Search

Dynamic hydrogels are attractive platforms for tissue engineering and regenerative medicine due to their ability to mimic key extracellular matrix (ECM) mechanical properties like strain-stiffening and stress relaxation while enabling enhanced processing characteristics like injectability, 3D printing, and self-healing. Systems based on imine-type dynamic covalent chemistry (DCvC) have become increasingly popular. However, most reported polymers comprising aldehyde groups are based on either end-group-modified synthetic or side-chain-modified natural polymers; synthetic versions of side-chain-modified polymers are noticeably absent. To facilitate access to new classes of dynamic hydrogels, we report the straightforward synthesis of a water-soluble copolymer with a tunable fraction of pendant aldehyde groups (12-64%) using controlled radical polymerization and their formation into hydrogel biomaterials with dynamic cross-links. We found the polymer synthesis to be well-controlled with the determined reactivity ratios consistent with a blocky gradient microarchitecture. Subsequently, we observed fast gelation kinetics with imine-type cross-linking. We were able to vary hydrogel stiffness from ≈2 to 20 kPa, tune the onset of strain-stiffening toward a biologically relevant regime (σ c ≈ 10 Pa), and demonstrate cytocompatibility using human dermal fibroblasts. Moreover, to begin to mimic the dynamic biochemical nature of the native ECM, we highlight the potential for temporal modulation of ligands in our system to demonstrate ligand displacement along the copolymer backbone via competitive binding. The combination of highly tunable composition, stiffness, and strain-stiffening, in conjunction with spatiotemporal control of functionality, positions these cytocompatible copolymers as a powerful platform for the rational design of next-generation synthetic biomaterials.

Monitoring of intracellular pH is of great importance since deviation of this parameter from the "normal" magnitudes can be considered as an indicator of various pathologies. Thus, the development of new efficient and biocompatible sensors suitable for application in biological systems and capable of quantitative pH estimation remains an urgent chemical task. Herein, we report the synthesis of a series of phosphorescent rhenium [Re(NN)(CO) 2 (PR 3 ) 2 ] + complexes based on the NN diimine ligands containing pH-responsive carboxylic groups and styrene-containing phosphine ligands. The complexes, which display the highest pH sensitivity, were copolymerized with polyvinylpyrrolidone using the RAFT protocol to impart water solubility and to protect the chromophores from interaction with molecular oxygen. The resulting copolymers show an emission lifetime response onto pH variations in the physiological range. Cellular experiments with Chinese hamster ovary cells (CHO-K1) reveal easy internalization of the probes in cell culture and an approximately uniform distribution in cells, with some preference for location in acidic compartments (late endosomes and lysosomes). Using nigericin to homogenize intra- and extracellular pH, we built a calibration of lifetime versus pH in live CHO-K1 cells. Analysis of the phosphorescence lifetime imaging microscopy (PLIM) data confirms the applicability of the obtained sensors for monitoring the intracellular pH in cell cultures.

A novel inorganic-organic-inorganic ternary bioactive material formulated on antimicrobial peptide-based polymer has been reported. Supramolecular approach has been employed to incorporate molecularly crowded tyrosine-based polymer stabilized silver nanoparticles into membrane bound vesicles exploiting polyoxometalate-triggered surface templating strategy. Utilizing the covalent reversible addition fragmentation chain transfer (RAFT) polymerization and exploiting templated supramolecular architectonics at biopolymer interface, the bioactive ternary polymeric nanohybrids have been designed against Shigellosis leveraging the antibacterial activities of silver nanoparticle, cationic amphiphilic tyrosine polymer and inorganic polyoxometalate. The detail investigation against Shigella flexneri 2a cell line demonstrates that the collaborative mechanism of the ternary hybrid composite enhances the bactericidal activity in comparison to only polyoxometalate and polymer stabilized silver nanoparticle with an altered mechanism of action which is established via detailed biological analysis., (© 2024 Wiley-VCH GmbH.)

Temperature-responsive hydrogels, or thermogels, have emerged as a leading platform for sustained delivery of both small molecule drugs and macromolecular biologic therapeutics. Although thermogel properties can be modulated by varying the polymer's hydrophilic-hydrophobic balance, molecular weight and degree of branching, varying the supramolecular donor-acceptor interactions on the polymer remains surprisingly overlooked. Herein, to study the influence of enhanced hydrogen bonding on thermogelation, we synthesized a family of amphiphilic polymers containing urea and urethane linkages using quinuclidine as an organocatalyst. Our findings showed that the presence of strongly hydrogen bonding urea linkages significantly enhanced polymer hydration in water, in turn affecting hierarchical polymer self-assembly and macroscopic gel properties such as sol-gel phase transition temperature and gel stiffness. Additionally, analysis of the sustained release profiles of Aflibercept, an FDA-approved protein biologic for anti-angiogenic treatment, showed that urea bonds on the thermogel were able to significantly alter the drug release mechanism and kinetics compared to usage of polyurethane gels of similar composition and molecular weight. Our findings demonstrate the unrealized possibility of modulating gel properties and outcomes of sustained drug delivery through judicious variation of hydrogen bonding motifs on the polymer structure., (© 2024 Wiley-VCH GmbH.)

A pH/temperature bi-responsive gallic acid magnetic imprinted polymer (PTBG-MIP) was synthesized on a Fe 3 O 4 @SiO 2 @KH570 carrier using methacrylic acid (MAA), p-Vinylphenylboronic acid (p-VPBA), and N-isopropyl-acrylamide (NIPAAm) as complex functional monomers. The density functional theory (DFT) was employed to optimize the molar ratio of multi-functional monomers-template complex, which proved to be an effective tool for predicting complex configuration based on electrostatic potential (ESP) analysis and the lowest binding energy. DFT calculation and analysis determined the optimized molar ratio of 2:1:1:1 for GA-MAA-NIPAAm-p-VPBA, which showed good agreement with experimental results. The PTBG-MIP-4 obtained under the optimized conditions exhibited high pH- and temperature- dependence in rebinding the template, displaying a maximum adsorption capacity (Q e ) of 62.26 mg g -1 and a highest selection factor (α) of 5.217. Additionally, the PTBG-MIP-4 exhibited exceptional physicochemical properties encompassing magnetization characteristics, morphology, surface sites distribution, and adsorption performance. The application efficiency of this imprinted composite in the extraction and purification of gallic acid from Galla chinensis was remarkably demonstrated., Competing Interests: Declaration of competing interest My major investigation fields lie to two aspects: (1) molecularly imprinted polymer and (2) chromatographic separation and analysis. Recently, my interest aims at creating novel approach to perform solid phase extraction of bioactive compounds from some Traditional Chinese Medicine and at developing new molecularly imprinted polymers material as stationary phase in liquid phase and gas chromatography., (Copyright © 2024. Published by Elsevier B.V.)

