Development of an Ionic Conductive Elastomer from the Photocopolymerization of a Ternary Polymerizable Deep Eutectic Solvent for Human Motions Sensing.

Polymerizable deep eutectic solvents (PDES) represent a novel class of ionic liquids characterized by the presence of polymerizable groups in their hydrogen-bond donor or acceptor components. Within the realm of flexible electronics, PDES is emerged as a promising material for the fabrication of sensors that exhibit both flexibility and stretchability. This research employs the UV-initiated photocopolymerization of a ternary PDES composed of choline chloride (ChCl), 2-hydroxyethyl acrylate (HEA), and itaconic acid (IA), to synthesize an ionic conductive elastomer (ICE) that boasts desirable comprehensive performances, which can be controlled by meticulously adjusting the ratios of these components.

Advanced Biomaterials Derived from Functional Polyphosphoesters: Synthesis, Properties, and Biomedical Applications.

Polyphosphoesters (PPEs) represent an innovative class of biodegradable polymers, with the phosphate ester serving as the core repeating unit of their polymeric backbone. Recently, biomaterials derived from functionalized PPEs have garnered significant interest in biomedical applications because of their commendable biocompatibility, biodegradability, and the capacity for functional modification. This review commences with a brief overview of synthesis methodologies and the distinctive properties of PPEs, including thermoresponsiveness, degradability, stealth effect, and biocompatibility.

Synthesis and Characterization of Graft Copolymers with Poly(ε-caprolactone) Side Chain Using Hydroxylated Poly(β-myrcene--α-methyl styrene).

Graft copolymers have unique application scenarios in the field of high-performance thermoplastic elastomers, resins and rubbers. β-myrcene (My) is a biomass monomer derived from renewable plant resources, and its homopolymer has a low glass transition temperature and high elasticity. In this work, a series of tapered copolymers P(My--AMS) (k = 1, 2, 3) were first synthesized in cyclohexane by one-pot anionic polymerization of My and α-methyl styrene (AMS) using sec-BuLi as the initiator.

A nanomedicine composed of polymer-ss-DOX and polymer-Ce6 prodrugs with monoclonal antibody targeting effect for anti-tumor chemo-photodynamic synergetic therapy.

Anticancer drugs used for systemic chemotherapy often exhibit off-target toxicity and uncontrolled drug release due to their lack of targeting. To improve the bioavailability of drugs and reduce side effects, we have developed a mixed micelle of nanomedicine composed of two prodrugs with surface modified monoclonal antibody for cancer therapy. In this system, Nimotuzumab was used as targeting ligands of the mixed micelles (named as DCMMs) that is composed of polymer-doxorubicin prodrug (abbreviated as PEG-b-P(GMA-ss-DOX)) and maleimide polyethylene glycol-chlorin e6 (abbreviated as Mal-PEG-Ce6).

Unexpected mechanically robust ionic conductive elastomer constructed from an itaconic acid-involved polymerizable DES.

An ionic conductive elastomer with good comprehensive properties is constructed from a ternary polymerizable deep eutectic solvent (PDES) containing choline chloride, acrylic acid and itaconic acid (IA). The IA component is found to boost the synergetic hydrogen bonds and greatly improve the mechanical strength of elastomer.

A CD326 monoclonal antibody modified core cross-linked curcumin-polyphosphoester prodrug for targeted delivery and cancer treatment.

Stimuli-responsive cross-linked micelles (SCMs) are ideal nanocarriers for anti-cancer drugs. Compared with non-cross-linked micelles, SCMs exhibit superior structural stability. At the same time, the introduction of an environmentally sensitive crosslinker into a drug delivery system allows SCMs to respond to single or multiple stimuli in the tumor microenvironment, which can minimize drug leakage during the blood circulation process.

Development of multifunctional ionogels derived from a dynamic deep eutectic solvent.

A new polymerizable and dynamic deep eutectic solvent (DES) consisting of choline chloride and α-lipoic acid is proposed. By virtue of thermally-initiated ring-opening polymerization (ROP) of cyclic disulfide and multiple dynamic interactions (disulfide, hydrogen, and coordination bonds), multifunctional ionogels with good comprehensive properties are developed and explored as potential flexible conductors.

Dextran-doxorubicin prodrug nanoparticles conjugated with CD147 monoclonal antibody for targeted drug delivery in hepatoma therapy.

