全文获取类型
收费全文 | 3060篇 |
免费 | 101篇 |
国内免费 | 335篇 |
专业分类
化学 | 1195篇 |
晶体学 | 39篇 |
力学 | 201篇 |
综合类 | 10篇 |
数学 | 638篇 |
物理学 | 1413篇 |
出版年
2024年 | 3篇 |
2023年 | 57篇 |
2022年 | 29篇 |
2021年 | 26篇 |
2020年 | 42篇 |
2019年 | 45篇 |
2018年 | 39篇 |
2017年 | 49篇 |
2016年 | 62篇 |
2015年 | 63篇 |
2014年 | 139篇 |
2013年 | 250篇 |
2012年 | 245篇 |
2011年 | 226篇 |
2010年 | 174篇 |
2009年 | 223篇 |
2008年 | 203篇 |
2007年 | 294篇 |
2006年 | 134篇 |
2005年 | 107篇 |
2004年 | 143篇 |
2003年 | 141篇 |
2002年 | 81篇 |
2001年 | 61篇 |
2000年 | 75篇 |
1999年 | 65篇 |
1998年 | 62篇 |
1997年 | 57篇 |
1996年 | 71篇 |
1995年 | 51篇 |
1994年 | 41篇 |
1993年 | 50篇 |
1992年 | 28篇 |
1991年 | 30篇 |
1990年 | 26篇 |
1989年 | 32篇 |
1988年 | 24篇 |
1987年 | 12篇 |
1986年 | 7篇 |
1985年 | 8篇 |
1984年 | 2篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1976年 | 3篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有3496条查询结果,搜索用时 15 毫秒
61.
62.
Eiichi Kimura Naomi Katsube Tohru Koike Motoo Shiro Shin Aoki 《Supramolecular chemistry》2013,25(2-3):95-102
We have previously shown that the nucleobase thymine binding to Zn2+ -cyclen (cyclen=1,4,7,10-tetraazacyclododecane) complex became stronger by appending acridine, naphthalene, or quinoline rings to the cyclen. Amongst these, the pendant bis((1-naphthyl)methyl) or bis((4-quinolyl)methyl) groups yielded the most effective thymine-recognizing Zn2+ -cyclen complexes [J. Am. Chem. Soc., 121 (1999) 5426]. The present study was undertaken to find causes of the bis(aromatic) ring effect by X-ray crystal structure analysis and NMR studies. The crystal structure of the Zn2+ -bis((1-naphthyl)methyl)-cyclen complex with a deprotonated 1-methylthymine (1-MeT) failed to show the anticipated evidence for the double ~ - ~ stacking interactions between the two naphthalenes and the Zn 2+ -bound 1-MeT m (1-MeT m =N(3')-deprotonated 1-MeT). Crystal data: formula C36 H47 N7 O7 Zn, M r =755.19, monoclinic, space group P21/ c (No. 14), a =15.438(2) Å, b =14.093(3) Å, c =16.726(2) Å, g =90.53(1) V =3638.7(8) Å 3 Z =4, R =0.035, R w =0.049. However, the 1H NMR studies of Zn2= -bis((4-quinolyl)methyl)-cyclen with 1-MeT in varying H2O/CH3 CN solution showed increasing upfield shifts of Me(5') and H(6') of the Zn2+ -bound 1-MeT in more aqueous media, indicating that the double intercalation with the two quinolines became more significant in more protic environments. We conclude that the double ~ - ~ stacking effect accounts for the enhanced recognition of thymine base by the appended bis((1-naphthyl)methyl) or bis((4-quinolinyl)methyl) groups. 相似文献
63.
64.
This study was conducted in a continuous three-stage system of anaerobic (R1)-anoxic(R2)-aerobic (R3) reactors with synthetic
wastewater containing phenol (1000 mg/L), chemical oxygen demand (COD) (3000 mg/L), CN− (30 mg/L), SCN−(400 mg/L), and NH
4
+
-N (600 mg/L) as principal pollutants and well-acclimated heterogeneous microbial cultures. The final effluent was partially
returned to R2 with a recycle ratio of 1. Anaerobic stage served to detoxify the feed by removing up to 80% of cyanide. Complete
SCN− removal and denitrification could be achieved in the anoxic stage by utilizing phenol as an internal source of carbon. Nitrification
efficiency of 93% was obtained in the aerobic reactor. The results demonstrated that the three-stage system can give the desired
final treated effluent quality (0 mg/L of phenol, 0.2 mg/L of CN−, 210 mg/L of COD, and 20 mg/L of NH
4
+
-N) and that the NO
3
−
-N concentration can be lowered by a higher recycle ratio. 相似文献
65.
M. Rapposch E. Kostiner S. F. Wayne H. Nowotny 《Monatshefte für Chemie / Chemical Monthly》1985,116(11):1237-1245
The crystal structure of molybdenum cementite Mo12Fe22C10 (-phase) has been determined by means of a single crystal x-ray diffraction study of crystal fragments. The lattice parameters were found to be:a=10.865 (3),b=7.767 (2),c=6.559 (2) Å and =120.13 (2)°, space group C2/m;Z=1. From the analysis ofPatterson maps and differenceFourier analysis the atomic parameters were derived, yielding a residual ofR=0.059. The crystal structure contains octahedral and triangular prismatic groups which accommodate the carbon atoms in their voids, as is usually found in interstitial compounds. The octahedral building group consists of four Mo- and two Fe-atoms, the triangular prism is built up by four Fe-and two Mo-atoms. The mode of filling of the metal polyhedra is discussed.
