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101.
Jovica Stojanovi Tamara ?or?evi Ljiljana Karanovi 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(11):i91-i94
During an investigation of the insufficiently known system M1O–M2O–X2O5–H2O (M1 = Cd2+, Sr2+ and Ba2+; M2 = Cu2+, Ni2+, Co2+, Zn2+ and Mg2+; X = P5+, As5+ and V5+), single crystals of the novel compound dicadmium copper(II) bis[phosphate(V)], Cd2Cu(PO4)2, were obtained. This compound belongs to a small group of compounds adopting a Cu3(PO4)2‐type structure and having the general formula M12M2(XO4)2 (M1/M2 = Cd2+, Cu2+, Mg2+ and Zn2+; X = As5+, P5+ and V5+). The crystal structure is characterized by the interconnection of infinite [Cu(PO4)2]n chains and [Cd2O10]n double chains, both extending along the a axis. Exceptional characteristics of this structure are its novel chemical composition and the occurrence of double chains of CdO6 polyhedra that were not found in related structures. In contrast to the isomorphous compounds, where the M1 cations are coordinated by five O atoms, the Cd atom is coordinated by six. The dissimilarity in the geometry of M1 coordination between Cd2Cu(PO4)2 and the isomorphous compounds is mostly due to the larger ionic radius of the Cd cation in comparison with the Cu, Mg and Zn cations. Sharing a common edge, two CdO6 polyhedra form Cd2O10 dimers. Each such dimer is bonded to another dimer sharing common vertices, forming [Cd2O10]n double chains in the [100] direction. The Cu atoms, located on an inversion centre (site symmetry ), form isolated CuO4 squares interconnected by PO4 tetrahedra, forming [Cu(PO4)2]n chains similar to those found in related structures. Conversely, the [Cd2O10]n double chains, which were not found in related structures, are an exclusive feature of this structure. 相似文献
102.
103.
Condić-Jurkić K Perchyonok VT Zipse H Smith DM 《Journal of computational chemistry》2008,29(14):2425-2433
High level ab initio and density functional calculations have been employed to determine the most appropriate manner in which to truncate an arginine-bound carboxylate motif, using the substrate mechanism of Pyruvate Formate-Lyase as a case study. The results show that, both qualitatively and quantitatively, a neutral carboxylic acid provides a more realistic approximation to the salt bridge arrangement than does a bare anionic carboxylate substituent. 相似文献
104.
Crabtree KN Hostetler KJ Munsch TE Neuhaus P Lahti PM Sander W Poole JS 《The Journal of organic chemistry》2008,73(9):3441-3451
The photochemistry of azidopyridine 1-oxides was studied using an array of glass and matrix isolation techniques. As with room temperature, the photochemistry of 4-azidopyridine 1-oxide is dominated by triplet nitrene chemistry. However, in the case of the 3-azide, matrix photolysis indicates the formation of diazabicyclo[4.1.0]hepta-2,4,6-triene N-oxide and diazacycloheptatetraene N-oxide intermediates as well as triplet nitrene. 相似文献
105.
The two new compounds, Sr4Cu3(AsO4)2(AsO3OH)4·3H2O (1) and Ba2Cu4(AsO4)2(AsO3OH)3(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As2O5-H2O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å3, Z=4 for 1; space group P42/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å3, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu2+-(XO4)3− layers (X=P5+, As5+) linked by M cations (M=alkali, alkaline earth, Pb2+, or Ag+) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu2O8 centrosymmetric dimers crosslinked by As1φ4 tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu2O8 centrosymmetric dimers of CuO5 edge-sharing polyhedra, crosslinked by As1O4 tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed. 相似文献
106.
Druzhinin SI Dubbaka SR Knochel P Kovalenko SA Mayer P Senyushkina T Zachariasse KA 《The journal of physical chemistry. A》2008,112(13):2749-2761
The newly synthesized aminobenzonitriles with two bulky amino substituents 4-(di-tert-butylamino)benzonitrile (DTABN) and 3-(di-tert-butylamino)benzonitrile (mDTABN) have strongly twisted amino groups in the ground state. From X-ray crystal analysis it is found that the amino twist angle theta of mDTABN equals 86.5 degrees , whereas a twist angle of around 75 degrees is deduced for DTABN from the extinction coefficient of its lowest-energy absorption band in n-hexane. Because of the electronic decoupling between the amino and benzonitrile groups caused by these large twist angles, the absorption of DTABN and mDTABN is relatively weak below 40000 cm-1, with extinction coefficients around 25 times smaller than those of the planar 4-(dimethylamino)benzonitrile (DMABN). DTABN as well as mDTABN undergo efficient intramolecular charge transfer (ICT) in the singlet excited state, in nonpolar (n-hexane) as well as in polar (acetonitrile) solvents. Their fluorescence spectra consist of an ICT emission band, without evidence for locally excited (LE) fluorescence. The occurrence of efficient ICT with mDTABN is different from the findings with all other N,N-dialkylaminobenzonitriles in the literature, for which ICT only appears with the para-derivative. From solvatochromic measurements, an ICT dipole moment of 17 D is determined for DTABN as well as for mDTABN, similar to that of DMABN. The picosecond fluorescence decays of DTABN (time resolution 3 ps) are effectively single exponential. Their decay time is equal to the ICT lifetime tau'0(ICT), which increases with solvent polarity from 0.86 ns in n-hexane to 3.48 ns in MeCN at 25 degrees C. The femtosecond excited-state absorption (ESA) spectra of DTABN in n-hexane and MeCN at 22 degrees C show a decay of the LE and a corresponding rise of the ICT absorption. The ICT reaction time is 70 fs in n-hexane and 60 fs in MeCN. DTABN and mDTABN may have a strongly twisted ICT state, similar to that of 6-cyanobenzoquinuclidine but different from that of DMABN. 相似文献
107.
