全文获取类型
收费全文 | 1049篇 |
免费 | 42篇 |
国内免费 | 1篇 |
专业分类
化学 | 717篇 |
晶体学 | 2篇 |
力学 | 52篇 |
数学 | 152篇 |
物理学 | 169篇 |
出版年
2024年 | 4篇 |
2023年 | 12篇 |
2022年 | 45篇 |
2021年 | 50篇 |
2020年 | 39篇 |
2019年 | 27篇 |
2018年 | 28篇 |
2017年 | 20篇 |
2016年 | 70篇 |
2015年 | 40篇 |
2014年 | 42篇 |
2013年 | 69篇 |
2012年 | 82篇 |
2011年 | 112篇 |
2010年 | 53篇 |
2009年 | 34篇 |
2008年 | 50篇 |
2007年 | 57篇 |
2006年 | 53篇 |
2005年 | 55篇 |
2004年 | 30篇 |
2003年 | 33篇 |
2002年 | 23篇 |
2001年 | 5篇 |
2000年 | 11篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1970年 | 1篇 |
1961年 | 1篇 |
1948年 | 1篇 |
1938年 | 1篇 |
1937年 | 1篇 |
1918年 | 1篇 |
1916年 | 1篇 |
排序方式: 共有1092条查询结果,搜索用时 15 毫秒
31.
Prof. Volker L. Deringer Prof. Chris J. Pickard Prof. Davide M. Proserpio 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16014-16019
The discovery of materials is increasingly guided by quantum-mechanical crystal-structure prediction, but the structural complexity in bulk and nanoscale materials remains a bottleneck. Here we demonstrate how data-driven approaches can vastly accelerate the search for complex structures, combining a machine-learning (ML) model for the potential-energy surface with efficient, fragment-based searching. We use the characteristic building units observed in Hittorf's and fibrous phosphorus to seed stochastic (“random”) structure searches over hundreds of thousands of runs. Our study identifies a family of hierarchically structured allotropes based on a P8 cage as principal building unit, including one-dimensional (1D) single and double helix structures, nanowires, and two-dimensional (2D) phosphorene allotropes with square-lattice and kagome topologies. These findings yield new insight into the intriguingly diverse structural chemistry of phosphorus, and they provide an example for how ML methods may, in the long run, be expected to accelerate the discovery of hierarchical nanostructures. 相似文献
32.
Alberta Terzi Nunzia Gallo Simona Bettini Teresa Sibillano Davide Altamura Marta Madaghiele Liberato De Caro Ludovico Valli Luca Salvatore Alessandro Sannino Cinzia Giannini 《Macromolecular bioscience》2020,20(5)
Collagen represents one of the most widely used biomaterial for scaffolds fabrication in tissue engineering as it represents the mechanical support of natural tissues. It also provides physical scaffolding for cells and it influences their attachment, growth, and tissue regeneration. Among all fibrillary collagens, type I is considered one of the gold standard for scaffolds fabrication, thanks to its high biocompatibility, biodegradability, and hemostatic properties. It can be extracted by chemical and enzymatic protocols from several collagen‐rich tissues, such as tendon and skin, of different animal species. Both the extraction processes and the manufacturing protocols for scaffolds fabrication provide structural and mechanical changes that can be tuned in order to deeply impact the properties of the final biomaterial. The aim of this review is to discuss the role of X‐rays to study structural changes of type I collagen from fresh collagen‐rich tissues (bovine, equine, fish) to the final scaffolds, with the aim to screen across available collagen sources and scaffolds fabrication protocols to be used in tissue regeneration. 相似文献
33.
We consider an elliptic operator of second order with Dirichlet boundary
conditions in a cylindrical domain. We show that a suitable interpretation of this
operator in a certain space of continuous functions vanishing on the boundary is
the infinitesimal generator of an analytic semigroup in the space of continuous
functions. We prove several inclusions of the domain of the infinitesimal generator
and of the real interpolation spaces between this domain and the basic space of
continuous functions. 相似文献
34.
