全文获取类型
收费全文 | 4510篇 |
免费 | 665篇 |
国内免费 | 381篇 |
专业分类
化学 | 3247篇 |
晶体学 | 51篇 |
力学 | 236篇 |
综合类 | 23篇 |
数学 | 526篇 |
物理学 | 1473篇 |
出版年
2024年 | 7篇 |
2023年 | 109篇 |
2022年 | 171篇 |
2021年 | 179篇 |
2020年 | 164篇 |
2019年 | 146篇 |
2018年 | 140篇 |
2017年 | 108篇 |
2016年 | 200篇 |
2015年 | 204篇 |
2014年 | 247篇 |
2013年 | 279篇 |
2012年 | 346篇 |
2011年 | 386篇 |
2010年 | 237篇 |
2009年 | 234篇 |
2008年 | 281篇 |
2007年 | 258篇 |
2006年 | 234篇 |
2005年 | 198篇 |
2004年 | 167篇 |
2003年 | 152篇 |
2002年 | 127篇 |
2001年 | 103篇 |
2000年 | 90篇 |
1999年 | 114篇 |
1998年 | 100篇 |
1997年 | 90篇 |
1996年 | 90篇 |
1995年 | 78篇 |
1994年 | 54篇 |
1993年 | 33篇 |
1992年 | 37篇 |
1991年 | 32篇 |
1990年 | 23篇 |
1989年 | 17篇 |
1988年 | 20篇 |
1987年 | 19篇 |
1986年 | 13篇 |
1985年 | 9篇 |
1984年 | 15篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 9篇 |
1978年 | 2篇 |
1976年 | 7篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1972年 | 2篇 |
排序方式: 共有5556条查询结果,搜索用时 31 毫秒
151.
The preparation, X-ray crystal structure, and magnetic properties of alternating 1,1- and 1,3-azido-bridged copper(II) complex [Cu(4,4'-dmbpy)(N3)2]n (1, 4,4'-dmbpy = 4,4'-dimethylbipyridine) have been reported. It crystallizes in triclinic system, space group P1, a = 7.9903(1) A, b = 9.3545(9) A, c = 10.754(2) A, alpha = 113.485(1) degrees, beta = 101.399(1) degrees, gamma = 101.897(1) degrees, Z = 2. The magnetic properties of 1 have been investigated in the temperature range 1.5-300 K. Alternating antiferromagnetic (-J = 191.0 cm(-1)) interaction through a 1,3-N3- bridge and ferromagnetic (J = 297.1 cm(-1)) interaction through a 1,1-N3- bridge are obtained for 1 by analyzing the magnetic susceptibility data with the Hamiltonian H = -Jsigma(S2iS2i-1--alphaS2iS2i+1). It's derivatives ([Mn(4,4'-dmbpy)(N3)2]n (2), [Ni(4,4'-dmbpy)(N3)2]n (3), and [Fe(4,4'-dmbpy)(N3)2]n (4) and the heterometallic derivatives [NiMn(4,4'-dmbpy)2(N3)4]n (5) and [CuMn(4,4'-dmbpy)2(N3)4]n (6) have also been synthesized and characterized by electronic and IR spectra. The X-ray powder diffraction and the magnetic properties of 6 have also been discussed. 相似文献
152.
A theoretical comparative study of complexes of porphyrin (P), porphyrazine (Pz), phthalocyanine (Pc), porphycene (Pn), dibenzoporphycene (DBPn), and hemiporphyrazine (HPz) with iron (Fe) has been carried out using a density functional theory (DFT) method. The difference in the core size and shape of the macrocycle has a substantial effect on the electronic structure and properties of the overall system. The ground states of FeP and FePc were identified to be the 3A2g [(d(xy))2(d(z)2)2(d(pi))2] state, followed by 3E(g) [(d(xy))2(d(z)2)1(d(pi))3]. For FePz, however, the 3E(g)-3A2g energy gap of 0.02 eV may be too small to distinguish between the ground and excited states. When the symmetry of the macrocycle is reduced from D4h to D2h, the degeneracy of the d(pi) (d(xz), d(yz)) orbitals is removed, and the ground state becomes 3B2g [(d(xy))2(d(z)2)1(d(yz))2(d(xz))1] or 3B3g [...(d(yz))1(d(xz))2] for FePn, FeDBPn, and FeHPz. The calculations also show how the change of the macrocycle can influence the axial ligand coordination of pyridine (Py) and CO to the Fe(II) complexes. Finally, the electronic structures of the mono- and dipositive and -negative ions for all the unligated and ligated iron macrocycles were elucidated, which is important for understanding the redox properties of these compounds. The differences in the observed electrochemical (oxidation and reduction) properties between metal porphycenes (MPn) and metal porphyrins (MP) can be accounted for by the calculated results (orbital energy level diagrams, ionization potentials, and electron affinities). 相似文献
153.
