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141.
Percec V Rudick JG Peterca M Heiney PA 《Journal of the American Chemical Society》2008,130(23):7503-7508
Self-organizable dendronized helical polymers provide a suitable architecture for constructing molecular nanomachines capable of expressing their motions at macroscopic length scales. Nanomechanical function is demonstrated by a library of self-organized helical dendronized cis-transoidal polyphenylacetylenes ( cis-PPAs) that possess a first-order phase transition from a hexagonal columnar lattice with internal order (varphi h (io)) to a hexagonal columnar liquid crystal phase (varphi h). These polymers can function as nanomechanical actuators. When extruded as fibers, the self-organizable dendronized helical cis-PPAs form oriented bundles. Such fibers have been shown capable of work by displacing objects up to 250-times their mass. The helical cis-PPA backbone undergoes reversible extension and contraction on a single molecule length scale resulting from cisoid-to-transoid conformational isomerization of the cis-PPA. Furthermore, we clarify supramolecular structural properties necessary for the observed nanomechanical function. 相似文献
142.
Nguyen MT Matus MH Jackson VE Vu TN Rustad JR Dixon DA 《The journal of physical chemistry. A》2008,112(41):10386-10398
Thermochemical parameters of carbonic acid and the stationary points on the neutral hydration pathways of carbon dioxide, CO 2 + nH 2O --> H 2CO 3 + ( n - 1)H 2O, with n = 1, 2, 3, and 4, were calculated using geometries optimized at the MP2/aug-cc-pVTZ level. Coupled-cluster theory (CCSD(T)) energies were extrapolated to the complete basis set limit in most cases and then used to evaluate heats of formation. A high energy barrier of approximately 50 kcal/mol was predicted for the addition of one water molecule to CO 2 ( n = 1). This barrier is lowered in cyclic H-bonded systems of CO 2 with water dimer and water trimer in which preassociation complexes are formed with binding energies of approximately 7 and 15 kcal/mol, respectively. For n = 2, a trimeric six-member cyclic transition state has an energy barrier of approximately 33 (gas phase) and a free energy barrier of approximately 31 (in a continuum solvent model of water at 298 K) kcal/mol, relative to the precomplex. For n = 3, two reactive pathways are possible with the first having all three water molecules involved in hydrogen transfer via an eight-member cycle, and in the second, the third water molecule is not directly involved in the hydrogen transfer but solvates the n = 2 transition state. In the gas phase, the two transition states have comparable energies of approximately 15 kcal/mol relative to separated reactants. The first path is favored over in aqueous solution by approximately 5 kcal/mol in free energy due to the formation of a structure resembling a (HCO 3 (-)/H 3OH 2O (+)) ion pair. Bulk solvation reduces the free energy barrier of the first path by approximately 10 kcal/mol for a free energy barrier of approximately 22 kcal/mol for the (CO 2 + 3H 2O) aq reaction. For n = 4, the transition state, in which a three-water chain takes part in the hydrogen transfer while the fourth water microsolvates the cluster, is energetically more favored than transition states incorporating two or four active water molecules. An energy barrier of approximately 20 (gas phase) and a free energy barrier of approximately 19 (in water) kcal/mol were derived for the CO 2 + 4H 2O reaction, and again formation of an ion pair is important. The calculated results confirm the crucial role of direct participation of three water molecules ( n = 3) in the eight-member cyclic TS for the CO 2 hydration reaction. Carbonic acid and its water complexes are consistently higher in energy (by approximately 6-7 kcal/mol) than the corresponding CO 2 complexes and can undergo more facile water-assisted dehydration processes. 相似文献
143.
Percec V Dulcey AE Peterca M Ilies M Sienkowska MJ Heiney PA 《Journal of the American Chemical Society》2005,127(50):17902-17909
The synthesis of dendritic dipeptides (4-3,4-3,5)12G2-CH2-X-L-Tyr-L-Ala-OMe with X = Boc, Moc, and Ac; their self-assembly in bulk and in solution; and the structural and retrostructural analysis of their supramolecular helical porous assemblies are reported. The dimensions, structure, internal order, thermal stability of the supramolecular helical pores, and conformations of the dendron and supramolecular dendrimer are programmed by the nature of the protective groups of the dipeptide. The ability of the protective groups to program the structure of the helical pore reveals the simplest design strategy that complements the more complex strategies based on the architecture of the dendron, the stereochemistry, and the structure of the dipeptide. 相似文献
144.
Complete Carbon-13 magnetic resonance spectral assignments of cocaine and atropine were made.13C Nmr spectra of atropine provides an interesting example of long range coupling on chemical shifts. 相似文献
145.