Sulfur dioxide (SO 2 ) has emerged as a promising gasotransmitter for various therapeutic applications, including antibacterial activities. However, the potential of polymeric SO 2 donors for antimicrobial activities remains largely unexplored. Herein, we report a water-soluble, redox-responsive, SO 2 -releasing amphiphilic block copolymer poly(polyethylene glycol methyl ether methacrylate) (PPEGMA)- b -poly(2-((2,4-dinitrophenyl)sulfonamido)ethyl methacrylate (PM)) (BCPx) to investigate their antibacterial properties. BCPx contains hydrophilic polyethylene glycol (PEG) pendants and a hydrophobic SO 2 -releasing PM block, facilitating the formation of self-assembled nanoparticles (BCPxNp) in an aqueous medium, studied by critical aggregation concentration (CAC) measurements, dynamic light scattering (DLS), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). BCPxNp exhibits sustained SO 2 release up to 12 h in the presence of glutathione (GSH), with a yield of 30-80% of theoretical SO 2 release. In vitro antibacterial studies unveil the outstanding antibacterial activity of BCP3Np against Gram-positive bacteria Bacillus subtilis , as evidenced by FESEM and live/dead cell fluorescence assay. We further elucidate the antibacterial mechanism through reactive oxygen species (ROS) generation studies. Overall, the polymer exhibits excellent biocompatibility at effective antimicrobial concentrations and provides insights into the design of a new class of SO 2 -releasing polymeric antibacterial agents.

Weak binding of carbohydrates with protein receptors possesses serious drawbacks in the advancement of therapeutics; however, the development of strategies for multipoint interactions between carbohydrates and protein can overcome these challenges. One such method is developed in this work where glycopolymer- grafted silica nanoparticles with a large number of carbohydrate units are prepared for the interactions with multiple binding sites of the protein. First, a glycomonomer, β-d-galactose-hydroxyethyl methacrylate (β-GEMA), was synthesized in a two-step process by coupling β-d-galactose pentaacetate and hydroxyethyl methacrylate (HEMA), followed by deacetylation for the preparation of poly(β-GEMA) glycopolymers (GPs). Further, the poly(β-GEMA) chains were grafted onto the silica nanoparticle (SiNP) surface by utilizing the " grafting - from " strategy of surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare p(β-GEMA)-grafted SiNPs (GNPs). Five different chain lengths ranging from 10 to 40 kDa of the GPs and the GNPs were prepared, and various characterization techniques confirmed the formation of GPs and grafting of the GPs on the SiNP surface. The particle size of GNPs and the number of GPs grafted on the SiNP surface showed a strong dependence on the chain length of the GPs. Further, the GNPs were subjected to a binding study with β-galactose-specific protein peanut agglutinin (PNA). A much stronger binding in the case of GNPs was observed with an association constant ∼320 times and ∼53 times than that of the monomeric methyl-β-d-galactopyranoside and the GPs, respectively. Additionally, the binding of the PNA with GNPs and GPs was also studied with varying chain lengths to understand the effects of the chain length on the binding affinity. A clear increase in binding constants was observed in the case of GNPs with increasing chain length of grafted GPs, attributed to the enhanced enthalpic and entropic contributions. This work holds its uniqueness in these improved interactions between carbohydrates and proteins, which can be used for carbohydrate-based targeted therapeutics.

A molecularly imprinting polymer (MIP) carrier with pH-responsivity was designed to construct a drug delivery system (DDS) focusing on controlled and sustainable capecitabine (CAPE) release. The pH-responsive characteristic was achieved by the functionalization of SiO 2 substrate with 4-formylphenylboronic acid, accompanied by the introduction of fluorescein isothiocyanate for the visualization of the intracellular localization of the nanocarrier. Experimental results indicated that CAPE was adsorbed onto the drug carrier with satisfactory encapsulation efficiency. The controlled release of CAPE was realized based on the break of borate ester bonds between -B(OH) 2 and cis-diols in the weakly acidic environment. Density functional theory computations were conducted to investigate the adsorption/release mechanism. Moreover, in vitro experiments confirmed the good biocompatibility and ideal inhibition efficiency of the developed DDS. The MIP can act as an eligible carrier and exhibits the great potential in practical applications for tumor treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A conjugated polymer, P4TTD-DPP, based on tetra-fused isoindigo- alt -diketopyrrolopyrrole, has been synthesized as a photothermal therapeutic nanotransducer within the near-infrared-II (NIR-II) window. P4TTD-DPP exhibits a notable mass extinction coefficient of 62.8 L g -1 cm -1 at 1064 nm. Additionally, P4TTD-DPP nanoparticles demonstrate remarkable photothermal conversion efficiency of 91.5% at 1064 nm and exhibit excellent anticancer efficacy under photothermal conditions.

Photoelectric functional materials with electrochemical reversible activity and fluorescence intensities have attracted significant interest due to their wide range of applications in optoelectronic devices. In this work, a series of photoresponsive and electroactive monomers based on thieno[3.4-c]pyrrole-4,6-dione (TPD) are synthesized and characterized. They possess planar geometry with smaller dihedral angles owing to the existence of a noncovalent conformation lock coming from the S atoms and the O atoms. Crystallographic, spectroscopic, and computational results reveal that the introduction of the TPD unit can endow the monomers with aggregation-induced emission (AIE), reduced energy levels, and increased electrochemical activity. The monomers were successfully polymerized through the electrochemical method, and the corresponding polymers displayed reversible electrochemical activity and stability. Moreover, polymer films based on 3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (ProE)-TPD have electrochromic properties in the near-infrared field with a high value of optical contrast ratio (∆T) of 27.1% at 1000 nm., (© 2024 John Wiley & Sons Ltd.)

The terpolymers of N-vinylpyrrolidone (VP) with acrylic acid and triethylene glycol methacrylate were synthesized with more than 90% yield by radical copolymerization in ethanol from monomeric mixtures of different molar composition (98:2:2, 95:5: 2 and 98:2:5) and their monomer composition, absolute molecular masses and hydrodynamic radii in aqueous media were determined. Using the MTT test, these terpolymers were established to be low toxic for non-tumor Vero cells and HeLa tumor cells. Polymer compositions of hydrophobic dye methyl pheophorbide a (MPP) based on studied terpolymers and linear polyvinylpyrrolidone (PVP) were obtained and characterized in water solution. Quantum-chemical modeling of the MPP-copolymer structures was conducted, and the possibility of hydrogen bond formation between terpolymer units and the MPP molecule was shown. Using fluorescence microscopy, the accumulation and distribution of polymer particles in non-tumor (FetMSC) and tumor (HeLa) cells was studied, and an increase in the accumulation of MPP with both types of particles was found.

Antibiotic residues persist in the environment and represent serious health hazards; thus, it is important to develop sensitive and effective detection techniques. This paper presents a bio-inspired way to make water-soluble fluorescent polymer carbon dots (PCDs@PVA) by heating biomass precursors and polyvinyl alcohol (PVA) together. For example, the synthesized PCDs@PVA are very stable with enhanced emission intensity. This property was observed in a wide range of environmental conditions, including those with changing temperatures, pH levels, UV light, and ionic strength. PCDs@PVA detected the antibiotic chlortetracycline (CTCs) with great selectivity against structurally related compounds and a low detection limit of 20 nM, demonstrating outstanding sensitivity and specificity. We confirmed the sensor's practical application through real sample analysis, yielding recovery rates of 98%-99% in samples of milk, honey, and river water. The synthesized PCDs@PVA fluorescence sensor was successfully used for CTCs detection in real samples., (© 2024 John Wiley & Sons Ltd.)

