全文获取类型
收费全文 | 4037篇 |
免费 | 598篇 |
国内免费 | 478篇 |
专业分类
化学 | 2960篇 |
晶体学 | 40篇 |
力学 | 231篇 |
综合类 | 35篇 |
数学 | 473篇 |
物理学 | 1374篇 |
出版年
2024年 | 10篇 |
2023年 | 99篇 |
2022年 | 100篇 |
2021年 | 138篇 |
2020年 | 190篇 |
2019年 | 166篇 |
2018年 | 143篇 |
2017年 | 114篇 |
2016年 | 181篇 |
2015年 | 184篇 |
2014年 | 172篇 |
2013年 | 296篇 |
2012年 | 292篇 |
2011年 | 301篇 |
2010年 | 215篇 |
2009年 | 215篇 |
2008年 | 244篇 |
2007年 | 196篇 |
2006年 | 194篇 |
2005年 | 195篇 |
2004年 | 179篇 |
2003年 | 120篇 |
2002年 | 116篇 |
2001年 | 111篇 |
2000年 | 113篇 |
1999年 | 101篇 |
1998年 | 86篇 |
1997年 | 81篇 |
1996年 | 84篇 |
1995年 | 62篇 |
1994年 | 72篇 |
1993年 | 50篇 |
1992年 | 44篇 |
1991年 | 34篇 |
1990年 | 41篇 |
1989年 | 25篇 |
1988年 | 24篇 |
1987年 | 25篇 |
1986年 | 18篇 |
1985年 | 22篇 |
1984年 | 13篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1981年 | 10篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1969年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有5113条查询结果,搜索用时 15 毫秒
241.
Jing Liu Fangjun Wang Jun Zhu Jiawei Mao Zheyi Liu Kai Cheng Hongqiang Qin Hanfa Zou 《Analytical and bioanalytical chemistry》2014,406(13):3103-3109
Conventional N-glycoproteome analysis usually applies C18 reversed-phase (RP) adsorbent for sample purification, which will lead to unavoidable sample loss due to the high hydrophilicity of N-glycopeptides. In this study, a porous graphitized carbon (PGC) absorbent was combined with a C18 adsorbent for N-glycopeptide purification in comprehensive N-glycoproteome analysis based on the hydrophobic and polar interactions between carbon and N-glycans. It was observed that the small hydrophilic N-glycopeptides that cannot retain onto C18 adsorbent can be captured by the graphitized carbon, while the large hydrophobic N-glycopeptides that cannot retain onto the graphitized carbon can be feasibly captured by the C18 adsorbent. Comparing with sample purification by using C18 adsorbent only, 28.5 % more N-glycopeptides were identified by combining both C18 and PGC adsorbents. The C18-PGC strategy was further applied for both sample purification and pre-fractionation of a complex protein sample from HeLa cell. After hydrophilic interaction chromatography enrichment, 1,484 unique N-glycopeptides with 1,759 unique N-glycosylation sites were finally identified. Online Abstract Figure
The overlap of identified N-glycosylation sites by different SPE strategies 相似文献
242.
The catalytic cross‐dehydrogenative coupling (CDC) reaction has received intense attention in recent years. The attractive feature of this coupling process is the formation of a C? C bond from two C? H moieties under oxidative conditions. In this Focus Review, recent advances in the palladium‐catalyzed CDC reactions of C(sp2)? H bond are summarized, with a focus on the period from 2011 to early 2013. 相似文献
243.
