Guanidinoamidized linear polyethyleneimine for gene delivery

Guanidine was introduced to low molecular weight linear polyethyleneimine(LPEI) via amide groups, to explore the effect of both guanidine degree and pendant chain length on its transfection behavior. The resulting guanidinoamidized LPEIs(GLPEIs) could dramatically reduce LPEI's toxicity, enhance its DNA-packaging capability, cellular uptake and therefore transfection efficiency. These polyplexes were taken up very efficiently via caveolae-mediated endocytosis and their transfection efficiencies in ovarian cancer cells were significantly improved compared to native LPEI10 k polyplexes. Among these GLPEIs, LPEI-C3-G100 showed higher DNA affinity even than LPEI25 k and the highest transfection efficiency, probably due to the optimization of polymer chain flexibility. Of notice, LPEI-C3-G100 polyplexes could more effectively accumulate into cytoplasm than LPEI25 k, although the transfection efficiency of LPEI-C3-G100 polyplexes was not superior to that of LPEI25 k polyplexes, which would be probably attributed to the more efficient release of LPEI25 k polyplexes than LPEI-C3-G100 polyplexes in the cytoplasm.     

Chiral complex-forming agents and trans-phase transfer agents

Synthesized 3-hydroxy- and 3-benzyloxy-1-benzylquinuclidinium salts are in their catalytic activity comparable to benzyl(triethyl)ammonium chloride and are inferior to catalysts of the tetraalkylammonium type.The asymmety-induced capability of chiral 3-hydroxy-1-alkylquinuclidinium salts is considerably inferior to the asymmetry-induced capability of the conformationally mobile N-benzylquininium chloride, which indicates the dependence of the asymmetric induction on the possibility of the approach of the -hydroxylic group and the ammonium center of the catalyst in the transition state of the reaction.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1836–1843, August, 1989.     

Chiral and phase transfer agents

Starting from 1,32,4-di-O-ethylidene-D-glucitol (1), two regioisomeric monoaza-18-crown-6 ethers withC ₂ symmetry were synthesized. A simple route was suggested for the preparation of a diol that is a convenient intermediate for the synthesis of chiral aza-crown ethers from diol1.For Part 7, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 782–785, April, 1993.     

Merrifield resin-supported chain transfer agents, precursors for RAFT polymerization

The modification of Merrifield resins to form chain transfer agent (CTA) precursors for reversible addition fragmentation chain transfer (RAFT) polymerization is investigated. A series of CTA precursor resins were prepared and characterized by FTIR and elemental analysis (EA). [reaction: see text]     

Alkoxyamine-cyanoborane adducts: efficient cyanoborane transfer agents

We report the synthesis of the hitherto unknown zwitterionic alkoxyamino cyanoboranes by reduction of O-alkyloximes with sodium cyanoborohydride; unprecedented cyanoboronated N-alkoxyformamidines were also isolated as by-products. Boronated alkoxyamines were found to be efficient cyanoborane transfer agents towards more basic amines, including aminosugars; they were also successfully transformed into neoglycoconjugates by the neoglycorandomization reaction with reducing sugars.     

The use of polyethyleneimine for fabrication of potentiometric cholinesterase biosensors

Potentiometric biosensors based on butyrylcholinesterase are developed by co-reticulation of the enzyme with glutaraldehyde on an electropolymerized polyethyleneimine film at the electrode surface. The BuChE-electrode was tested as biochemical sensor for detection of an organophosphorus pesticide, trichlorfon in liquid, the detection being based on the enzyme inhibition. The enzyme electrode showed a detection limit for trichlorfon below 10⁻⁷ M.     

Borane chain transfer reaction in olefin polymerization using trialkylboranes as chain transfer agents

This article discusses a new borane chain transfer reaction in olefin polymerization that uses trialkylboranes as a chain transfer agent and thus can be realized in conventional single site polymerization processes under mild conditions. Commercially available triethylborane (TEB) and synthesized methyl‐B‐9‐borabicyclononane (Me‐B‐9‐BBN) were engaged in metallocene/MAO [depleted of trimethylaluminum (TMA)]‐catalyzed ethylene (Cp₂ZrCl₂ and rac‐Me₂Si(2‐Me‐4‐Ph)₂ZrCl₂ as a catalyst) and styrene (Cp*Ti(OMe)₃ as catalyst) polymerizations. The two trialkylboranes were found—in most cases—able to initiate an effective chain transfer reaction, which resulted in hydroxyl (OH)‐terminated PE and s‐PS polymers after an oxidative workup process, suggesting the formation of the B‐polymer bond at the polymer chain end. However, chain transfer efficiencies were influenced substantially by the steric hindrances of both the substituent on the trialkylborane and that on the catalyst ligand. TEB was more effective than TMA in ethylene polymerization with Cp₂ZrCl₂/MAO, whereas it became less effective when the catalyst changed to rac‐Me₂Si(2‐Me‐4‐Ph)₂ZrCl₂. Both TEB and Me‐B‐9‐BBN caused an efficient chain transfer in the Cp₂ZrCl₂/MAO‐catalyzed ethylene polymerization; nevertheless, Me‐B‐9‐BBN failed in vain with rac‐Me₂Si(2‐Me‐4‐Ph)₂ZrCl₂/MAO. In the case of styrene polymerization with Cp*Ti(OMe)₃/MAO, thanks to the large steric openness of the catalyst, TEB exhibited a high efficiency of chain transfer. Overall, trialkylboranes as chain transfer agents perform as well as B? H‐bearing borane derivatives, and are additionally advantaged by a much milder reaction condition, which further boosts their applicability in the preparation of borane‐terminated polyolefins. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3534–3541, 2010     

