全文获取类型
收费全文 | 1202篇 |
免费 | 38篇 |
国内免费 | 4篇 |
专业分类
化学 | 884篇 |
晶体学 | 24篇 |
力学 | 36篇 |
数学 | 59篇 |
物理学 | 241篇 |
出版年
2023年 | 5篇 |
2021年 | 7篇 |
2020年 | 14篇 |
2019年 | 12篇 |
2018年 | 11篇 |
2017年 | 7篇 |
2016年 | 18篇 |
2015年 | 25篇 |
2014年 | 24篇 |
2013年 | 61篇 |
2012年 | 48篇 |
2011年 | 59篇 |
2010年 | 27篇 |
2009年 | 35篇 |
2008年 | 76篇 |
2007年 | 69篇 |
2006年 | 81篇 |
2005年 | 102篇 |
2004年 | 67篇 |
2003年 | 48篇 |
2002年 | 54篇 |
2001年 | 21篇 |
2000年 | 29篇 |
1999年 | 9篇 |
1998年 | 9篇 |
1997年 | 13篇 |
1996年 | 15篇 |
1995年 | 20篇 |
1994年 | 19篇 |
1993年 | 18篇 |
1992年 | 10篇 |
1991年 | 15篇 |
1990年 | 10篇 |
1989年 | 9篇 |
1988年 | 16篇 |
1987年 | 15篇 |
1986年 | 13篇 |
1985年 | 17篇 |
1984年 | 19篇 |
1983年 | 6篇 |
1982年 | 15篇 |
1981年 | 13篇 |
1980年 | 11篇 |
1979年 | 9篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1974年 | 7篇 |
1973年 | 8篇 |
1965年 | 4篇 |
1963年 | 5篇 |
排序方式: 共有1244条查询结果,搜索用时 625 毫秒
21.
E Makino N Iwasaki N Yagi T Ohashi H Kato Y Ito H Azuma 《Chemical & pharmaceutical bulletin》1990,38(1):201-207
Various pyrazine derivatives were synthesized and their antiallergic activity was examined. The inhibitory activity on allergic histamine release of the compounds bearing a 5-tetrazolyl group was more potent than that of the corresponding carboxyl derivatives. The introduction of -CONH- or -NHCO- between the pyrazine ring and the 5-tetrazolyl group as a spacer greatly enhanced the activity. N-(1H-Tetrazol-5-yl)-2-pyrazinecarboxamide (I-3) was estimated to exhibit nearly the same potency as disodium cromoglycate (DSCG). The structure-activity relationship among various derivatives modified by introducing some substituents onto the 3-, 5- or 6-position of the pyrazine ring of I-3 was investigated. The activity remained unchanged or was reduced when such substituents as methyl, chloro, methoxy, methylamino and dimethylamino were introduced at the 3- or 5-position. In contrast, 6-substitution with various alkylamino groups more or less increased the activity. Among them, the 6-dimethylamino (I-17c) and 6-(1-pyrrolidinyl) (I-34) derivative were proved to be most potent. The IC50 values (concentration which produces 50% inhibition of the allergic histamine release) of I-17c and I-34 were determined to be 4.7 x 10(-10) and 4.6 x 10(-10) M, respectively. These two compounds produced a potent inhibitory activity on passive cutaneous anaphylaxis (PCA) in rat, not only by the intravenous route (ED50 = 0.0096 mg/kg for both compounds) but also by the oral route (ED50 = 0.19 and 0.18 mg/kg, respectively). On the other hand, when the pyrazine ring of some representative compounds was replaced with a pyridine ring, the inhibitory activity on histamine release was significantly reduced. 相似文献
22.
Xichen CaiMichihiro Hara Kiyohiko KawaiSachiko Tojo Mamoru FujitsukaTetsuro Majima 《Tetrahedron letters》2003,44(32):6117-6120
Some triplet energy-transfer reactions initiated by photoexcitation of the triplet excited state of dibenz[a,h]anthracene to higher triplet excited states (DBA(Tn)) were observed in the presence of the triplet energy quenchers (Q) such as naphthalene, biphenyl, p-dichlorobenzene, and o-dicyanobenzene. In the case of carbon tetrachloride (CCl4) as Q, DBA(Tn)-sensitized decomposition of CCl4 occurred. 相似文献
23.