Antibody-drug conjugates (ADCs) are a class of tumor cell-targeting drugs that have developed rapidly in recent years. From the perspective of further improving ADC targeting and developing natural macromolecules as drug carriers, it is still challenging and necessary to try new targeted drug delivery modalities. In this study, we have developed an antibody-modified prodrug nanoparticle based on biomacromolecule dextran (DEX) to delivery antitumour drug doxorubicin (DOX).

A hybrid hydrogel constructed using drug loaded mesoporous silica and multiple response copolymer as an intelligent dressing for wound healing of diabetic foot ulcers.

Traditional wound dressings have poor mechanical properties and a single function, which cannot achieve rapid healing of diabetic wounds in a unique physiological microenvironment. In order to develop multifunctional hydrogel dressings with appropriate biological activity to accelerate wound healing and obtain better clinical therapeutic effects, herein we report a hybrid system based on drug loaded mesoporous silica and injectable polymer hydrogels mixed with hypoglycemic drug metformin (Met) as a dressing for diabetic wounds. Firstly, a copolymer with the phenylboronic acid group in the side group, poly(acrylamide--dimethylaminopropylacrylamide--methacrylamidophenylboronic acid) (abbreviated as PB), was prepared.

CD163 Monoclonal Antibody Modified Polymer Prodrug Nanoparticles for Targeting Tumor-Associated Macrophages (TAMs) to Enhance Anti-Tumor Effects.

Tumor-associated macrophages (TAMs)-based immunotherapy is a promising strategy. Since TAMs are mainly composed of M2-type macrophages, they have a promoting effect on tumor growth, invasion, and metastasis. M2-type macrophages contain a specific receptor CD163 on their surface, providing a prerequisite for active targeting to TAMs.

Injectable and Degradable POSS-Polyphosphate-Polysaccharide Hybrid Hydrogel Scaffold for Cartilage Regeneration.

The limited self-repair capacity of articular cartilage has motivated the development of stem cell therapy based on artificial scaffolds that mimic the extracellular matrix (ECM) of cartilage tissue. In view of the specificity of articular cartilage, desirable tissue adhesiveness and stable mechanical properties under cyclic mechanical loads are critical for cartilage scaffolds. Herein, we developed an injectable and degradable organic-inorganic hybrid hydrogel as a cartilage scaffold based on polyhedral oligomeric silsesquioxane (POSS)-cored polyphosphate and polysaccharide.

A dual-response drug delivery system with X-ray and ROS to boost the anti-tumor efficiency of TPZ enhancement of tumor hypoxia levels.

The selective anti-tumor activity and less toxic nature of hypoxia-activated prodrugs including tirapazamine (TPZ) are harbored by hypoxia levels in tumors, the inadequacy of which leads to failure in clinical trials. Thus, the development of effective clinical applications of TPZ requires advanced strategies to intensify hypoxia levels in tumors effectively and safely. In this study, we designed and fabricated a paclitaxel (PTX)-loaded dual-response delivery system with a low dose (, 2 Gy) of X-ray and reactive oxygen species on the basis of diselenide block copolymers.

Functional cRGD-Conjugated Polymer Prodrug for Targeted Drug Delivery to Liver Cancer Cells.

To overcome the limitation of conventional nanodrugs in tumor targeting efficiency, coupling targeting ligands to polymeric nanoparticles can enhance the specific binding of nanodrugs to tumors. Cyclo(Arg-Gly-Asp-d-Phe-Lys) (abbreviated as c(RGDfK)) peptide has been widely adopted due to its high affinity to the tumor marker αβ integrin receptor. In this study, we develop a cRGD peptide-conjugated camptothecin (CPT) prodrug, which enables self-assembly of nanoparticles for precise targeting and enrichment in tumor tissue.

ABC-Type, Bola-Form Giant Surfactants: Synthesis and Self-Assembly.

Due to the fast phase separation kinetics and small feature size, the self-assembly of giant molecules has attracted lots of attention. However, there is not much study on multicomponent giant surfactants. In this work, through a modular synthetic strategy, different polyhedral oligomeric silsesquioxane (POSS)-based molecular nanoparticles are installed with diverse functionalities (hydrophobic octavinyl POSS (VPOSS), hydrophilic dihydroxyl-functionalized POSS (DPOSS), and omniphobic perfluoroalkyl-chain-functionalized POSS (FPOSS)) on the ends of one polystyrene (PS) chain to build up a series of triblock bola-form giant surfactants denoted as XPOSS-PS -FPOSS (X represents V or D).

