全文获取类型
收费全文 | 22752篇 |
免费 | 2011篇 |
国内免费 | 4908篇 |
专业分类
化学 | 26169篇 |
晶体学 | 136篇 |
力学 | 276篇 |
综合类 | 115篇 |
数学 | 426篇 |
物理学 | 2549篇 |
出版年
2024年 | 63篇 |
2023年 | 358篇 |
2022年 | 686篇 |
2021年 | 799篇 |
2020年 | 1185篇 |
2019年 | 992篇 |
2018年 | 1025篇 |
2017年 | 937篇 |
2016年 | 1013篇 |
2015年 | 951篇 |
2014年 | 1442篇 |
2013年 | 2242篇 |
2012年 | 1248篇 |
2011年 | 1556篇 |
2010年 | 1178篇 |
2009年 | 1287篇 |
2008年 | 1379篇 |
2007年 | 1502篇 |
2006年 | 1389篇 |
2005年 | 1298篇 |
2004年 | 1274篇 |
2003年 | 972篇 |
2002年 | 582篇 |
2001年 | 483篇 |
2000年 | 499篇 |
1999年 | 418篇 |
1998年 | 375篇 |
1997年 | 332篇 |
1996年 | 302篇 |
1995年 | 295篇 |
1994年 | 248篇 |
1993年 | 192篇 |
1992年 | 189篇 |
1991年 | 140篇 |
1990年 | 111篇 |
1989年 | 104篇 |
1988年 | 82篇 |
1987年 | 53篇 |
1986年 | 48篇 |
1985年 | 53篇 |
1984年 | 48篇 |
1983年 | 26篇 |
1982年 | 36篇 |
1981年 | 35篇 |
1980年 | 26篇 |
1979年 | 24篇 |
1978年 | 27篇 |
1977年 | 29篇 |
1976年 | 36篇 |
1974年 | 38篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Formation of Octameric Methylaluminoxanes by Hydrolysis of Trimethylaluminum and the Mechanisms of Catalyst Activation in Single‐Site α‐Olefin Polymerization Catalysis 下载免费PDF全文
Dr. Janne T. Hirvi Prof. Manfred Bochmann Dr. John R. Severn Prof. Mikko Linnolahti 《Chemphyschem》2014,15(13):2732-2742
Hydrolysis of trimethylaluminum (TMA) leads to the formation of methylaluminoxanes (MAO) of general formula (MeAlO)n(AlMe3)m. The thermodynamically favored pathway of MAO formation is followed up to n=8, showing the major impact of associated TMA on the structural characteristics of the MAOs. The MAOs bind up to five TMA molecules, thereby inducing transition from cages into rings and sheets. Zirconocene catalyst activation studies using model MAO co‐catalysts show the decisive role of the associated TMA in forming the catalytically active sites. Catalyst activation can take place either by Lewis‐acidic abstraction of an alkyl or halide ligand from the precatalyst or by reaction of the precatalyst with an MAO‐derived AlMe2+ cation. Thermodynamics suggest that activation through AlMe2+ transfer is the dominant mechanism because sites that are able to release AlMe2+ are more abundant than Lewis‐acidic sites. The model catalyst system is demonstrated to polymerize ethene. 相似文献
992.
In the presence of zinc chloride, the in situ generated β‐enamino ester from the reaction of morpholine, piperidine and pyrrolidine with methyl propiolate reacted, with aromatic aldehydes and thiourea in ethanol resulting in the functionalized tetrahydropyrimidin‐2‐thiones in satisfactory yields and with good diastereoselectivity. When aromatic aldehydes bearing electron‐withdrawing group were used in the reaction, the 4‐hydroxytetrahydropyrimidin‐2‐thione derivatives were obtained as the main product. 相似文献
993.
The one‐pot four‐component reaction of benzohydrazide, acetylenedicarboxylate, aromatic aldehydes and malononitrile in ethanol with triethylamine as base catalyst afforded functionalized 1‐benzamido‐1,4‐dihydropyridines in satisfactory yields. Under similar conditions, picolinohydrazide or nicotinohydrazide can also be successfully utilized in the reactions to give corresponding functionalized 1,4‐dihydropyridines. 1H NMR data indicated that an equilibrium of cis/trans‐conformations exist in 1‐benzamido‐1,4‐dihydropyridines. 相似文献
994.
