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113.
Merlin Rosales Angel Gonzlez YusbeIi Guerrero Ins Pacheco Roberto A. Snchez-Delgado 《Journal of molecular catalysis. A, Chemical》2007,270(1-2):241-249
A kinetic study of the homogeneous hydroformylation of 1-hexene to the corresponding aldehydes (heptanal and 2-methyl-hexanal) was carried out using a rhodium catalyst formed by addition of 1 equiv. of 1,2-bis(diphenylphosphino)ethane (dppe) to Rh(acac)(CO)2 under mild reaction conditions (80 °C, 1–7 atm H2 and 1–7 atm CO) in toluene; in all cases linear to branched ratios were close to 2. The reaction rate is first-order in dissolved hydrogen concentration at pressures below 3 atm, but independent of this parameter at higher pressures. In both regimes (low and high H2 pressure), the initial rate was first-order with respect to the concentration of Rh and fractional order with respect to 1-hexene concentration. Increasing CO pressure had a positive effect on the rate up to a threshold value above which inhibition of the reaction was observed; the range of positive order on CO concentration is smaller when the total pressure is increased. The kinetic data and related coordination chemistry are consistent with a mechanism involving RhH(CO)(dppe) as the active species initiating the cycle, hydrogenolysis of the acyl intermediate as the rate-determining step of the catalytic cycle at low hydrogen pressure, and migratory insertion of the olefin into the metal-hydride bond as rate limiting at high hydrogen pressure. This catalytic cycle is similar to the one commonly accepted for RhH(CO)(PPh3)3 but different from previous proposals for Rh-diphosphine catalysts. 相似文献
114.
Merlin Rosales Angel González Cristhina Moratinos Johán Urdaneta 《Journal of organometallic chemistry》2005,690(12):3095-3098
The hydroformylation of medium-chain C6 olefins and of allyl alcohol was achieved with paraformaldehyde in dioxane solution using rhodium catalysts with mono-, bi-, and tri-dentate phosphine ligands. The highest activities with n/i ratios around 2, were obtained for a system derived from [Rh(dppe)2]+, prepared in situ by reaction of Rh(acac)(CO)2 with 2 eq of dppe. 相似文献
115.
Merlin Heß Tom E. Stennett Felipe Fantuzzi Rüdiger Bertermann Marvin Schock Marius Schfer Torsten Thiess Holger Braunschweig 《Chemical science》2020,11(34):9134
Sequential treatment of [Rh(COE)2Cl]2 (COE = cyclooctene) with PiPr3, alkyne derivatives and tBuN BMes (Mes = 2,4,6-trimethylphenyl) provided functionalized rhodium η4-1,2-azaborete complexes of the form (η4-azaborete)RhCl(PiPr3). The scope of this reaction was expanded to encompass alkynes with hydrogen, alkyl, aryl, ferrocenyl, alkynyl, azaborinyl and boronate ester substituents. Treatment of these complexes with PMe3 led to insertion of the rhodium atom into the B–C bond of the BNC2 ring, forming 1-rhoda-3,2-azaboroles. Addition of N-heterocyclic carbenes to azaborete complexes led to highly unusual rearrangements to rhodium η2,κ1-allenylborylamino complexes via deprotonation and C–N bond cleavage. Heating and photolysis of an azaborete complex also led to rupture of the C–N bond followed by subsequent rearrangements, yielding an η4-aminoborylallene complex and two isomeric η4-butadiene complexes.Rhodium η4-azaborete complexes can be transformed into a variety of species with ring-opened, BN-containing ligands by treatment with Lewis bases. 相似文献
116.