CD147 Monoclonal Antibody Targeted Reduction-Responsive Camptothecin Polyphosphoester Nanomedicine for Drug Delivery in Hepatocellular Carcinoma Cells.

In the treatment of tumor-targeted small-molecule anti-cancer drugs, antibody-mediated therapies, especially for antibody-drug conjugates (ADCs), have revealed great latent force. However, the therapeutic drugs provided by ADCs possess limitation. Considering that the combination of antibodies and nano-drugs can broaden their applicability in the field of tumor treatment, herein, we developed an antibody conjugated polymeric prodrug nanoparticles SAE-PEG--PBYP--CPT for targeted camptothecin (CPT) delivery to liver tumor cells.

Glucose-Sensitive Core-Cross-Linked Nanoparticles Constructed with Polyphosphoester Diblock Copolymer for Controlling Insulin Delivery.

This work aims to construct biocompatible, biodegradable core-cross-linked and insulin-loaded nanoparticles which are sensitive to glucose and release insulin via cleavage of the nanoparticles in a high-concentration blood glucose environment. First, a polyphosphoester-based diblock copolymer (PBYP--Gluc)--PEEP was prepared via ring-opening copolymerization (ROP) and the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) in which PBYP and PEEP represent the polymer segments from 2-(but-3-yn-1-yloxy)-2-oxo-1,3,2-dioxaphospholane and 2-ethoxy-2-oxo-1,3,2-dioxaphospholane, respectively, and Gluc comes from 2-azidoethyl-β-d-glucopyranoside (Gluc-N) that grafted with PBYP. The structure and molecular weight of the copolymer were characterized by H NMR, P NMR, GPC, FT-IR, and UV-vis measurements.

Glucose-Sensitive Polyphosphoester Diblock Copolymer for an Insulin Delivery System.

In this study, we report a diblock copolymer based on a polyphosphate backbone and pendant phenylboronic acid with glucose sensitivity. The copolymer, abbreviated as (PBYP--MPBA)--PEEP, was prepared via a combination of ring-opening copolymerization, "click" chemistry, and amide reaction, in which the PBYP and PEEP blocks, respectively, represent two kinds of polyphosphoester structures and MPBA represents 3-mercaptopropionic acid modified with 3-aminophenylboronic acid. The amphiphilic copolymer (PBYP--MPBA)--PEEP could self-assemble into core-shell nanoparticles (NPs) in aqueous solutions.

Low-Dose X-ray-Responsive Diselenide Nanocarriers for Effective Delivery of Anticancer Agents.

X-ray-responsive nanocarriers for anticancer drug delivery have shown great promise for enhancing the efficacy of chemoradiotherapy. A critical challenge remains for development of such radiation-controlled drug delivery systems (DDSs), which is to minimize the required X-ray dose for triggering the cargo release. Herein, we design and fabricate an effective DDS based on diselenide block copolymers (as nanocarrier), which can be triggered to release their cargo with a reduced radiation dose of 2 Gy due to their sensitivity to both X-ray and the high level of reactive oxygen species (ROS) in the microenvironment of cancer cells.

Fabrication of aminated poly(glycidyl methacrylate)-based polymers for co-delivery of anticancer drugs and the p53 gene.

Aminated poly(glycidyl methacrylate)s-based polymers for gene delivery not only can reduce toxicity and improve solubility, but can improve gene transfection efficiency and reduce protein aggregation. In this study, we first prepared poly(glycidyl methacrylate) (PGMA) via reversible addition-fragmentation chain transfer (RAFT) polymerization, and then the obtained PGMA homopolymer was post-modified with ethanol amine (EA), 1-amino-2-propanol (AP), 3-(dibutylamino)propylamine (DA) and N-(2-hydroxyethyl)ethylenediamine (HA), respectively, to yield four kinds of PGMA-based gene vectors containing hydroxyl groups (abbreviated as PGEA, PGAP, PGDA and PGHA). The effects of the different side chains and hydroxyl groups on the biological properties of these four cationic polymers were investigated.

A fully degradable and photocrosslinked polysaccharide-polyphosphate hydrogel for tissue engineering.

Extracellular matrix degradability meditates cell behaviors and gains increasing importance in the development of implantation materials for tissue engineering. Here, we developed a fully biodegradable hydrogel combining the unique features of synthetic polyphosphate polymer and natural polysaccharide polymer. Polyphosphate copolymer poly(butynyl phospholane)-random-poly(ethylethylene phosphate) (PBYP-r-PEEP) bearing pendent alkynes was synthesized through a facile one-pot reaction.