Xiu‐Li Hao Yuan‐Yuan Ma Dr. Yong‐Hui Wang Long‐Yang Xu Dr. Fu‐Chen Liu Mao‐Mao Zhang Prof. Yang‐Guang Li 《化学:亚洲杂志》2014,9(3):819-829
Investigation into a hydrothermal reaction system with transition‐metal (TM) ions, 1,4‐bis(1,2,4‐triazol‐1‐lmethyl)benzene (BBTZ) and various charge‐tunable Keggin‐type polyoxometalates (POMs) led to the preparation of four new entangled coordination networks, [CoII(HBBTZ)(BBTZ)2.5][PMo12O40] ( 1 ), [CuI(BBTZ)]5[BW12O40] ? H2O ( 2 ), [CuII(BBTZ)]3[AsWV3WVI9O40] ? 10 H2O ( 3 ), and [CuII5(BBTZ)7(H2O)6][P2W22Cu2O77(OH)2] ? 6 H2O ( 4 ). All compounds were characterized by using elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The mixed valence of W centers in compound 3 was further confirmed by using XPS spectroscopy and bond‐valence sum calculations. In the structural analysis, the entangled networks of 1 – 4 demonstrate zipper‐closing packing, 3D polythreading, 3D polycatenation, and 3D self‐penetration, respectively. Moreover, with the enhancement of POM negative charges and the use of different TM types, the number of nodes in the coordination networks of 1 – 4 increased and the basic metal–organic building motifs changed from a 1D zipper‐type chain (in 1 ) to a 2D pseudorotaxane layer (in 2 ) to a 3D diamond‐like framework (in 3 ) and finally to a 3D self‐penetrating framework (in 4 ). The photocatalytic properties of compounds 1 – 4 for the degradation of methylene blue under UV light were also investigated; all compounds showed good catalytic activity and the photocatalytic activity order of Keggin‐type species was initially found to be {XMo12O40}>{XW12O40}>{XW12?nTMnO40}. 相似文献
244.
氧化石墨烯(GO)片的基面和边缘上存在大量的含氧官能团,能很好地分散在水中,因而具有很好的加工性和广阔的应用前景。在较高浓度范围下,GO水分散液中存在着强烈的竞争性相互作用,从而对流变行为产生较大影响。在本文中,通过稳态、动态等流变实验以及理论分析,研究了pH值、温度和不同的有机溶剂对GO分散液流变行为的影响。结果表明,降低pH值、适当增加温度以及加入吡啶均可促进GO水分散液从粘弹性液体到凝胶态的转变。利用DLVO (Deryagin-Landau-Verwey-Overbeek)理论,探讨了GO片之间的范德华作用力以及双电层排斥作用的相互关系,及其对流变性能的影响。通过群体平衡模型(PBE)分析了GO分散液的屈服应力与体积分数的正相关关系。同时,通过蠕变和松弛实验发现,高浓度的GO分散液中结构变化及流变行为在很多方面与高聚物相似,利用Poyting-Thomson模型能较好地拟合其粘弹性行为。上述研究结果为深入研究复杂的GO分散体系提供理论支撑和实验依据。 相似文献
245.
246.
Hollow multishelled structure(HoMS)is one of the most promising multifunctional structures.The high complexity of its structure makes the general and controllable synthesis of HoMS rather challenging.By integration of multidisciplinary knowledge,a great achievement in HoMSs has been obtained in the past decade.Especially,the developed sequential templating approach has significantly boomed the progress of HoMS in composition and structure diversity and application area.The implementation of the temporal-spatial ordering in HoMS makes it indispensable in solving the key scientific problems in energy conversion,catalysis and drug delivery areas.Further development in HoMSs with novel intricate structures will bring new understandings.In this review,we systematically introduce the development history of HoMSs,summarize the inspiration inherited from the previous research on hollow structures,and discuss the milestones in the development of HoMSs,with a focus on the sequential templating approach for HoMS fabrication,attractive temporal-spatial ordering property and dynamic smart behavior for advanced applications.We hope to reveal the inherent relationship between the precise synthesis of HoMS and its highly tunable compositional and structural characteristics,and point out its future direction to boost HoMS area further. 相似文献
247.