Optimization of LiFePO4 nanoparticle suspensions with polyethyleneimine for aqueous processing

Addition of dispersants to aqueous based lithium-ion battery electrode formulations containing LiFePO(4) is critical to obtaining a stable suspension. The resulting colloidal suspensions enable dramatically improved coating deposition when processing electrodes. This research examines the colloidal chemistry modifications based on polyethyleneimine (PEI) addition and dispersion characterization required to produce high quality electrode formulations and coatings for LiFePO(4) active cathode material. The isoelectric point, a key parameter in characterizing colloidal dispersion stability, of LiFePO(4) and super P C45 were determined to be pH = 4.3 and 3.4, respectively. PEI, a cationic surfactant, was found to be an effective dispersant. It is demonstrated that 1.0 wt % and 0.5 wt % PEI were required to stabilize the LiFePO(4) and super P C45 suspension, respectively. LiFePO(4) cathode suspensions with 1.5 wt % PEI demonstrated the best dispersibility of all components, as evidenced by viscosity and agglomerate size of the suspensions and elemental distribution within dry cathodes. The addition of PEI significantly improved the LiFePO(4) performance.     

Trimethyl(trihalomethyl)silanes as dihalomethylene transfer agents

Trimethyl(trichloromethyl)silane and trimethyl(tribromomethyl)silane react with anhydrous potassium fluoride in diglyme to give good yields of CX₂ transfer products (dihalocyclopropanes) with olefins. Catalysis by 18-crown-6 ether is observed.     

Vinylphosphonic esters as end-capping agents in group transfer polymerization

Diethyl vinylphosphonate does not undergo group transfer polymerization (GTP), but does react with the silyl ketene acetal end group of PMMA prepared by GTP to give α-(2-diethoxyphosphinylethyl) PMMA. Copolymerization of MMA and small amounts of diethyl vinylphosphonate led to copolymer. The telechelic PMMA diphosphonic acid, α-(2-dihydroxyphosphinylethyl) ω-dihydroxyphosphinylPMMA, was synthesized by initiation of GTP of MMA with diethyl 3-methoxy-3-trimethylsiloxy-2-propene-1-phosphonate, followed by termination with diethyl vinylphosphonate, silylation of the phosphonic ester with bromotrimethylsilane, and hydrolysis. Reaction of living poly (methyl methacrylateco-n-butyl methacrylate), prepared by GTP, with bis (trimethylsilyl) vinylphosphonate followed by hydrolysis gave α-(2-dihydroxyphosphinylethyl) poly (methyl methacrylateco-n-butyl methacrylate).     

Chain transfer in ethylene polymerization. VII. Very reactive and depletable transfer agents

The study of chain transfer in the free-radical polymerization of ethylene was extended to very reactive transfer agents, particularly aldehydes and mercaptans The chaintransfer constant C_s for aldehydes was insensitive to temperature changes but was strongly reduced as pressure was increased. Mercaptans were found to deplete during polymerization (C_s > 1.0). The conventional Mayo equation was integrated to allow accurate calculation of C_s for depleting transfer agents.     

Dicationic disiloxane ionic liquids as heat transfer agents in vacuo

Russian Chemical Bulletin - Bis(trifluoromethylsulfonyl)imidic dicationic liquids containing a disiloxane linker between the imidazole cations have been synthesized. Their thermal stability was...     

Novel catalyst for dihydrogen evolution from water based on rhodium complexes with polyethyleneimine

Catalytic activity of homogeneous and heterogeneous rhodium complexes with polyethyleneimine or ethylenediamine at various Rh:N ratios has been studied in the reaction of water reduction to dihydrogen by V _aq ²⁺ and Cr _aq ²⁺ and the applicability of these catalysts for photocatalytic evolution of H₂ from water is discussed.

---

Rh:N V _ap ²⁺ Cr _aq ²⁺ .

     

Synthesis and performances for treating oily wastewater of polyether copolymers based on polyethyleneimine

The demulsification of the oily wastewater generated in the oil recovery process is very important in the crude oil exploitation. In present work, 10 block copolymers based on polyethyleneimine were synthesized, and their performances for treating oily wastewater were studied. The evaluation of demulsification efficiency, the effects of temperature, and the dosage on the treatment of oily wastewater by prepared copolymers were also investigated. To explore the causes of the differences, the interface activity of prepared copolymer molecules at water‐oil interface was investigated by the interfacial tension, and a mechanism diagram of demulsification of wastewater by the prepared copolymers was proposed. The demulsification of wastewater could be divided into 3 processes that were (1) adsorption, (2) congestion, and (3) coalescence. The prepared copolymer molecule acted as a hand in the oily wastewater to achieve the demulsification.