Sidorkin VF Doronina EP Chipanina NN Aksamentova TN Shainyan BA 《The journal of physical chemistry. A》2008,112(27):6227-6234
The structure and the hydrogen bonding in the systems formed by the intramolecularly H-bonded systems, namely, maltol (3-hydroxy-2-methyl-4-pyrone), 5, 2,4,6-trinitrophenol, 6, acetylacetone enol, 7, with Lewis bases, phosgene, 8, dioxane, 9, and DMSO, 10, have been studied by density functional theory (B3LYP) and MP2 using the 6-311G* basis set. The continuum solvent effect was simulated by IEF-PCM model. The hydrogen bond analysis using the atoms in molecules (AIM) method was applied by using the MP2(full)/6-311++G** electron density to establish the nature of the bifurcate hydrogen bond (BHB) in these systems as well as contributory factors for its stabilization. The nature of interaction in the intermolecular H-complexes formed by compounds 5- 7 with the Lewis bases 8- 10 was shown to depend on the strength of the intramolecular hydrogen bond O...H and the strength of the base. The critical values of the CO...H and NO...H angles for which the formation of BHB is possible, have been determined. 相似文献
108.
Yoder CH Agee TM Schaeffer CD Carroll MJ Fleisher AJ DeToma AS 《Inorganic chemistry》2008,47(22):10765-10770
The lack of understanding of the structural and electronic factors that affect the often difficult to observe germanium resonance has been a major deterrent to studies of bonding interactions at germanium. We utilized the symmetrical system GeR 4 to determine what structural factors inherent in the R group affect the shape and position of the (73)Ge resonance. The (73)Ge resonances of symmetrical tetrakis germanium compounds of the type GeR 4 (R = alkyl, aryl), GeX 4 (X = F, Cl, Br, I), Ge(OR) 4 (R = alkyl, methoxyalkyl, dimethylaminoalkyl), Ge(NR 2) 4 (R = alkyl), and Ge(SR) 4 (R = alkyl, dimethylaminoalkyl) were examined for evidence of intramolecular coordination. Although many of these compounds have sharp resonances due to idealized tetrahedral symmetry with relatively long relaxation times, others have broad or no observable resonances due to fast quadrupolar relaxation. We hypothesize that the perturbation of symmetry by even weak Lewis interactions or conformational changes causes broadening of the resonance before the interaction can become sufficiently strong to cause the significant low-frequency shift generally associated with hypercoordination in most nuclei. Intermolecular coordination to GeCl 4 is believed to be responsible for the low-frequency shifts in (73)Ge resonances and the associated changes in peak widths in mixtures with bases such as tributylphosphine oxide (TBPO) and triethylphosphine oxide (TEPO). Adduct formation with these bases is confirmed by broad (31)P resonances that are resolved into five peaks at -40 degrees C. The exchange-broadened resonances due to the 1:1 and 1:2 TEPO adducts are also observed at -40 degrees C in the (73)Ge spectrum. Thus, relatively strong bonding to the germanium in GeCl 4 results in both low-frequency shifts and broadening of the resonance. The broad (73)Ge resonances that occur in some compounds may be in part due to exchange as well as quadrupolar relaxation. 相似文献
109.
A Single Methylene Group in Oligoalkylamine‐Based Cationic Polymers and Lipids Promotes Enhanced mRNA Delivery 下载免费PDF全文
Anita Jarzębińska Dr. Tamara Pasewald Jana Lambrecht Olga Mykhaylyk Linda Kümmerling Dr. Philipp Beck Dr. Günther Hasenpusch Priv.‐Doz. Dr. Carsten Rudolph Prof. Dr. Christian Plank Dr. Christian Dohmen 《Angewandte Chemie (International ed. in English)》2016,55(33):9591-9595
The development of chemically modified mRNA holds great promise as a new class of biologic therapeutics. However, the intracellular delivery and endosomal escape of mRNA encapsulated in nanoparticles has not been systematically investigated. Here, we synthesized a diverse set of cationic polymers and lipids from a series of oligoalkylamines and subsequently characterized their mRNA delivery capability. Notably, a structure with an alternating alkyl chain length between amines showed the highest transfection efficiency, which was linked to a high buffering capacity in a narrow range of pH 6.2 to 6.5. Variation in only one methylene group resulted in enhanced mRNA delivery to both the murine liver as well as porcine lungs after systemic or aerosol administration, respectively. These findings reveal a novel fundamental structure–activity relationship for the delivery of mRNA that is independent of the class of mRNA carrier and define a promising new path of exploration in the field of mRNA therapeutics. 相似文献
110.
Frontispiece: Synthesis of Calcium(II) Amidinate Precursors for Atomic Layer Deposition through a Redox Reaction between Calcium and Amidines 下载免费PDF全文