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81.
Aquo, ammonia and pyridine complexes of copper(II) with 5,5-thiodisalicylic acid have been investigated by TG and DTG. All these complexes decompose in three distinct steps, viz. dehydration, loss of axial bases and decarboxylation of the aromatic ligand. The thermal curves of the aquo and pyridine complexes show water loss in two distinct steps. The decreasing order of thermal stability of the complexes is py > NH3 > H2O.
Zusammenfassung Aquo-, Ammoniak- und Pyridinkomplexe von Kupfer(II) mit 5,5-Thiodisalicylsäure wurden durch TG und DTG untersucht. Diese Komplexe werden in den drei Stufen, Dehydratisierung, Verlust axialer Basen und Decarboxylierung des aromatischen Liganden zersetzt. Die Abbaukurven der Aquo- und Pyridinkomplexe zeigen einen Wasserverlust in zwei Stufen. Die abnehmende Reihenfolge der Thermostabilität der Komplexe ist py > NH3 > H2O.
, (II) 5,5- . , : , . - , . : > NH3 > 2.相似文献
82.
Gupta Madan Mohan Srivastava Alpana Tripathi Arvind Kumar Misra Himanshu Verma Ram Kishore 《平面色谱法杂志一现代薄层色谱法》2006,19(4):282-287
JPC – Journal of Planar Chromatography – Modern TLC - High-performance thin-layer chromatography (HPTLC) has been used for normal-phase separation of the components of hexane,... 相似文献
83.
Thazha P Prakash Andrew M Kawasaki Allister S Fraser Guillermo Vasquez Muthiah Manoharan 《The Journal of organic chemistry》2002,67(2):357-369
A versatile synthetic route has been developed for the synthesis of 2'-O-[2-[(N,N-dimethylamino)oxy]ethyl] (abbreviated as 2'-O-DMAOE) modified purine and pyrimidine nucleosides and their corresponding nucleoside phosphoramidites and solid supports. To synthesize 2'-O-DMAOE purine nucleosides, the key intermediate B (Scheme 1) was obtained from the 2'-O-allyl purine nucleosides (13a and 15) via oxidative cleavage of the carbon-carbon bond to the corresponding aldehydes followed by reduction. To synthesize pyrimidine nucleosides, opening the 2,2'-anhydro-5-methyluridine 5 with the borate ester of ethylene glycol gave the key intermediate B. The 2'-O-(2-hydroxyethyl) nucleosides were converted, in excellent yield, by a regioselective Mitsunobu reaction, to the corresponding 2'-O-[2-[(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)oxy]ethyl] nucleosides (18, 19, and 20). These compounds were subsequently deprotected and converted into the 2'-O-[2-[(methyleneamino)oxy]ethyl] derivatives (22, 23, and 24). Reduction and a second reductive amination with formaldehyde yielded the corresponding 2'-O-[2-[(N,N-dimethylamino)oxy]ethyl] nucleosides (25, 26, and 27). These nucleosides were converted to their 3'-O-phosphoramidites and controlled-pore glass solid supports in excellent overall yield. Using these monomers, modified oligonucleotides containing pyrimidine and purine bases were synthesized with phosphodiester, phosphorothioate, and both linkages (phosphorothioate and phosphodiester) present in the same oligonucleotide as a chimera in high yields. The oligonucleotides were characterized by HPLC, capillary gel electrophoresis, and ESMS. The effect of this modification on the affinity of the oligonucleotides for complementary RNA and on nuclease stability was evaluated. The 2'-O-DMAOE modification enhanced the binding affinity of the oligonucleotides for the complementary RNA (and not for DNA). The modified oligonucleotides that possessed the phosphodiester backbone demonstrated excellent resistance to nuclease with t(1/2) > 24 h. 相似文献
84.
Moriarty RM Rani N Enache LA Rao MS Batra H Guo L Penmasta RA Staszewski JP Tuladhar SM Prakash O Crich D Hirtopeanu A Gilardi R 《The Journal of organic chemistry》2004,69(6):1890-1902
A general and novel solution to the synthesis of biologically important stable analogues of prostacyclin PGI(2), namely benzindene prostacyclins, has been achieved via the stereoselective intramolecular Pauson-Khand cyclization (PKC). This work illustrates for the first time the synthetic utility and reliability of the asymmetric PKC route for synthesis and subsequent manufacture of a complex drug substance on a multikilogram scale. The synthetic route surmounts issues of individual step stereoselectivity and scalability. The key step in the synthesis involves efficient stereoselection effected in the PKC of a benzoenyne under the agency of the benzylic OTBDMS group, which serves as a temporary stereodirecting group that is conveniently removed via benzylic hydrogenolysis concomitantly with the catalytic hydrogenation of the enone PKC product. Thus the benzylic chiral center dictates the subsequent stereochemistry of the stereogenic centers at three carbon atoms (C(3a), C(9a), and C(1)). 相似文献
85.
The force constants, Coriolis coupling constants and mean amplitudes of vibration at 0, 298.16 and 500 K for GaF63?FeF63? have been reported for the first time employing recent vibrational data. The results are discussed in the light of available information. 相似文献
86.
Semi theoretical models have been proposed to account for the mechanism of membrane oscillations involving, electrokinetic phenomena in systems where (i) concentration difference deltaC is finite and deltaP is varying but the current is fixed, and (ii) deltaC=0, pressure difference deltaP is fixed across the membrane and imposed current is fixed. The formalism leads to the van der Pol equation in both cases. Computer simulation has also been attempted, which indicates oscillations in the former case. 相似文献
87.
