全文获取类型
收费全文 | 333篇 |
免费 | 42篇 |
国内免费 | 39篇 |
专业分类
化学 | 194篇 |
晶体学 | 6篇 |
力学 | 5篇 |
综合类 | 3篇 |
数学 | 62篇 |
物理学 | 144篇 |
出版年
2023年 | 2篇 |
2022年 | 4篇 |
2021年 | 5篇 |
2020年 | 4篇 |
2019年 | 3篇 |
2018年 | 7篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 9篇 |
2014年 | 13篇 |
2013年 | 12篇 |
2012年 | 9篇 |
2011年 | 16篇 |
2010年 | 8篇 |
2009年 | 14篇 |
2008年 | 22篇 |
2007年 | 17篇 |
2006年 | 23篇 |
2005年 | 22篇 |
2004年 | 11篇 |
2003年 | 11篇 |
2002年 | 10篇 |
2001年 | 16篇 |
2000年 | 13篇 |
1999年 | 20篇 |
1998年 | 9篇 |
1997年 | 11篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 7篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1990年 | 9篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1972年 | 5篇 |
1971年 | 2篇 |
1969年 | 2篇 |
1935年 | 2篇 |
1906年 | 1篇 |
排序方式: 共有414条查询结果,搜索用时 15 毫秒
401.
Tavares Xda S Blum AP Nakamura DT Puskar NL Shanata JA Lester HA Dougherty DA 《Journal of the American Chemical Society》2012,134(28):11474-11480
Drug-receptor binding interactions of four agonists, ACh, nicotine, and the smoking cessation compounds varenicline (Chantix) and cytisine (Tabex), have been evaluated at both the 2:3 and 3:2 stoichiometries of the α4β2 nicotinic acetylcholine receptor (nAChR). Previous studies have established that unnatural amino acid mutagenesis can probe three key binding interactions at the nAChR: a cation-π interaction, and two hydrogen-bonding interactions to the protein backbone of the receptor. We find that all drugs make a cation-π interaction to TrpB of the receptor. All drugs except ACh, which lacks an N(+)H group, make a hydrogen bond to a backbone carbonyl, and ACh and nicotine behave similarly in acting as a hydrogen-bond acceptor. However, varenicline is not a hydrogen-bond acceptor to the backbone NH that interacts strongly with the other three compounds considered. In addition, we see interesting variations in hydrogen bonding interactions with cytisine that provide a rationalization for the stoichiometry selectivity seen with this compound. 相似文献
402.
Dougherty TJ Sumlin AB Greco WR Weishaupt KR Vaughan LA Pandey RK 《Photochemistry and photobiology》2002,76(1):91-97
A study has been carried out to define the importance of the peripheral benzodiazepine receptor (PBR) as a binding site for a series of chlorin-type photosensitizers, pyropheophorbide-a ethers, the subject of a previous quantitative structure-activity relationship study by us. The effects of the PBR ligand PK11195 on the photodynamic activity have been determined in vivo for certain members of this series of alkyl-substituted ethers: two of the most active derivatives (hexyl and heptyl), the least active derivative (dodecyl [C12]) and one of intermediate activity (octyl [C8]). The photodynamic therapy (PDT) effect was inhibited by PK11195 for both of the most active derivatives, but no effect on PDT activity was found for the less active C12 or C8 ethers. The inhibitory effects of PK11195 were predicted by the binding of only the active derivatives to the benzodiazepine site on albumin, ie. human serum albumin (HSA)-Site II. Thus, as with certain other types of photosensitizers, it has been demonstrated with this series of pyropheophorbide ethers that in vitro binding to HSA-Site II is a predictor of both optimal in vivo activity and binding to the PBR in vivo. 相似文献
403.
Mock MT Potter RG O'Hagan MJ Camaioni DM Dougherty WG Kassel WS DuBois DL 《Inorganic chemistry》2011,50(23):11914-11928
Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H(2) gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)(2) (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX(3) compounds having a hydride affinity (HA) greater than or equal to the HA of BEt(3). This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)(2) and [HNi(dmpe)(2)](+), to form B-H bonds. The hydride donor abilities (ΔG(H(-))°) of HCo(dmpe)(2) and [HNi(dmpe)(2)](+) were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX(3) compounds. The collective data guided our selection of BX(3) compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)(2) was observed to transfer H(-) to BX(3) compounds with X = H, OC(6)F(5), and SPh. The reaction with B(SPh)(3) is accompanied by the formation of dmpe-(BH(3))(2) and dmpe-(BH(2)(SPh))(2) products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)(2) and B(SPh)(3) in the presence of triethylamine result in the formation of Et(3)N-BH(2)SPh and Et(3)N-BH(3) with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)(2)](+) with B(SPh)(3) under analogous conditions give Et(3)N-BH(2)SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)(2)(SPh)](+). The synthesis and characterization of HCo(dedpe)(2) (dedpe = Et(2)PCH(2)CH(2)PPh(2)) from H(2) and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)(2)Co(dedpe)(2)][BF(4)]. 相似文献
404.
