全文获取类型
收费全文 | 44781篇 |
免费 | 11902篇 |
国内免费 | 1438篇 |
专业分类
化学 | 43727篇 |
晶体学 | 353篇 |
力学 | 514篇 |
数学 | 2376篇 |
物理学 | 3191篇 |
无线电 | 7960篇 |
出版年
2023年 | 63篇 |
2022年 | 75篇 |
2021年 | 303篇 |
2020年 | 1835篇 |
2019年 | 3248篇 |
2018年 | 1519篇 |
2017年 | 1081篇 |
2016年 | 4045篇 |
2015年 | 4171篇 |
2014年 | 4150篇 |
2013年 | 4799篇 |
2012年 | 3637篇 |
2011年 | 2891篇 |
2010年 | 3348篇 |
2009年 | 3309篇 |
2008年 | 2950篇 |
2007年 | 2261篇 |
2006年 | 1903篇 |
2005年 | 2050篇 |
2004年 | 1784篇 |
2003年 | 1617篇 |
2002年 | 2244篇 |
2001年 | 1515篇 |
2000年 | 1436篇 |
1999年 | 466篇 |
1998年 | 114篇 |
1997年 | 118篇 |
1996年 | 96篇 |
1995年 | 76篇 |
1994年 | 75篇 |
1993年 | 61篇 |
1992年 | 62篇 |
1991年 | 48篇 |
1990年 | 61篇 |
1989年 | 63篇 |
1988年 | 40篇 |
1987年 | 28篇 |
1986年 | 22篇 |
1985年 | 53篇 |
1984年 | 36篇 |
1983年 | 27篇 |
1982年 | 29篇 |
1981年 | 32篇 |
1980年 | 26篇 |
1979年 | 35篇 |
1978年 | 21篇 |
1977年 | 30篇 |
1976年 | 24篇 |
1975年 | 24篇 |
1973年 | 30篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
11.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
12.
13.
Towards a Better Prediction of Cell Settling on Nanostructure Arrays—Simple Means to Complicated Ends
下载免费PDF全文
![点击此处可从《Advanced functional materials》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Nina Buch‐Månson Sara Bonde Jessica Bolinsson Trine Berthing Jesper Nygård Karen L. Martinez 《Advanced functional materials》2015,25(21):3246-3255
Vertical arrays of nanostructures (NSs) are emerging as promising platforms for probing and manipulating live mammalian cells. The broad range of applications requires different types of interfaces, but cell settling on NS arrays is not yet fully controlled and understood. Cells are both seen to deform completely into NS arrays and to stay suspended like tiny fakirs, which have hitherto been explained with differences in NS spacing or density. Here, a better understanding of this phenomenon is provided by using a model that takes into account the extreme membrane deformation needed for a cell to settle into a NS array. It is shown that, in addition to the NS density, cell settling depends strongly on the dimensions of the single NS, and that the settling can be predicted for a given NS array geometry. The predictive power of the model is confirmed by experiments and good agreement with cases from the literature. Furthermore, the influence of cell‐related parameters is evaluated theoretically and a generic method of tuning cell settling through surface coating is demonstrated experimentally. These findings allow a more rational design of NS arrays for the numerous exciting biological applications where the mode of cell settling is crucial. 相似文献
14.
Close‐Packed Two‐Dimensional Silver Nanoparticle Arrays: Quadrupolar and Dipolar Surface Plasmon Resonance Coupling
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Sukang Yun Soonchang Hong Jesus A. I. Acapulco Jr. Ho Young Jang Songyi Ham Kyungeun Lee Prof. Seong Kyu Kim Prof. Sungho Park 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6165-6172
Silver nanoparticles (NPs) ranging in size from 40 to 100 nm were prepared in high yield by using an improved seed‐mediated method. The homogeneous Ag NPs were used as building blocks for 2D assembled Ag NP arrays by using an oil/water interface. A close‐packed 2D array of Ag NPs was fabricated by using packing molecules (3‐mercaptopropyltrimethoxysilane) to control the interparticle spacing. The homogeneous 2D Ag NP array exhibited a strong quadrupolar cooperative plasmon mode resonance and a dipolar red‐shift relative to individual Ag NPs suspended in solution. A well‐arranged 2D Ag NP array was embedded in polydimethylsiloxane film and, with biaxial stretching to control the interparticle distance, concomitant variations of the quadrupolar and dipolar couplings were observed. As the interparticle distance increased, the intensity of the quadrupolar cooperative plasmon mode resonance decreased and dipolar coupling completely disappeared. The local electric field of the 2D Ag NP array was calculated by using finite difference time domain simulation and qualitatively showed agreement with the experimental measurements. 相似文献
15.