Davide Addona 《Semigroup Forum》2013,87(3):509-536
We consider the nonautonomous Ornstein-Uhlenbeck operator in some weighted spaces of continuous functions in $\mathbb{R}^{N}$ . We prove sharp uniform estimates for the spatial derivatives of the associated evolution operator P s,t , which we use to prove optimal Schauder estimates for the solution to some nonhomogeneous parabolic Cauchy problems associated with the Ornstein-Uhlenbeck operator. We also prove that, for any t>s, the evolution operator P s,t is compact in the previous weighted spaces. 相似文献
35.
36.
In this paper, we perform an analytical and numerical study of the extreme values of specific observables of dynamical systems possessing an invariant singular measure. Such observables are expressed as functions of the distance of the orbit of initial conditions with respect to a given point of the attractor. Using the block maxima approach, we show that the extremes are distributed according to the generalised extreme value distribution, where the parameters can be written as functions of the information dimension of the attractor. The numerical analysis is performed on a few low dimensional maps. For the Cantor ternary set and the Sierpinskij triangle, which can be constructed as iterated function systems, the inferred parameters show a very good agreement with the theoretical values. For strange attractors like those corresponding to the Lozi and He?non maps, a slower convergence to the generalised extreme value distribution is observed. Nevertheless, the results are in good statistical agreement with the theoretical estimates. It is apparent that the analysis of extremes allows for capturing fundamental information of the geometrical structure of the attractor of the underlying dynamical system, the basic reason being that the chosen observables act as magnifying glass in the neighborhood of the point from which the distance is computed. 相似文献
37.
Aromatic nitroderivatives are compounds of considerable environmental concern, because some of them are phytotoxic (especially the nitrophenols, and particularly 2,4-dinitrophenol), others are mutagenic and potentially carcinogenic (e.g., the nitroderivatives of polycyclic aromatic hydrocarbons, such as 1-nitropyrene), and all of them absorb sunlight as components of the brown carbon. The latter has the potential to affect the climatic feedback of atmospheric aerosols. Most nitroderivatives are secondarily formed in the environment and, among their possible formation processes, photonitration upon irradiation of nitrate or nitrite is an important pathway that has periodically gained considerable attention. However, photonitration triggered by nitrate and nitrite is a very complex process, because the two ionic species under irradiation produce a wide range of nitrating agents (such as •NO2, HNO2, HOONO, and H2OONO+), which are affected by pH and the presence of organic compounds and, in turn, deeply affect the nitration of aromatic precursors. Moreover, aromatic substrates can highly differ in their reactivity towards the various photogenerated species, thereby providing different behaviours towards photonitration. Despite the high complexity, it is possible to rationalise the different photonitration pathways in a coherent framework. In this context, this review paper has the goal of providing the reader with a guide on what to expect from the photonitration process under different conditions, how to study it, and how to determine which pathway(s) are prevailing in the formation of the observed nitroderivatives. 相似文献
38.
Jiawang Zhou Ljiljana Stojanovi Andrey A. Berezin Tommaso Battisti Abigail Gill Benson M. Kariuki Davide Bonifazi Rachel Crespo-Otero Michael R. Wasielewski Yi-Lin Wu 《Chemical science》2021,12(2):767
Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.The number and position of halogen substituents in purely organic π–π* chromophores critically affect the efficiency of phosphorescence. 相似文献
39.
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
40.
Lorenzo Di Terlizzi Prof. Stefano Protti Prof. Davide Ravelli Prof. Maurizio Fagnoni 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(26):e202200313
With the aim of generating new, thermally inaccessible diradicals, potentially able to induce a double-strand DNA cleavage, the photochemistry of a set of chloroaryl-substituted carboxylic acids in polar media was investigated. The photoheterolytic cleavage of the Ar−Cl bond occurred in each case to form the corresponding triplet phenyl cations. Under basic conditions, the photorelease of the chloride anion was accompanied by an intramolecular electron-transfer from the carboxylate group to the aromatic radical cationic site to give a diradical species. This latter intermediate could then undergo CO2 loss in a structure-dependent fashion, according to the stability of the resulting diradical, or abstract a hydrogen atom from the medium. In aqueous environment at physiological pH (pH=7.3), both a phenyl cation and a diradical chemistry was observed. The mechanistic scenario and the role of the various intermediates (aryl cations and diradicals) involved in the process was supported by computational analysis. 相似文献