An efficient synthesis of Biginelli-type compounds using potassium phthalimide as a green, mild, and commercially available organocatalyst in a one-pot, multi-component cyclocondensation reaction of cyclopentanone, aldehydes, and urea/thiourea is reported. The present methodology is a green approach to access 4-aryl-7-(aryImethylene)-3,4,6,7-tetrahydro-1H-cyclopenta[d]pyrimidin-2(5H)-ones/thiones. It offers several merits such as simple operational procedures, no use of hazardous organic solvents, and cheap and environmentally friendly solid basic catalyst. 相似文献
995.
In this study, 1,3-disulfonic acid imidazolium hydrogen sulfate (DSIMHS) is used as an efficient and reusable ionic liquid for the green, mild, and efficient synthesis of xanthenes under solvent-free conditions. Simple and easy work-up, low cost, green process, short reaction times and excellent yields of the products are the advantages of this procedure. Further, the catalyst can be recycled and reused at least for four times without a noticeably decrease in its catalytic activity. 相似文献
996.
Nader Ghaffari Khaligh 《催化学报》2014,35(7):1036-1042
3-Methyl-1-sulfonic acid imidazolium hydrogen sulfate has been used as an efficient, halogen-free,and reusable Brnsted acidic ionic liquid catalyst for the synthesis of ethyl-4-aryl/heteryl- hexahydro-trimehtyl-5-oxoquinoline-3-carboxylates via the one-pot condensation of dimedone with aryl/heteryl aldehydes, ethyl acetoacetate, and ammonium acetate under solvent-free conditions. This method has the advantage of being clean and simple, as well as providing the desired product in high yield over a short reaction time. Furthermore, the catalyst could be recycled and reused four times without any discernible reduction in activity. 相似文献
997.
Photo-induced graft copolymerization of methyl methacrylate(MMA) onto sodium salt of partially carboxymethylated guar gum(Na-PCMGG, DS = 0.291) was carried out in an aqueous medium using ceric ammonium nitrate(CAN) as photoinitiator to synthesize a novel graft copolymer, Na-PCMGG-g-PMMA, which may find its potential application as a metal adsorbent. The influences of synthesis variables such as concentrations of photoinitiator(CAN), nitric acid and monomer(MMA) as well as reaction time, temperature and amount of substrate on the grafting yields were studied and the reaction conditions for optimum photo-grafting were evaluated. At optimum concentration, the maximum values of the grafting yields achieved were G = 271.61% and GE = 63.89%. The experimental results were found to be in very good agreement with the proposed kinetic scheme. The photo-graft copolymerization of MMA onto Na-PCMGG( DS = 0.291) was also carried out in the presence and absence of ultraviolet radiation for studying the efficiency of the photoinitiator. The influence of carboxymethyl groups introduced onto the guar gum molecules with regard to its behavior towards ultra-violet radiation induced grafting with MMA was also investigated. Photo-grafting process was confirmed and the products were characterized with the help of the spectroscopic(1H-NMR and FTIR) and SEM techniques. 相似文献
998.
999.
以2-氯-5-氯甲基吡啶(CCMP)、无水乙二胺和硝基胍为原料,运用串联反应方法合成了吡虫啉[化学名:1-(6-氯-3-吡啶甲基)-N-硝基-2-咪唑啉亚胺]。该方法反应中间体无需纯化处理,操作简单,同时解决了活性中间体进一步进行副反应的难题。通过单因素实验,探讨了pH、反应溶剂、温度以及时间等因素对产物收率的影响,得到的优化工艺条件为:以乙腈为溶剂,nCCMP∶n无水乙二胺∶n硝基胍=1∶5∶1,于30℃反应120min,产率可达96.35%。其结构经1H NMR、13C NMR、IR表征。 相似文献
1000.
采用紫外光谱动力学方法测定了抗肿瘤对映贝壳杉烯二萜冬凌草甲素和冬凌草乙素与谷胱苷肽迈克尔加成反应的级数、速率常数和平衡常数.结果表明,冬凌草甲素和冬凌草乙素与与谷胱苷肽迈克尔加成反应符合二级动力学方程,25℃下的速率常数分别为16.196 0L·(mol·s)-1和7.480 5L·(mol·s)-1,平衡常数分别为177.98L/mol和85.60L/mol.冬凌草甲素与谷胱苷肽迈克尔加成反应速率和反应程度均比冬凌草乙素的大得多,反应活性更好.对映贝壳杉烯二萜通过与机体发生迈克尔加成反应而产生抗肿瘤作用;因此,冬凌草甲素可能比冬凌草乙素具有更好的抗肿瘤活性. 相似文献