Efficient Click Synthesis of a Protonized and Reduction-Sensitive Amphiphilic Small-Molecule Prodrug Containing Camptothecin and Gemcitabine for a Drug Self-Delivery System.

Drug self-delivery systems consisting of small-molecule active drugs with nanoscale features for intracellular delivery without the need for additional polymeric carriers have drawn much attention recently. In this work, we proposed a highly efficient strategy to fabricate protonized and reduction-responsive self-assembled drug nanoparticles from an amphiphilic small-molecule camptothecin-ss-1,2,3-triazole-gemcitabine conjugate (abbreviated as CPT-ss-triazole-GEM) for combination chemotherapy, which was prepared via a Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) "click" reaction. To obtain this drug-triazole-drug conjugate, we first prepared a CPT derivate containing a propargyl group linked with a disulfide group and a GEM derivate attached to an azide group.

Polymer-Doxorubicin Prodrug with Biocompatibility, pH Response, and Main Chain Breakability Prepared by Catalyst-Free Click Reaction.

Click chemistry has increasing applications of the development of polymer materials and modification of drug carriers. The amino-yne click polymerization reacts quickly at room temperature without catalyst, and the enamine bond (--) gained from the reaction is sensitive to acid and can be used to prepare stimulus-responsive polymeric prodrugs. Herein, we report an alkynyl-terminated polymer containing alternately distributed low molecular weight polyethylene glycol (PEG) and hexamethylenediamino (HMDA) linked by enamine bonds, abbreviated as A-P(PEG-HMDA)A, which was synthesized within 3 h at 35 °C without catalyst.

Versatile Construction of Single-Tailed Giant Surfactants with Hydrophobic Poly(ε-caprolactone) Tail and Hydrophilic POSS Head.

Giant surfactants refer to a new kind of amphiphile by incorporating functional molecular nanoparticles with polymer tails. As a size-amplified counterpart of small-molecule surfactants, they serve to bridge the gap between small-molecule surfactants and amphiphilic block copolymers. This work reports the design and synthesis of single-tailed giant surfactants carrying a hydrophobic poly(ε-caprolactone) (PCL) as the tail and a hydrophilic cage-like polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the head.

Zwitterionic shielded polymeric prodrug with folate-targeting and pH responsiveness for drug delivery.

Zwitterionic polymers are a class of polymers that acts as both Lewis base and Lewis acid in solution. These polymers not only have excellent properties of hydration, anti-bacterial adhesion, charge reversal and easy chemical modification, but also have characteristics of long-term circulation and suppress nonspecific protein adsorption in vivo. Here, we describe a novel folate-targeted and acid-labile polymeric prodrug under the microenvironment of tumor cells, abbreviated as FA-P(MPC-co-PEGMA-BZ)-g-DOX, which was synthesized via a combination of reversible addition-fragmentation chain transfer (RAFT) copolymerization, Schiff-base reaction, Click chemistry, and a reaction between the amine group of doxorubicin (DOX) and aldehyde functionalities of P(MPC-co-PEGMA-BZ) pendants, wherein MPC and PEGMA-BZ represent 2-(methacryloyloxy)ethyl phosphorylcholine and polyethylene glycol methacrylate ester benzaldehyde, respectively.

Multifunctional Polymeric Prodrug with Simultaneous Conjugating Camptothecin and Doxorubicin for pH/Reduction Dual-Responsive Drug Delivery.

Amphiphilic polymeric prodrugs show improved therapeutic indices with respect to traditional hydrophobic anticancer drugs because these prodrugs can self-assemble into nanoparticles, prolong the circulation of drugs in the blood, improve the accumulation of drugs in the disease site, reduce the side effects of drugs, and achieve therapeutic effect. Here, we describe a novel pH/reduction dual-responsive polymeric prodrug, abbreviated as CPT- ss-poly(BYP- co-EEP), with simultaneous conjugating camptothecin (CPT) and doxorubicin (DOX), wherein BYP and EEP represent two cyclic phosphate monomers, respectively, that is, 2-(but-3-yn-1-yloxy)-2-oxo-1,3,2-dioxaphospholane and 2-ethoxy-2-oxo-1,3,2-dioxaphospholane. This prodrug was prepared through a polyphosphoester-DOX conjugate using a CPT derivative (CPT- ss-OH) as the initiator.