Efficient Surface Passivation of Ti-Based Layered Materials by a Nonfluorine Branched Copolymer for Durable and High-Power Sodium-Ion Batteries.

There is a crucial need for low-cost energy storage technology based on abundant sodium ions to realize sustainable development with renewable energy resources. Poly(vinylidene fluoride) (PVDF) is applied as a binder in sodium-ion batteries (SIBs). Nevertheless, PVDF is also known to suffer from a larger irreversible capacity, especially when PVDF is used as the binder of negative electrode materials. In this research, a poly(acrylonitrile)-grafted poly(vinyl alcohol) copolymer (PVA-g-PAN) is tested as a binder with Ti-based layered oxides as potential negative electrode materials for SIBs. The chemical stability tests of PVDF and PVA-g-PAN contacted with metallic sodium have been conducted, which reveals that PVDF experiences a defluorination process, while PVA-g-PAN demonstrates excellent chemical stability. Composite electrodes with PVA-g-PAN demonstrate superior electrochemical performances when compared with the PVDF binder, allowing improvement for initial CE, higher rate capability, and long cyclability over 1500 cycles. Detailed characterization of electrodes via soft X-ray photoelectron spectroscopy and field emission scanning electron microscopy demonstrates that the PVA-g-PAN branched structure allows a more uniform distribution of acetylene black with higher coatability, unlocking enhanced rate performances and efficient passivation of Ti-based oxides without the excessive electrolyte decomposition. These findings open a new way to design practical and durable sodium-ion batteries with a high-power density.

Recent Advances in the Application of ATRP in the Synthesis of Drug Delivery Systems.

Advances in atom transfer radical polymerization (ATRP) have enabled the precise design and preparation of nanostructured polymeric materials for a variety of biomedical applications. This paper briefly summarizes recent developments in the synthesis of bio-therapeutics for drug delivery based on linear and branched block copolymers and bioconjugates using ATRP, which have been tested in drug delivery systems (DDSs) over the past decade. An important trend is the rapid development of a number of smart DDSs that can release bioactive materials in response to certain external stimuli, either physical (e.g., light, ultrasound, or temperature) or chemical factors (e.g., changes in pH values and/or environmental redox potential). The use of ATRPs in the synthesis of polymeric bioconjugates containing drugs, proteins, and nucleic acids, as well as systems applied in combination therapies, has also received considerable attention.

Toward Super-Tough Poly(l-lactide) via Constructing Pseudo-Cross-link Network in Toughening Phase Anchored by Stereocomplex Crystallites at the Interface.

We demonstrated a novel strategy to toughen poly(l-lactide) (PLLA) by constructing pseudo-cross-link networks based on chain entanglements of long-chain branched structure in the toughening phase, which were anchored by stereocomplex (SC) crystallites at the interface. The formation of pseudo-cross-link network was achieved by simple blending of the copolymer of long-chain branched polycaprolactone and poly(d-lactide) (LB-PCL- b-DLA) with PLLA without introducing any chemical cross-linking structure or nonbiodegradable component. The microscopic morphology analysis suggests that the interface-formed SC crystallites not only enhanced the interfacial interaction between LB-PCL and PLLA but also obviously increased the matrix crystallization rate. Different from those blends without SC crystallites or long-chain branched structures, nano-microgels were observed in chloroform solution of the PLLA/LB-PCL- b-DLA blend, suggesting the formation of pseudo-cross-link network. The pseudo-cross-link network in LB-PCL toughening phase endows PLLA a significantly improved impact toughness (49.5 kJ/m2), which is almost 13 times than that of neat PLLA. Moreover, matrix crystallinity and spherulite size of the PLLA matrix also play significant roles in toughening. Only sufficiently crystallized PLLA with proper spherulite size can effectively trigger the matrix shear yielding, meanwhile, facilitate the energy dissipating.

"Thiol-ene" grafting of silica particles with three-dimensional branched copolymer for HILIC/cation-exchange chromatographic separation and N-glycopeptide enrichment.

Three-dimensional branched copolymer, with N,N'-methylene bisacrylamide as the crosslinker and 3-allyloxy-2-hydroxy-1-propane sulfonic acid sodium salt as the monomer, was grafted from silica particles by thiol-ene click reaction. The obtained hydrophilic material with sulfonic acid groups was successfully applied for chromatography separation and glycopeptide enrichment. The separation mechanism was proven as the mixed mode of hydrophilic interaction and cation-exchange by investigating the effect of various chromatographic factors on the retention of polar analytes. By such mixed-mode chromatography, nucleosides, nucleobases, and acidic compounds were successfully separated. The column efficiency was up to 136,000 theoretical plates m-1 for cytidine, which was much higher than those of previous reports. Furthermore, benefitting from the large amount of hydrophilic groups provided by the branched copolymer, the material was used for the selective enrichment of glycopeptides. Results demonstrated the great potential of such material for chromatography separation and glycoproteome analysis. Graphical abstract The branched copolymer modified HILIC/cation-exchange particles Sil@Poly(AHPS-co-MBAAm) were prepared via thiol-ene click copolymerization reaction. Such Sil@Poly(AHPS-co-MBAAm) particles showed great performance in the separation of polar compounds and the enrichment of glycopeptides.