Lin LC Tyan YC Shih TS Chang YC Liao PC 《Rapid communications in mass spectrometry : RCM》2004,18(12):1310-1316
An isotope-dilution electrospray ionization tandem mass spectrometry (ESI-MS/MS) method with an on-line sample clean-up device, for the quantitative analysis of human urine for the benzene exposure biomarker S-phenylmercapturic acid (SPMA), was developed and validated. The sample clean-up system was constructed from an autosampler, a reversed-phase C18 trap cartridge, a two-position switching valve, and controlling computer software and hardware. The sample clean-up system was interfaced via 1/20 splitting to the ESI source of a triple-quadrupole mass spectrometer using negative ion mode and multiple reaction monitoring for SPMA and the isotope-labeled internal standard. A strategy was adopted to acquire pooled blank urine matrix and quality control samples spiked with standards. Validated procedures and data on method specificity, detection limits, standard curves, precision and recovery, sample storage stability, and inter-laboratory comparison are presented. The analytical system was fully automated. No tedious manual sample clean-up procedures are required. With the selectivity and the sensitivity provided by ESI-MS/MS detection, the analytical system can be used for high-throughput and accurate determination of SPMA levels in human urine samples, as a biomarker for environmental as well as occupational benzene exposure. 相似文献
154.
运用三足四齿配体三(2-甲基吡啶)胺(TPA)或三(2-甲基苯丙咪唑)胺(TBA),得到两个双核铁(III)配合物,[Fe2L2(μ2-O)(μ2-p-NH2-C6H4COO)]3+
(L = TPA, 1 和 L = TBA,
2)。两个配合物均为单斜晶系,空间群为P2(1)/c.晶胞参数 1: a =
1.4529(4), b = 1.6622(5), c = 2.0625(6) nm, β= 100.327(5)º,
V = 4.900(3) nm3, z = 4, F(000) = 2344, 分子量Mr = 1142.91, Dc
= 1.549 g/cm3, R1 = 0.0544,
R2 = 0.0962. 2: a = 1.3378(4), b = 2.1174(7), c =
2.4351(7) nm, β= 97.315(6)º, V = 6.842(4) nm3,
z = 4, F (000) = 3116, 分子量Mr = 1505.08, Dc
= 1.444 g/cm3, R1 = 0.0793, R2 = 0.1623. 在两个双核铁(III)配合物中,中心的三价铁和配体TPA或TBA上的四个氮原子和两个氧原子通过不同的桥形成一个畸变的八面体构型。 相似文献
155.
Two solid‐state carbodiimide compounds, LiM2(NCN)Br3 (M = Sr, Eu), with characteristic empty tetrahedral M4 entities have been synthesized using a flux route, and their structures were determined by single‐crystal X‐ray diffraction. The new phases LiSr2(NCN)Br3 and LiEu2(NCN)Br3 are isotypical with the corresponding iodides and crystallize in the cubic system (( , Z = 16) but with smaller unit cells (a = 14.641(1) Å for LiSr2(NCN)Br3 and 14.572(1) Å for LiEu2(NCN)Br3). The extended structures comprise two interpenetrating three‐dimensional networks: the first one is built from isolated M4 tetrahedra capped by NCN2? anions on their triangular faces while the second is made from vertex‐sharing LiBr6 octahedra. The linear NCN2? anions exhibit the symmetrical carbodiimide shape and serve as linkers between the tetrahedral entities. 相似文献
156.
Chuan-Kun Ran Li-Li Liao Tian-Yu Gao Yong-Yuan Gui Da-Gang Yu 《Current Opinion in Green and Sustainable Chemistry》2021
- Download : Download high-res image (140KB)
- Download : Download full-size image
157.
The title compound, a masked 3,6-di-n-propyl-o-benzoquinone, was synthesized from 3,6-di-n-propylcatechol in 82% yield. Its Diels-Alder reactions with methyl propiolate, phenylacetylene, 1-octyne, dimethyl acetylenedicarboxylate, diphenylacetylene and 3-hexyne were studied. The yields of the adducts were excellent except for the last two cases in which the unimolecular decomposition of the title compound to generate 3,6-di-n-propylcatechol methylene ether predominates. The regiochemistry of the adducts derived from monosubstituted acetylenes were determined by the correlation of 13C chemical shifts of the adducts and the corresponding bicyclo[2.2.2]octa-5,7-diene-2,3-diones obtained from the hydrolysis of the spirolactone ring of the Diels-Alder adducts. Photolysis of these α-diketones gave the corresponding aromatic compounds in high yields. These synthetic sequences provide an effective entry to bicyclo[2.2.2]octa-5,7-diene-2,3-diones and polysubstituted benzene derivatives. 相似文献
158.
