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951.
Baroudi A Alicea J Flack P Kirincich J Alabugin IV 《The Journal of organic chemistry》2011,76(6):1521-1537
We report a metal-free procedure for transformation of phenols into esters and amides of benzoic acids via a new radical cascade. Diaryl thiocarbonates and thiocarbamates, available in a single high-yielding step from phenols, selectively add silyl radicals at the sulfur atom of the C═S moiety. This addition step, analogous to the first step of the Barton-McCombie reaction, produces a carbon radical which undergoes 1,2 O→C transposition through an O-neophyl rearrangement. The usually unfavorable equilibrium in the reversible rearrangement step is shifted forward via a highly exothermic C-S bond scission in the O-centered radical, which furnishes the final benzoic ester or benzamide product. The metal-free preparation of benzoic acid derivatives from phenols provides a potentially useful alternative to metal-catalyzed carbonylation of aryl triflates. 相似文献
952.
Mohammednoor Altarawneh Phillip V. Smith Eric M. Kennedy 《Applied Surface Science》2008,254(14):4218-4224
The interaction between a 2-chlorophenol (C6H4OHCl) molecule and the Cu(1 1 1) surface has been investigated using density functional theory as an initial step in gaining a better understanding of the catalyzed formation of dioxin compounds on a clean copper surface. The 2-chlorophenol molecule is found to form several weakly bonded, horizontally and vertically oriented configurations. Dissociative modes have also been investigated. For the latter, the formation of phenyl and benzyne fragments is found to be more energetically favourable than the formation of 2-chlorophenoxy radicals. 相似文献
953.
Filopodia are long, fingerlike membrane tubes supported by cytoskeletal filaments. Their shape is determined by the stiffness of the actin filament bundles found inside them and by the interplay between the surface tension and bending rigidity of the membrane. Although one might expect the Euler buckling instability to limit the length of filopodia, we show through simple energetic considerations that this is in general not the case. By further analyzing the statics of filaments inside membrane tubes, and through computer simulations that capture membrane and filament fluctuations, we show under which conditions filopodia of arbitrary lengths are stable. We discuss several in vitro experiments where this kind of stability has already been observed. Furthermore, we predict that the filaments in long, stable filopodia adopt a helical shape. 相似文献
954.
Chaitanya Mudivarthi Supratik Datta Phillip G. Evans Alison B. Flatau 《Journal of magnetism and magnetic materials》2010,322(20):3028-3034
The magnetic anisotropy of a ferromagnetic material that is free to deform is defined as the effective anisotropy, which is the sum of intrinsic anisotropy and magnetostriction-induced anisotropy. Prior works [1] and [2] (Baltzer, 1957; Kittel, 1949) indicate that if the material is undeformed then the measured anisotropy is same as its intrinsic anisotropy. When magnetostrictive materials are used as actuators or sensors they are often mechanically loaded, resulting in a restriction on the deformation. To capture their behavior in such scenarios, a modelling approach is required. Therefore, in this work, the thermodynamic accuracy of the common expressions for magnetostriction-induced and stress-induced anisotropies is first investigated. A 3D magnetoelastic model is then developed using Armstrong's implementation of an energy model. This 3D magnetoelastic model is capable of predicting the stresses induced when the magnetostriction of these materials is constrained. Using this model, it is shown that when the bulk magnetostriction of the material is clamped, the measured anisotropy will not in general be the same as the intrinsic anisotropy. It is also shown that when the magnetostriction is clamped at the microscopic level, i.e. if the material is locally constrained at the exchange length scales, then the measured anisotropy is the intrinsic anisotropy. 相似文献
955.
The application of an active braze alloy (ABA) known as Copper ABA® (Cu–3.0Si–2.3Ti–2.0Al wt.%) to join Al2O3 to Kovar® (Fe–29Ni–17Co wt.%) has been investigated. This ABA was selected to increase the operating temperature of the joint beyond the capabilities of typically used ABAs such as Ag–Cu–Ti-based alloys. Silica present as a secondary phase in the Al2O3 at a level of ~5 wt.% enabled the ceramic component to bond to the ABA chemically by forming a layer of Si3Ti5 at the ABA/Al2O3 interface. Appropriate brazing conditions to preserve a near-continuous Si3Ti5 layer on the Al2O3 and a continuous Fe3Si layer on the Kovar® were found to be a brazing time of ≤15 min at 1025 °C or ≤2 min at 1050 °C. These conditions produced joints that did not break on handling and could be prepared easily for microscopy. Brazing for longer periods of time, up to 45 min, at these temperatures broke down the Si3Ti5 layer on the Al2O3, while brazing at ≥1075 °C for 2–45 min broke down the Fe3Si layer on the Kovar® significantly. Further complications of brazing at ≥1075 °C included leakage of the ABA out of the joint and the formation of a new brittle silicide, Ni16Si7Ti6, at the ABA/Al2O3 interface. This investigation demonstrates that it is not straightforward to join Al2O3 to Kovar® using Copper ABA®, partly because the ranges of suitable values for the brazing temperature and time are quite limited. Other approaches to increase the operating temperature of the joint are discussed. 相似文献
956.
