全文获取类型
收费全文 | 649篇 |
免费 | 15篇 |
国内免费 | 1篇 |
专业分类
化学 | 530篇 |
晶体学 | 10篇 |
力学 | 3篇 |
数学 | 44篇 |
物理学 | 78篇 |
出版年
2024年 | 1篇 |
2023年 | 6篇 |
2022年 | 19篇 |
2021年 | 26篇 |
2020年 | 15篇 |
2019年 | 15篇 |
2018年 | 18篇 |
2017年 | 16篇 |
2016年 | 27篇 |
2015年 | 14篇 |
2014年 | 25篇 |
2013年 | 45篇 |
2012年 | 39篇 |
2011年 | 56篇 |
2010年 | 27篇 |
2009年 | 34篇 |
2008年 | 34篇 |
2007年 | 34篇 |
2006年 | 37篇 |
2005年 | 21篇 |
2004年 | 42篇 |
2003年 | 19篇 |
2002年 | 20篇 |
2001年 | 8篇 |
2000年 | 11篇 |
1999年 | 3篇 |
1997年 | 3篇 |
1996年 | 13篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1985年 | 6篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
排序方式: 共有665条查询结果,搜索用时 15 毫秒
21.
Alberto Fernández Jesús J. Fernández Margarita López-Torres José M. Vila 《Journal of organometallic chemistry》2005,690(16):3669-3679
Reaction of the ligand C6H5N(H)NCMe(C5H4N) (a) with palladium(II) acetate in toluene gave the mononuclear cyclometallated complex [Pd{C6H4N(H)NCMe(C5H4N)}(AcO)] (1a). Reaction of 1a with sodium chloride gave the analogous chlorine compound [Pd{C6H4N(H)NCMe(C5H4N)}(Cl)] (3a) which could also be prepared by reaction of a with lithium tetrachloropalladate and sodium acetate in methanol for 48 h; whereas shorter reaction times afforded the non-cyclometallated complex [Pd{C6H5N(H)NCMe(C5H4N)}(Cl)2] (2a). Reaction of the ligand 2-ClC6H4N(H)NCMe(C5H4N) · HCl (b), with palladium(II) acetate, or with lithium tetrachloropalladate and sodium acetate, yielded the cyclometallated complex [Pd2-ClC6H3N(H)NCMe(C5H4N)(Cl)] (1b). Treatment of 3a and 1b with silver trifluoromethanesulphonate (triflate) and triphenylphosphine in acetone gave the mononuclear complexes [Pd{2-RC6HnN(H)NCMe(C5H4N)}(PPh3)][CF3SO3], (R = H, n = 4, 4a; R = Cl, n = 3, 2b) with the ligand as C,N,N′ terdentate and substitution of chlorine by triphenylphosphine. Reaction of 3a and 1b with silver triflate and the tertiary diphosphine Ph2P(CH2)4PPh2 (dppb) in a 2:1 molar ratio gave the dinuclear cyclometallated complexes [{Pd[2-RC6H3N(H)NCMe(C5H4N)]}2(μ-Ph2P(CH2)4PPh2)][CF3SO3]2 (R = H, 5a; R = Cl, 3b) with a μ2-diphosphine bridging ligand. Similarly, treatment of 3a and 1b with silver triflate and the tertiary triphosphines MeC(CH2PPh2)3 (tripod) and (Ph2PCH2CH2)2PPh (triphos), in 3:1 molar ratio, gave the novel trinuclear complexes [{Pd[C6H4N(H)NCMe(C5H4N)]}3{μ3-MeC(CH2Ph2)3}][CF3SO3]3 (6a) and [{Pd[2-ClC6H3N(H)NCMe(C5H4N)]}3{μ3-(PPh2CH2CH2)2PPh}][CF3SO3] 3 (4b) regioselectively, with the phosphine as a μ3-bridging ligand. When the reaction between 3a and triphos was carried out in 1:1 molar ratio the mononuclear complex [Pd{C6H4N(H)NCMe(C5H4N)}{(PPh2CH2CH2)2PPh-P,P,P}][ClO4] (7a) was obtained. The crystal structures of 2b, 3a and 4a have been determined by X-ray crystallography. 相似文献
22.