Percec V Mitchell CM Cho WD Uchida S Glodde M Ungar G Zeng X Liu Y Balagurusamy VS Heiney PA 《Journal of the American Chemical Society》2004,126(19):6078-6094
Structural analysis of three libraries of up to five generations of self-assembling dendrons based on AB(3), AB(2), and combinations of AB(3) with AB(2) building blocks (Percec et al. J. Am. Chem. Soc. 2001, 123, 1302) facilitated the discovery of several nanoscale lattices previously unknown for organic compounds (3-D Pm3n cubic, 3-D P4(2)/mnm tetragonal, and a crystallographically forbidden 12-fold symmetry liquid quasicrystal) and provided fundamental correlations between the molecular structure of the dendron and the shape and the diameter of the supramolecular dendrimers which, in these experiments, were limited to less than 75 A. That study concluded that alternative design principles should be elaborated for the assembly of supramolecular dendrimers of larger dimensions. Here we report design principles, synthesis and analysis of first and higher generations AB(3) and AB(2) self-assembling dendrons, based on various primary structures, and combinations of (AB)(y)-AB(3) and (AB)(y)-AB(2) (i.e., from nondendritic AB where y = 1 to 11 and dendritic AB(3) and AB(2)) building blocks that produced the largest structural (including six new lattices) and dimensional (100 to 217 A diameter) diversity of supramolecular dendrimers. 相似文献
146.
Virgil Percec Monika J. Sienkowska 《Journal of polymer science. Part A, Polymer chemistry》2009,47(2):628-634
Pentaerythritol tetrakis(2‐iodopropionate) was used as a tetrafunctional initiator for the Na2S2O4 catalyzed SET‐DTLRP of n‐butyl acrylate in water at room temperature. The resulting tetrafunctional poly(n‐butyl acrylate) macroinitiator with Mn = 14,864 or Mn = 3627 per arm was used to initiate the SET‐DTLRP of vinyl chloride and provide the first examples of four‐arm star‐block copolymers [PVC‐b‐PBA‐CH(CH3)? CO? O? CH2]4C. The Mn of the PVC segment from each arm of the four‐arm star‐block copolymer varied between 353 and 33,622. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 628–634, 2009 相似文献
147.
Elena Pahonu Maria Proks Sergiu Shova Gina Lupacu Diana‐Carolina Ilie tefania‐Felicia Brbuceanu Laura‐Ileana Socea Mihaela Badea Virgil Punescu Dorin Istrati Aurelian Gulea Doina Drgnescu Cristina Elena Dinu Pîrvu 《应用有机金属化学》2019,33(11)
A series of Cu(II), Co(II), Pd(II), Pt(II), Zn(II), Cd(II) and Fe(III) complexes were designed and synthesized using Schiff base 1‐phenyl‐2,3‐dimethyl‐4‐(N‐3‐formyl‐6‐methylchromone)‐3‐pyrazolin‐5‐one (HL). The new metal complexes were investigated using various physicochemical techniques including elemental and thermal analyses, molar electric conductivity and magnetic susceptibility measurements, as well as spectroscopic methods. Also, the crystal structures of ligand HL and the Pd(II) complex were determined using single‐crystal X‐ray diffraction analysis. For all compounds, the antimicrobial activity was studied against a series of standard strains: Staphylococcus aureus, Bacillus cereus, Enterococcus faecalis, Escherichia coli, Acinetobacter baumannii, Candida albicans, Candida krusei and Cryptococcus neoformans. The in vitro antiproliferative activity of the ligand and complexes was evaluated against ten cancer cell lines: MSC, A375, B16 4A5, HT‐29, MCF‐7, HEp‐2, BxPC‐3, RD, MDCK and L20B. At 10 μM concentration a significant cytotoxic effect of the Co(II), Pd(II) and Cd(II) complexes was observed against B16 4A5 murine melanoma cells. The Zn(II) complex is active against HEp‐2, RD and MDCK cancer cell lines, where IC50 values vary between 1.0 and 77.6 and for BxPC‐3 the activity index versus doxorubicin is 3.7 times higher. 相似文献
148.
Gerard Lligadas Janine S. Ladislaw Tamaz Guliashvili Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2008,46(1):278-288
The single‐electron transfer living radical polymerization (SET‐LRP) of methyl acrylate initiated with bromoform (CHBr3) and iodoform (CHI3) and catalyzed by Cu(0)/Me6‐TREN in DMSO at 25 °C provides a reliable method to prepare poly (methyl acrylate) (PMA) with active chain ends and controlled structure that can undergo subsequent functionalization to provide strategies for the synthesis of different block copolymers and other complex architectures. A detailed kinetic and structural analysis was used to assess the scope and the limitations of CHBr3 and CHI3 as initiators under SET‐LRP conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 278–288, 2008 相似文献
149.
150.
Virgil Percec 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1479-1496
Abstract This paper reviews the principles of self-assembly of rodlike viruses, such as tobacco mosaic virus (TMV), and discusses with selected examples the strategy used in our laboratory to produce synthetic systems which self-assemble via related principles. 相似文献