The polymeric nanoparticles (PNPs) loaded with prednisolone were developed to exhibit pH-responsive properties owing to the attachment of a hydrazone linkage between the copolymer chitosan and mPEG. In the diseased cellular environment, the hydrazone bond tends to break due to reduced pH, leading to the release of the drug from the PNPs at the required site of action. The fabricated PNPs exhibit spherical morphology, optimum size (∼200 nm), negative surface charge, and monodispersed particle size distribution. The encapsulation efficiency of the PNPs was determined to be 71.1 ± 0.79 % and two experiments (polymer weight loss and drug release) confirmed the pH-responsive properties of the PNPs. The cellular study cytotoxicity assay showed biocompatibility of PNPs and drug molecule-mediated toxicity to A549 cells. The ligand atrial natriuretic peptide-attached PNPs internalized into A549 cells via natriuretic peptide receptor-A to achieve target specificity. The PNPs cytotoxicity and pH-response medicated inflammation reduction functionality was studied in inflammation-induced RAW264.7 cell lines. The study observed the PNPs effectively reduced the inflammatory mediators NO and ROS levels in RAW264.7. The results showed that pH-responsive properties of PNPs and this novel fabricated delivery system effectively treat inflammatory and cancer diseases., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Poly(ionic liquid)s combine the unique properties of ionic liquids (ILs) within ionic polymers holding significant promise for energy storage applications. It is reported here the synthesis and characterization of a new family of poly(ionic liquid)s synthesized from cationic piperazinium ionic liquid monomers. The cationic poly(acrylamide piperazinium) in combination with sulfonamide anions like bis(trifluoromethanesulfonyl) imide (TFSI) and bis(fluorosulfonyl) imide (FSI) are characterized as solid polymer electrolytes. The polymer electrolytes in combination with pyrrolidonium ILs and LiFSI show high ionic conductivity, 5×10 -3 S cm -1 at 100 °C. Piperazinium polymer electrolytes show excellent compatibility with lithium metal reversible plating and stripping at high current density and low temperature 40 °C., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Polymers with well-defined structures, synthesized through metal-catalyzed processes, and having end groups exhibiting different polarity and reactivity than the backbone, are gaining considerable attention in both scientific and industrial communities. These polymers show potential applications as fundamental building blocks and additives in the creation of innovative functional materials. Investigations are directed toward identifying the most optimal and uncomplicated synthetic approach by employing a combination of living coordination polymerization mediated by rare-earth metal complexes and C-H bond activation reaction by σ-bond metathesis. This combination directly yields catalysts with diverse functional groups from a single precursor, enabling the production of terminal-functionalized polymers without the need for sequential reactions, such as termination reactions. The utilization of this innovative methodology allows for precise control over end-group functionalities, providing a versatile approach to tailor the properties and applications of the resulting polymers. This perspective discusses the principles, challenges, and potential advancements associated with this synthetic strategy, highlighting its significance in advancing the interface of metalorganic chemistry, polymer chemistry, and materials science., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Photo-responsive liquid crystal polymers (LCPs) have potential application value in flexible robots, artificial muscles, and microfluidic control. In recent years, significant progress has been made in the development of LCPs. However, the preparation of LCPs with continuous and controllable stepwise deformation capabilities remains a challenge. In this study, visible photo-responsive cyanostilbene monomer, UV photo-responsive azobenzene monomer, and multiple hydrogen bond crosslinker are used to prepare photo-responsive LCPs capable of achieving continuously and controllable stepwise deformation. The comprehensive investigation of the multiple light response ability and photo-induced deformation properties of these copolymers is conducted. The results reveal that in the first stage of photo-induced deformation under 470 nm blue light irradiation, the deformation angle decreases with a reduction in cyanostilbene content in the copolymer component, ranging from 40° in AZ0-CS4 to 0° in AZ4-CS0. In the second stage of photo-induced deformation under 365 nm UV irradiation, the deformation angle increases with the increase of azobenzene content, ranging from 0° of AZ0-CS4 to 89.4° of AZ4-CS0. Importantly, the deformation between these two stages occurs as a continuous process, allowing for a direct transition from the first-stage to the second-stage deformation by switching the light source from 470 to 365 nm., (© 2024 Wiley‐VCH GmbH.)

In this paper, a simple, bottom up, bioinspired technique is proposed for the synthesis of highly stable colloids of silica supported spherical silver nanoparticles (SiO 2 @Ag) that act as efficient catalytic and antimicrobial coatings for an organic substrate, filter paper. The core - shell structure and the highly branched dendritic polymer, poly(ethylene)imine, enabled the precise control of growth rate and morphology of silica and silver nanoparticles. The polymer also enabled the deposition of these nanoparticles onto an organic substrate, filter paper, through immersion by modifying its surface. The catalytic and antibacterial properties of these samples were assessed. The results obtained from this analysis showed a complete degradation of an aqueous pollutant, 4-nitrophenol, for 6 successive catalytic cycles without intermediate purification steps. Furthermore, the polymeric silica-silver suspension proved to express antibacterial activity against both Gram-positive and Gram-negative bacteria (Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa). The antibacterial properties were evaluated according to the disk diffusion method, whereas the Minimum Inhibitory Concentration was also determined. The samples were examined by Scanning Electron Microscopy, Transmission Electron Microscopy, X-ray diffraction analysis, z-potential analysis, Fourier Transform Infrared Spectroscopy and Ultraviolet-visible Spectroscopy., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Hydrophilicity is one important drawback of bio-based aerogels. To overcome this issue, a novel approach for the preparation of mesoporous, water repellent aerogels is introduced, which combines synthesis of cross-linked bio-based copolymers from methacrylate copolymerizations, followed by solvent exchange and supercritical drying steps. The influence of monomers with different nonpolar ester groups (methyl, vanillin, tetrahydrofurfuryl) on textural properties and water contact angles of the dry products is assessed. Final aerogels show generally high overall porosities (≈96%), low densities (0.07-0.11 g cm -3 ) as well as fine, mainly mesoporous networks, and specific surface areas in the range of 120-240 m 2  g -1 . Hereby, choice of the methacrylate ester groups results in differences of the resulting pore-size distributions. Water repellency tests show stable static water contact angles in the hydrophobic range (≈100°) achieved for the substrate containing the vanillin ester group. On the contrary the other substrates absorb water quickly, which indicates a decisive role of the ester group. The presented approach opens up a new pathway to bio-based aerogels with intrinsic hydrophobicity. It is suggested that the properties are tailored by the choice of the monomer structure, hence enabling further adaption and optimization of the products., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

