全文获取类型
收费全文 | 5083篇 |
免费 | 238篇 |
国内免费 | 280篇 |
专业分类
化学 | 1182篇 |
晶体学 | 25篇 |
力学 | 106篇 |
综合类 | 27篇 |
数学 | 2236篇 |
物理学 | 2025篇 |
出版年
2023年 | 24篇 |
2022年 | 109篇 |
2021年 | 80篇 |
2020年 | 51篇 |
2019年 | 54篇 |
2018年 | 70篇 |
2017年 | 68篇 |
2016年 | 63篇 |
2015年 | 59篇 |
2014年 | 83篇 |
2013年 | 289篇 |
2012年 | 160篇 |
2011年 | 351篇 |
2010年 | 283篇 |
2009年 | 555篇 |
2008年 | 544篇 |
2007年 | 450篇 |
2006年 | 463篇 |
2005年 | 285篇 |
2004年 | 162篇 |
2003年 | 135篇 |
2002年 | 245篇 |
2001年 | 180篇 |
2000年 | 152篇 |
1999年 | 100篇 |
1998年 | 92篇 |
1997年 | 60篇 |
1996年 | 94篇 |
1995年 | 41篇 |
1994年 | 53篇 |
1993年 | 24篇 |
1992年 | 38篇 |
1991年 | 22篇 |
1990年 | 13篇 |
1989年 | 20篇 |
1988年 | 11篇 |
1987年 | 9篇 |
1986年 | 9篇 |
1985年 | 14篇 |
1984年 | 9篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1980年 | 13篇 |
1979年 | 11篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1973年 | 6篇 |
排序方式: 共有5601条查询结果,搜索用时 15 毫秒
91.
从α-蒎烯直接催化酯化高选择性地合成乙酸正龙脑酯的研究-催化剂与反应机理初探 总被引:1,自引:0,他引:1
本文提出了新的硼酸类催化剂体系HB,用该体系对α-蒎烯与无水乙酸相互作用直接合成乙酸正龙脑酯作了较系统的研究。反应得到两种系列产物-酯化产物和异构化产物,酯化产物主要是乙酸正龙脑酯,葑醇酯和松油酯,异构化产物主要是莰烯、烯和松油烯等,总酯化产率为50%以上,其中乙酸正龙脑酯为20%以上,是至今从α-蒎烯直接合成乙酸正龙脑酯的最好结果。通过对产物的 ̄1HNMK图谱分析及动力学考察,确证反应主产物是正龙脑酯而不是异龙脑酯。文章对H_2SO_4、HClO_4、多聚磷酸(PPA)和杂多酸(12-磷钨酸)等催化剂进行了实验考察、对比和评述,表明了自制的HB催化剂体系具有高选择性合成乙酸正龙脑酯的显著优点,并对其反应机理作了初步探讨。 相似文献
92.
《Surface and interface analysis : SIA》2003,35(2):188-198
This paper reports a detailed study of how repeated r.f. magnetron sputtering from a hydroxyapatite (HA) powder target affects the nature and reproducibility of a sequential series of thin‐film coatings deposited onto Ti6Al4V substrates. An evaluation of the effective lifespan of the HA sputter targets and the reproducibility of the calcium phosphate (CaP) coatings produced from them has been made from Fourier transform infrared spectroscopy, XPS and, as appropriate, atomic force microscopy and SEM/energy dispersive x‐ray analyses. The annulus region of the target surface, from which sputtering under r.f. magnetron conditions normally occurs, showed severe surface degradation after only one deposition run, as indicated by significant PO43? and OH? depletion. This deterioration continued after each subsequent deposition cycle but to a much lesser extent than that observed in the initial sputtering period. The layers produced from all of the sputter runs contained the expected Ca2+ and PO43? species characteristic of a CaP system but were OH? deficient in the as‐deposited state. However, the chemical and morphological properties of the coatings did not change significantly until after the third consecutive sputter cycle. Hence, these data indicate that, even though a significant level of degradation of the HA target occurs at the outset of the sputtering procedure, the general plasma conditions employed here have a dominant influence on the coating properties until a critical degradation condition is met. As such, the compacted HA powder targets of interest can have a life‐cycle greater than single usage without detriment to the chemistry and morphology of the coatings produced from them. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
93.
钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用 总被引:3,自引:0,他引:3
用pH-电位滴定法测定了Pd(L)(Aa)+三元配合物及相应的二元配合物,在25±0.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO3)条件下的稳定常数及表征常数。其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa)。从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献。 相似文献
94.
