Development of a Robust PET-RAFT Polymerization Using Graphitic Carbon Nitride (g-C3N4)

The metal-free semiconductor, graphitic carbon nitride (g-C3N4), was introduced into RAFT polymerization for the first time. The production of linear polyacrylate and polyacrylamide has been achieved via PET-RAFT polymerization using g-C3N4 as a photoactive organocatalyst without prior deoxygenation. The resulting polymers display controlled molecular weights, narrow polymer dispersities, and high end-group fidelity as exemplified by 1H NMR analysis, MALDI-TOF-MS measurement, and chain extension experiment. Temporal control is illustrated by intermittent light and dark cycles, with polymer growth arrested in the absence of irradiation. The effects of changing RAFT agents (i.e., trithiocarbonates), solvents, catalyst concentrations, and degrees of polymerization in this system have been investigated. The successful polymerization of nonpurified monomer (i.e., still containing radical inhibitors) demonstrates the robust nature of the presented PET-RAFT system

Spider-silk inspired polymeric networks by harnessing the mechanical potential of β-sheets through network guided assembly.

The high toughness of natural spider-silk is attributed to their unique β-sheet secondary structures. However, the preparation of mechanically strong β-sheet rich materials remains a significant challenge due to challenges involved in processing the polymers/proteins, and managing the assembly of the hydrophobic residues. Inspired by spider-silk, our approach effectively utilizes the superior mechanical toughness and stability afforded by localised β-sheet domains within an amorphous network. Using a grafting-from polymerisation approach within an amorphous hydrophilic network allows for spatially controlled growth of poly(valine) and poly(valine-r-glycine) as β-sheet forming polypeptides via N-carboxyanhydride ring opening polymerisation. The resulting continuous β-sheet nanocrystal network exhibits improved compressive strength and stiffness over the initial network lacking β-sheets of up to 30 MPa (300 times greater than the initial network) and 6 MPa (100 times greater than the initial network) respectively. The network demonstrates improved resistance to strong acid, base and protein denaturants over 28 days

From UV to NIR: A Full-Spectrum Metal-Free Photocatalyst for Efficient Polymer Synthesis in Aqueous Conditions

Photo‐mediation offers unparalleled spatiotemporal control over controlled radical polymerizations (CRP). Photo‐induced electron/energy transfer reversible addition–fragmentation chain transfer (PET‐RAFT) polymerization is particularly versatile owing to its oxygen tolerance and wide range of compatible photocatalysts. In recent years, broadband‐ and near‐infrared (NIR)‐mediated polymerizations have been of particular interest owing to their potential for solar‐driven chemistry and biomedical applications. In this work, we present the first example of a novel photocatalyst for both full broadband‐ and NIR‐mediated CRP in aqueous conditions. Well‐defined polymers were synthesized in water under blue, green, red, and NIR light irradiation. Exploiting the oxygen tolerant and aqueous nature of our system, we also report PET‐RAFT polymerization at the microliter scale in a mammalian cell culture medium

Beyond Traditional RAFT: Alternative Activation of Thiocarbonylthio Compounds for Controlled Polymerization.

Recent developments in polymerization reactions utilizing thiocarbonylthio compounds have highlighted the surprising versatility of these unique molecules. The increasing popularity of reversible addition-fragmentation chain transfer (RAFT) radical polymerization as a means of producing well-defined, 'controlled' synthetic polymers is largely due to its simplicity of implementation and the availability of a wide range of compatible reagents. However, novel modes of thiocarbonylthio activation can expand the technique beyond the traditional system (i.e., employing a free radical initiator) pushing the applicability and use of thiocarbonylthio compounds even further than previously assumed. The primary advances seen in recent years are a revival in the direct photoactivation of thiocarbonylthio compounds, their activation via photoredox catalysis, and their use in cationic polymerizations. These synthetic approaches and their implications for the synthesis of controlled polymers represent a significant advance in polymer science, with potentially unforeseen benefits and possibilities for further developments still ahead. This Research News aims to highlight key works in this area while also clarifying the differences and similarities of each system

Progress and Perspectives Beyond Traditional RAFT Polymerization.

The development of advanced materials based on well-defined polymeric architectures is proving to be a highly prosperous research direction across both industry and academia. Controlled radical polymerization techniques are receiving unprecedented attention, with reversible-deactivation chain growth procedures now routinely leveraged to prepare exquisitely precise polymer products. Reversible addition-fragmentation chain transfer (RAFT) polymerization is a powerful protocol within this domain, where the unique chemistry of thiocarbonylthio (TCT) compounds can be harnessed to control radical chain growth of vinyl polymers. With the intense recent focus on RAFT, new strategies for initiation and external control have emerged that are paving the way for preparing well-defined polymers for demanding applications. In this work, the cutting-edge innovations in RAFT that are opening up this technique to a broader suite of materials researchers are explored. Emerging strategies for activating TCTs are surveyed, which are providing access into traditionally challenging environments for reversible-deactivation radical polymerization. The latest advances and future perspectives in applying RAFT-derived polymers are also shared, with the goal to convey the rich potential of RAFT for an ever-expanding range of high-performance applications

