This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669) and the second in December 2009 (Aust. J. Chem. 2009, 62, 1402). This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Living Radical Polymerization by the RAFT Process - A Second Update

Radical addition-fragmentation chemistry in polymer synthesis

A living radical polymerization (LRP) is a free radical polymerization that aims at displaying living character, (i.e., does not terminate or transfer and is able to continue polymerization once the initial feed is exhausted by addition of more monomer). However, termination reactions are inherent to a radical process, and modern LRP techniques seek to minimize such reactions, therefore providing control over the molecular weight and the molecular weight distribution of a polymeric material. In addition, the better LRP techniques incorporate many of the desirable features of traditional free radical polymerization, such as compatibility with a wide range of monomers, tolerance of many functionalities, and facile reaction conditions. The control of molecular weight and molecular weight distribution has enabled access to complex architectures and site specific functionality that were previously impossible to achieve via traditional free radical polymerizations. These LRPs are classified in three different subgroups: (1) stable free-radical polymerization such as nitroxide mediated polymerization (NMP),1,2 (2) degenerative transfer polymerization, such as iodine transfer polymerization (ITP and RITP),3,4 single electron transfer-degenerative transfer living radical polymerization(SET-DTLRP),5,6reversibleaddition-fragmentation chain transfer (RAFT),7,8 and macromolecular design via the interchange of xanthates (MADIX)9,10 polymerization, and (3) metal mediated catalyzed polymerization, such as atom transfer radical polymerization (ATRP),11-14 single electron transfer-living radical polymerization (SET-LRP),15 and organotellurium mediated living radical polymrization16-19 Among the existing LRP techniques, RAFT and MADIX are probably the most versatile processes, as they are tolerant * E-mail: T.P.D., T.Davis@UNSW.edu.au; S.P., S.Perrier@ chem.usyd.edu.au. † Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences & Engineering, UNSW. ‡ Centre for Advanced Macromolecular Design (CAMD), School of Biotechnology & Biomolecular Sciences, UNSW. § The University of Sydney. Chem. Rev. 2009, 109, 5402–5436 5402

Bioapplications of RAFT polymerization.

Thermosensitive water-soluble copolymers with doubly responsive reversibly interacting entities

Reversible addition–fragmentation chain transfer (RAFT) radical polymerization and the synthesis of water-soluble (co)polymers under homogeneous conditions in organic and aqueous media

We report aqueous, room temperature RAFT polymerization of N-isopropylacrylamide (NIPAM) and, subsequently, its block copolymerization utilizing a poly(N,N-dimethylacrylamide) macro-CTA. A series of thermally responsive AB diblock and ABA triblock copolymers have been prepared. These polymers contain hydrophilic N,N-dimethylacrylamide (DMA) A blocks of fixed molecular weight and temperature-responsive NIPAM B blocks of varied chain length. Using a combination of 1H NMR spectroscopy, T2 relaxation measurements, dynamic light scattering (DLS), and static light scattering (SLS), we demonstrate that these block copolymers are indeed capable of reversibly forming micelles in response to changes in solution temperature and that the micellar size and transition temperature are dependent on both the NIPAM block length and the polymer architecture (diblock vs triblock).

Direct Synthesis of Thermally Responsive DMA/NIPAM Diblock and DMA/NIPAM/DMA Triblock Copolymers via Aqueous, Room Temperature RAFT Polymerization†

Background. Hepatocellular carcinoma (HCC) (hepatocarcinoma) is the most common (about 85% of cases) malignant liver tumor originating from hepatocytes. According to officially published statistics for the city of Moscow for 2019,329 people were registered with the first-ever diagnosed C22 malignant neoplasms (liver and intrahepatic bile ducts, including 6.7% of those who were actively identified. The absolute number of such patients registered at the end of the year was 716, which is 5.7 per 100 000 of the population. The contingent accumulation index is 2.2 (the average for Russia is 1.5). With that,43.1% of patients had stage IV. Mortality rate during the first year after diagnosis is 53.9% (in Russia on the whole, this value is 66.5%). Drug systemic therapy is the method of choice for HCC which is not subject to surgical intervention and local methods of treatment. 
Materials and methods. A retrospective analysis of the efficacy and safety of lenvatinib in patients diagnosed with HCC was carried out in real clinical practice at the Outpatient Oncology Care Center of the Moscow City Oncological Hospital №62. The data analysis covers the period from February 2016 to June 2021. The analysis included 15 patients with a morphologically verified diagnosis of HCC treated with lenvatinib. For the majority of patients,11 (73.3%) patients received lenvatinib as first-line therapy. 
Results. The median progression-free survival was 11.2 months for the entire observation group. In the first line of therapy, the PFS result was the highest and amounted to 12.3 months. The median dose received by patients was 10.9 mg. The level of disease control was 86.6%. The most clinically significant adverse events were grade 2 neutropenia, grade 2 thrombocytopenia, grade 2 asthenia, grade 23 hypertension. Lenvatinib had a manageable safety profile. 
Conclusion. The performed analysis confirms the data of the REFLECT study on the efficacy of lenvatinib both in healthy patients and in patients with a spectrum of comorbidities with significant (more than 50% of the liver parenchyma) liver damage.

Own Experience of Using Lenvatinib in Patients with Advanced Hepatocellular Carcinoma in Real Clinical Practice based on Moscow City Oncological Hospital №62

Yuliya Vasileva

Papers

Direct Synthesis of Thermally Responsive DMA/NIPAM Diblock and DMA/NIPAM/DMA Triblock Copolymers via Aqueous, Room Temperature RAFT Polymerization†

Own Experience of Using Lenvatinib in Patients with Advanced Hepatocellular Carcinoma in Real Clinical Practice based on Moscow City Oncological Hospital №62