全文获取类型
收费全文 | 37190篇 |
免费 | 9658篇 |
国内免费 | 1410篇 |
专业分类
化学 | 42452篇 |
晶体学 | 319篇 |
力学 | 503篇 |
数学 | 2417篇 |
物理学 | 2567篇 |
出版年
2023年 | 20篇 |
2022年 | 33篇 |
2021年 | 172篇 |
2020年 | 1269篇 |
2019年 | 2626篇 |
2018年 | 1020篇 |
2017年 | 671篇 |
2016年 | 3433篇 |
2015年 | 3574篇 |
2014年 | 3488篇 |
2013年 | 4132篇 |
2012年 | 3019篇 |
2011年 | 2239篇 |
2010年 | 2926篇 |
2009年 | 2833篇 |
2008年 | 2428篇 |
2007年 | 1841篇 |
2006年 | 1503篇 |
2005年 | 1672篇 |
2004年 | 1475篇 |
2003年 | 1348篇 |
2002年 | 2048篇 |
2001年 | 1410篇 |
2000年 | 1320篇 |
1999年 | 397篇 |
1998年 | 87篇 |
1997年 | 72篇 |
1996年 | 70篇 |
1995年 | 81篇 |
1994年 | 70篇 |
1993年 | 70篇 |
1992年 | 55篇 |
1991年 | 48篇 |
1990年 | 42篇 |
1989年 | 34篇 |
1988年 | 31篇 |
1987年 | 41篇 |
1986年 | 34篇 |
1985年 | 44篇 |
1984年 | 34篇 |
1983年 | 32篇 |
1982年 | 37篇 |
1981年 | 33篇 |
1980年 | 37篇 |
1979年 | 30篇 |
1978年 | 39篇 |
1977年 | 31篇 |
1975年 | 27篇 |
1974年 | 30篇 |
1973年 | 36篇 |
排序方式: 共有10000条查询结果,搜索用时 20 毫秒
971.
Jeong Hyun Yeum Byung Chul Ji Chul Joo Lee Ji Youl Lee Sang‐Seob Lee Sam Soo Kim Joon Ho Kim Won Seok Lyoo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1103-1111
To prepare water‐soluble, syndiotacticity‐rich poly(vinyl alcohol) (PVA) microfibrils for various industrial applications, we synthesized syndiotacticity‐rich, low molecular weight PVA by the solution polymerization of vinyl pivalate (VPi) in tetrahydrofuran (THF) at low temperatures with 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN) as an initiator and successive saponification of poly(vinyl pivalate) (PVPi). Effects of the initiator and monomer concentrations and the polymerization temperature were investigated in terms of the polymerization behaviors and molecular structures of PVPi and the corresponding syndiotacticity‐rich PVA. The polymerization rate of VPi in THF was proportional to the 0.91 power of the ADMVN concentration, indicating the heterogeneous nature of THF polymerization. The low‐temperature solution polymerization of VPi in THF with ADMVN proved to be successful in obtaining water‐soluble PVA with a number‐average degree of polymerization (Pn) of 300–900, a syndiotactic dyad content of 60–63%, and an ultimate conversion of VPi into PVPi of over 75%. Despite the low molecular weight of PVA with Pn = 800, water‐soluble PVA microfibrillar fibers were prepared because of the high level of syndiotacticity. In contrast, for PVA with Pn = 330, shapeless and globular morphologies were observed, indicating that molecular weight has an important role in the in situ fibrillation of syndiotacticity‐rich PVA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1103–1111, 2002 相似文献
972.
Mohammad Abul‐Haj Miguel Quirs Juan M. Salas 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(8):934-935
The title compound, [Ni(NCS)2(C5H4N4O)2(H2O)2], crystallizes in the triclinic space group P. The molecular unit contains two neutral molecules of 4,5‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidin‐5‐one (5HtpO) coordinated through the N atom in position 3, two thiocyanate ligands coordinated through their N atoms and two water molecules completing an octahedral environment around the NiII ion, which lies on a centre of inversion. The structure is stabilized by hydrogen bonding. Distances in the coordination sphere are Ni—N3(5HtpO) 2.132 (2), Ni—O(water) 2.085 (2) and Ni—N(thiocyanato) 2.040 (2) Å. 相似文献
973.