Rosales Merlin González Ángel Mora Milagros Nader Nidal Navarro Janeth Sánchez Ligbel Soscún Humberto 《Transition Metal Chemistry》2004,29(2):205-211
Kinetic and mechanistic studies of the homogeneous hydrogenation of cyclohexanone were carried out using the cationic complexes [MH(CO)(NCMe)2(PPh3)2]BF4 (M = Ru, Os) as the catalyst precursors, which were very efficient under mild reaction conditions in 2-methoxyethanol solution. For both complexes, the catalytic hydrogenation of cyclohexanone proceeds according to the rate law r = k[M][H2]. The activation parameters were also calculated, the activation energy for the osmium catalyst being higher than for the ruthenium(I). All experimental data are consistent with a mechanism involving the oxidative addition of hydrogen as the rate-determining step of the catalytic cycle. Finally, the [MH(CO)(NCMe)2(PPh3)2]BF4 complexes were efficient precatalysts for the selective reduction of 2-cyclohexen-1-one to cyclohexanone; the reduction of the CO group of cyclohexanone only begins to take place when the ,-unsaturated ketone has been consumed. 相似文献
117.
Jong‐Bum Kim Wenxi Huang Matthew D. Miller Gregory L. Baker Merlin L. Bruening 《Journal of polymer science. Part A, Polymer chemistry》2003,41(3):386-394
Although atom transfer radical polymerization (ATRP) is often a controlled/living process, the growth rate of polymer films during surface‐initiated ATRP frequently decreases with time. This article investigates the mechanism behind the termination of film growth. Studies of methyl methacrylate and methyl acrylate polymerization with a Cu/tris[2‐(dimethylamino)ethyl]amine catalyst system show a constant but slow growth rate at low catalyst concentrations and rapid growth followed by early termination at higher catalyst concentrations. For a given polymerization time, there is, therefore, an optimum intermediate catalyst concentration for achieving maximum film thickness. Simulations of polymerization that consider activation, deactivation, and termination show trends similar to those of the experimental data, and the addition of Cu(II) to polymerization solutions results in a more constant rate of film growth by decreasing the concentration of radicals on the surface. Taken together, these studies suggest that at high concentrations of radicals, termination of polymerization by radical recombination limits film growth. Interestingly, stirring of polymerization solutions decreases film thickness in some cases, presumably because chain motion facilitates radical recombination. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 386–394, 2003 相似文献
118.
We report the use of a variety of polyelectrolyte multilayers (PEMs) as selective skins in composite membranes for nanofiltration (NF) and diffusion dialysis. Deposition of PEMs occurs through simple alternating adsorption of polycations and polyanions, and separations can be optimized by varying the constituent polyelectrolytes as well as deposition conditions. In general, the use of polycations and polyanions with lower charge densities allows separation of larger analytes. Depending on the polyelectrolytes employed, PEM membranes can remove salt from sugar solutions, separate proteins, or allow size-selective passage of specific sugars. Additionally, because of the minimal thickness of PEMs, NF pure water fluxes through these membranes typically range from 1.5 to 3 m3/(m2 day) at 4.8 bar. Specifically, to separate sugars, we employed poly(styrene sulfonate) (PSS)/poly(diallyldimethylammonium chloride) (PDADMAC) films, which allow 42% passage of glucose along with a 98% rejection of raffinose and a pure water flux of 2.4 m3/(m2 day). PSS/PDADMAC membranes are also capable of separating NaCl and sucrose (selectivity of approximately 10), while high-flux chitosan/hyaluronic acid membranes [pure water flux of 5 m3/(m2 day) at 4.8 bar] may prove useful in protein separations. 相似文献
119.
DeCamp MF Reis DA Cavalieri A Bucksbaum PH Clarke R Merlin R Dufresne EM Arms DA Lindenberg AM MacPhee AG Chang Z Lings B Wark JS Fahy S 《Physical review letters》2003,91(16):165502
We measure transient strain in ultrafast laser-excited Ge by time-resolved x-ray anomalous transmission. The development of the coherent strain pulse is dominated by rapid ambipolar diffusion. This pulse extends considerably longer than the laser penetration depth because the plasma initially propagates faster than the acoustic modes. X-ray diffraction simulations are in agreement with the observed dynamics. 相似文献
120.
Raman scattering by phonons and by magnon pairs has been observed in Fe3BO6. Of the predicted 60 Raman-active modes, 39 have been identified and classified according to their symmetries. The two-magnon band shows a strong decrease in intensity with increasing temperature, and almost vanishes close to TN = 508 K. The origin of this effect is attributed to the existence of a nearly dispersionless magnon branch. 相似文献