Chatani N Amako K Tobisu M Asaumi T Fukumoto Y Murai S 《The Journal of organic chemistry》2003,68(4):1591-1593
The reaction of benzofuran-2,3-dione derivatives 1 with CO and alkenes (or alkynes) results in a carbonylative [2+2+1] cycloaddition in which the ester-carbonyl group is incorporated into a two-atom assembling unit to give spirolactone derivatives 2. This reaction provides the first example of an ester-carbonyl group participating in a carbonylative cycloaddition reaction. 相似文献
24.
Ogawa T Araki M Miyamae T Okayama T Hagiwara M Sakurada S Morikawa T 《Chemical & pharmaceutical bulletin》2003,51(7):759-771
To improve the oral bioavailability of a dermorphin tetrapeptide analog, N(alpha)-1-iminoethyl-Tyr-D-MetO-Phe-MebetaAla-OH (III), which has a potent analgesic activity after oral administration, various derivatives were synthesized to increase lipophilicity by esterification of the C-terminal carboxyl group and/or acylation of the phenolic hydroxyl group on Tyr1. Antinociceptive activity was evaluated after subcutaneous or oral administration using the mouse tail pressure test. As a result, increased antinociceptive activity after oral administration as well as an improved ED50(p.o.)/ED50(s.c.) ratio, which is an indicator of oral bioavailability, were found for some compounds. With regard to the improvement of bioavailability, derivatives with acylation of the phenolic hydroxyl group on Tyr1 showed better results than derivatives with esterification of the C-terminal carboxyl group. In particular, an ED50(p.o.)/ED50(s.c.) ratio equivalent to that of morphine was found for an acetylated derivative, N(alpha)-1-iminoethyl-Tyr(COMe)-D-MetO-Phe-MebetaAla-OH (7a), as well as for a methoxycarbonylated derivative, N(alpha)-1-iminoethyl-Tyr(CO2Me)-D-MetO-Phe-MebetaAla-OH (7l). 相似文献
25.
26.
Sakamoto M Cai X Hara M Fujitsuka M Majima T 《The journal of physical chemistry. A》2005,109(11):2452-2458
The properties and reactivities of the xanthone (Xn) ketyl radical (XnH*) in the doublet excited state (XnH*(D1)) were examined by using two-color two-laser flash photolysis. The absorption and fluorescence of XnH*(D1) were observed for the first time. Several factors governing the deactivation processes of XnH*(D1) such as interaction and reaction with solvent molecules were discussed. The remarkable change of reactivity of XnH*(D1) compared with that in the ground state (XnH*(D0)) was indicated from the experimental results. The rapid halogen abstraction of XnH*(D1) from some halogen donors such as carbon tetrachloride (CCl4) was found to occur. The halogen abstraction occurred more efficiently in the polar solvents than in the nonpolar solvents. It is suggested that the polar solvents promote the spin distribution of XnH*(D1) of the phenyl ring favorable to the halogen abstraction. 相似文献
27.
Osamu Matsumoto Eiji Hayami Mamoru Samejima Yasushi Kanzaki 《Plasma Chemistry and Plasma Processing》1984,4(1):33-42
The nitriding of titanium with argon-nitrogen (3%) and argon-nitrogen (3%)-hydrogen (2%) plasma jets at pressures of 190 torr was studied. The reaction kinetics obeyed mainly a parabolic law. The parabolic kinetic constants were 10–10–10–8 g2 cm–4 s–1, which were 2–3 orders of magnitude larger than those in R.F. discharges. From emission spectroscopy, nitrogen atoms in the excited states were observed. The nitrogen atoms can promote the nitriding reaction. The effect of the addition of hydrogen to nitrogen is also briefly discussed. 相似文献
28.
