To gain insight into the attachment of =Si^＋ （SC） ion （regarded as guest） to the lowest generation, NH2-terminated poly（amidoamine） （PAMAM） dendrimers （regarded as host） in the liquid phase, density functio...To gain insight into the attachment of =Si^＋ （SC） ion （regarded as guest） to the lowest generation, NH2-terminated poly（amidoamine） （PAMAM） dendrimers （regarded as host） in the liquid phase, density functional theory is used to investigate the structures and energetics of the host-guest complex. The effect of solvent on the structures and energetics is also investigated. Various initial configurations of the ion bound to PAMAM are tested, and two stable conformers are found, i.e, types A （=Si^＋ is bound to the amine site） and C （=Si^＋ is bound to the amide site）. Types A and C are the most stable due to the chemical bond formations of Si-N° （amine nitrogen atoms） and Si-O, respectively. The IR spectra for the lowest energy conformers are thoroughly analyzed and compared with the available experimental data.展开更多
Poly （amidoamine） dendrimers are emerging as versatile and derivatizable nano-scale drug delivery vehicles. In our study, cis-4,7,10,13,16,19-docosahexenoic acid and doxorubicin were conjugated to generation 2.5 PAM...Poly （amidoamine） dendrimers are emerging as versatile and derivatizable nano-scale drug delivery vehicles. In our study, cis-4,7,10,13,16,19-docosahexenoic acid and doxorubicin were conjugated to generation 2.5 PAMAM. The molecular architecture of the carrier was designed for optimized blood circulation and optimized drug release through the use of pH-sensitive hydrazone linkages. In vitro, DHA-PAMAM-DOX conjugates were able to release twice as much doxorubicin at pH 4.5 （lysosomal pH） as at pH 7.4, ensuring more pronounced antitumor activity. Upon intravenous administration to ICR mice, the DHA-PAMAM-DOX delivery systems resulted in more plasma exposure of doxorubicin than free doxorubicin solution. In efficacy studies performed with B6D2F1 mice bearing B16 melanoma tumors, DHA-PAMAM-DOX was significantly more efficient in inhibiting tumor growth than free doxorubicin at the dose equivalent to 5 mg/kg doxorubicin. Our research provides evidence that DHA-PAMAM-DOX conjugates have the potential to enhance the effect of cancer therapy in the course of delivering anticancer drugs to their target sites.展开更多
A facile and green approach has been developed for the in situ synthesis of hybrid nanomaterials based on dendrite-shaped Pd nanostructures supported on graphene （RG）. The as-synthesized hybrid nanomaterials （RG-Pd...A facile and green approach has been developed for the in situ synthesis of hybrid nanomaterials based on dendrite-shaped Pd nanostructures supported on graphene （RG）. The as-synthesized hybrid nanomaterials （RG-PdnDs） have been thoroughly characterized by high resolution transmission electron microscopy, X-ray photoelectron spectroscop）~ atomic force microscop）~ Raman spectroscopy and electrochemical techniques. The mechanism of formation of such dendrite- shaped Pd nanostructures on the graphene support has been elucidated using transmission electron microscopy （TEM） measurements. The RG induces the formation of, and plays a decisive role in shaping, the dendrite morphology of Pd nanostructures on its surface. Cyclic voltammetry and chronoamperometry techniques have been employed to evaluate the electrochemical performance of RG-PdnDs towards oxidation of methanol. The electrochemical （EC） activities of RG-PdnDs are compared with graphene-supported spherical-shaped Pd nanostructures, Pd nanodendrites alone and a commercial available Pd/C counterpart. The combined effect of the graphene support and the dendrite morphology of RG-PdnDs triggers the high electrocatalytic activity and results in robust tolerance to CO poisoning.展开更多
The Bergman cyclization has strongly impacted on a number of fields including pharmaceutics, synthetic chemistry, and material science. The diradical intermediates stemmed from enediynes can not only cause DNA cleavag...The Bergman cyclization has strongly impacted on a number of fields including pharmaceutics, synthetic chemistry, and material science. The diradical intermediates stemmed from enediynes can not only cause DNA cleavage under physiological conditions but also function as monomer or initiator participants in polymer science. The homo-polymerization of enediynes through the Bergman cyclization to fabricate conjugated polymers is a fascinating strategy due to the advantages of facial operation, high efficiency, tailored structure, and catalyst-free operation. Moreover, conjugated polymers generated through the Bergman cyclization show many remarkable properties, such as excellent thermal stability, good solubility, and processability, which enables these polymers to be further manufactured into carbon-rich materials. Recent times have seen extensive efforts devoted to the application of the Bergman cyclization in polymer science and materials chemistry. A variety of synthetic strategies have been developed to fabricate structurally unique materials via the Bergman cyclization, including the fabrication of rod-like polymers with polyester, dendrimers and chiral imide side chains, functionalization of carbon nanomaterials by surface-grafting conjugated polymers, formation of nanoparticles by intramolecular collapse of single polymer chains, and the construction of carbon nanomembranes with different morphologies. Future developments involving the Bergman cyclization in polymer science, probably by altering the reaction mechanism to precisely control the microstructure of polymeric products, are also proposed in this review article.展开更多
文摘To gain insight into the attachment of =Si^＋ （SC） ion （regarded as guest） to the lowest generation, NH2-terminated poly（amidoamine） （PAMAM） dendrimers （regarded as host） in the liquid phase, density functional theory is used to investigate the structures and energetics of the host-guest complex. The effect of solvent on the structures and energetics is also investigated. Various initial configurations of the ion bound to PAMAM are tested, and two stable conformers are found, i.e, types A （=Si^＋ is bound to the amine site） and C （=Si^＋ is bound to the amide site）. Types A and C are the most stable due to the chemical bond formations of Si-N° （amine nitrogen atoms） and Si-O, respectively. The IR spectra for the lowest energy conformers are thoroughly analyzed and compared with the available experimental data.