New Approaches towards the Design of Tough Amphiphilic Polymeric Co-networks

© The Royal Society of Chemistry 2020. Since the 1960s, polymer network hydrogels have been used for various applications. However, these applications have been restricted to non-load-bearing ones, due to the inherent mechanical weakness of common hydrogels. This weakness is attributed to the irregular crosslinking density, the high proportion of singly-attached (dangling and, therefore, elastically inactive) chains and the broadly varying distance between crosslinking points. In recent years, ground-breaking studies focusing on the development of novel approaches to fabricate near-ideal polymer network hydrogels with excellent mechanical properties have been developed. In this chapter, these new approaches will be outlined, with specific interest in amphiphilic polymer co-networks (APCNs), i.e. networks containing both hydrophilic and hydrophobic domains. The ability to generate these near-ideal networks, which often also possess 'smart' stimuli-responsive properties, would allow APCNs to be used in a wide range of advanced applications, including soft robotics, biomaterials and materials science. These new synthetic methodologies will be described in this chapter and will be separated into either fundamentally altering the network architecture and/or by employing facile and orthogonal coupling chemistries

Polyrotaxane-based thin film composite membranes for enhanced nanofiltration performance

© 2020 An urgent need exists for the development of advanced water purification technologies to meet the increasing global demand being placed on freshwater resources. Membrane-based separation technologies for size-selective contaminant removal represent a promising approach to achieve this goal. Here, a novel thin film composite nanofiltration membrane is prepared via interfacial polymerization of α-cyclodextrin on a commercially available polyacrylonitrile substrate. Subsequent in-situ inclusion complexation of alkyne-functionalized poly(ethylene glycol) (PEG) is then used to tune the polyrotaxane-based pores for size-dependent filtration. The resultant membrane shows excellent size-selective rejection rates for organic dye (e.g. rhodamine B, >99%) as well as heavy-metal ions (e.g. Co(II), >90%), while crucially maintaining high water permeance (e.g. H2O: 7.1 L h−1 m−2 bar−1). The facile and straightforward synthetic approach to the fabrication of polyrotaxane nanofiltration membranes, combined with their strong nanofiltration separation performance, holds significant promise for membrane-based water purification applications

Novel cyclic di-GMP effectors of the YajQ protein family control bacterial virulence

Bis-(3 ',5 ') cyclic di-guanylate (cyclic di-GMP) is a key bacterial second messenger that is implicated in the regulation of many critical processes that include motility, biofilm formation and virulence. Cyclic di-GMP influences diverse functions through interaction with a range of effectors. Our knowledge of these effectors and their different regulatory actions is far from complete, however. Here we have used an affinity pull-down assay using cyclic di-GMP-coupled magnetic beads to identify cyclic di-GMP binding proteins in the plant pathogen Xanthomonas campestris pv. campestris (Xcc). This analysis identified XC_3703, a protein of the YajQ family, as a potential cyclic di-GMP receptor. Isothermal titration calorimetry showed that the purified XC_3703 protein bound cyclic di-GMP with a high affinity (K-d similar to 2 mu M). Mutation of XC_3703 led to reduced virulence of Xcc to plants and alteration in biofilm formation. Yeast two-hybrid and far-western analyses showed that XC_3703 was able to interact with XC_2801, a transcription factor of the LysR family. Mutation of XC_2801 and XC_3703 had partially overlapping effects on the transcriptome of Xcc, and both affected virulence. Electromobility shift assays showed that XC_3703 positively affected the binding of XC_2801 to the promoters of target virulence genes, an effect that was reversed by cyclic di-GMP. Genetic and functional analysis of YajQ family members from the human pathogens Pseudomonas aeruginosa and Stenotrophomonas maltophilia showed that they also specifically bound cyclic di-GMP and contributed to virulence in model systems. The findings thus identify a new class of cyclic di-GMP effector that regulates bacterial virulence

Vitamin D supplementation and breast cancer prevention : a systematic review and meta-analysis of randomized clinical trials

In recent years, the scientific evidence linking vitamin D status or supplementation to breast cancer has grown notably. To investigate the role of vitamin D supplementation on breast cancer incidence, we conducted a systematic review and meta-analysis of randomized controlled trials comparing vitamin D with placebo or no treatment. We used OVID to search MEDLINE (R), EMBASE and CENTRAL until April 2012. We screened the reference lists of included studies and used the “Related Article” feature in PubMed to identify additional articles. No language restrictions were applied. Two reviewers independently extracted data on methodological quality, participants, intervention, comparison and outcomes. Risk Ratios and 95% Confident Intervals for breast cancer were pooled using a random-effects model. Heterogeneity was assessed using the I2 test. In sensitivity analysis, we assessed the impact of vitamin D dosage and mode of administration on treatment effects. Only two randomized controlled trials fulfilled the pre-set inclusion criteria. The pooled analysis included 5372 postmenopausal women. Overall, Risk Ratios and 95% Confident Intervals were 1.11 and 0.74–1.68. We found no evidence of heterogeneity. Neither vitamin D dosage nor mode of administration significantly affected breast cancer risk. However, treatment efficacy was somewhat greater when vitamin D was administered at the highest dosage and in combination with calcium (Risk Ratio 0.58, 95% Confident Interval 0.23–1.47 and Risk Ratio 0.93, 95% Confident Interval 0.54–1.60, respectively). In conclusions, vitamin D use seems not to be associated with a reduced risk of breast cancer development in postmenopausal women. However, the available evidence is still limited and inadequate to draw firm conclusions. Study protocol code: FARM8L2B5L