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排序方式: 共有338条查询结果,搜索用时 31 毫秒
281.
Niklas von Wolff Joëlle Char Dr. Xavier Frogneux Dr. Thibault Cantat 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(20):5708-5711
The conversion of SO2 into arylsulfones under metal-free conditions was achieved for the first time by reacting SO2 with (hetero)arylsilanes and alkylhalides in the presence of a fluoride source. The mechanism of this transformation was elucidated based on DFT calculations, which highlight the influence of SO2 in promoting C−Si bond cleavage. 相似文献
282.
Lena Berning David Schlütermann Annabelle Friedrich Niklas Berleth Yadong Sun Wenxian Wu María Jos Mendiburo Jana Deitersen Hannah U. C. Brass Margaretha A. Skowron Michle J. Hoffmann Günter Niegisch Jrg Pietruszka Bjrn Stork 《Molecules (Basel, Switzerland)》2021,26(5)
Cisplatin-based treatment is the standard of care therapy for urothelial carcinomas. However, complex cisplatin resistance mechanisms limit the success of this approach. Both apoptosis and autophagy have been shown to contribute to this resistance. Prodigiosin, a secondary metabolite from various bacteria, exerts different biological activities including the modulation of these two cellular stress response pathways. We analyzed the effect of prodigiosin on protein levels of different autophagy- and apoptosis-related proteins in cisplatin-sensitive and -resistant urothelial carcinoma cells (UCCs). Furthermore, we investigated the effect on cell viability of prodigiosin alone or in combination with cisplatin. We made use of four different pairs of cisplatin-sensitive and -resistant UCCs. We found that prodigiosin blocked autophagy in UCCs and re-sensitized cisplatin-resistant cells to apoptotic cell death. Furthermore, we found that prodigiosin is a potent anticancer agent with nanomolar IC50 values in all tested UCCs. In combination studies, we observed that prodigiosin sensitized both cisplatin-sensitive and -resistant urothelial carcinoma cell lines to cisplatin treatment with synergistic effects in most tested cell lines. These effects of prodigiosin are at least partially mediated by altering lysosomal function, since we detected reduced activities of cathepsin B and L. We propose that prodigiosin is a promising candidate for the therapy of cisplatin-resistant urothelial carcinomas, either as a single agent or in combinatory therapeutic approaches. 相似文献
283.
Niklas Wellander 《Applications of Mathematics》2002,47(3):255-283
The Maxwell equations with uniformly monotone nonlinear electric conductivity in a heterogeneous medium, which may be non-periodic, are homogenized by two-scale convergence. We introduce a new set of function spaces appropriate for the nonlinear Maxwell system. New compactness results, of two-scale type, are proved for these function spaces. We prove existence of a unique solution for the heterogeneous system as well as for the homogenized system. We also prove that the solutions of the heterogeneous system converge weakly to the solution of the homogenized system. Furthermore, we prove corrector results, important for numerical implementations. 相似文献
284.
Dr. Roberta Tesch Dr. Christian Becker Dr. Matthias Philipp Müller Dr. Michael Edmund Beck M. Sc. Lena Quambusch Dr. Matthäus Getlik M. Sc. Jonas Lategahn M. Sc. Niklas Uhlenbrock Dr. Fanny Nascimento Costa M. Sc. Marcelo D. Polêto M. Sc. Pedro de Sena Murteira Pinheiro M. Sc. Daniel Alencar Rodrigues Prof. Carlos Mauricio R. Sant'Anna Prof. Fabio Furlan Ferreira Prof. Hugo Verli Prof. Carlos Alberto Manssour Fraga Prof. Daniel Rauh 《Angewandte Chemie (International ed. in English)》2018,57(31):9970-9975
PIK‐75 is a phosphoinositide‐3‐kinase (PI3K) α‐isoform‐selective inhibitor with high potency. Although published structure–activity relationship data show the importance of the NO2 and the Br substituents in PIK‐75, none of the published studies could correctly determine the underlying reason for their importance. In this publication, we report the first X‐ray crystal structure of PIK‐75 in complex with the kinase GSK‐3β. The structure shows an unusual U‐shaped conformation of PIK‐75 within the active site of GSK‐3β that is likely stabilized by an atypical intramolecular Br???NO2 halogen bond. NMR and MD simulations show that this conformation presumably also exists in solution and leads to a binding‐competent preorganization of the PIK‐75 molecule, thus explaining its high potency. We therefore suggest that the site‐specific incorporation of halogen bonds could be generally used to design conformationally restricted bioactive substances with increased potencies. 相似文献
285.
