全文获取类型
收费全文 | 61910篇 |
免费 | 4652篇 |
国内免费 | 11521篇 |
专业分类
化学 | 55741篇 |
晶体学 | 576篇 |
力学 | 619篇 |
综合类 | 799篇 |
数学 | 8576篇 |
物理学 | 11772篇 |
出版年
2023年 | 923篇 |
2022年 | 957篇 |
2021年 | 1975篇 |
2020年 | 1875篇 |
2019年 | 1825篇 |
2018年 | 1583篇 |
2017年 | 1660篇 |
2016年 | 2175篇 |
2015年 | 2211篇 |
2014年 | 2884篇 |
2013年 | 4949篇 |
2012年 | 3341篇 |
2011年 | 3860篇 |
2010年 | 3348篇 |
2009年 | 4171篇 |
2008年 | 4332篇 |
2007年 | 4523篇 |
2006年 | 4020篇 |
2005年 | 3117篇 |
2004年 | 2906篇 |
2003年 | 2625篇 |
2002年 | 2148篇 |
2001年 | 1852篇 |
2000年 | 1415篇 |
1999年 | 1166篇 |
1998年 | 1121篇 |
1997年 | 997篇 |
1996年 | 943篇 |
1995年 | 888篇 |
1994年 | 837篇 |
1993年 | 870篇 |
1992年 | 802篇 |
1991年 | 499篇 |
1990年 | 404篇 |
1989年 | 327篇 |
1988年 | 266篇 |
1987年 | 238篇 |
1986年 | 240篇 |
1985年 | 352篇 |
1984年 | 264篇 |
1983年 | 151篇 |
1982年 | 295篇 |
1981年 | 480篇 |
1980年 | 433篇 |
1979年 | 473篇 |
1978年 | 378篇 |
1977年 | 283篇 |
1976年 | 244篇 |
1974年 | 80篇 |
1973年 | 156篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
1.
2.
Photocatalytic CO2 reduction to C1 fuels is considered to be an important way for alleviating increasingly serious energy crisis and environmental pollution. Due to the environment-friendly, simple preparation, easy formation of highly-stable metal-nitrogen(M-Nx) coordination bonds, and suitable band structure, polymeric carbon nitride-based single-atom catalysts(C3N4-based SACs) are expected to become a potential for CO2 reduction under visible-light irradiation. In this review, we summarize the recent advancement on C3N4-based SACs for photocatalytic CO2 reduction to C1 products, including the reaction mechanism for photocatalytic CO2 reduction to C1 products, the structure and synthesis methods of C3N4-based SACs and their applications toward photocatalytic CO2 reduction reaction(CO2RR) for C1 production. The current challenges and future opportunities of C3N4-based SACs for photoreduction of CO2 are also discussed. 相似文献
3.
Kento Nishikibe Keisuke Nishikawa Momochika Kumagai Matsumi Doe Yoshiki Morimoto 《化学:亚洲杂志》2022,17(1):e202101137
There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis. 相似文献
4.
Dariusz Marek Adam Domaski Joanna Domaska Jakub Szygua Tadeusz Czachrski Jerzy Klamka 《Entropy (Basel, Switzerland)》2021,23(5)
In this article, a way to employ the diffusion approximation to model interplay between TCP and UDP flows is presented. In order to control traffic congestion, an environment of IP routers applying AQM (Active Queue Management) algorithms has been introduced. Furthermore, the impact of the fractional controller and its parameters on the transport protocols is investigated. The controller has been elaborated in accordance with the control theory. The TCP and UDP flows are transmitted simultaneously and are mutually independent. Only the TCP is controlled by the AQM algorithm. Our diffusion model allows a single TCP or UDP flow to start or end at any time, which distinguishes it from those previously described in the literature. 相似文献
5.
