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91.
RA Shenoi JK Narayanannair JL Hamilton BF Lai S Horte RK Kainthan JP Varghese KG Rajeev M Manoharan JN Kizhakkedathu 《Journal of the American Chemical Society》2012,134(36):14945-14957
Multifunctional biocompatible and biodegradable nanomaterials incorporating specific degradable linkages that respond to various stimuli and with defined degradation profiles are critical to the advancement of targeted nanomedicine. Herein we report, for the first time, a new class of multifunctional dendritic polyether polyketals containing different ketal linkages in their backbone that exhibit unprecedented control over degradation in solution and within the cells. High-molecular-weight and highly compact poly(ketal hydroxyethers) (PKHEs) were synthesized from newly designed α-epoxy-ω-hydroxyl-functionalized AB(2)-type ketal monomers carrying structurally different ketal groups (both cyclic and acyclic) with good control over polymer properties by anionic ring-opening multibranching polymerization. Polymer functionalization with multiple azide and amine groups was achieved without degradation of the ketal group. The polymer degradation was controlled primarily by the differences in the structure and torsional strain of the substituted ketal groups in the main chain, while for polymers with linear (acyclic) ketal groups, the hydrophobicity of the polymer may play an additional role. This was supported by the log?P values of the monomers and the hydrophobicity of the polymers determined by fluorescence spectroscopy using pyrene as the probe. A range of hydrolysis half-lives of the polymers at mild acidic pH values was achieved, from a few minutes to a few hundred days, directly correlating with the differences in ketal group structures. Confocal microscopy analyses demonstrated similar degradation profiles for PKHEs within live cells, as seen in solution and the delivery of fluorescent marker to the cytosol. The cell viability measured by MTS assay and blood compatibility determined by complement activation, platelet activation, and coagulation assays demonstrate that PKHEs and their degradation products are highly biocompatible. Taken together, these data demonstrate the utility this new class of biodegradable polymer as a highly promising candidate in the development of multifunctional nanomedicine. 相似文献
92.
An improved synthesis of V-PROLI/NO, a cytochrome P450-activated nitric oxide (NO) prodrug, in an overall yield of 26% in four steps from prolinol is reported; the previously published yield of this transformation was 1%. Using this revised strategy, the sarcosine analogue (14) of V-PROLI/NO was prepared. Finally, the methyl ester of V-PROLI/NO (15) was found to be an esterase-activated prodrug form of V-PROLI/NO. 相似文献
93.
[reaction: see text] Reaction of 4,4-dicarbomethoxy-1-octene-6-yne (1) with triethylsilane and a catalytic 1:1 mixture of [Rh(COD)(2)](+) SbF(6)(-) and (R)-BIPHEMP (5 mol %) at 70 degrees C for 90 min gave (Z)-1,1-dicarbomethoxy-3-(1-triethylsilyl)ethylidene-4-methylcyclopentane (2) in 81% isolated yield with 98% de and 92% ee. 相似文献
94.
When p-dinitrobenzene is reacted with Et(3)B in t-BuOH or THF in the presence of t-BuOK, it yields p-nitroethylbenzene. In this report we examine the scope of this transformation by monitoring the effect of various parameters on the reaction. It has been found that the reaction is extremely sensitive to temperature and rather insensitive to the base-solvent combination used. It is also insensitive to the steric hindrance of the base: good yields were obtained using sodium 2,6-diisopropylphenoxide or when using NaH. Alkylation was obtained with a large variety of alkylboranes ranging from linear to polycyclic. Yields drop significantly if one of the nitro groups is replaced by another electron-withdrawing group. In all cases studied (CHO, PHCO, SO(2)Ph, and CN), it is the latter group which was preferentially displaced by the alkyl group. According to the suggested mechanism, the radical anion of the substrate combines with the alkyl radical released from the boranyl radical to form a Meisenheimer complex. The reaction takes place at the ring carbon bearing the highest spin density in accordance with ab initio calculations at the B3LYP/6-31+G level. 相似文献
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Harikumar Bhaskaran Nair Kurup Maliyeckal R. Prathapachandra Jayaprakash Thakidiyil N. 《Transition Metal Chemistry》1997,22(5):507-509
Transition metal complexes of 2-formylthiophene S-methyldithiocarbazate have been synthesized and characterized. Analytical data show that the complexes are of the type [ML3], where M = Fe3+, and [ML2], where M=Ni2+, Cu2+ or Zn2+. The i.r. spectra suggest coordination to the metal through the azomethine nitrogen and thiolate sulfur. The magnetic and spectroscopic data indicate a square planar geometry for the complexes, except for the Fe3+ complex, which is octahedral. The e.s.r. parameters are indicative of a square planar N2S2 system for the Cu2+ complex. 相似文献