N-carboxyanhydride ring-opening polymerization-induced self-assembly (NCA ROPISA) offers a convenient route for generating poly(amino acid)-based nanoparticles in a single step, crucially avoiding the need for post-polymerization self-assembly. Most examples of NCA ROPISA make use of a poly(ethylene glycol) (PEG) hydrophilic stabilizing block, however this non-biodegradable, oil-derived polymer may cause an immunological response in some individuals. Alternative water-soluble polymers are therefore highly sought. This work reports the synthesis of wholly poly(amino acid)-based nanoparticles, through the chain-extension of a polysarcosine macroinitiator with L-Phenylalanine-NCA (L-Phe-NCA) and Alanine-NCA (Ala-NCA), via aqueous NCA ROPISA. The resulting polymeric structures comprise of predominantly anisotropic, rod-like nanoparticles, with morphologies primarily influenced by the secondary structure of the hydrophobic poly(amino acid) that enables their formation., (© 2024 The Authors. Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Stretchable conjugated polymers with conjugation break spacers (CBSs) synthesized via random terpolymerization have gained considerable attention because of their efficacy in modulating mobility and stretchability. This study incorporates a series of dianhydrohexitol diastereomers of isosorbide (ISB) and isomannide (IMN) units into the diketopyrrolopyrrole-based backbone as CBSs. It is found that the distorted CBS (IMN) improves the mobility-stretchability properties of the polymer with a highly coplanar backbone, whereas the extended CBS (ISB) enhances those of the polymer with a noncoplanar backbone. Additionally, the different configurations of ISB and IMN sufficiently affect the solid-state packing, aggregation capabilities, crystallographic parameters, and mobility-stretchability properties of the polymer. The IMN-based polymers exhibit the highest mobility of 1.69 cm 2 V -1 s -1 and crystallinity retentions of (85.7, 78.6)% under 20% and 60% strains, outperforming their ISB-based or unmodified counterparts. The improvement is correlated with a robust aggregation capability. Furthermore, the CBS content affects aggregation behavior, notably affecting mobility. This result indicates that incorporating CBSs into the polymer can enhance backbone flexibility via movement and rotation of the CBS without affecting the crystalline regions., (© 2024 Wiley‐VCH GmbH.)

Carbon-chain dendritic polymers hold unique properties and promising applications. However, synthesizing carbon-chain dendrimers, beyond conjugated ones, remains a challenge. Here, the use of the iterative single unit monomer insertion technique for synthesizing 2.5 generation partial-carbon-chain dendrimers (G2.5) is described, utilizing bismaleimide as the core, a maleimide-trithiocarbonate conjugate as the branching unit, and indene as the spacer unit, following a divergent growth strategy. The optimized conditions for synthesizing the maleimide-trithiocarbonate branching unit are a bismaleimide to trithiocarbonate ratio of 5:1 and a reaction time of 30 min. The structures are verified using 1 H nuclear magnetic resonance, gel permeation chromatography, and matrix-assisted laser desorption/ionization-time of flight mass spectra. A four-arm star polymer is then synthesized using the G2.5 as the core. This synthesis of a partial-carbon-chain dendrimer establishes a foundational step toward creating all-carbon-chain ones and may open new application avenues in material science., (© 2024 Wiley‐VCH GmbH.)

Conjugated polymers with integrating properties of delayed fluorescence and photovoltaic responses simultaneously are scarcely reported due to the generally contradictory requirements for molecular structures to achieve the two properties. Herein, an O-B(F)←N functionalized fused unit (M) with multiple resonance features, small energy gap between lowest singlet excited state (S 1 ) and triplet excited state (T 1 ) (ΔE ST = 0.23 eV), and delayed fluorescence (τ D = 0.75 µs), is designed. Selecting three benzodithiophene (BDT) derivatives as co-units to copolymerize with M, leading to a series of O-B(F)←N embedded polymers also maintaining delayed fluorescence (τ D = 0.4-0.5 µs). Moreover, p-type semiconductor characteristics are tested for these polymers with hole mobilities in the range of 10 -6 -10 -5 cm 2 /Vs. Devices with obviously photovoltaic responses are prepared using these polymers as donors and Y6 as the acceptor, affording a preliminary efficiency of 5.05%. This work successfully demonstrates an effective strategy to design conjugated polymers with integrating properties of delayed fluorescence and photovoltaic performance simultaneously by introducing O-B(F)←N functional groups to polymer backbones., (© 2024 Wiley‐VCH GmbH.)

In this contribution, the transformation of polydicyclopentadiene (PDCPD) from thermoset into vitrimer is introduced. First, two N-coordinated diboronic diols are successfully synthesized via the reaction of N,N,N-tri(2-hydroxyethyl)amine and/or N,N,N",N"-tetrakis(2-hydroxyethyl)ethylene diamine with 4-(hydroxymethyl) phenylboronic acid and then they are transformed into two N-coordinated cyclic boronic diacrylates. The latter two dienes carrying electron-withdrawing substituents are used for the ring opening insertion metathesis copolymerization (ROIMP) of dicyclopentadiene to afford the crosslinked PDCPD. In the crosslinked PDCPD networks, N-coordinated cyclic boronic ester bonds are integrated. It is found that the as-obtained PDCPD networks displayed the excellent reprocessing properties. In the meantime, the fracture toughness is significantly improved. Owing to the inclusion of N-coordinated cyclic boronic ester bonds, the modified PDCPDs have the thermal stability much superior to plain PDCPD. The results reported in this work demonstrate that PDCPD can successfully be transformed into the vitrimers via the introduction of N-coordinated cyclic boronic ester bonds., (© 2024 Wiley‐VCH GmbH.)

Nonconventional luminophores have received increasing attention, owing to their fundamental importance, advantages in outstanding biocompatibility, easy preparation, environmental friendliness, and potential applications in sensing, imaging, and encryption. Purely organic molecules with outstanding fluorescence and room-temperature phosphorescence (RTP) have emerged as a new library of benign afterglow agents. However, the cost, toxicity, high reactivity, and poor stability of materials also limit their practical applications. Therefore, some natural products, synthetic compounds, and biomolecules have entered horizons of people. The as-designed exhibits sky blue and green fluorescence emission and green RTP emission (a lifetime of 343 ms and phosphorescence quantum of 15.3%) under air condition. This study presents an organic fluorescence for biological imaging and RTP for anti-counterfeiting and encryption based on amino acids, maleic anhydride and 4-vinylbenzenesulfonic acid sodium salt hydrate. This study provides a strategy for nonconventional luminophores in designing and synthesizing pure organic RTP materials., (© 2024 Wiley‐VCH GmbH.)

Inspired by the favorable impact of heteroatom-containing groups in phenoxy-imine titanium and late transition metal catalysts, a series of novel pyridylamido hafnium catalysts bearing ─OMe (Cat-OMe), ─CF 3 (Cat-CF 3 ), and ─C 6 F 5 (Cat-C 6 F 5 ) substituents are designed and synthesized. Together with the established hafnium catalysts Cat-H and Cat-iPr by Dow/Symyx, these catalysts are applied in the polymerization of α-olefins, including 1-hexene, 1-octene, and 4M1P, as well as in the copolymerization of these α-olefins with a specifically designed polar monomer. The enhancement of polymer molecular weight derived from catalyst modification and the incorporation of polar monomers is discussed in detail. Notably, the new catalysts are all highly active for α-olefins polymerization, with catalyst Cat-CF 3 producing isotactic polymers with the highest molecular weight (M w = 1649 kg mol -1 ); in copolymerization with polar monomers, catalyst Cat-OMe yields isotactic copolymer with the highest molecular weight (M w = 2990 kg mol -1 ). Interestingly, catalyst Cat-C 6 F 5 bearing a ─C 6 F 5 group in the N-aryl moiety gives rise to poly(α-olefin) with reduced stereoselectivity. The findings of this study underscore the potential of heteroatom-containing groups in the development of early transition metal catalysts and the synthesis of polymer with novel structures., (© 2024 Wiley‐VCH GmbH.)