基金China International Science and Technology Cooperation Program for Key Projects (Grant No. 2008DFA31070)
文摘Poly （amidoamine） dendrimers are emerging as versatile and derivatizable nano-scale drug delivery vehicles. In our study, cis-4,7,10,13,16,19-docosahexenoic acid and doxorubicin were conjugated to generation 2.5 PAMAM. The molecular architecture of the carrier was designed for optimized blood circulation and optimized drug release through the use of pH-sensitive hydrazone linkages. In vitro, DHA-PAMAM-DOX conjugates were able to release twice as much doxorubicin at pH 4.5 （lysosomal pH） as at pH 7.4, ensuring more pronounced antitumor activity. Upon intravenous administration to ICR mice, the DHA-PAMAM-DOX delivery systems resulted in more plasma exposure of doxorubicin than free doxorubicin solution. In efficacy studies performed with B6D2F1 mice bearing B16 melanoma tumors, DHA-PAMAM-DOX was significantly more efficient in inhibiting tumor growth than free doxorubicin at the dose equivalent to 5 mg/kg doxorubicin. Our research provides evidence that DHA-PAMAM-DOX conjugates have the potential to enhance the effect of cancer therapy in the course of delivering anticancer drugs to their target sites.
文摘A facile and green approach has been developed for the in situ synthesis of hybrid nanomaterials based on dendrite-shaped Pd nanostructures supported on graphene （RG）. The as-synthesized hybrid nanomaterials （RG-PdnDs） have been thoroughly characterized by high resolution transmission electron microscopy, X-ray photoelectron spectroscop）~ atomic force microscop）~ Raman spectroscopy and electrochemical techniques. The mechanism of formation of such dendrite- shaped Pd nanostructures on the graphene support has been elucidated using transmission electron microscopy （TEM） measurements. The RG induces the formation of, and plays a decisive role in shaping, the dendrite morphology of Pd nanostructures on its surface. Cyclic voltammetry and chronoamperometry techniques have been employed to evaluate the electrochemical performance of RG-PdnDs towards oxidation of methanol. The electrochemical （EC） activities of RG-PdnDs are compared with graphene-supported spherical-shaped Pd nanostructures, Pd nanodendrites alone and a commercial available Pd/C counterpart. The combined effect of the graphene support and the dendrite morphology of RG-PdnDs triggers the high electrocatalytic activity and results in robust tolerance to CO poisoning.
基金supported by the National Natural Science Foundation of China(21474027,91023008,20874026,20704013)Shanghai Shuguang Project(07SG33)+1 种基金New Century Excellent Talents in University,Ph D Programs Foundation of Ministry of Education of China,Shanghai Leading Academic Discipline Project(B502)the"Eastern Scholar Professorship"support from Shanghai Local Government
文摘The Bergman cyclization has strongly impacted on a number of fields including pharmaceutics, synthetic chemistry, and material science. The diradical intermediates stemmed from enediynes can not only cause DNA cleavage under physiological conditions but also function as monomer or initiator participants in polymer science. The homo-polymerization of enediynes through the Bergman cyclization to fabricate conjugated polymers is a fascinating strategy due to the advantages of facial operation, high efficiency, tailored structure, and catalyst-free operation. Moreover, conjugated polymers generated through the Bergman cyclization show many remarkable properties, such as excellent thermal stability, good solubility, and processability, which enables these polymers to be further manufactured into carbon-rich materials. Recent times have seen extensive efforts devoted to the application of the Bergman cyclization in polymer science and materials chemistry. A variety of synthetic strategies have been developed to fabricate structurally unique materials via the Bergman cyclization, including the fabrication of rod-like polymers with polyester, dendrimers and chiral imide side chains, functionalization of carbon nanomaterials by surface-grafting conjugated polymers, formation of nanoparticles by intramolecular collapse of single polymer chains, and the construction of carbon nanomembranes with different morphologies. Future developments involving the Bergman cyclization in polymer science, probably by altering the reaction mechanism to precisely control the microstructure of polymeric products, are also proposed in this review article.