Leila Takahashi-Ruiz Joseph D. Morris Phillip Crews Tyler A. Johnson April L. Risinger 《Molecules (Basel, Switzerland)》2022,27(13)
Microtubule-stabilizing agents (MSAs) are a class of compounds used in the treatment of triple-negative breast cancer (TNBC), a subtype of breast cancer where chemotherapy remains the standard-of-care for patients. Taxanes like paclitaxel and docetaxel have demonstrated efficacy against TNBC in the clinic, however new classes of MSAs need to be identified due to the rise of taxane resistance in patients. (−)-Zampanolide is a covalent microtubule stabilizer that can circumvent taxane resistance in vitro but has not been evaluated for in vivo antitumor efficacy. Here, we determine that (−)-zampanolide has similar potency and efficacy to paclitaxel in TNBC cell lines, but is significantly more persistent due to its covalent binding. We also provide the first reported in vivo antitumor evaluation of (−)-zampanolide where we determine that it has potent and persistent antitumor efficacy when delivered intratumorally. Future work on zampanolide to further evaluate its pharmacophore and determine ways to improve its systemic therapeutic window would make this compound a potential candidate for clinical development through its ability to circumvent taxane-resistance mechanisms. 相似文献
957.
958.
Phillip Jackson Martin Diefenbach Ragampeta Srinivas Detlef Schroeder Helmut Schwarz 《ChemInform》2000,31(28):no-no
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option. 相似文献
959.
Dr. Phillip M. Danby Andrew Jeong Dr. Lyann Sim Dr. Ryan P. Sweeney Jacob F. Wardman Ryan Karimi Dr. Andreas Geissner Dr. Liam J. Worrall Prof. Dr. Jolene. P. Reid Prof. Dr. Natalie C. J. Strynadka Prof. Dr. Stephen G. Withers 《Angewandte Chemie (International ed. in English)》2023,62(21):e202301258
Suitably configured allyl ethers of unsaturated cyclitols act as substrates of β-glycosidases, reacting via allylic cation transition states. Incorporation of halogens at the vinylic position of these carbasugars, along with an activated leaving group, generates potent inactivators of β-glycosidases. Enzymatic turnover of these halogenated cyclitols (F, Cl, Br) displayed a counter-intuitive trend wherein the most electronegative substituents yielded the most labile pseudo-glycosidic linkages. Structures of complexes with the Sulfolobus β-glucosidase revealed similar enzyme-ligand interactions to those seen in complexes with a 2-fluorosugar inhibitor, the lone exception being displacement of tyrosine 322 from the active site by the halogen. Mutation of Y322 to Y322F largely abolished glycosidase activity, consistent with lost interactions at O5, but minimally affected (7-fold) rates of carbasugar hydrolysis, yielding a more selective enzyme for unsaturated cyclitol ether hydrolysis. 相似文献
960.
Dr. Mengting Liu Dr. Masao Ohashi Qingyang Zhou Dr. Jacob N. Sanders Prof. Erin P. McCauley Prof. Phillip Crews Prof. K. N. Houk Prof. Yi Tang 《Angewandte Chemie (International ed. in English)》2023,62(40):e202311266
We uncovered and reconstituted a concise biosynthetic pathway of the strained dipeptide (+)-azonazine A from marine-derived Aspergillus insulicola. Formation of the hexacyclic benzofuranoindoline ring system from cyclo-(l -Trp-N-methyl-l -Tyr) is catalyzed by a P450 enzyme through an oxidative cyclization. Supplementing the producing strain with various indole-substituted tryptophan derivatives resulted in the generation of a series of azonazine A analogs. 相似文献