全文获取类型
收费全文 | 569篇 |
免费 | 16篇 |
专业分类
化学 | 413篇 |
晶体学 | 4篇 |
力学 | 15篇 |
数学 | 89篇 |
物理学 | 64篇 |
出版年
2023年 | 5篇 |
2022年 | 27篇 |
2021年 | 25篇 |
2020年 | 19篇 |
2019年 | 16篇 |
2018年 | 5篇 |
2017年 | 9篇 |
2016年 | 32篇 |
2015年 | 21篇 |
2014年 | 13篇 |
2013年 | 35篇 |
2012年 | 48篇 |
2011年 | 54篇 |
2010年 | 34篇 |
2009年 | 43篇 |
2008年 | 48篇 |
2007年 | 42篇 |
2006年 | 19篇 |
2005年 | 23篇 |
2004年 | 20篇 |
2003年 | 9篇 |
2002年 | 7篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有585条查询结果,搜索用时 15 毫秒
101.
Eder do Couto TavaresMarcelo Ribeiro Leite Oliveira Jan JanczakCamila Grossi Vieira Leandro de Carvalho AlvesRodrigo Antunes Castro Lígia Maria Mendonça VieiraRenata Hernandez Lindemann Genivaldo Júlio PerpétuoLeila Léa Yuan Visconte Mayura Marques Magalhães Rubinger 《Polyhedron》2012,31(1):494-501
Four zinc(II)-bis(trithiocarbimato) complexes with the general formula A2[Zn(RSO2NCS3)2] [A = Ph4P+: R = CH3 (1), 4-CH3C6H4 (2); A = Bu4N+: R = CH3 (3), 4-CH3C6H4 (4)] were obtained by the reaction of sulfur with the correspondent zinc(II)-bis(dithiocarbimato) complexes. Additionally, the compound (Ph4P)2[(CH3SO2NCS2)2S)] (5) was prepared from the potassium methylsulfonildithiocarbimate by oxidation with iodine. The compounds were characterized by elemental analyses and IR, 1H NMR and 13C NMR spectroscopies. The compounds 4 and 5 were also characterized by X-ray diffraction techniques. The compound 4 crystallizes in the centrosymmetric space group C2/c of the monoclinic system. The Zn(II) is in a distorted tetrahedral environment (ZnS4) in compound 4, and differ from the coordination mode observed in compound 1, which involves one sulfur and one nitrogen atom of each trithiocarbimate ligand. Compound 5 is the first example of a compound containing a bis(N-alkylsulfonyldithiocarbimate)-sulfide dianion and crystallises in the non-centrosymmetric space group P41212 of the tetragonal system. 相似文献
102.
J.F. Monteiro A.A.L. Ferreira I. Antunes D.P. Fagg J.R. Frade 《Journal of solid state chemistry》2012
Chemical potential phase stability diagrams were calculated from relevant thermodynamic properties and used to predict the thermodynamic driving force under prospective conditions of room temperature mechanosynthesis. One analysed the dependence of chemical potential diagrams on temperature and partial pressure of evolving gases such as oxygen or carbon dioxide, as expected on using strontium peroxide or strontium carbonate as precursor reactants for the alkali earth component. Thermodynamic calculations were also obtained for changes in titania precursor reactants, including thermodynamic predictions for reactivity of strontium carbonate with amorphous titania. Experimental evidence showed that strontium titanate can be obtained by mechanosynthesis of strontium carbonate+anatase mixtures, due to previous amorphization under high energy milling. Ability to perform mechanosynthesis with less energetic milling depends on the suitable choice of alternative precursor reactants, which meet the thermodynamic requirements without previous amorphization; this was demonstrated by mechanosynthesis from anatase+strontium peroxide mixtures. 相似文献
103.
The two-dimensional cyano-bridged coordination polymer Er(H(2)O)(4)[W(CN)(8)] exhibits a magnetic transition at 12 K and an unusual field-dependent transition from short-range to ferromagnetic ordering. 相似文献
104.
