全文获取类型
收费全文 | 6743篇 |
免费 | 1102篇 |
国内免费 | 904篇 |
专业分类
化学 | 4536篇 |
晶体学 | 48篇 |
力学 | 45篇 |
综合类 | 45篇 |
数学 | 31篇 |
物理学 | 1269篇 |
综合类 | 2775篇 |
出版年
2024年 | 37篇 |
2023年 | 116篇 |
2022年 | 256篇 |
2021年 | 306篇 |
2020年 | 429篇 |
2019年 | 275篇 |
2018年 | 236篇 |
2017年 | 217篇 |
2016年 | 306篇 |
2015年 | 339篇 |
2014年 | 379篇 |
2013年 | 518篇 |
2012年 | 404篇 |
2011年 | 415篇 |
2010年 | 294篇 |
2009年 | 313篇 |
2008年 | 325篇 |
2007年 | 428篇 |
2006年 | 375篇 |
2005年 | 322篇 |
2004年 | 276篇 |
2003年 | 309篇 |
2002年 | 231篇 |
2001年 | 186篇 |
2000年 | 189篇 |
1999年 | 146篇 |
1998年 | 151篇 |
1997年 | 146篇 |
1996年 | 119篇 |
1995年 | 119篇 |
1994年 | 107篇 |
1993年 | 90篇 |
1992年 | 86篇 |
1991年 | 75篇 |
1990年 | 53篇 |
1989年 | 53篇 |
1988年 | 35篇 |
1987年 | 25篇 |
1986年 | 23篇 |
1985年 | 9篇 |
1984年 | 5篇 |
1983年 | 6篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1977年 | 1篇 |
1975年 | 3篇 |
1974年 | 7篇 |
1973年 | 3篇 |
排序方式: 共有8749条查询结果,搜索用时 0 毫秒
91.
Singlet oxygen generation ability of squarylium cyanine dyes 总被引:1,自引:0,他引:1
P. F. Santos L. V. Reis P. Almeida A. S. Oliveira L. F. Vieira Ferreira 《Journal of photochemistry and photobiology. A, Chemistry》2003,160(3):159-161
The quantum yields for singlet oxygen generation of several squarylium cyanine dyes derived from benzothiazole, benzoselenazole and quinoline, displaying absorption within the so-called “phototherapeutic window” (600–1000 nm), were determined, envisioning their potential usefulness for photodynamic therapy (PDT). The determination was performed by a direct method measuring the luminescence decay of the dyes in the near infrared. Considering the absorption and the quantum yields displayed by some of the dyes, these seemed to be potential candidates as sensitizers for PDT. 相似文献
92.
氧气氛中紫外光辐照官能化HDPE的结构与性能研究 总被引:2,自引:0,他引:2
采用FT-IR,XPS,WAXD,DXC,凝胶和表面自由能力分析,研究了氧化氛中紫外辐照官能化高密度聚乙烯(HDPE)的化学结构、晶体结构和表面自由能的变化。与空气相比,在氧气氛中紫外辐照HDPE能提高C-O,C(=O)O和C=O等含氧基团的引入速度,同时又能降低HDPE中的凝胶含量,在空气和氧气氛中紫外辐照后,HDPE的晶型没有发生变化,仍为正交晶系;HDPE的晶胞参数a,b,c以及(110),(200),(020),(011),(111)等晶面间距基本保持不变;HDPE的熔融温度下降,但熔融热焓升高,结晶度增大,表面自由能增大,且在氧气氛中辐照HDPE的变化幅度较大。 相似文献
93.
Novel meander with Co3+ und Au3+: Na4[AuCoO5] = Na8 1∞ [(O2/2 (CoO)O2AuO2/2)2] By “reaction with the wall” we obtained for the first time transparent brown single crystals of Na4[AuCoO5] while heating intimate mixtures of Co3O4, Na2O2, and K2O2 (Co: Na: K = 1.00:4.91:2.20; 650°C/44d) in a sealed gold-tube: monoclinic, P21/m, with a = 555.69(4) pm, b = 1042.11 (8) pm, c = 555.69(4) pm, β = 117.387(5)°, Z = 2. Characteristic features of Na4[AuCoO5] are meandric chains [(O2/2 (CoO)O2AuO2/2)2]. The structure has been determined by four-circle diffractometer data (Siemens AED 2; Mo? Kα , graphite, 881 I0(hkl), R = 0.0366, Rw = 0.0316), parameters as given in the text. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, these via Mean Fictive Ionic Radii, and Charge-distribution, CHARDI, are calculated and discussed. 相似文献
94.
An optical oxygen-sensing material based on the fluorescence intensity changes of pyrene-1-butyric acid (PBA) chemisorption film has been developed and characterised. The fluorescence intensity of PBA film decreased with increase of oxygen concentration. The I0/I100 value of PBA film is estimated to be 6.14±0.15 and large Stern-Volmer constant (KSV=0.028±0.13 Torr−1) is obtained. After irradiation for 24 h with 150 W tungsten lamp, little changes of oxygen-sensing properties were observed. These results indicate that PBA film is highly oxygen-sensitive and photostability device. The response times of the PBA chemisorption film were 10.0 s for switching from argon to oxygen, and 53.0 s for switching from oxygen to argon. Moreover, the optical sensor based on the PBA chemisorption film was applied to the measurement of oxygen concentration in aqueous solution. 相似文献
95.