Successful therapeutic delivery of siRNA with polymeric nanoparticles seems to be a promising but not vastly understood and complicated goal to achieve. Despite years of research, no polymer-based delivery system has been approved for clinical use. Polymers, as a delivery system, exhibit considerable complexity and variability, making their consistent production a challenging endeavor. However, a better understanding of the polymerization process of polymer excipients may improve the reproducibility and material quality for more efficient use in drug products. Here, we present a combination of Design of Experiment and Python-scripted data science to establish a prediction model, from which important parameters can be extracted that influence the synthesis results of polybeta-amino esters (PBAEs), a common type of polymer used preclinically for nucleic acid delivery. We synthesized a library of 27 polymers, each one at different temperatures with different reaction times and educt ratios using an orthogonal central composite (CCO-) design. This design allowed a detailed characterization of factor importance and interactions using a very limited number of experiments. We characterized the polymers by analyzing the resulting composition by 1H-NMR and the size distribution by GPC measurements. To further understand the complex mechanism of block polymerization in a one-pot synthesis, we developed a Python script that helps us to understand possible step-growth steps. We successfully developed and validated a predictive response surface and gathered a deeper understanding of the synthesis of polyspermine-based amphiphilic PBAEs.

The current work describes the efficient creation and employment of a new S-citalopram selective polymeric sorbent, made from poly(divinylbenzene-maleic anhydride-styrene). The process began by using suspension polymerization technique in the synthesis of poly(styrene-maleic anhydride-divinylbenzene) microparticles. These were then modified with ethylenediamine, developing an amido-succinic acid-based polymer derivative. The S-citalopram, a cationic molecule, was loaded onto these developed anionic polymer particles. Subsequently, the particles were post-crosslinked using glyoxal, which reacts with the amino group residues of ethylenediamine. S-citalopram was extracted from this matrix using an acidic solution, which also left behind stereo-selective cavities in the S-citalopram imprinted polymer, allowing for the selective re-adsorption of S-citalopram. The attributes of the polymer were examined through methods such as 13 C NMR, FTIR, thermogravemetric and elemental analyses. SEM was used to observe the shapes and structures of the particles. The imprinted polymers demonstrated a significant ability to adsorb S-citalopram, achieving a capacity of 878 mmol/g at a preferred pH level of 8. It proved efficient in separating enantiomers of (±)-citalopram via column methods, achieving an enantiomeric purity of 97 % for R-citalopram upon introduction and 92 % for S-citalopram upon release., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Coating metal structures with a protective material is a popular strategy to prevent their deterioration due to corrosion. However, maintaining the barrier properties of coatings after their mechanical damage is challenging. Herein, we prepared multifunctional coatings with self-healing ability to conserve their anticorrosion performance after damage. The coating was formed by blending synthesized redox-responsive copolymers with the ability to release a corrosion inhibitor upon the onset of corrosion with synthesized self-healing polyurethanes containing disulfide bonds. The corrosion rate of steel substrates coated with a blend is approximately 24 times lower than that of steel coated with only self-healing polyurethane. An exceptional healing efficiency, as high as 95%, is obtained after mechanical damage. The antibiofouling property against bacterial and microalgal attachments on coatings is facilitated by the repellent characteristic of fluorinated segments and the biocidal activity of the inhibitor moieties in the copolymer.

Electrospun polymeric nanofibers are essential in various fields for various applications because of their unique properties. Their features are similar to extracellular matrices, which suggests them for applications in healthcare fields, such as antimicrobials, tissue engineering, drug delivery, wound healing, bone regeneration, and biosensors. This review focuses on the synthesis of electrospun polymeric nanofibers, their surface modification, and their biomedical applications. Nanofibers can be fabricated from both natural and synthetic polymers and their composites. Even though they mimic extracellular matrices, their surface features (physicochemical characteristics) are not always capable of fulfilling the purpose of the target application. Therefore, they need to be improved via surface modification techniques. Both needle-based and needleless electrospinning are thoroughly discussed. Various techniques and setups employed in each method are also reviewed. Furthermore, pre- and postspinning modification approaches for electrospun nanofibers, including instrument design and the modification features for targeted biomedical applications, are also extensively discussed. In this way, the remarkable potential of electrospun polymeric nanofibers can be highlighted to reveal future research directions in this dynamic field.

Polymeric materials with antibacterial properties hold great promise for combating multidrug-resistant bacteria, which pose a significant threat to public health. However, the synthesis of most antibacterial polymers typically involves complicated and time-consuming procedures. In this study, we demonstrate a simple and efficient strategy for synthesizing functional poly(vinylpyridinium salt)s via pyridinium-yne click polymerization. This click polymerization could proceed with high atom economy under mild conditions without any external catalyst, yielding soluble and thermally stable poly(vinylpyridinium salt)s with satisfactory molecular weights and well-defined structures in excellent yields. Additionally, the incorporation of luminescent units such as fluorene, tetraphenylethylene, and triphenylamine into the polymer backbone confers excellent aggregation-enhanced emission properties upon the resulting polymers, rendering them suitable for bacterial staining. Moreover, the existence of pyridinium salt imparts intrinsic antibacterial activity against multidrug-resistant bacteria to the polymers, enabling them to effectively inhibit wound bacterial infection and significantly expedite the healing process. This work not only provides an efficient method to prepare antibacterial polymers, but also opens up the possibility of various applications of polymers in healthcare and other antibacterial fields., (© 2024 Wiley-VCH GmbH.)

Careful recruitment of the components of the HDAC inhibitory template culminated in veliparib-based anilide 8 that elicited remarkable cell growth inhibitory effects against HL-60 cell lines mediated via dual modulation of PARP [(IC 50 (PARP1) = 0.02 nM) and IC 50 (PARP2) = 1 nM)] and HDACs (IC 50 value = 0.05, 0.147 and 0.393 μM (HDAC1, 2 and 3). Compound 8 downregulated the expression levels of signatory biomarkers of PARP and HDAC inhibition. Also, compound 8 arrested the cell cycle at the G0/G1 phase and induced autophagy. Polymer nanoformulation (mPEG-PCl copolymeric micelles loaded with compound 8) was prepared by the nanoprecipitation technique. The mPEG-PCL diblock copolymer was prepared by ring-opening polymerization method using stannous octoate as a catalyst. The morphology of the compound 8@mPEG-PCL was examined using TEM and the substance was determined to be monodispersed, spherical in form, and had an average diameter of 138 nm. The polymer nanoformulation manifested pH-sensitive behaviour as a greater release of compound 8 was observed at 6.2 pH as compared to 7.4 pH mimicking physiological settings. The aforementioned findings indicate that the acidic pH of the tumour microenvironment might stimulate the nanomedicine release which in turn can attenuate the off-target effects precedentially claimed to be associated with HDAC inhibitors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Masson SAS. All rights reserved.)