The polyphenolic profiles and antioxidant effects of Agastache rugosa Kuntze (Banga) flower,leaf, stem and root 下载免费PDF全文
Yun‐Hi Kim Won Sup Lee Soo Jung Lee Jong Sung Jin A. M. Abd El‐Aty Ho‐Chul Shin Jae‐Han Shim Sung Chul Shin 《Biomedical chromatography : BMC》2016,30(2):225-231
Agastache rugosa Kuntze (Korean mint) is used as a spice and in folk medicine in East Asia. The present study identified a total of 18 polyphenols from the flower, leaf, stem and roots of this plant using high‐performance liquid chromatography–tandem mass spectrometry. Fourteen of these compounds had not previously been identified in these plant tissues. Each polyphenol was validated in comparison with external calibration curves constructed using structurally related compounds, with determination coefficients >0.9993. The limits of detection and quantification were 0.092–0.650 and 0.307–2.167 mg/L, respectively. Recoveries of 61.92–116.44% were observed at two spiking levels, with 0.91–11% precision, expressed as relative standard deviation (except anthraquinone spiked at 10 mg/L). Hydroxycinnamic acid was the most abundant compound in the root, while the flowers showed the highest total flavonoid level. Antioxidant activities, determined in terms of reducing power, Fe2+ chelating activity and the radical scavenging activities using α,α‐diphenyl‐β‐picrylhydrazyl and 2‐2?‐azino‐bis‐3‐ethylbenzothiazoline‐6‐sulfonic acid, increased in a concentration‐dependent manner; the highest activity was identified in the stems, followed by leaves > flowers > roots. These findings indicate that A. rugosa is a good source of bioactive compounds and can be used as a functional food. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
974.
Synthesis,structure and catalytic polymerization activity of half‐sandwich cyclometallated iridium complexes 下载免费PDF全文
A series of mononuclear half‐sandwich cyclometallated iridium complexes with Schiff base ligands were synthesized in good yields. Five air‐stable C,N‐chelate mode complexes were obtained smoothly through metal‐mediated C─H bond activation. Treatments of dimeric metal complexes [Cp*IrCl2]2 with ligands L1–L5 afforded the corresponding C,N‐chelate mononuclear half‐sandwich iridium(III) complexes 1 – 5 . These iridium complexes exhibit high catalytic activity for norbornene polymerization. Both steric and electronic effects of the substituted groups have influences on the behaviors of the polymerization process. All complexes were characterized using infrared and NMR spectroscopies and elemental analysis. Molecular structures of complexes 1 , 2 and 5 were further confirmed using single‐crystal X‐ray analysis. 相似文献
975.
976.
Seed‐Mediated Synthesis of Gold Tetrahedra in High Purity and with Tunable,Well‐Controlled Sizes 下载免费PDF全文
Yiqun Zheng Wenying Liu Tian Lv Ming Luo Dr. Hefei Hu Dr. Ping Lu Dr. Sang‐Il Choi Chao Zhang Dr. Jing Tao Prof. Yimei Zhu Prof. Zhi‐Yuan Li Prof. Younan Xia 《化学:亚洲杂志》2014,9(9):2635-2640
We report a facile synthesis of Au tetrahedra in high purity and with tunable, well‐controlled sizes via seed‐mediated growth. The success of this synthesis relies on the use of single‐crystal, spherical Au nanocrystals as the seeds and manipulation of the reaction kinetics to induce an unsymmetrical growth pattern for the seeds. In particular, the dropwise addition of a precursor solution with a syringe pump, assisted by cetyltrimethylammonium chloride and bromide at appropriate concentrations, was found to be critical to the formation of Au tetrahedra in high purity. Their sizes could be readily tuned in the range of 30–60 nm by simply varying the amount of precursor added to the reaction solution. The current strategy not only enables the synthesis of Au tetrahedra with tunable and controlled sizes but also provides a facile and versatile approach to reducing the symmetry of nanocrystals made of a face‐centered cubic lattice. 相似文献
977.
Charlotte Duval Cécile Nouvel Jean‐Luc Six 《Journal of polymer science. Part A, Polymer chemistry》2014,52(8):1130-1138
Poly(d,l ‐lactide‐co‐glycolide) (PLGA) copolyesters are commonly used in biomedical applications. Researches were carried out on nontoxic or low‐toxic catalysts that are enough efficient to provide short polymerization times, adequate microstructure chains and similar properties than the commercial PLGA materials. In this study, PLGA were synthesized by ring‐opening copolymerization (ROP) using three different catalysts. Stannous octoate is the first catalyst we used, as it is very efficient, even its toxicity is still on debate. Two others low‐toxic catalysts [zinc lactate and bismuth subsalicylate (BiSS)] were also evaluated. The comparison of these ROP was realized in terms of kinetics and control of the polymerization. Then, the influence of the catalyst on the PLGA microstructure chains is reported. Finally, abiotic hydrolytic degradation rate is studied. Results described in this article show that BiSS is one very attractive catalyst to produce low toxic PLGA for biomedical applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1130–1138 相似文献
978.
979.