95.
L.A. Isupova I.S. Yakovleva I.I. Gainutdinov Yu.T. Pavlyukhin V.A. Sadykov 《Reaction Kinetics and Catalysis Letters》2004,81(2):373-382
The phase composition and microstructure of samples of the La1-xCaxFeO3-y system prepared via a ceramic route were characterized by M?ssbauer spectroscopy. In all cases, iron was found in the 3+ state. The ordering
of anion vacancies in the samples with the composition in the range of 0.8 > x ≥ 0.4, which corresponds to a microheterogeneous
solid solution, generates new distorted octahedral and fivefold/tetrahedral sites revealed by two typical sextets. The disordering
of this solid solution and small (10-100 ?) sizes of domains with a perovskite, braunmillerite or Grenier phase structure
caused the appearance of a superparamagnetic doublet, which grows with the Ca content up to x = 0.8 but disappears in the
sample of pure braunmillerite. The appearance of Fe cations in a distorted coordination correlates with the increased activity
of the samples with a microheterogeneous structure in the CO catalytic oxidation and with their reducibility by H2.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
96.
9 氯甲基蒽 ( 1 )与 3 ,5 二甲氧基苄醇 ( 2 )在相转移催化剂存在下反应生成 9 ( 3 ,5 二甲氧基苄基氧甲基 )蒽 ( 3 ) .( 3 )的苯溶液在紫外光照射下发生蒽环与苯环间的分子内 [4π + 4π]光致环加成反应 ,定量地生成多环化合物 ( 4 ) .( 4 )在热的作用下发生逆反应 ,定量地转化成原料 ( 3 ) .这种光致可逆反应可应用于制备光开关材料 . 相似文献
97.
Javad Mostaghimi Pierre Proulx Maher I. Boulos 《Plasma Chemistry and Plasma Processing》1984,4(3):199-217
A theoretical investigation of the effect of different parameters on the flow and the temperature fields in a radiofrequency
inductively coupled plasma is carried out. The parameters studied are: central injection gas flow rate, total gas flow rate,
input power, and the type of plasma gas. The results obtained for argon and nitrogen plasmas at atmospheric pressure indicate
that the flow and the temperature fields in the coil region, as well as the heat flux to the wall of the plasma confinement
tube, are considerably altered by the changes in the torch operating conditions. 相似文献
98.
The geometries of the most stable isomers of gold telluride systems AuTe, Au2Te, and AuTe2 are determined using the MP2 method. The aspect of gold—telluride interaction, the electron correlation, and relativistic
effects on geometry and stability are investigated at the MP2 and CCSD(T) theoretical levels. The results show that the electron
correlation and relativistic effects are responsible not only for gold—gold attraction but also for additional gold—telluride
interaction. The gold—telluride interaction is strong enough to modify the known pattern of bare gold clusters. Both effects
are essential for determining the geometry and relative stability of this type of systems. 相似文献
99.
The reaction of cis-[ClP(μ-NtBu)]2 with N,N′-dimethylurea leads to the formation of both mono- and di-substituted derivatives [ClP(μ-NtBu)2P(NMeCON(H)Me)] and [(μ-NtBu)P(NMeCON(H)Me)]2, instead of monomeric, dimeric or higher oligomeric macrocycles. The structure of [ClP(μ-NtBu)2P(NMeCON(H)Me)] shows rare non-bonded P?Cl and intermolecular hydrogen bonding interactions leading to a 2D-sheet like structure. 相似文献
100.
Preparation, Properties and Crystal Structure of Bis(phthalocyaninato)cerium(IV) The anodic or chemical oxidation with dibenzoylperoxide of solutions of bis(phthalocyaninato)cerate(III) in dichloromethane yields selectively sparely soluble bis(phthalocyaninato)cerium(IV), [Ce(Pc(2-)) 2 ]. Green, monoclinic needles cristallize with a = 18.783(12) Å b = 18.739(16) Å c= 15.618(10) Å ß114.30(7)°; Z = 4; space group C2/c. [Ce(Pc(2–)) 2 ] is a sandwich complex in which the cerium Atom is eightfold coordinated by the isoindole nitrogens of the two staggered convex Pc-rings. The u.v.-vis., m.i.r., f.i.r. and resonance Raman spectra are consistent with the structure. 相似文献