Hydrogen-bond interaction assisted branched copolymer HILIC material for separation and N-glycopeptides enrichment.

Hydrophilic interaction chromatography (HILIC) has attracted increasing attention in recent years due to its efficient application in the separation of polar compounds and the enrichment of glycopeptides. However, HILIC materials are still of weak hydrophilicity and thereby present weak retention and selectivity. In this work, branched copolymer modified hydrophilic material Sil@Poly(THMA-co-MBAAm), with high hydrophilicity and unique "claw-like" polyhydric groups, were prepared by "grafting from" thiol-ene click reaction. Due to the abundant functional groups provided by branched copolymer, the material showed excellent retention for nucleosides, necleobases, acidic compounds, sugars and peptides. Furthermore, Sil@Poly(THMA-co-MBAAm) was also applied for the N-glycosylation sites profiling towards the digests of the mouse brain, and 1997N-glycosylated peptides were identified, corresponding to 686 glycoprotein groups. Due to the assisted hydrogen-bond interaction, the selectivity for glycopeptide enrichment in the real sample reached 94.6%, which was the highest as far as we know. All these results indicated that such hydrogen-bond interaction assisted branched copolymer HILIC material possessed great potential for the separation and large scale glycoproteomics analysis.

Synthesis and in vivo magnetic resonance imaging evaluation of biocompatible branched copolymer nanocontrast agents.

Branched copolymer nanoparticles (D(h) =20-35 nm) possessing 1,4,7, 10-tetraazacyclododecane-N,N',N″,N‴-tetraacetic acid macrocycles within their cores have been synthesized and applied as magnetic resonance imaging (MRI) nanosized contrast agents in vivo. These nanoparticles have been generated from novel functional monomers via reversible addition-fragmentation chain transfer polymerization. The process is very robust and synthetically straightforward. Chelation with gadolinium and preliminary in vivo experiments have demonstrated promising characteristics as MRI contrast agents with prolonged blood retention time, good biocompatibility, and an intravascular distribution. The ability of these nanoparticles to perfuse and passively target tumor cells through the enhanced permeability and retention effect is also demonstrated. These novel highly functional nanoparticle platforms have succinimidyl ester-activated benzoate functionalities within their corona, which make them suitable for future peptide conjugation and subsequent active cell-targeted MRI or the conjugation of fluorophores for bimodal imaging. We have also demonstrated that these branched copolymer nanoparticles are able to noncovalently encapsulate hydrophobic guest molecules, which could allow simultaneous bioimaging and drug delivery.

Star-branched amphiphilic PLA-b-PDMAEMA copolymers for co-delivery of miR-21 inhibitor and doxorubicin to treat glioma.

The combined treatment of chemotherapeutant and microRNA (miR) has been proven to be a viable strategy for enhancing chemosensitivity due to its synergistic effect for tumor therapy. However, the co-delivery of drugs and genes remains a major challenge as they lack efficient co-delivery carriers. In this study, three amphiphilic star-branched copolymers comprising polylactic acid (PLA) and polydimethylaminoethyl methacrylate (PDMAEMA) with AB3, (AB3)2,and (AB3)3 molecular architectures were synthesized respectively by a combination of ring-opening polymerization, atom transfer radical polymerization, and click chemistry via an "arm-first" approach. The star copolymers possessed a low critical micelle concentration (CMC) and formed nano-sized micelles with positive surface charges in water as well as exhibiting a much lower cytotoxicity than PEI 25 kDa. Nevertheless, their gene transfection efficiency and tumor inhibition ability showed a remarkable dependence on their molecular architecture. The (AB3)3 architecture micelle copolymer exhibited the highest transfection efficiency, about 2.5 times higher than PEI. In addition, after co-delivering DOX and miR-21 inhibitor (miR-21i) into LN229 glioma cells, the micelles could mediate escaping miR-21i from lysosome degradation and the release of DOX to the nucleus, which significantly decreased the miR-21 expression. Moreover, co-delivery of DOX and miR-21i surprisingly exhibited an anti-proliferative efficiency compared with DOX or the miR-21i treatment alone. These results demonstrated that amphiphilic star-branched copolymers are highly promising for their combinatorial delivery of genes and hydrophobic therapeutants.