A model iodophenyl imidazole ribonucleoside has been synthesized to study biodistribution properties in laboratory animals. The key intermediate 5-amino-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)imidazole-4-[N-(p-iodophenyl)carboxamide] ( 5 ) was synthesized by coupling N-succinimidyl-5-amino-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)imidazole-4-carboxylate ( 4 ) and p-iodoaniline. Deacetylation of the intermediate compound gave 5-amino-1-β-D-ribofuranosylimidazole-4-[N-(p-iodophenyl)]carboxamide ( 6 ). Ring annulation via diazotization of 5 gave 7-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)imidazo[4,5-d]-v-triazin-[3-N-(p-iodophenyl)]-4-one ( 7 ). Subsequent deacetylation of 7 afforded 7-β-D-ribofuranosylimidazo[4,5-d]-v-triazin-[3-N-(p-iodophenyl)]-4-one ( 8 ). The radiolabeled compounds, [125I] 5 and [125I] 6 were prepared in a manner similar to the corresponding unlabeled compounds except that p-[125I]iodoaniline was used for coupling with 4 . Biodistribution studies of iodine-125-labeled 5 and 6 were performed in female Fischer rats and tumor bearing nude mice. Compound 6 showed uptake in the brain and proliferating tissues such as tumor and bone-marrow. 相似文献
88.
The authors present six general integral formulas (four definite integrals and two contour inegrals) for theH-function of several complex variables, which was introduced and studied in a series of earlier papers by H. M. Srivastava and R. Panda (cf., e.g., [25] through [29]; see also [14] through [18], [20], [24], [32], [34], [35], [37], and [38]). Each of these integral formulas involves a product of the multivariableH-function and a general class of polynomials with essentially arbitrary coefficients which were considered elsewhere by H. M. Srivastava [21]. By assigning suiatble special values to these coefficients, the main results (contained in Theorems 1, 2 and 3 below) can be reduced to integrals involving the classical orthogonal polynomials including, for example, Hermite, Jacobi [and, of course, Gegenbauer (or ultraspherical), Legendre, and Tchebycheff], and Laguerre polynomials, the Bessel polynomials considered by H. L. Krall and O. Frink [9], and such other classes of generalized hypergeometric polynomials as those studied earlier by F. Brafman [3] and by H. W. Gould and A. T. Hopper [8]. On the other hand, the multivariableH-functions occurring in each of our main results can be reduced, under various special cases, to such simpler functions as the generalized Lauricella hypergeometric functions of several complex variables [due to H. M. Srivastava and M. C. Daoust (cf. [22] and [23])] which indeed include a great many of the useful functions (or the products of several such functions) of hypergeometric type (in one and more variables) as their particular cases (see,e. g., [1], [10] and [39]). Many of the aforementioned applications of our integral formulas (contained in Theorems 1, 2 and 3 below) are considered briefly. Further usefulness of some of these consequences of Theorems 1 and 2 in terms of the classical orthogonal polynomials is illustrated by considering a simple problem involving the orthogonal expansion of the multivariableH-function in series of Jacobi polynomials. It is also shown how these general integrals are related to a number of results scattered in the literature. 0261 0262 V 相似文献
89.
IR relative integrated intensities and half-widths of rocking (R) and wagging (W) bands of water in MnCl2 · 2H2O and CoCl2 · 2H2O are presented at 300 K and 120 K. Departure of observed intensity into DW/DR from those predicted by the fixed dipole model is attributed to anisotropic dynamic changes in dipole during these oscillations. A quantity representing the variation of this anisotropy between W and R oscillations is computed and its origin is discussed. An increase by 20% to 50% in both DW and DR on lowering the temperature has also been discussed. 相似文献
90.
Masson JF Battaglia TM Davidson MJ Kim YC Prakash AM Beaudoin S Booksh KS 《Talanta》2005,67(5):918-925
The elimination or minimization of non-specific protein adsorption from serum is critical for the use of surface plasmon resonance (SPR) sensors for in vitro and in vivo analysis of complex biological solutions. The ultimate goals in this application are to minimize non-specific adsorption of protein and to maximize analyte signal. A reduction of the non-specific protein adsorption from serum of up to 73% compared to carboxymethylated-dextran 500 kDa (CM-dextran) was achieved following a survey of eight biocompatible polymers and 10 molecular weights of CM-dextran. These coatings minimize non-specific adsorption on the sensor while also serving as immobilization matrices for antibody fixation to the probes. Polymers including polysaccharides: CM-dextrans, CM-hyaluronic acid, hyaluronic acid, and alginic acid were investigated. Humic acid, polylactic acid, polyacrylic acid, orthopyridyldisuldfide–polyethyleneglycol–N-hydroxysuccinimide (OPSS–PEG–NHS), and a synthesized polymer; polymethacrylic-acid-co-vinyl-acetate (PMAVA) were also used. The non-specific protein adsorption reduction was measured over a 14 day period at 0 °C for each polymer. Calibration curves using some of these polymers were constructed to show the performance and low detection limit possibilities of these new antibody supports. For many of the polymers, this is the first demonstration of employment as an antibody support for an optical or surface active sensor. CM-dextran is the polymer offering the largest signal for the antigen detection. However, the biocompatible polymers demonstrate a greater stability to non-specific binding in serum. These biocompatible polymers offer different alternatives for CM-dextran. 相似文献