Electropolymerization is one of the most important methodologies to synthesize and develop conducting polymers. The complexity of the polymerization mechanism, ion doping processes and structural defects are considered to be symbiotic and unavoidable, making the stagnant state and huge band gap with advanced interdisciplinary research fields and important applications in the last three decades. Herein, we provide a point of view into controlled electropolymerization by regioselective activation reactions of monomers, where self-dimerizations instead of self-electropolymerizations were utilized. The resulting dimers play a role in the connections between functional building blocks to form functional polymers on demand. This account highlights the typical findings in controlled electropolymerizations as a forum for discussing new opportunities in exploiting novel designs and applications. 相似文献
248.
Mn4+-activated double perovskite phosphors with composition diversity have presented excellent luminescent performances. However, the charge imbalance between Mn4+ and matrix cations would increase non-radiative recombination and reduce the structural stability. Here, novel high-efficiency stable Li+/Mn4+ co-incorporated Sr2YSbO6 red phosphors are successfully synthesized via a solid-state reaction method for warm w-LEDs, where the Li+ ions have the effect of charge balance for Sr2YSbO6:Mn4+ and reduce the non-radiative energy transfer among Mn4+ ions. It is demonstrated that the substitution of Li+–Mn4+ pairs for Sb5+ can enhance the bonding with low-shifted diffraction peaks and high emission intensity, and prolong the decay lifetime, compared with those of Mn4+ single-doped ones. Impressively, the thermal stability is enhanced to 89.72% from 84.61% at the original value of 303 K. Finally, a w-LED device based on the optimal phosphor Sr2YSbO6:0.01Mn4+/0.01Li+ red component exhibits a correlated color temperature of 4487 K and color rendering index of 80.2. Therefore, the incorporated Li+ ions serve as both charge compensator and co-activator in Mn4+-activated double perovskite phosphors with the aim of high luminescent performance and thermal stability. 相似文献
249.
Chiral 2-oxazolines are valuable building blocks and famous ligands for asymmetric catalysis. The most common synthesis involves the reaction of an amino alcohol with a carboxylic acid. In this paper, an efficient synthesis of 2-oxazolines has been achieved via the stereospecific isomerization of 3-amido-2-phenyl azetidines. The reactions were studied in the presence of both Brønsted and Lewis acids, and Cu(OTf)2 was found to be the most effective. 相似文献
250.
San-E Zhu Jian-Hui Zhang Yu Gong Li-Feng Dou Li-Hua Mao Hong-Dian Lu Chun-Xiang Wei Hong Chen Xue-Fei Wang Wei Yang 《Molecules (Basel, Switzerland)》2021,26(5)
A broadband visible light-absorbing [70]fullerene-BODIPY-triphenylamine triad (C70-B-T) has been synthesized and applied as a heavy atom-free organic triplet photosensitizer for photooxidation. By attaching two triphenylmethyl amine units (TPAs) to the π-core of BODIPY via ethynyl linkers, the absorption range of the antenna is extended to 700 nm with a peak at 600 nm. Thus, the absorption spectrum of C70-B-T almost covers the entire UV–visible region (270–700 nm). The photophysical processes are investigated by means of steady-state and transient spectroscopies. Upon photoexcitation at 339 nm, an efficient energy transfer (ET) from TPA to BODIPY occurs both in C70-B-T and B-T, resulting in the appearance of the BODIPY emission at 664 nm. Direct or indirect (via ET) excitation of the BODIPY-part of C70-B-T is followed by photoinduced ET from the antenna to C70, thus the singlet excited state of C70 (1C70*) is populated. Subsequently, the triplet excited state of C70 (3C70*) is produced via the intrinsic intersystem crossing of C70. The photooxidation ability of C70-B-T was studied using 1,5-dihydroxy naphthalene (DHN) as a chemical sensor. The photooxidation efficiency of C70-B-T is higher than that of the individual components of C70-1 and B-T, and even higher than that of methylene blue (MB). The photooxidation rate constant of C70-B-T is 1.47 and 1.51 times as that of C70-1 and MB, respectively. The results indicate that the C70-antenna systems can be used as another structure motif for a heavy atom-free organic triplet photosensitizer. 相似文献