A (di)graph is supereulerian if it contains a spanning eulerian sub(di)graph. This property is a relaxation of hamiltonicity. Inspired by this analogy with hamiltonian cycles and by similar results in supereulerian graph theory, we analyze a number of sufficient Ore type conditions for a digraph to be supereulerian. Furthermore, we study the following conjecture due to Thomassé and the first author: if the arc‐connectivity of a digraph is not smaller than its independence number, then the digraph is supereulerian. As a support for this conjecture we prove it for digraphs that are semicomplete multipartite or quasitransitive and verify the analogous statement for undirected graphs. 相似文献
16.
Unexpected benzimidazole ring formation from a quinoneimide species in the presence of ammonium acetate as supporting electrolyte used in the coupling of electrochemistry with mass spectrometry
下载免费PDF全文
![点击此处可从《Rapid communications in mass spectrometry : RCM》网站下载免费的PDF全文](/ch/ext_images/free.gif)
17.
Yuwei Wang Jia-Jun Yan Shengnan Hu Prof. David James Young Prof. Hong-Xi Li Prof. Zhi-Gang Ren 《化学:亚洲杂志》2021,16(18):2681-2686
A photoluminescent bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(MeOH)2(H2O)](ClO4)4 ( 1 , bdppthi=N,N’-bis(diphenylphosphanylmethyl)-tetrahydroimidazole} was synthesized from the PNNP type ligand bdppthi generated in-situ. Upon excitation at 365 nm, 1 exhibited strong phosphorescent emission at 630 nm, which was selectively quenched by NH3 in air or water. The sensing of NH3 was rapid and recoverable, with detection limits of 53 ppm (v/v) in N2 and 21 μmol/L (0.36 ppm, w/w) for NH3 ⋅ H2O in water. Cluster 1 could potentially serve as a bifunctional chemical sensor for the efficient detection of ammonia in waste-gas and waste-water. 相似文献
18.
19.
The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Biao Wu Dr. Shaoguang Li Prof. Yibo Lei Prof. Huaiming Hu Dr. Nader de Sousa Amadeu Prof. Dr. Christoph Janiak Dr. Jennifer S. Mathieson Dr. De‐Liang Long Prof. Leroy Cronin Prof. Xiao‐Juan Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2588-2593
By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A2L3 complexes (A represents anion, here orthophosphate PO43?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes. 相似文献
20.
Yong Xu Yun Li Songlin Li Francis Balestra Gerard Ghibaudo Wenwu Li Yen‐Fu Lin Huabin Sun Jing Wan Xinran Wang Yufeng Guo Yi Shi Yong‐Young Noh 《Advanced functional materials》2020,30(20)
Unreliable mobility values, and particularly greatly overestimated values and severely distorted temperature dependences, have recently hampered the development of the organic transistor field. Given that organic field‐effect transistors (OFETs) have been routinely used to evaluate mobility, precise parameter extraction using the electrical properties of OFETs is thus of primary importance. This review examines the origins of the various mobilities that must be determined for OFET applications, the relevant extraction methods, and the data selection limitations, which help in avoiding conceptual errors during mobility extraction. For increased precision, the review also discusses device fabrication considerations, calibration of both the specific gate‐dielectric capacitance and the threshold voltage, the contact effects, and the bias and temperature dependences, which must actually be handled with great care but have mostly been overlooked to date. This review serves as a systematic overview of the OFET mobility extraction process to ensure high precision and will also aid in improving future research. 相似文献