Yuan-Fang Wang Rong-Fang Li Qing-Lun Wang Li-Hua Yu Guang-ming Yang Dai-Zheng Liao 《Transition Metal Chemistry》2004,29(7):728-731
Two compounds, [Co(bpy)2(NiL)](ClO4)2
(1)and {[Co(phen)3](NiL)}(ClO4)2
(2), have been synthesized: (H2L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacylotetradeca-7,12-diene, bpy=2,2-bypyridine and phen = 1,10-phenanthroline). Compound (1) contains a discrete binuclear [Co(bpy)2(NiL)]2+ cation, while compound (2) is composed of [Co(phen)3]2+ cations and NiL neutral fragments. The magnetic properties of compound (1) have been dealt with by isotropic one-ion approximation of the CoII ion with a spin--orbit coupling in an Oh symmetry environment. The electronic spectra of these two compounds have also been discussed. 相似文献
159.
Liao YC Subramani HJ Franses EI Basaran OA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(23):9926-9930
Surfactants are routinely used to control the breakup of drops and jets in many applications such as inkjet printing, crop spraying, and DNA or protein microarraying. The breakup of surfactant-free drops and jets has been extensively studied. By contrast, little is known about the closely related problem of interface rupture when surfactants are present. Solutions of a nonionic surfactant, pentaethylene glycol monododecyl ether, or C12E5, in water and in 90 wt % glycerol/water are used to show the effects of surfactant and viscosity on the deformation and breakup dynamics of stretching liquid bridges. Equilibrium surface tensions for both solutions can be fitted with the Langmuir-Szyskowski equation. All experiments have been done at 24 degrees C. The critical micelle concentrations for C12E5 are 0.04 and 0.4 mM in water and the glycerol/water solution, respectively. With high-speed imaging, the dynamic shapes of bridges held captive between two rods of 3.15 mm diameter are captured and analyzed with a time resolution of 0.1-1 ms. The bridge lengths are 3.15 mm initially and about 5-7 mm at pinch-off. Breakup occurs after stretching for about 0.2-0.3 s, depending on the solution viscosity and the surfactant concentration. When the liquid bridges break up, the volume of the sessile drop left on the bottom rod is about 3 times larger than that of the pendant drop left on the top rod. This asymmetry is due to gravity and is influenced by the equilibrium surface tensions. Surfactant-containing low-viscosity water bridges are shown to break up faster than surfactant-free ones because of the effect of gravity. With or without surfactant, water bridges form satellite drops. Surfactant-containing high-viscosity glycerol/water bridges break up more slowly than surfactant-free ones because of strong viscous effects. Moreover, the shapes of the sessile drops close to breakup exhibit a "pear-like" tip; whether a satellite forms depends on the surface age of the bridge before stretching commences. These unexpected effects arising from the addition of surfactants are due to the capillary pressure reduction and Marangoni flows linked to dynamic surface tension. 相似文献
160.
In this study, the vertical motion of a particle in a quiescent fluid falling toward a horizontal plane wall is analyzed, based on simplified models. Using the distance between the particle and wall as a parameter, the effects of various forces acting on the particle and the particle motion are examined. Without the colloidal and Brownian forces being included, the velocity of small particles is found to be approximately equal to the inverse of the drag force correction function used in this study as the particle approaches the near-wall region. Colloidal force is added to the particle equation of motion as the particle moves a distance comparable to its size. It is found that the particle might become suspended above or deposited onto the wall, depending on the Hamaker constant, the surface potentials of the particle and wall, and the thickness of the electrical double layer (EDL). For strong EDL repulsive force and weaker van der Waals (VDW) attractive force, the particle will become suspended above the wall at a distance at which the particle velocity is zero. This location is referred to as the equilibrium distance. The equilibrium distance is found to increase with increased in EDL thickness when a repulsive force barrier appears in the colloidal force interaction. For the weak EDL repulsive force and strong VDW attractive force case, the particle can become deposited onto the wall without the Brownian motion effect. The Brownian jump length was found to be very small. Many Brownian jumps would be required in a direction toward the wall for a suspended particle to become deposited. 相似文献