Margarita Acevedo Alain Fradet 《Journal of polymer science. Part A, Polymer chemistry》1993,31(3):817-830
2,2′-Bis(4,4-dimethyl-5(4H)-oxazolone) ( B3 ) and 2,2′-(1,2-ethylene)-bis(4,4-dimethyl-5(4H)oxazolone) ( B4 ) have been reacted in the bulk with α, ω-diamino polyamide-12 ( PA12 ) of M?n = 1000. The reactions have been studied by SEC, and 1H- and 13C-NMR and resulting polymers characterized by DSC and TGA. The chain coupling reaction is fast and gives high molar mass polymers within 10 min at 200°C with B4 while some side reactions occur with B3 leading to polymers of lower molar mass. The crystallinity of resulting polymers is lower than that of starting oligomer. However, the thermal stability is higher. Model reactions using B3 or B4 and hexamethylene diamine or 1-dodecanamine have been carried out and studied. An intramolecular cyclodehydration giving 2-imidazolin-5-ones takes place during the reactions. Higher cyclization extent is found in the presence of amino group excess. 2-Imidazolin-5-one heterocyclic structures are also observed in the chains of the polymers obtained from PA12 and B3 or B4 . © 1993 John Wiley & Sons, Inc. 相似文献
23.
Josep Castells Elisabet Duñach Fernando Geijo Francisco López-Calahorra Margarita Prats Olga Sanahuja Laura Villanova 《Tetrahedron letters》1980,21(23):2291-2294
Triethylamine catalyzed Michael additions of benzoins to chalcone can prevail over the expected Michael-Stetter additions when certain thiazolium ion conjugate bases - prepared from the pertinent thiazolium salts and triethylamine- are used as catalysts. 相似文献
24.
It is known that full Peano Arithmetic does not have the jointembedding property(JEP). At the other extreme of the hierarchy,Open Induction also fails to have this property. We prove, using some conservation results about fragments ofarithmetic, that if T is a theoryconsistent with PA and T I (bounded existential parameter-freeinduction), then any two m dels of PA which jointly embed ina model of T also jointly embed in an elementary extension ofone of them. In particular, any fragment of PA extending I fails to have JEP. 相似文献
25.
POSTIRRADIATION PROPERTIES OF A UV-SENSITIVE VARIANT OF CHO 总被引:1,自引:0,他引:1
Richard D. Wood Margarita De Veciana Bonnie Presson -Tincknell 《Photochemistry and photobiology》1982,36(2):169-174
Abstract A UV-hypersensitive mutant of Chinese hamster ovary (CHO) cells, termed 43-3B, has been used in a comparative study with the wild type CHO in order to determine the involvement of repair in several postirradiation phenomena. 43-3B has the same growth rate and chromosome number as the wild type CHO-9. It is hypersensitive to UV irradiation (D0 of 0.3 J/m2 as compared to 3.2 J/m2 for the wild type). 43-3B shows only about 17% of the UV-stimulated unscheduled DNA repair synthesis of CHO-9 as measured by autoradiography. When breaks in supercoiled chromatin are measured after UV by the nucleoid sedimentation method, the mutant appears to be capable of carrying out only limited incision. A much reduced ability to recover control rates of semiconservative DNA synthesis after UV irradiation was observed in the repair-deficient 43-3B cell line, suggesting that the removal of UV-induced replication blocks by excision repair is the most important factor in allowing recovery of UV-inhibited DNA synthesis. Recovery of colony-forming ability between fractionated UV exposures was observed in the wild type CHO-9, but little recovery was seen in 43-3B. This indicates that excision repair capability can also be important in split-fluence recovery. 相似文献
26.
Bernabé-Pineda M Ramírez-Silva MT Tapia-Benavides R Rojas-Hernández A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(5):1071-1076
The importance assigned to chelating agents in diverse areas has impelled studies concerning their development as related to metal ions representing a biological concern. The synthesis of di-isopropyliminodiacetoamide (D) is presented in this work. The acidity constant obtained for D was pKa = 5.79 +/- 0.04 with the aid of program SUPERQUAD. The equilibrium constants for D with Cu(II) were obtained with the aid of program SQUAD for CuD2+ and CuD2(2)+ species giving log beta1 = 4.795 +/- 0.002 and log beta2 = 8.374 +/- 0.004, respectively. 相似文献
27.
