The Use of Branching Agents in the Synthesis of PBAT.

Biodegradable polyesters represent an advanced alternative to polyolefin plastics in various applications. Polybutylene adipate terephthalate (PBAT) can compete with polyolefins in terms of their mechanical characteristics and melt processing conditions. The properties of PBAT depend on the molecular weight, dispersity, and architecture of the copolymer. Long-chain branching (LCB) of the PBAT backbone is an efficient method for the improvement of the copolymer characteristics. In the present work, we studied branching agents (BAs) 1-7 of different structures in the two-stage polycondensation of 1,4-butanediol, dimethyl terephthalate, and adipic acid and investigated the composition and melt rheology of the copolymers. According to the results of the research, 1,1,1-tris(hydroxymethyl)ethane 2 and 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid 5 outperformed glycerol 1 as BAs in terms of shear thinning behavior and viscoelasticity.

Functionalized Biodegradable Polymers via Termination of Ring-Opening Polymerization by Acyl Chlorides.

Aliphatic polyesters are an important class of polymeric materials for biomedical applications due to their versatile and tunable chemistry, biocompatibility and biodegradability. A capability of direct bonding with biomedically significant molecules, provided by the presence of the reactive end functional groups (FGs), is highly desirable for prospective polymers. Among FGs, N-hydroxysuccinimidyl activated ester group (NHS) and maleimide fragment (MI) provide efficient covalent bonding with -NH- and -SH containing compounds. In our study, we found that NHS- and MI-derived acyl chlorides efficiently terminate living ring-opening polymerization of ε-caprolactone, L-lactide, ethyl ethylene phosphonate and ethyl ethylene phosphate, catalyzed by 2,6-di-tert-butyl-4-methylphenoxy magnesium complex, with a formation of NHS- and MI-functionalized polymers at a high yields. Reactivity of these polymers towards amine- and thiol-containing model substrates in organic and aqueous media was also studied.

Rib fracture after median sternotomy for thymoma: an unreported complication.

A 47-year-old man was admitted to the clinic with histologically diagnosed thymoma of the anterior mediastinum, pT3N0M1a, stage IYA, type B3. He underwent surgery for primary tumor resection through a median sternotomy and left thoracotomy at the 7th intercostal space to remove pleural metastases. On the first postoperative day, massive bleeding occurred, a resternotomy was carried out but failed to save the patient. A fracture of the right first rib, which injured the right vertebral artery, had caused massive bleeding and was diagnosed at autopsy. Surgeons should keep in mind this potentially fatal complication of a median sternotomy.

A New Approach to Developing Long-Acting Injectable Formulations of Anti-HIV Drugs: Poly(Ethylene Phosphoric Acid) Block Copolymers Increase the Efficiency of Tenofovir against HIV-1 in MT-4 Cells.

Despite the world's combined efforts, human immunodeficiency virus (HIV), the causative agent of AIDS, remains one of the world's most serious public health challenges. High genetic variability of HIV complicates the development of anti-HIV vaccine, and there is an actual clinical need for increasing the efficiency of anti-HIV drugs in terms of targeted delivery and controlled release. Tenofovir (TFV), a nucleotide-analog reverse transcriptase inhibitor, has gained wide acceptance as a drug for pre-exposure prophylaxis or treatment of HIV infection. In our study, we explored the potential of tenofovir disoproxil (TFD) adducts with block copolymers of poly(ethylene glycol) monomethyl ether and poly(ethylene phosphoric acid) (mPEG-b-PEPA) as candidates for developing a long-acting/controlled-release formulation of TFV. Two types of mPEG-b-PEPA with numbers of ethylene phosphoric acid (EPA) fragments of 13 and 49 were synthesized by catalytic ring-opening polymerization, and used for preparing four types of adducts with TFD. Antiviral activity of [mPEG-b-PEPA]TFD or tenofovir disoproxil fumarate (TDF) was evaluated using the model of experimental HIV infection in vitro (MT-4/HIV-1IIIB). Judging by the values of the selectivity index (SI), TFD exhibited an up to 14-fold higher anti-HIV activity in the form of mPEG-b-PEPA adducts, thus demonstrating significant promise for further development of long-acting/controlled-release injectable TFV formulations.

Zirconium and hafnium complexes based on 2-aryl-8-arylaminoquinoline ligands: synthesis, molecular structure, and catalytic performance in ethylene copolymerization.

A general and efficient approach toward new zirconium and hafnium complexes based on 2-aryl-8-arylaminoquinoline ligands was developed. These precursors, when activated with MAO/borate cocatalyst and supported on silica, result in active olefin polymerization catalysts. The ethylene copolymers produced under industrially relevant conditions show very high molecular weights and unique microstructures defined by the multisite nature of the catalyst. A site-diversification mechanism is proposed to explain the presence of at least five individual sites, as deduced from 3D-TREF analysis of ethylene-butene copolymers.