-assisted isomerization in a donor-bridge-acceptor molecule in solution. 相似文献
37.
Roberta Cassano Massimo Cuconato Gabriella Calviello Simona Serini Sonia Trombino 《Molecules (Basel, Switzerland)》2021,26(4)
Melanoma is one of the most aggressive forms of skin cancer, with few possibilities for therapeutic approaches, due to its multi-drug resistance and, consequently, low survival rate for patients. Conventional therapies for treatment melanoma include radiotherapy, chemotherapy, targeted therapy, and immunotherapy, which have various side effects. For this reason, in recent years, pharmaceutical and biomedical research has focused on new sito-specific alternative therapeutic strategies. In this regard, nanotechnology offers numerous benefits which could improve the life expectancy of melanoma patients with very low adverse effects. This review aims to examine the latest advances in nanotechnology as an innovative strategy for treating melanoma. In particular, the use of different types of nanoparticles, such as vesicles, polymers, metal-based, carbon nanotubes, dendrimers, solid lipid, microneedles, and their combination with immunotherapies and vaccines will be discussed. 相似文献
38.
Carlo Bruno Eleonora Ussano Gianni Barucca Davide Vanossi Giovanni Valenti Edward A. Jackson Andrea Goldoni Lucio Litti Simona Fermani Luca Pasquali Moreno Meneghetti Claudio Fontanesi Lawrence T. Scott Francesco Paolucci Massimo Marcaccio 《Chemical science》2021,12(23):8048
The presence of non-hexagonal rings in the honeycomb carbon arrangement of graphene produces rippled graphene layers with valuable chemical and physical properties. In principle, a bottom-up approach to introducing distortion from planarity of a graphene sheet can be achieved by careful insertion of curved polyaromatic hydrocarbons during the growth of the lattice. Corannulene, the archetype of such non-planar polyaromatic hydrocarbons, can act as an ideal wrinkling motif in 2D carbon nanostructures. Herein we report an electrochemical bottom-up method to obtain egg-box shaped nanographene structures through a polycondensation of corannulene that produces a new conducting layered material. Characterization of this new polymeric material by electrochemistry, spectroscopy, electron microscopy (SEM and TEM), scanning probe microscopy, and laser desorption-ionization time of flight mass spectrometry provides strong evidence that the anodic polymerization of corannulene, combined with electrochemically induced oxidative cyclodehydrogenations (Scholl reactions), leads to polycorannulene with a wavy graphene-like structure.A bottom-up synthesis of wavy graphene structures obtained through an anodic polymerization process, combined with an electrochemically triggered oxidative cyclodehydrogenation, of the bowl-shaped polyaromatic hydrocarbon corannulene. 相似文献
39.
The study of the ageing of two paper types was performed on monitoring it during a simulated process by means of the measure of the photocatalytic degradation of the paper cellulose. Such evaluation was possible due to the combined responses of a photosensor based on titanium dioxide in suspension, of an enzymatic biosensor based on superoxide dismutase (SOD), of a specific conductivity sensor and of an enzymatic biosensor based on glucose oxidase. 相似文献
40.
Gehrhus B Hitchcock PB Parruci M 《Dalton transactions (Cambridge, England : 2003)》2005,(16):2720-2725
The thermally stable silylene Si[(NCH2But)2C6H4-1,2] 1 undergoes oxidative addition reactions with the lithium amides LiNRR'(R = SiMe3, R' = But; R = SiMe3, R' = C6H3Me2-2,6; R = R' = Me or R = R' = Pri) to afford the new lithium amides Li(THF)2[N(R)Si(SiMe3){(NCH2But)2C6H4-1,2}][R = But2 or R = C6H3Me2-2,6 (3a)] or the new tris(amino)functionalised silyllithiums Li(THF)x[Si{(NCH2But)2C6H4-1,2}NRR'][R = SiMe3, R' = C6H3Me2-2,6, x = 2 (3); R = R'= Me, x = 3 (4) or R = R' = Pri, x = 3 (5)]. Compounds 4 and 5 are stable at ambient temperature but compound 3 is thermally labile and converts into 3a upon heating. The pathway for the formation of 2 and 3 is discussed and the X-ray structures of 2-5 are presented. 相似文献