Manabu Tsujino Tetsuhiko Isobe Mamoru Senna 《Journal of Sol-Gel Science and Technology》2000,19(1-3):785-789
A tetraethoxysilane (TEOS)-derived sol aged for 0 h–6 h at room temperature was mixed with a polyurethane (PU) matrix. A composite of silk fibroin (SF) powders and acrylamide (AAm) was dispersed in the sol-PU mixture and dried isothermally at temperatures between 25°C and 120°C to obtain composite films. Three competitive reactions take place, i.e., those between silica-silica, SF-PU and silica-organic phases, during formation of the composite films. These reactions determine the properties such as morphology and homogeneity of the composite films. IR absorption bands for amide groups (–CONH–), C=O (amide I, 1730 cm–1) and N–H (amide II, 1530 cm–1) become larger with decreasing aging time of TEOS-derived sol, or increasing drying temperature. DTA exothermic peak due to the thermal decomposition of SF-AAm composite, on the composite films prepared from the 0 h-aged sol or dried at more than 50°C, shifts toward higher temperature by 44 K or more than 63 K respectively, as compared to the SF-AAm composite. Shorter aging time of TEOS-derived sol and higher drying temperature increased the extent of dispersibility, among SF-AAm composite, PU and silica, to bring a composite film more homogeneous. 相似文献
29.
Masanori Sakamoto Takashi Tachikawa Sung Sik Kim Mamoru Fujitsuka Tetsuro Majima 《Chemphyschem》2007,8(11):1701-1706
The association behavior of the dyes 5(6)-carboxyfluorescein and nitrilotriacetic acid (NTA)-modified 5(6)-carboxyfluorescein (F-NTA) in a poly(vinyl alcohol) (PVA) film and in a PVA film containing metal nanoparticles is investigated. Well-dispersed gold nanoparticles (AuNps) and Ni(II)-adsorbed AuNps are formed in the PVA film using in situ photochemical fabrication method. 5(6)-carboxyfluorescein and F-NTA are doped into the films. The F-NTA forms an H-aggregate in the PVA film containing Ni(II)-adsorbed AuNps. It is suggested that the interaction between NTA and Ni(II) adsorbed on the AuNps promotes the formation of the H-aggregate. 相似文献
30.
Nakamura T Ikemoto JY Fujitsuka M Araki Y Ito O Takimiya K Aso Y Otsubo T 《The journal of physical chemistry. B》2005,109(30):14365-14374
The dramatic changes of the lifetimes of the charge-separated (CS) states were confirmed in zinc porphyrin (ZnP)-oligothiophene (nT)-fullerene (C(60)) linked triads (ZnP-nT-C(60)) with the solvent polarity. After the selective excitation of the ZnP moiety of ZnP-nT-C(60), an energy transfer took place from the (1)ZnP moiety to the C(60) moiety, generating ZnP-nT-(1)C(60). In polar solvents, the CS process also took place directly via the (1)ZnP moiety, generating ZnP(*+)-nT-C(60)(*-), as well as the energy transfer to the C(60) moiety. After this energy transfer, an indirect CS process took place from the (1)C(60) moiety. In the less polar solvent anisole, the radical cation (hole) of ZnP(*+)-nT-C(60)(*-) shifted to the nT moiety; thus, the nT moiety behaves as a cation trapper, and the rates of the hole shift were evaluated to be in the order of 10(8) s(-1); then, the final CS states ZnP-nT(*+)-C(60)(*-) were lasting for 6-7 mus. In the medium polar solvent o-dichlorobenzene (o-DCB), ZnP-nT(*+)-C(60)(*-) and ZnP(*+)-nT-C(60)(*-) were present as an equilibrium, because both states have almost the same thermodynamic stability. This equilibrium resulted in quite long lifetimes of the CS states (450-910 mus) in o-DCB. In the more polar benzonitrile, the generation of ZnP-nT(*+)-C(60)(*-) was confirmed with apparent short lifetimes (0.6-0.8 mus), which can be explained by the fast hole shift to more stable ZnP(*+)-nT-C(60)(*-) followed by the faster charge recombination. It was revealed that the relation between the energy levels of two CS states, which strongly depend on the solvent polarity, causes dramatic changes of the lifetimes of the CS states in ZnP-nT-C(60); that is, the most appropriate solvents for the long-lived CS state are intermediately polar solvents such as o-DCB. Compared with our previous data for H(2)P-nT-C(60), in which H(2)P is free-base porphyrin, the lifetimes of the CS states of ZnP-nT-C(60) are approximately 30 times longer than those in o-DCB. 相似文献