Amarante TR Neves P Tomé C Abrantes M Valente AA Paz FA Pillinger M Gonçalves IS 《Inorganic chemistry》2012,51(6):3666-3676
The reaction of [MoO(2)Cl(2)(di-tBu-bipy)] (1) (di-tBu-bipy = 4,4'-di-tert-butyl-2,2'-bipyridine) with water at 100-120 °C in a Teflon-lined stainless steel autoclave, in an open reflux system, or in a microwave synthesis system gave the octanuclear complex [Mo(8)O(22)(OH)(4)(di-tBu-bipy)(4)] (2) as a microcrystalline powder in good yields. Single crystals of 2 suitable for X-ray diffraction were obtained by the reaction of MoO(3) and di-tBu-bipy in water at 160 °C for 3 days. The molecular structure of 2 comprises a purely inorganic core, Mo(4)O(8)(μ(3)-OH)(2)(μ(2)-O)(2), attached to two peripheral oxo-bridged binuclear units, Mo(2)O(4)(μ(2)-O)(2)(OH)(di-tBu-bipy)(2). The inorganic core is composed of a unique assembly of four {MoO(5)} distorted square pyramids connected to each other via edge-sharing. Overall, the octanuclear complex adopts a highly distorted form strongly resembling an "S"-shaped molecular unit. Complex 2 was applied in the catalytic epoxidation of the biorenewable olefins DL-limonene (Lim) and methyl oleate (Ole), using tert-butylhydroperoxide (TBHP) as an oxygen donor, under mild reaction conditions (55 °C, air). The reactions of Lim and Ole gave the respective epoxide monomers in fairly high selectivities at high conversions (89% 1,2-epoxy-p-menth-8-ene selectivity at 96% Lim conversion; 99% methyl 9,10-epoxystearate selectivity at 94% Ole conversion, reached within 24 h reaction). Iodometric titrations revealed no measurable "non-productive" decomposition of TBHP. 相似文献
105.
Patrícia A. Filipe Carlos A. Braumann Carlos J. Roquete 《Methodology and Computing in Applied Probability》2012,14(1):49-56
The evolution of the growth of an individual in a random environment can be described through stochastic differential equations
of the form dY
t
= β(α − Y
t
)dt + σdW
t
, where Y
t
= h(X
t
), X
t
is the size of the individual at age t, h is a strictly increasing continuously differentiable function, α = h(A), where A is the average asymptotic size, and β represents the rate of approach to maturity. The parameter σ measures the intensity of the effect of random fluctuations on growth and W
t
is the standard Wiener process. We have previously applied this monophasic model, in which there is only one functional form
describing the average dynamics of the complete growth curve, and studied the estimation issues. Here, we present the generalization
of the above stochastic model to the multiphasic case, in which we consider that the growth coefficient β assumes different values for different phases of the animal’s life. For simplicity, we consider two phases with growth coefficients
β
1 and β
2. Results and methods are illustrated using bovine growth data. 相似文献
106.
Discrete Ti−O−Ti Complexes: Visible-Light-Activated,Homogeneous Alternative to TiO2 Photosensitisers
Kira Behm Dr. Eszter Fazekas Prof. Martin J. Paterson Dr. Filipe Vilela Dr. Ruaraidh D. McIntosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9486-9494
A series of novel bimetallic TiIV amine bis(phenolate) complexes was synthesised and fully characterised. X-ray crystallography studies revealed distorted octahedral geometries around the Ti centres with single or double oxo-bridges connecting the two metals. These robust, air- and moisture-stable complexes were employed as photosensitisers generating singlet oxygen following irradiation with visible light (420 nm) LED module in a commercial flow reactor. All five complexes showed high activity in the photo-oxygenation of α-terpinene and achieved complete conversion to ascaridole in four hours at ambient temperature. The excellent selectivity of these photosensitisers towards ascaridole (vs. transformation to p-cymene) was demonstrated with control experiments using a traditional TiO2 catalyst. Further comparative studies employing the free pro-ligands as well as a monometallic analogue highlighted the importance of the ‘TiO2-like’ moiety in the polymetallic catalysts. Computational studies were used to determine the nature of the ligand to metal charge transfer (LMCT) states and singlet–triplet gaps for each complex, the calculated trends in the UV-vis absorption spectra across the series agreed well with the experimental results. 相似文献
107.