Furosemide (FUR), banned in sports events by the World Anti-Doping Agency, is a key target in drug tests, necessitating a pretreatment material capable of selectively, rapidly, and sufficiently separating/enriching analytes from complex matrices. Herein, a metal-mediated magnetic molecularly imprinted polymer (mMIP) was rationally designed and synthesized for the specific capture of FUR. The preparations involved the utilization of chromium (III) as the binding pivot, (3-aminopropyl)triethoxysilane as functional monomer, and Fe 3 O 4 as core, all assembled via free radical polymerization. Both the morphologies and adsorptive properties of the mMIP were characterized using multiple methods. The resulting Cr(III)-mediated mMIP (ChM-mMIP) presented excellent selectivity and specificity toward FUR. Under optimized conditions, the adsorption capacity reached 128.50 mg/g within 10 min, and the imprinting factor was 10.41. Moreover, it was also successfully applied as a dispersive solid-phase extraction material, enabling the detection of FUR concentration as low as 20 ng/mL in human urine samples when coupled with a high-performance liquid chromatography/photodiode array. Overall, this study offers a valuable strategy for the development of novel recognition material., (© 2024 Wiley‐VCH GmbH.)

Redox-conducting polymers based on SalEn-type complexes have attracted considerable attention due to their potential applications in electrochemical devices. However, their charge transfer mechanisms, physical and electrochemical properties remain unclear, hindering their rational design and optimization. This study aims to establish the influence of monomer geometry on the polymer's properties by investigating the properties of novel nonplanar SalEn-type complexes, poly[N,N'-bis(salicylidene)propylene-2-(hydroxy)diaminonickel(II)], and its analog with 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-substituted bridge (MTS). To elucidate the charge transfer mechanism, operando UV-Vis spectroelectrochemical analysis, electrochemical impedance spectroscopy, and electron paramagnetic resonance are employed. Introducing TEMPO into the bridge moiety enhanced the specific capacity of the poly(MTS) material to 95 mA h g -1 , attributed to TEMPO's and conductive backbone's charge storage capabilities. Replacement of the ethylenediimino-bridge with a 1,3-propylenediimino- bridge induced significant changes in the complex geometry and material's morphology, electrochemical, and spectral properties. At nearly the same potential, polaron and bipolaron particles emerged, suggesting intriguing features at the overlap point of the electroactivity potentials ranges of polaron-bipolaron and TEMPO, such as a disruption in the connection between TEMPO and the conjugation chain or intramolecular charge transfer. These results offer valuable insights for optimizing strategies to create organic materials with tailored properties for use in catalysis and battery applications., (© 2024 Wiley‐VCH GmbH.)

Controlling the end-groups of biocompatible polymers is crucial for enabling polymer-based therapeutics and nanomedicine. Typically, end-group diversification is a challenging and time-consuming endeavor, especially for polymers prepared via ionic polymerization mechanisms with limited functional group tolerance. In this study, we present a facile end-group diversification approach for poly(2-oxazoline)s (POx), enabling quick and reliable production of heterotelechelic polymers to facilitate POxylation. The approach relies on the careful tuning of reaction parameters to establish differential reactivity of a pentafluorobenzyl initiator fragment and the living oxazolinium chain-end, allowing the selective introduction of N-, S-, O-nucleophiles via the termination of the polymerization, and a consecutive nucleophilic para-fluoro substitution. The value of this approach for the accelerated development of nanomedicine is demonstrated through the synthesis of well-defined lipid-polymer conjugates and POx-polypeptide block-copolymers, which are well-suited for drug and gene delivery. Furthermore, we investigated the application of a lipid-POx conjugate for the formulation and delivery of mRNA-loaded lipid nanoparticles for immunization against the SARS-COV-2 virus, underscoring the value of POx as a biocompatible polymer platform., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The systematic study of two ionic porous organic polymers (iPOPs) based on viologens and their first applications in the electrochromic field are reported. The viologen-based iPOPs are synthesized by electrochemical polymerization with cyano groups, providing a simple and controllable method for iPOPs that solves the film preparation problems common to viologens. After the characterization of these iPOPs, a detailed study of their electrochromic properties is conducted. The iPOP films based on viologens structure exhibit excellent electrochromic properties. In addition, the resulting iPOP films show high sensitivity to electrolyte ions of different sizes in the redox process. Electrochemical and electrochromic data of the iPOPs explain this phenomenon in detail. These results demonstrate that iPOPs of this type are ideal candidates as electrochromic materials due to their inherent porous structures and ion-rich properties., (© 2024 Wiley‐VCH GmbH.)

Controlled synthesis of 3D polymer networks presents a significant challenge because of the complexity of the polymerization reaction in solution. In this study, a polymerization system that facilitates the prediction of a polymer network structure via percolation simulations is realized. The most significant difference between general percolation simulations and experimental polymerization systems is the mobility of the molecules during the reaction. A crystal component-linking method that connects the precisely arranged monomer as a supramolecular crystalline state to imitate the simple percolation theory is adopted. The percolation simulation based on the crystal structure of the arranged monomers is used to accurately calculate the gelation point, gel fraction, degree of swelling, and atomic formula, which correspond with the experimental results. This suggests that the network structures polymerized via the crystal component-linking method can be predicted precisely by a simple percolation simulation. Further, the percolation simulation predicts the structures of the loop, branched polymer, and crosslinking point, which are difficult to measure experimentally. The polymerization of precisely-arranged immobilized monomers in supramolecular structures is promising in synthesizing precisely controlled polymer networks., (© 2024 Wiley‐VCH GmbH.)

Protein-polymer conjugates and polymeric nanomaterials hold great promise in many applications including biomaterials, medicine, or nanoelectronics. In this work, the first polymerization-induced self-assembly (PISA) approach performed in aqueous medium enabling protein-polymer conjugates and nanoparticles entirely composed of amino acids is presented by using ring-opening polymerization (ROP). It is indeed shown that aqueous ring-opening polymerization-induced self-assembly (ROPISA) can be used with protein or peptidic macroinitiators without prior chemical modification and afford the simple preparation of nanomaterials with protein-like property, for example, to implement biomimetic thermoresponsivity in drug delivery., (© 2024 The Authors. Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