Philip Boehm Niklas Kehl Prof. Dr. Bill Morandi 《Angewandte Chemie (International ed. in English)》2023,62(4):e202214071
A rhodium-catalyzed anti-Markovnikov hydroiodination of aromatic and aliphatic terminal alkynes is reported. Depending on the choice of ligand and substrate, either (E)- or (Z)-configured alkenyl iodides are obtained in high to exclusive isomeric purity. The reaction exhibits a broad substrate scope and high functional group tolerance, employing easily accessible or commercially available aliphatic iodides as HI surrogates through a shuttle process. The synthesized vinyl iodides were applied in several C−C and C−heteroatom bond-forming reactions with full retention of the stereoselectivity. The developed method could be used to significantly shorten the total synthesis of a marine cis-fatty acid. Additionally, initial deuterium-labeling experiments and stoichiometric reactions shed some light on the potential reaction mechanism. 相似文献
286.
Niklas Radhoff Dr. Constantin G. Daniliuc Prof. Dr. Armido Studer 《Angewandte Chemie (International ed. in English)》2023,62(34):e202304771
Design, synthesis and application of benzene bioisosteres have attracted a lot of attention in the past 20 years. Recently, bicyclo[2.1.1]hexanes have emerged as highly attractive bioisosteres for ortho- and meta-substituted benzenes. Herein we report a mild, scalable and transition-metal-free protocol for the construction of highly substituted bicyclo[2.1.1]hexan-2-ones through Lewis acid catalyzed (3+2)-cycloaddition of bicyclo[1.1.0]-butane ketones with disubstituted ketenes. The reaction shows high functional group tolerance as documented by the successful preparation of various 3-alkyl-3-aryl as well as 3,3-bisalkyl bicyclo[2.1.1]hexan-2-ones (26 examples, up to 89 % yield). Postfunctionalization of the exocyclic ketone moiety is also demonstrated. 相似文献
287.
Pietruszka J Schöne N Frey W Grundl L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(17):5178-5197
Allylboronates are highly attractive reagents for allyl additions. Enantiomerically pure, stable reagents with a stereogenic centre in alpha-position to boron are especially versatile, albeit often difficult to synthesize. Starting from boron-containing allyl alcohols 6 and 7, which are discussed in detail herein, a set of reagents were obtained via [3,3]-sigmatropic rearrangements and consecutive transformations in the side chain. The configurations could be established first by chemical correlation, but also by X-ray crystallography (16, 18, 34, and 39). Allyl additions were performed resulting in the formation of predominantly (Z)-configured homoallylic alcohols (31, 43-45) with high enantiomeric excess. Detailed investigations on the matched-mismatched interaction between the reagents 15/16 (and ent-15/ent-16, respectively) and isopropylidene glyceraldehyde 42d are presented. 相似文献
288.
289.
Winter B Aziz EF Ottosson N Faubel M Kosugi N Hertel IV 《Journal of the American Chemical Society》2008,130(22):7130-7138
Charge-transfer-to-solvent (CTTS) excited states of aqueous chloride are studied by a novel experimental approach based on resonant inner-shell photoexcitation, Cl(-)aq 2p --> e(i), i = 1-4, which denotes a series of excitations to lowest and higher CTTS states. These states are clearly identified through the occurrence of characteristic spectator Auger decays to double Cl 3p valence-hole states, where the CTTS states can be more stabilized as compared to single Cl(-)aq 2p core excitations and optical valence excitations. Furthermore, we have found for the first time that the CTTS electron e(i) bound by a single Cl 2p hole not only behaves as a spectator e(i) --> e'(i), bound by a double valence-hole state before relaxation of the excited electron (i) itself, but also shows electron dynamics to the relaxed lowest state, e(i) --> e'(1*). This interpretation is supported by ab initio calculations. The key to performing photoelectron and Auger-electron spectroscopy studies from aqueous solutions is the use of a liquid microjet in ultrahigh vacuum in conjunction with synchrotron radiation. 相似文献
290.
Gador N Samoylova E Smith VR Stolow A Rayner DM Radloff W Hertel IV Schultz T 《The journal of physical chemistry. A》2007,111(46):11743-11749
Femtosecond pump-probe spectroscopy was combined with photoelectron-photoion coincidence detection to investigate the electronic structure and dynamics of isolated adenine (A) and thymine (T) dimers and the adenine-thymine (AT) base pair. The photoelectron spectra show that pipi* and npi* states are only weakly perturbed in the hydrogen-bound dimers as compared to the monomers. For cationic base pairs with internal energies greater than 1 eV, we observed considerable cluster fragmentation into protonated monomers. This process selectively removed signals from the npi* --> n-1 ionization channel in all dimers. The photoelectron spectra are compared to time-resolved mass spectra and confirm the assignment of short-lived pipi* and npi* populations in the adenine, thymine, and mixed AT dimers. 相似文献