Jeff Y. F. Wong Dr. John M. Tobin Dr. Filipe Vilela Dr. Graeme Barker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(53):12439-12445
1,3,4-Oxadiazoles are a common motif in pharmaceutical chemistry, but few convenient methods for their modification exist. A fast, convenient, high yielding and general α-substitution of 1,3,4-oxadiazoles has been developed using a metalation-electrophilic trapping protocol both in batch and under continuous flow conditions in contradiction to previous reports which suggest that α-metalation of this ring system results in ring fragmentation. In batch, lithiation is accomplished at an industrially convenient temperature, −30 °C, with subsequent trapping giving isolated yields of up to 91 %. Under continuous flow conditions, metalation is carried out at room temperature, and subsequent in flow electrophilic trapping gave up to quantitative isolated yields. Notably, lithiation in batch at room temperature results only in ring fragmentation and we propose that the superior mixing in flow allows interception and exploitation of an unstable intermediate before decomposition can occur. 相似文献
108.
Josephine Blersch Dr. Vitor Francisco Catarina Rebelo Dr. Adrian Jiménez-Balsa Helena Antunes Dr. Carlo Gonzato Dr. Sandra Pinto Dr. Susana Simões Prof. Dr. Klaus Liedl Prof. Dr. Karsten Haupt Prof. Dr. Lino Ferreira 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(5):2001-2007
RNA-based therapies offer a wide range of therapeutic interventions including the treatment of skin diseases; however, the strategies to efficiently deliver these biomolecules are still limited due to obstacles related to the cellular uptake and cytoplasmic delivery. Herein, we report the synthesis of a triggerable polymeric nanoparticle (NP) library composed of 160 formulations, presenting physico-chemical diversity and differential responsiveness to light. Six formulations were more efficient (up to 500 %) than commercially available lipofectamine in gene-knockdown activity. These formulations showed differential internalization by skin cells and the endosomal escape was rapid (minutes range). The NPs were effective in the release of siRNA and miRNA. Acute skin wounds treated with the top hit NP complexed with miRNA-150-5p healed faster than wounds treated with scrambled miRNA. Light-activatable NPs offer a new strategy to topically deliver non-coding RNAs. 相似文献
109.
O. Peña A.B. Antunes M.N. Baibich P.N. Lisboa-Filho V. Gil C. Moure 《Journal of magnetism and magnetic materials》2007
The erbium-based manganite ErMnO3 has been partially substituted at the manganese site by the transition-metal elements Ni and Co. The perovskite orthorhombic structure is found from x(Ni)=0.2–0.5 in the nickel-based solid solution ErNixMn1−xO3, while it can be extended up to x(Co)=0.7 in the case of cobalt, provided that the synthesis is performed under oxygenation conditions to favor the presence of Co3+. Presence of different magnetic entities (i.e., Er3+, Ni2+, Co2+, Co3+, Mn3+, and Mn4+) leads to quite unusual magnetic properties, characterized by the coexistence of antiferromagnetic and ferromagnetic interactions. In ErNixMn1−xO3, a critical concentration xcrit(Ni)=1/3 separates two regimes: spin-canted AF interactions predominate at x<xcrit, while the ferromagnetic behavior is enhanced for x>xcrit. Spin reversal phenomena are present both in the nickel- and cobalt-based compounds. A phenomenological model based on two interacting sublattices, coupled by an antiferromagnetic exchange interaction, explains the inversion of the overall magnetic moment at low temperatures. In this model, the ferromagnetic transition-metal lattice, which orders at Tc, creates a strong local field at the erbium site, polarizing the Er moments in a direction opposite to the applied field. At low temperatures, when the contribution of the paramagnetic erbium sublattice, which varies as T−1, gets larger than the ferromagnetic contribution, the total magnetic moment changes its sign, leading to an overall ferrimagnetic state. The half-substituted compound ErCo0.50Mn0.50O3 was studied in detail, since the magnetization loops present two well-identified anomalies: an intersection of the magnetization branches at low fields, and magnetization jumps at high fields. The influence of the oxidizing conditions was studied in other compositions close to the 50/50=Mn/Co substitution rate. These anomalies are clearly connected to the spin inversion phenomena and to the simultaneous presence of Co2+ and Co3+ magnetic moments. Dynamical aspects should be considered to well identify the high-field anomaly, since it depends on the magnetic field sweep rate. 相似文献
110.
This paper describes a two-dimensional numerical model to solve the generalized Serre equations. In order to solve the system equations, written in the conservative form, we use an explicit finite-difference method based on the MacCormack time-splitting scheme. The numerical method and the computational model are validated by comparing one- and two-dimensional numerical solutions with theoretical and experimental results. Finally, the two-dimensional model (in a horizontal plane) is tested in a domain with complicated boundary conditions. 相似文献