High sulfur content polymeric materials, known for their intriguing properties such as high refractive indices and high electrochemical capacities, have garnered significant interest in recent years for their applications in optics, antifouling surfaces, triboelectrics, and electrochemistry. Despite the high interest, most high sulfur-content polymers reported to date are either bulk materials or thin films, and there is a general lack of research into sulfur-rich polymer colloids. Water-dispersed, sulfur-rich particles are anticipated to broaden the range of applications for sulfur-containing materials. In this study, the preparation and size control parameters are presented of an aqueous dispersion of sulfur-rich polymers with the sulfur content of dispersed particles exceeding 75 wt%. Employing polymeric stabilizers with varying hydrophilic-lipophilic balance (HLB), along with changing the rank of inorganic polysulfides, allow for the control of particle size in the range of 360 nm - 1.8 µm. The sulfur-rich colloid demonstrates antioxidant properties in water, demonstrating the potential for the use of sulfur-rich polymeric materials readily removable, heterogeneous radical scavengers., (© 2024 The Authors. Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Conductive hydrogels play a crucial role in advancing technologies like implantable bioelectronics and wearable electronic devices, owing to their favorable conductivity and appropriate mechanical properties. Here, a novel bottom-up approach is reported for crafting conductive nanocomposite hydrogels to achieve enhancing conductive and mechanical properties. In this approach, new poly(ɛ-caprolactone)-based block copolymers with sulfonic groups are first synthesized and self-assembled into uniform polyanionic nanoplatelets. Subsequently, these negatively charged nanoplatelets, with sulfonic groups on the surface, are employed as nanoadditives for the polymerization of 3,4-ethylenedioxythiophene (EDOT), resulting in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/nanoplatelet complex with 3.8 times enhanced electrical conductivity compared with their counterparts prepared using block copolymers (BCPs). Blending the (PEDOT:PSS)/nanoplatelet complex with calcium alginate, nanocomposite hydrogels are successfully prepared. In comparison with hydrogels with (PEDOT:PSS)/BCP complexes prepared by a top-down method, the nanocomposite hydrogels are found to show twice as strong mechanical strength and 1.6 times higher conductivity. This work provides valuable insights into the bottom-up construction of conductive hydrogels for bioelectronics using well-controlled polymeric nanoplatelets., (© 2024 Wiley‐VCH GmbH.)

In this study, a new analytical method was developed using magnetic molecularly imprinted polymers (MMIPs) by employing eco-friendly supramolecular ternary deep eutectic solvents to synthesize these MMIPs for selective extraction of rifaximin. The characterization analysis and adsorption affinity investigation were conducted. The results showed fast adsorption (15 min) with high adsorption capacity (43.20 mg g -1 ) and selectivity for rifaximin. Various extraction parameters were optimized, achieving recoveries ranging from 86.67% to 99.47% in spiked milk samples using high-performance liquid chromatography (HPLC). The detection and quantification limits were 0.01 mg L -1 and 0.03 mg L -1 , respectively. The method exhibited low RSDs (<4.70%) and excellent selectivity, with MMIPs reusable up to seven times with only a 10% performance loss. This study proposes a convenient and reliable method for trace-level rifaximin extraction from milk using eco-friendly MMIPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Alkylresorcinols are important biomarkers for evaluating whole wheat foods. However, their structures encompass a broad spectrum of homologs, making isolating and analyzing individual alkylresorcinol notably challenging. Herein, we synthesized highly selective molecularly imprinted polymers (MIPs) utilizing a facile and cost-effective precipitation polymerization method and 5-heneicosylresorcinol (AR C21:0 ) as the template molecule. Various crucial preparation parameters were systematically optimized, such as different porogens, functional monomers, imprinting ratios, and polymerization time. The polymers were characterized through scanning electron microscopy and Fourier transform infrared spectroscopy, and their adsorption performances were thoroughly evaluated. MIPs exhibited a notably enhanced adsorption capacity compared with that of non-imprinted polymers, reaching an optimal adsorption amount of 71.75 mg·mL -1 and imprinting factor of 2.02. Altogether, the synthesized MIPs showed superior affinity and selectivity for AR C21:0 , as confirmed by their selective extraction, suggesting their potential applications in the analysis, separation, and monitoring of AR C21:0 in whole wheat foods., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Development of biocompatible nanomaterials with mitochondria-targeting and multimodal therapeutic activities is important for cancer treatment. Herein, we designed and synthesized a multifunctional pyrrole-based nanomaterial with photothermal effects and mitochondria-targeting properties from polypyrrole and the pro-apoptotic peptide KLA. Different from traditional strategies for the preparation of PPy nanoparticles, we innovatively used the KLA peptide as the template and CuCl 2 as the catalyst to trigger the oxidative polymerization of pyrrole for PPy-KLA-Cu nanoparticle formation. Besides, due to the presence of mixed-valence Cu(I)/Cu(II) states, PPy-KLA-Cu nanoparticles also exhibited multienzyme-like activities, such as peroxidase, ascorbate oxidase and glutathione peroxidase activities, which can be exploited to elevate the intracellular ROS level and simultaneously consume GSH in cancer cells. More importantly, the heat generated by PPy-KLA-Cu nanoparticles from NIR irradiation could enhance the nanozymatic activities for ROS elevation and increase the KLA-induced anticancer activity via mitochondrial dysfunction, realizing multimodal treatment of cancer cells with improved therapeutic efficacy.

One of the gut-derived uremic toxins 4-ethylphenyl sulfate (4-EPS) exhibits significantly elevated plasma levels in chronic kidney diseases and autism, and its early quantification in bodily fluids is important. Therefore, the development of rapid and sensitive technologies for 4-EPS detection is of significant importance for clinical diagnosis. In the current work, the synthesis of a molecularly imprinted biopolymer (MIBP) carrying 4-EPS specific cavities only using the biopolymer polydopamine (PDA) and molybdenum disulfide (MoS 2 ) nanosheets has been reported. The fabricated electrode was prepared using screen-printed carbon electrodes on a polyvinyl chloride substrate. The synthesized material was characterized using several techniques, and electrochemical studies were performed using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The DPV technique for the electrochemical sensing of 4-EPS using the fabricated sensor (PDA@MoS 2 -MIBP) determined a sensitivity of 0.012 μA/ng mL/cm 2 and a limit of detection of 30 ng/mL in a broad linear range of 1-2200 ng/mL. Also, the interferent study was performed to evaluate the selectivity of the fabricated sensor along with the control and stability study. Moreover, the performance of the sensor was evaluated in the spiked urine sample, and a comparison was made with the data obtained by ultraperformance liquid chromatography-tandem mass spectroscopy.

Polymer prodrugs are based on the covalent linkage of therapeutic molecules to a polymer structure which avoids the problems and limitations commonly encountered with traditional drug-loaded nanocarriers in which drugs are just physically entrapped ( e.g. , burst release, poor drug loadings). In the past few years, reversible-deactivation radical polymerization (RDRP) techniques have been extensively used to design tailor-made polymer prodrug nanocarriers. This synthesis strategy has received a lot of attention due to the possibility of fine tuning their structural parameters ( e.g. , polymer nature and macromolecular characteristics, linker nature, physico-chemical properties, functionalization, etc. ), to achieve optimized drug delivery and therapeutic efficacy. In particular, adjusting the nature of the drug-polymer linker has enabled the easy synthesis of stimuli-responsive polymer prodrugs for efficient spatiotemporal drug release. In this context, this review article will give an overview of the different stimuli-sensitive polymer prodrug structures designed by RDRP techniques, with a strong focus on the synthesis strategies, the macromolecular architectures and in particular the drug-polymer linker, which governs the drug release kinetics and eventually the therapeutic effect. Their biological evaluations will also be discussed.