DFT calculations have been carried out for 2-, 3- and 4-methoxybenzyl alcohol radical cations (1+, 3+ and 4+, respectively) and the α-methyl derivatives 2+ and 5+ using the UB3LYP/6-31G(d) method. The theoretical results have been compared with the experimental rate constants for deprotonation of 1+-5+ under acidic and basic conditions. In acidic solution, the decay of 1+-5+ proceeds by cleavage of the C-H bond, while in the presence of −OH all the radical cations undergo deprotonation from the α-OH group. This pH-dependent change in mechanism has been interpreted qualitatively in terms of simple frontier molecular orbital theory. The −OH induced α-O-H deprotonation is consistent with a charge controlled reaction, whereas the C-H deprotonation, observed when the base is H2O, appears to be affected by frontier orbital interactions. 相似文献
96.
SrTi0.9M0.1O3-δ钙钛矿型氧化物催化剂甲烷氧化偶联反应性能的研究 总被引:2,自引:0,他引:2
The structure and catalytic properties of SrTi0.9M0.1O3-δ (M=Mg,Al, Zr) perovskite-type catalysts for ox-idative coupling of methane (OCM) have been studied by using X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption of oxygen(O2-TPD) methods. It has been shown that doping the cations of lower valence (e.g. Mg2+, Al3+) to the B site of SrTi0.9M0.1O3-δ perovskite-type catalysts results in the higher content of adsorbed oxygen species on the surface of catalysts and thus higher C2-selectivity for OCM reaction. It is suggested that the oxygen vacancies of SrTi0.9M0.1O3-δ (M=Mg, Al, Zr) perovskite-type catalysts are the sites responsible for oxygen activation, and the adsorbed oxygen species on the surface of SrTi0.9M0.1O3-δ catalysts are the main active species for OCM reaction. 相似文献
97.
《Electroanalysis》2005,17(2):186-190
We report for the first time on the electroassisted biomimetic activation of molecular oxygen by a newly prepared electropolymerized polypyrrole‐manganese phthalocyanine film. The prepared films and their intervention in the electroassisted catalytic reduction of molecular oxygen were analyzed by cyclic voltammetry and UV‐visible spectrophotometry on optically transparent electrodes. The obtained results demonstrate the probable existence of the key‐steps responsible for the suggested formation of the highly reactive manganese oxo intermediate. 相似文献
98.
The detection of oxygen in magneto-optical layers is of fundamental importance for the characterization of the stability of RE-TM material. The magnetic properties are directly influenced by oxide formation. Oxygen depth profiles are carried out by using the SIMS technique. A comparison with magnetic measurements showed a clear conformity. We were able to study the oxidation behaviour of various layers at room temperature and at higher values up to 250° C for several hours. It could be shown that aluminum is a successful material for the protection of RE-films against oxidation. The difficulties of translating SIMS counting rates into concentration values were overcome by using EPMA. Specially prepared reference samples were measured by this technique and could then be used as standard samples for SIMS. 相似文献
99.
金属/氮/碳催化剂(M/N/C,M=Fe、Co等)是最有发展前景的非贵金属电催化剂之一,其性能依赖于催化剂表面的活性物种密度.通过常规的热解含氮前驱物与金属盐的方法制得的催化剂往往存在金属活性物种被包埋而不能有效利用的缺点.考虑到石墨相氮化碳(g-C3N4)富含类吡啶氮和亚纳米孔腔结构,将g-C3N4包覆在高导电性碳纳米笼(hCNC)表面,进而利用表层g-C3N4的配位和限域作用锚定大量Co2+离子,获得的Co/g-C3N4/hCNC复合物经热解后形成了活性位高度暴露、导电性好、孔结构丰富的Co/N/C催化剂.800℃热解得到的最优化催化剂在碱性介质中展现出优异氧还原活性,其起始电位(0.97 V)与商业Pt/C催化剂相当,且抗甲醇干扰性能和稳定性优异.此项研究提供了一种构建具有高度暴露活性位的M/N/C催化剂的有效策略. 相似文献
100.
Ogata Atsushi Mizuno Koichi Kushiyama Satoshi Yamamoto Toshiaki 《Plasma Chemistry and Plasma Processing》1998,18(3):363-373
The behavior of lattice oxygen species of the ferroelectric material during methane oxidation was investigated using a nonthermal plasma reactor packed with BaTiO
3
pellets. Lattice oxygen species in BaTiO
3
play an important role in the formation of N
2
O and the oxidation of CH
4
. The oxidation products such as CO and CO
2
were formed from independent reaction pathways. Lattice oxygen species were able to preferentially oxidize the carbon species deposited on the pellet surface into CO. Also, N
2
O and NO
x
were independently formed in the N
2–O
2
reaction, suggesting that different oxygen species give N
2
O and NO
x. N
2
O was produced by the oxidation of molecular nitrogen with lattice oxygen species. 相似文献