405.
406.
407.
DISTRIBUTION AND ELIMINATION OF PHOTOFRIN II IN MICE 总被引:7,自引:0,他引:7
David A. Bellnier Yau-Kwan Ho Ravindra K. Pandey Joseph R. Missert Thomas J. Dougherty 《Photochemistry and photobiology》1989,50(2):221-228
The distribution and elimination of [14C]PII, the radioisotopically-labeled equivalent of the mixture of porphyrins known as Photofrin II used in the photodynamic treatment of solid tumors, were determined in tumor-free and SMT-F tumor-bearing DBA/2 Ha-DD mice. Following i.p. injection, drug was absorbed from the peritoneum with a half-life of about 1 h; elimination from plasma was rapid, declining about 1.4 logs in concentration over 48 h following i.v. administration. However, some [14C]-activity was still detectable after 75 days. Normal tissues take up the drug within about 7.5 h after administration, with peak concentrations distributed as follows: liver, adrenal gland, urinary bladder greater than pancreas, kidney, spleen greater than stomach, bone, lung, heart greater than muscle much greater than brain. Only skeletal muscle, brain, and skin located contralaterally to subcutaneously implanted SMT-F tumors had peak [14C]-activities lower than tumor tissue; skin overlying SMT-F tumors showed concentrations not significantly different (P greater than 0.3) from tumor. After 75 days all tissues examined retained some fraction of [14C]-activity, ranging from 16% for kidney to 61% for spleen, of the initial peak tissue levels. The primary route of elimination of Photofrin II was through the bile-gut pathway, with greater than 59% of the administered [14C]-activity recovered in the feces, and only about 6% in the urine, over 192 h. HPLC analyses of fecal extracts showed that mostly monomeric and other low molecular weight porphyrin components of Photofrin II were eliminated. The higher molecular weight oligomeric fractions of Photofrin II were retained in liver and spleen up to 14 days after injection. 相似文献
408.
杯[8]芳烃键合硅胶固定相的制备、表征及色谱性能 总被引:1,自引:0,他引:1
杯芳烃通过疏水Π-Π、氢键和静电等作用能与中性分子及离子形成包合物,在离子选择性电极、催化、分离和酶模拟等领域受到关注.已报道的杯芳烃键合固定相的制备方法[1~3]都是先合成含杯芳烃硅烷化试剂,然后通过硅胶硅烷化反应制备键合固定相.其制备路线反应过程长,各种有机中间体纯化操作复杂.前文[4]曾以氯丙基键合硅胶为中间体,通过固相连续反应制备了氮杂冠醚键合硅胶固定相.本文采用固相连续反应制备了一种新型的对-叔丁基杯[8]芳烃键合固定相,通过元素分析、红外光谱等手段获得键合相分子结构信息,以多环芳烃和二取代苯位置异构体为溶质,对固定相的色谱性能及保留机理进行了研究. 相似文献
409.
一种新型MAO改性的高活性铬基气相聚乙烯催化剂 总被引:1,自引:0,他引:1
制备了一种新型的CrO3/SiO2/MAO(/EtOAlEt2)乙烯聚合催化剂,在微机控制的自动评价装置上进行了乙烯气相聚合评价试验,研究了催化剂制备中有机铝化合物对催化剂的改性作用.结果表明,MAO作为还原剂可以明显提高催化剂的聚合活性,显著影响乙烯聚合反应动力学,得到的聚乙烯树脂融体流动速率较低.同时采用MAO和EtOAlEt2作为还原剂制备催化剂时,二者具有显著的协同效应,催化剂聚合活性高,临氢效应敏感高,树脂的融体流动速率高. 相似文献
410.
Maksymovych P Sorescu DC Dougherty D Yates JT 《The journal of physical chemistry. B》2005,109(47):22463-22468
The chemisorption of the undissociated CH3SH molecule on the Au(111) surface has been studied at 5 K using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The molecule was found to adsorb on atop Au sites on the defect-free surface. CH3SH undergoes hindered rotation about the Au-S bond on the defect-free surface which is seen in STM as a time-averaged 6-fold pattern. The pattern suggests that the potential minima directions occur for the rotating molecule at the six hollow sites surrounding the atop adsorption site. The barrier for rotation, obtained by DFT calculations, is approximately 0.1 kcal.mol(-1). At low coverages, preferential adsorption occurs at defect sites in the surface, namely, the herringbone "elbows" and random atomic step sites. Molecules adsorbed on these sites do not exhibit rotational freedom. 相似文献