In the development of dendritic cell (DC) vaccines, the maturation of DCs is a critical stage. Adjuvants play a pivotal role in the maturation of DCs, with a major concern being to ensure both efficacy and safety. This study introduces an innovative approach that combines high efficacy with safety through the synthesis of micro-adjuvants grafted with copolymers of 2-(methacrylamido) glucopyranose (MAG) and methacryloxyethyl trimethyl ammonium chloride (DMC). The utilization of metal-free surface-initiated atom transfer radical polymerization enables the production of safe and recyclable adjuvants. These micrometer-sized adjuvants surpass the optimal size range for cellular endocytosis, enabling the retrieval and reuse of them during the ex vivo maturation process, mitigating potential toxicity concerns associated with the endocytosis of non-metabolized nanoparticles. Additionally, the adjuvants exhibit a "micro-ligand-mediated maturation enhancement" effect for DC maturation. This effect is influenced by the shape of the particle, as evidenced by the distinct promotion effects of rod-like and spherical micro-adjuvants with comparable sizes. Furthermore, the porous structure of the adjuvants enables them to function as cargo-carrying "micro-shuttles", releasing antigens upon binding to DCs to facilitate efficient antigen delivery., (© 2024 Wiley-VCH GmbH.)

Sonodynamic therapy (SDT), which involves the activation of sonosensitizers to generate cytotoxic reactive oxygen species under ultrasound irradiation, is a promising noninvasive modality for cancer treatment. However, the clinical translational application of SDT is impeded by the lack of efficient sonosensitizers, the inefficient accumulation of sonosensitizers at tumor sites, and the complicated immunosuppressive tumor microenvironment. Herein, we developed a facilely synthesized multifunctional porous organic polymer nanosonosensitizer (mHM@HMME) for enhanced SDT. Specifically, mHM@HMME nanosonosensitizers were prepared by incorporating chemotherapeutic mitoxantrone into the one-step synthesis process of disulfide bond containing porous organic polymers, followed by loading with organic sonosensitizer (HMME) and camouflaging with a cancer cell membrane. Due to the cancer cell membrane camouflage, this multifunctional mHM@HMME nanosonosensitizer showed prolonged blood circulation and tumor targeting aggregation. Under ultrasound irradiation, the mHM@HMME nanosonosensitizer exhibited a satisfactory SDT performance both in vitro and in vivo. Moreover, the potent SDT combined with glutathione-responsive drug release in tumor cells induced robust immunogenic cell death to enhance the antitumor effect of SDT in turn. Overall, this facilely synthesized multifunctional mHM@HMME nanosonosensitizer shows great potential application in enhanced SDT.

In this study, we demonstrate the fabrication of polymersomes, protein-blended polymersomes, and polymeric microcapsules using droplet microfluidics. Polymersomes with uniform, single bilayers and controlled diameters are assembled from water-in-oil-in-water double-emulsion droplets. This technique relies on adjusting the interfacial energies of the droplet to completely separate the polymer-stabilized inner core from the oil shell. Protein-blended polymersomes are prepared by dissolving protein in the inner and outer phases of polymer-stabilized droplets. Cell-sized polymeric microcapsules are assembled by size reduction in the inner core through osmosis followed by evaporation of the middle phase. All methods are developed and validated using the same glass-capillary microfluidic apparatus. This integrative approach not only demonstrates the versatility of our setup, but also holds significant promise for standardizing and customizing the production of polymer-based artificial cells., (© 2024. The Author(s).)

Smart nanoassemblies degradable through the cleavage of acid-labile linkages have attracted significant attention because of their biological relevance found in tumor tissues. Despite their high potential to achieve controlled/enhanced drug release, a systematic understanding of structural factors that affect their pH sensitivity remains challenging, particulary in the consruction of effective acid-degradable shell-sheddable nanoassemblies. Herein, the authors report the synthesis and acid-responsive degradation through acid-catalyzed hydrolysis of three acetal and ketal diols and identify benzaldehyde acetal (BzAA) exhibiting optimal hydrolysis profiles in targeted pH ranges to be a suitable candidate for junction acid-labile linkage. The authors explore the synthesis and aqueous micellization of well-defined poly(ethylene glycol)-based block copolymer bearing BzAA linkage covalently attached to a polymethacrylate block for the formation of colloidally-stable nanoassemblies with BzAA groups at core/corona interfaces. Promisingly, the investigation on acid-catalyzed hydrolysis and disassembly shows that the formed nanoassemblies meet the criteria for acid-degradable shell-sheddable nanoassemblies: slow degradation at tumoral pH = 6.5 and rapid disassembly at endo/lysosomal pH = 5.0, while colloidal stability at physiological pH = 7.4. This work guides the design principle of acid-degradable shell-sheddable nanoassemblies bearing BzAA at interfaces, thus offering the promise to address the PEG dilemma and improve endocytosis in tumor-targeting drug delivery., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Non-traditional intrinsic luminescent (NTIL) polymer is an emerging field, and its color-tunable modification is highly desirable but still rarely investigated. Here, a click chemistry approach for the color-tunable modifications of NTIL polymers by introducing clickable polymerization-induced emission luminogen (PIEgen), is demonstrated. Through Cu-catalyzed azide-alkyne cycloaddition click chemistry, a series of PIEgens is successful prepared, which is further polymerized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Interestingly, after clickable modification, these monomers are nonemissive in both solution and aggregation states; while, the corresponding polymers exhibit intriguing aggregation-induced emission (AIE) characteristics, confirming their PIEgen characteristics. By varying alkynyl substitutions, color-tunable NTIL polymers are achieved with emission wavelength varying from 448 to 498 nm, revealing a series of PIEgens and verifying the importance of modification of NTIL polymers. Further luminescence energy transfer application is carried out as well. This work therefore designs a series of clickable PIEgens and opens a new avenue for the modification of NTIL polymers via click chemistry, which may cause inspirations to the research fields including luminescent polymer, NTIL, click chemistry, AIE and modification., (© 2024 Wiley‐VCH GmbH.)

Mesoionic N-heterocyclic olefins (mNHOs) have recently emerged as a novel class of highly nucleophilic and super-basic σ-donor compounds. Making use of these properties in synthetic polymer chemistry, it is shown that a combination of a specific mNHO and a Mg-based Lewis acid (magnesium bis(hexamethyldisilazide), Mg(HMDS) 2 ) delivers poly(propylene oxide) in quantitative yields from the polymerization of the corresponding epoxide (0.1 mol% mNHO loading). The initiation mechanism involves monomer activation by the Lewis acid and direct ring-opening of the monomer by nucleophilic attack of the mNHO, forming a zwitterionic propagating species. Modulation of the mNHO properties is thereby a direct tool to impact initiation efficiency, revealing a sterically unencumbered triazole-derivative as particularly useful. The joint application of mNHOs together with borane-type Lewis acids is also outlined, resulting in high conversions and fast polymerization kinetics. Importantly, while molar mass distributions remain relatively broad, indicating faster propagation than initiation, the overall molar masses are significantly lower than found in the case of regular NHOs, underlining the increased nucleophilicity and ensuing improved initiation efficiency of mNHOs., (© 2024 The Authors. Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)