全文获取类型
收费全文 | 6456篇 |
免费 | 1309篇 |
国内免费 | 529篇 |
专业分类
化学 | 5756篇 |
晶体学 | 104篇 |
力学 | 402篇 |
综合类 | 44篇 |
数学 | 493篇 |
物理学 | 1495篇 |
出版年
2024年 | 13篇 |
2023年 | 67篇 |
2022年 | 160篇 |
2021年 | 220篇 |
2020年 | 333篇 |
2019年 | 289篇 |
2018年 | 200篇 |
2017年 | 242篇 |
2016年 | 395篇 |
2015年 | 376篇 |
2014年 | 451篇 |
2013年 | 562篇 |
2012年 | 504篇 |
2011年 | 479篇 |
2010年 | 475篇 |
2009年 | 469篇 |
2008年 | 468篇 |
2007年 | 436篇 |
2006年 | 408篇 |
2005年 | 347篇 |
2004年 | 324篇 |
2003年 | 303篇 |
2002年 | 142篇 |
2001年 | 110篇 |
2000年 | 84篇 |
1999年 | 58篇 |
1998年 | 54篇 |
1997年 | 79篇 |
1996年 | 43篇 |
1995年 | 42篇 |
1994年 | 30篇 |
1993年 | 16篇 |
1992年 | 15篇 |
1991年 | 20篇 |
1990年 | 16篇 |
1989年 | 9篇 |
1988年 | 12篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1963年 | 1篇 |
1959年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有8294条查询结果,搜索用时 15 毫秒
1.
Yi Han Zibo Xue Dr. Guangwu Li Dr. Yanwei Gu Dr. Yong Ni Dr. Shaoqiang Dong Prof. Chunyan Chi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9111-9116
Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials. 相似文献
2.
Dr. Sebastian Lars Müller Xinglong Zhou Dr. Peter Leonard Oxana Korzhenko Dr. Constantin Daniliuc Prof. Dr. Frank Seela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):3077-3090
Silver-mediated α-dC–Ag+–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong Tm increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag+–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology. 相似文献
3.
An N. Le Ruiqi Liang Prof. Dr. Mingjiang Zhong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8177-8189
Mixed-graft block copolymers (mGBCPs) consist of two or more types of polymeric side chains grafted on a linear backbone in a random, alternating, or pseudo-alternating sequence. They can phase-separate with the backbone serving as the interface of the blocks, and the side chains dominate their self-assembly behavior. mGBCPs are an accessible polymer architecture for exploring the idea of encoding polymer properties through the macromolecular architecture, as there are two distinct structural components that can be tuned: the backbone and the side chains. In this Concept article, the current literature on the synthesis of mGBCPs is reviewed, and the advantages and disadvantages of each synthetic method are noted. The self-assembly of mGBCPs is also discussed where possible. Finally, directions for future research on mGBCP synthesis and self-assembly are suggested. 相似文献
4.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献
5.
Guanidine‐Based Polymer Brushes Grafted onto Silica Nanoparticles as Efficient Artificial Phosphodiesterases
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)
Claudia Savelli Riccardo Salvio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5856-5863
Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom‐transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface‐initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety and an inert hydrophilic methacrylate species afforded hybrid nanoparticles that were characterized with potentiometric titrations, thermogravimetric analysis, and SEM. The activity of the hybrid nanoparticles was tested in the transesterification of the RNA model compound 2‐hydroxypropyl para‐nitrophenylphosphate (HPNP) and diribonucleoside monophosphates. A high catalytic efficiency and a remarkable effective molarity, thus overcoming the effective molarities previously observed for comparable systems, indicate the existence of an effective cooperation of the guanidine/guanidinium units and a high level of preorganization in the nanostructure. The investigated system also exhibits a marked and unprecedented selectivity for the diribonucleoside sequence CpA. The results presented open up the way for a novel and straightforward strategy for the preparation of supramolecular catalysts. 相似文献
6.
Lan-Lan Zhang Dr. Wen-Ke Miao Dr. Li-Jun Ren Yu-Kun Yan Dr. Yue Lin Prof. Wei Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(58):13396-13401
Organic polymers and inorganic clusters belong to two different disciplines and have completely different properties and structures. When a cluster is attached to the backbone of a polymer as a pendant, the resultant hybrid polymers (polyclusters) exhibit unique behaviours totally different from those of conventional polymers owing to the nanoscale size of the cluster and its particular interactions. Herein, the aggregation of a poly(polyoxometalate)—a polynorbornene backbone with inorganic polyoxometalate cluster pendants—upon addition of a non-solvent to its dilute solution is reported. A three-dimensional network of tangled and snake-like nanothreads was observed. Direct visualisation of individual nanoscale clusters enabled identification of single chains within the nanothreads. These observations suggest that during the process of aggregation, the hybrid polymer forms curved or extended chains as a consequence of an armouring effect in which the collapsed cluster pendants wrap around the backbone. The collapse occurs because they become less soluble in the solvent/non-solvent mixture. The extended chains then become entwined and form nanoropes consisting of multiple chains wound around each other. This study provides a deeper understanding of the nature of polyclusters and should also prove useful for their future development and application. 相似文献
7.
Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films
下载免费PDF全文
![点击此处可从《Journal of Polymer Science.Polymer Physics》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Zhe Qiang Maurice L. Wadley Bryan D. Vogt Kevin A. Cavicchi 《Journal of Polymer Science.Polymer Physics》2015,53(15):1058-1064
Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064 相似文献
8.
Guangrui Chen Yuxing Yan Dr. Jie Wang Prof. Yong Sik Ok Guiyuan Zhong Prof. Bu Yuan Guan Prof. Yusuke Yamauchi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19831-19836
Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition. 相似文献
9.
属间远缘杂交水稻耐旱性生理特性的比较研究 总被引:4,自引:0,他引:4
采用在YOSHIDA水稻专用培养营养液中添加一定量的PEG 6000的方法,比较研究了模拟干旱胁迫条件下属间远缘杂交新型水稻品种“远诱1号”(Y)及其水稻亲本“圭630”(G)、高梁亲本“桃长红”(T)以及生产推广杂交组合“汕优63”(S)等试验材料某些生态生理特性的差异。研究结果表明,在-1.0MPa的高渗胁迫下,Y、G、T的萌发系数均有不同程度的下降,正常培养条件下的萌发系数GC分别为36.9 相似文献
10.
D. C. Oliveira Y. Messaddeq K. Dahmouche S. J. L. Ribeiro R. R. Gonçalves A. Vesperini D. Gindre J.-M. Nunzi 《Journal of Sol-Gel Science and Technology》2006,40(2-3):359-363
Organic-inorganic hybrid materials were prepared from an ureasil precursor (ureapropyltriethoxysilane designated as UPTES)
and acrylic acid modified zirconium (IV) n-propoxide. Thin films containing rhodamine 6G (Rh6G) were prepared by spin-coating on glass substrates with different Zr:Si molar ratios (Zr:Si = 75:25, 50:50 and 25:75). Refractive
index, thickness, number of propagating modes and attenuation coefficient were measured at 543.5, 632.8 and 1550 nm wavelengths
by the prism coupling technique. Distributed feedback (DFB) laser effect was observed and studied as a function of films thickness
and refractive index. 相似文献