Die Kristallstruktur von Molybdän-Zementit, Mo12Fe22C10 (-Phase)
Zusammenfassung Die Kristallstruktur von Molybdän-Zementit, Mo12Fe22C10 (-Phase) wird auf Grund von Einkristall-Beugungsaufnahmen unter Anwendung vonPatterson-and DifferentialFourier-Analysen bestimmt. In der monoklinen Elementarzelle (a=1.870;b=7.67;c=6.563 Å, =120.1°) Raumgruppe C 2/m befindet sich eine Formeleinheit Mo12Fe22C10 (oderZ=2, Mo6Fe11C5). DerR-Wert von 6% für 1200 Reflexe unterstreicht die Richtigkeit der Struktur, die aus oktaedrischen und trigonal prismatischen Gruppen aufgebaut ist. Die Oktaedergruppe besteht aus 4 Mo- und 2-Fe-Atomen, die trigonal prismatische Gruppe aus 4 Fe- und 2 Mo-Atomen. Die Kohlenstoffatome füllen die Lücken dieser Bauelemente, wie es für typische Einlagerungscarbide (Komplexcarbide) erwartet werden kann.相似文献
66.
One novel complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2'-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic, space group P-1 with a=0.70479(14), b=1.1211(2), c=1.6718(3) nm, α=103.806(3), β=90.795(3), γ=104.207(3)°, V=1.2399(4) nm3, Mr=512.41, Dc=1.373 g/cm3, Z=2, F(000)=532, μ=0.733 mm-1, R=0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2'-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported. 相似文献
67.
A new ion-pair complex,[BzMeQl]2[Ni(mnt)2] 1 ([BzMeQl]+=1-benzyl-4-methylquino-linium,mnt2-= maleonitriledithiolate) has been synthesized and structurally characterized by IR,ESI-MS and X-ray diffraction methods. Complex 1 is of triclinic,space group P1,with a=9.079(2),b=10.154(2),c=11.243(2),α=81.58(1),β=69.63(1),γ=68.02(1)°,V=940.1(3)3,Dc=1.427 g/cm3,Z=1,F(000)=418 and R=0.0442. A 2D layer structure is formed via the cation-cation π…π and C–H…π interactions observed in the solid state of the complex. 相似文献
68.
G.?A.?Mun I.?K.?Nam R.?R.?SarsengalievEmail author Z.?S.?Nurkeeva P.?I.?Urkimbaeva K.?Park 《Colloid and polymer science》2004,282(10):1111-1117
Amphiphilic hydrogels of copolymers of the vinyl ether of ethylene glycol and vinyl isobutyl ether were synthesized by -radiation-induced free radical polymerization. Hydrogels with certain copolymer compositions showed thermo-sensitive behavior in aqueous solutions. The swelling behavior of the hydrogels in cetylpyridinium bromide aqueous solution was studied. Increased swelling of the hydrogels was observed in the surfactant solutions. The increased swelling was more prominent for the hydrogels with a higher content of hydrophobic moiety in the copolymer composition, and with higher surfactant concentration. The reason for this phenomenon is discussed. Treatment of some hydrogels in the surfactant solutions resulted in higher swelling ability in distilled water with distinct thermo-induced contraction over a narrow temperature interval. 相似文献
69.
Shimon?Tanaka Hideya?Kawasaki Masao?Suzuki Masahiko?Annaka Norio?Nemoto Mats?Almgren Hiroshi?MaedaEmail author 《Colloid and polymer science》2004,282(10):1140-1145
Vesicle formation in a mixture of oleyldimethylamine oxide (OleylDMAO) and sodium oleate (NaOl) was investigated by viscoelastic measurements and cryoscopic transmission electron micrograph (cryo-TEM) observations. The viscoelastic properties changed with increasing mole fraction of NaOl (X
NaOl) from the Maxwell behavior of OleylDMAO solutions (X
NaOl=0) suggesting a transient network of long flexible chains. For X
NaOl=0.2 and 0.4 mixtures, both the shear storage modulus G and the shear loss modulus G showed weak dependences on angular frequency with a relation G>G. From cryo-TEM observations, vesicles coexisted with threadlike micelles in mixtures of X
NaOl=0.2 and 0.3. As X
NaOl increased further (X
NaOl=0.5 and 0.6), threadlike micelles disappeared and the coexistence of vesicles and globular micelles was observed. At X
NaOl=0.5, the viscosity decreased remarkably, which was consistent with the disappearance of threadlike micelles. The results indicated that vesicles were formed by the addition of NaOl to OleylDMAO solutions, contrary to the expectation of a decrease of the packing parameter with the introduction of electric charges. 相似文献
70.
A novel complex [Pb(qina)2(DMSO)]·H2O was synthesized, of which qina- is the quinaldic acid radical and DMSO the dimethyl sulfoxide. Elemental analysis, IR spectra, and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. This complex belongs to monoclinic system, space group P121/n1, with a = 7.1553(17), b = 17.543(2), c = 17.306(2)(A),β = 91.671(4)°, C22H20N2O6PbS, Mr = 647.65, Z = 4, V= 2171.5(6)(A)3, Dc= 1.981g/cm3,μ = 7.908 mm-1, F(000) = 1248, -9≤h≤6, -23≤k≤ 19, -22≤l≤22, R= 0.0221 and wR =0.0488. Weak coordinate bond is formed between oxygen atom in DMSO and Pb(Ⅱ ). There are also weak interactions, such as π-π interaction, hydrogen bonds and so on, among the complex molecules. 相似文献