Rosa Estrada-Reyes Daniel B. Quero-Chvez Salvador Alarcn-Elizalde Montserrat G. Cercs Citlali Trueta Luis A. Constantino-Jonapa Julin Oikawa-Sala Jesús Argueta Ricardo Cruz-Garduo Margarita L. Dubocovich Gloria A. Benítez-King 《Molecules (Basel, Switzerland)》2022,27(17)
Melatonin (MEL), an indolamine with diverse functions in the brain, has been shown to produce antidepressant-like effects, presumably through stimulating neurogenesis. We recently showed that the combination of MEL with ketamine (KET), an NMDA receptor antagonist, has robust antidepressant-like effects in mice, at doses that, by themselves, are non-effective and have no adverse effects. Here, we show that the KET/MEL combination increases neurogenesis in a clone derived from human olfactory neuronal precursors, a translational pre-clinical model for effects in the human CNS. Neurogenesis was assessed by the formation of cell clusters > 50 µm in diameter, positively stained for nestin, doublecortin, BrdU and Ki67, markers of progenitor cells, neurogenesis, and proliferation. FGF, EGF and BDNF growth factors increased the number of cell clusters in cultured, cloned ONPs. Similarly, KET or MEL increased the number of clusters in a dose-dependent manner. The KET/MEL combination further increased the formation of clusters, with a maximal effect obtained after a triple administration schedule. Our results show that the combination of KET/MEL, at subeffective doses that do not produce adverse effects, stimulate neurogenesis in human neuronal precursors. Moreover, the mechanism by which the combination elicits neurogenesis is meditated by melatonin receptors, CaM Kinase II and CaM antagonism. This could have clinical advantages for the fast treatment of depression. 相似文献
28.
Rosa I. Ventura-Aguilar Csar Gnzalez-Andrade Mnica Hernndez-Lpez Zormy N. Correa-Pacheco Pervin K. Teksür Margarita de L. Ramos-García Silvia Bautista-Baos 《Molecules (Basel, Switzerland)》2022,27(14)
The fungus Aspergillus flavus causes serious damage to maize grains and its by-products, such as tortilla. Currently, animal and plant derivatives, such as chitosan and propolis, and plant extract residues, respectively, are employed as alternatives of synthetic fungicides. The objective of this research was to evaluate the efficacy of several formulations based on propolis-chitosan-pine resin extract on the in vitro growth of A. flavus, the growth of maize grain plantlets and the quality of stored tortillas at 4 and 28 °C. The most outstanding formulation was that based on 59.7% chitosan + 20% propolis nanoparticles + 20% pine resin extract nanoparticles; since the in vitro conidia germination of A. flavus did not occur, disease incidence on grains was 25–30% and in tortillas, 0% infection was recorded, along with low aflatoxin production (1.0 ppb). The grain germination and seedling growth were markedly reduced by the nanocoating application. The percentage weight loss and color of tortillas were more affected by this coating compared to the control, and the rollability fell within the scale of non-ruptured at 4 °C and partially ruptured at 28 °C. The next step is to evaluate the toxicity of this formulation. 相似文献
29.
Margarita Yu. Vozhdaeva Alfiya R. Kholova Igor A. Melnitskiy Ilya I. Beloliptsev Yulia S. Vozhdaeva Evgeniy A. Kantor Albert T. Lebedev 《Molecules (Basel, Switzerland)》2021,26(7)
The main drawback of drinking water chlorination involves the formation of quite hazardous disinfection by-products (DBPs), represented mainly by halogenated species. Based on the authors’ monitoring data since 2002, the prevalence of chlorine over bromine in the composition of volatile DBPs was shown for the drinking water in Ufa (Russia). However, the situation was completely reversed in the case of semi-volatile DBPs. The principal goal of the present study involved rationalization of the results of the long-term monitoring. Gas chromatography–mass spectrometry (GC-MS) was used for the qualitative and quantitative analysis of volatile DBPs. Identification of semi-volatile compounds was carried out with GC-MS, while gas chromatography with an atomic emission detector (GC-AED) was used for their quantification. A significant contribution of oxygen to the composition of semi-volatile compounds proves the decisive role of the dissolved organic matter oxidative destructive processes. Statistical analysis revealed notable linear correlations for trihalomethane and haloacetic acid formation vs. chlorine dose. On the contrary, halogenated semi-volatile products do not demonstrate any correlations with the water quality parameters or chlorine dose. Principal component analysis (PCA) placed them into separate groups. The results allow for proposing that formation of the organohalogenated species involved the fast penetration of bromine into the humic matter molecules and, further, their oxidative destruction by active chlorine. 相似文献
30.
Urazov Kazhmukhan Dergacheva Margarita Tameev Alexey Gribkova Oxana Mit’ Konstantin 《Journal of Solid State Electrochemistry》2021,25(1):237-245
Journal of Solid State Electrochemistry - One-step method for the electrodeposition of thin Cu2ZnSnSe4 (CZTSe) film onto a polyaniline/FTO/glass substrate was developed. Polyaniline film was... 相似文献