《中国物理 B》2021,30(5):56501-056501
Thermal expansion control is always an obstructive factor and challenging in high precision engineering field. Here,the negative thermal expansion of Nb F_3 and Nb OF_2 was predicted by first-principles calculation with density functional theory and the quasi-harmonic approximation(QHA). We studied the total charge density, thermal vibration, and lattice dynamic to investigate the thermal expansion mechanism. We found that the presence of O induced the relatively strong covalent bond in Nb OF_2, thus weakening the transverse vibration of F and O in Nb OF_2, compared with the case of Nb F_3.In this study, we proposed a way to tailor negative thermal expansion of metal fluorides by introducing the oxygen atoms.The present work not only predicts two NTE compounds, but also provides an insight on thermal expansion control by designing chemical bond type. 相似文献
6.
Mohammad Javad TAGHIZADEH Maryam Saleh MOHAMMADNIA Masoumeh GHALKHANI Esmail SOHOULI 《高等学校化学研究》2022,38(2):546-551
Azaperone, with anti-anxiety and anti-aggressive activities used in veterinary medicine, is a member of the butyrophenone class. It is ordinarily utilized for a wide range of indications, such as sedation, obstetrics, and anesthesia. In this research, an improved synthetic route is presented for azaperone using a phase-transfer catalyst(PTC). In general, it was synthesized as a dopamine antagonist in four steps. The bis(2-chloroethyl) amine intermediate is easily obtained after the conversion of the alcohol groups into the chloride leaving group using thionyl chloride(95% yields). The alkylation of commercially available 2-amino pyridine in the presence of PTC was then carried out, giving 1-(pyridin-2-yl) piperazine with 75% yield. 1-(Pyridin-2-yl) piperazine was finally alkylated using 4-chloro-1-(4-fluorophenyl) butan-1-one to achieve azaperone with 60% yield. The butyrophenone intermediate was obtained via the Friedel-Crafts reaction of fluorobenzene with 4-chlorobutyryl chloride in the presence of AlCl3. High efficiency, gentle reaction conditions, and fast and simple procedure are the advantages of this method. Also, the electrochemical oxidation behaviour of azaperone was investigated using cyclic and differential pulse voltammetry techniques. Cyclic voltammetric studies indicated an irreversible process for azaperone electro-oxidation with a peak potential of 0.78 V in a phosphate buffer solution(pH=7.0) vs. Ag/AgCl(saturated KCl) electrode. The value of the peak current vs. the azaperone concentration was enhanced linearly in the range of 10―70 μmol/L, and the detection limit was found to be 3.33 μmol/L. 相似文献
7.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
8.
直接碳燃料电池(DCFC)是一种清洁高效利用碳资源发电的装置。其因能量转换率高,对环境污染小,燃料选择范围广等优点获得了越来越多的关注。DCFC的性能与使用的燃料密切相关,为了探究燃料对DCFC的影响,本文分别阐述了石墨、炭黑、中密度纤维板、生物质、煤、活性炭的特性及改性方法,分析讨论了燃料表面含氧官能团以及燃料中的金属催化剂对阳极电化学反应的促进作用,发现燃料表面化学性质要比比表面积更加重要。同时,本文也提出了对生物质这一优良的可再生资源的期待,为未来DCFC燃料的发展提供参考。 相似文献
9.
《Journal of Saudi Chemical Society》2022,26(3):101483
Alkenyl boron-esters and acrylonitrile groups are key structural functional groups found in dyes, pesticides, fluorescent compounds, functional materials, and biologically active drugs. Considerable efforts have been devoted for the introduction of boron-esters and acrylonitrile groups by using alkenes and alkynes conversion routes for boronation, hydroboronation, dehydrogenative boronation, cyanation, hydrocyanation, alkylcyanation, cyanomethylation. These reported methodologies are very valuable for the industrial production of acrylonitriles and alkenyl boron esters. 相似文献
10.
Chinese Annals of Mathematics, Series B - In the present article, the authors find and establish stability of multiplier ideal sheaves, which is more general than strong openness. 相似文献