Polyethylenimines are cationic polymers with potential as delivery vectors in gene therapy and with proven antimicrobial activity. However, the antiviral activity of polyethylenimines has not been addressed in detail thus far. We have studied the inhibitory effects of a linear 25-kDa polyethylenimine on infections with human papillomaviruses and human cytomegaloviruses. Preincubation of cells with polyethylenimine blocked primary attachment of both viruses to cells, resulting in a significant reduction of infection. In addition, the dissemination of human cytomegalovirus in culture cells was efficiently reduced by recurrent administration of polyethylenimine. Polyethylenimine concentrations required for inhibition of human papillomavirus and cytomegalovirus did not cause any cytotoxic effects. Polyethylenimines and their derivatives may thus be attractive molecules for the development of antiviral microbicides.

ABSTRACT:The ring-opening metathesis polymerization using ruthenium carbene initiators developed by Grubbs et al. is one of the most functional group tolerant living polymerization methods known. One of the most used postpolymerization functionalization methods used today is the copper-catalyzed 1,3-dipolar cycloaddition between alkynes and organic azides. Organic azides are, however, not tolerated by ruthenium carbene initiators, and nonprotected alkynes have been shown to slow down the propagation reaction or react with the propagating species leading to broad molecular weight distributions. Here we report the copolymer synthesis of three orthogonally functionalizable monomers: one carrying an activated pentafluorophenyl ester, one a maleimide unit, and a third one a trialkylsilyl-protected alkyne. From these monomers, statistical terpolymers as well as diblock copolymers were synthesized with different molecular weights and monomer compositions or block ratios, respectively. Excellent control over molecular weight and molecular weight distribution could be achieved using Grubbs' firstgeneration ruthenium carbene initiator. Herein we present the synthesis and orthogonal triple postpolymerization functionalization of these copolymers.

Today's olefin metathesis catalysts show high reactivity, selectivity, and functional group tolerance, and allow the design of new syntheses of precisely functionalized polymers. Here we describe a general "one-pot" synthesis for narrow polydispersity bis-end-functional (5homotelechelic) ROMP polymers exploiting the propagating ruthenium complex inherent selectivity for strained norbornenes over acyclic internal olefins. This approach represents a straightforward general method of homotelechelic polymers carrying almost any functional end group (within the limitations of the catalyst's functionality tolerance). Complete pre-functionalization of the initiator is realized in situ within minutes and without the need of further purification steps. The excess acyclic olefin re-enters the catalytic cycle after monomer consumption is complete giving a homotelechelic polymer. 1 H NMR spectroscopic and MALDI-ToF-MS analysis show highly efficient end group functionalization. V C 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4183-4190

Amphiphilic block copolymers can be conveniently prepared via convergent syntheses, allowing each individual polymer block to be prepared via the polymerization technique that gives the best architectural control. The convergent ''click-chemistry'' route presented here, gives access to amphiphilic diblock copolymers prepared from a ring opening metathesis polymer and polyethylene glycol. Because of the high functional group tolerance of ruthenium carbene initiators, highly functional ring opening metathesis polymerization (ROMP) polymer blocks can be prepared. The described synthetic route allows the conjugation of these polymer blocks with other end-functional polymers to give well-defined and highly functional amphiphilic diblock copolymers. V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46:

We examined the timeline by which methyl jasmonate (MeJA) reprograms new carbon partitioning into key metabolite pools. The radioactive isotope ¹¹C (t(¹/₂) 20.4 min), administered to intact leaves of Nicotiana tabacum L. (cv Samsun) as ¹¹CO(2) gas enabled us to measure changes in new carbon partitioning into soluble sugar and amino acid pools of [¹¹C]photosynthate. A 500 μM MeJA treatment resulted in a decrease in the [¹¹C]soluble sugar pool and an increase in the [¹¹C]amino acid pool after 4 h. This pattern was more pronounced 15 h after treatment. We also examined the timeline for ¹¹C-partitioning into aromatic amino acid metabolites of the shikimate pathway. [¹¹C]Tyrosine, [C¹¹C]phenylalanine and [¹¹C]tryptophan were elevated 1.5-fold, 12-fold and 12-fold, respectively, relative to controls, 4 h after MeJA treatment, while endogeneous pools were unchanged. This suggests that only new carbon is utilized during early stages of defense induction. By 15 h, [C¹¹C]tyrosine and [¹¹C]phenylalanine returned to baseline while [¹¹C]tryptophan was elevated 30-fold, suggesting that MeJA exerts selective control over the shikimate pathway. Finally, we measured trans-cinnamic acid levels as a gauge of downstream phenolic metabolism. Levels were unchanged 4 h after MeJA treatment relative to controls, but were increased 2-fold by 15 h, indicating a lag in response of secondary metabolism.