Advanced Application of Polymer Nanocarriers in Delivery of Active Ingredients from Traditional Chinese Medicines.

Active ingredients from Traditional Chinese Medicines (TCMs) have been a cornerstone of healthcare for millennia, offering a rich source of bioactive compounds with therapeutic potential. However, the clinical application of TCMs is often limited by challenges such as poor solubility, low bioavailability, and variable pharmacokinetics. To address these issues, the development of advanced polymer nanocarriers has emerged as a promising strategy for the delivery of TCMs. This review focuses on the introduction of common active ingredients from TCMs and the recent advancements in the design and application of polymer nanocarriers for enhancing the efficacy and safety of TCMs. We begin by discussing the unique properties of TCMs and the inherent challenges associated with their delivery. We then delve into the types of polymeric nanocarriers, including polymer micelles, polymer vesicles, polymer hydrogels, and polymer drug conjugates, highlighting their application in the delivery of active ingredients from TCMs. The main body of the review presents a comprehensive analysis of the state-of-the-art nanocarrier systems and introduces the impact of these nanocarriers on the solubility, stability, and bioavailability of TCM components. On the basis of this, we provide an outlook on the future directions of polymer nanocarriers in TCM delivery. This review underscores the transformative potential of polymer nanocarriers in revolutionizing TCM delivery, offering a pathway to harness the full therapeutic potential of TCMs while ensuring safety and efficacy in a modern medical context.

Synthesis of Amphiphilic Block Copolymer and Its Application in Pigment-Based Ink.

Amphiphilic block copolymers-based aqueous color inks show great potential in the field of visual communication design. However, the conventional step-by-step chemistry employed to synthesize the amphiphilic block copolymers is intricate, with low yield and high economic and environmental costs. In this work, we present a novel method for preparing an amphiphilic AB di-block copolymer of PCL-b-PAA by employing a combined polymerization strategy that involves both cationic ring-opening polymerization (ROP) of the ε-caprolactone monomer and the reversible addition-fragmentation chain-transfer (RAFT) polymerization on the acrylic acid monomer simultaneously. The corresponding polycaprolactone (PCL) and polyacrylic acid (PAA) serve as the hydrophobic and hydrophilic units, respectively. The effectiveness of the amphiphilic AB di-block copolymer as the polymeric pigment dispersant for water-based color inks is evaluated. The amphiphilic AB di-block copolymer of PCL-b-PAA exhibits a molecular weight of 1400 g mol-1, which is consistent with the theoretical value and suitable for polymeric dispersant application. The high surface excess (Γmax) of the PCL-b-PAA in water indicates a densely packed molecular morphology at the water/air interface. Additionally, micelles can be stably formed in the aqueous PCL-b-PAA solution at very low concentrations by demonstrating a low CMC value of 10-4 wt% and a micelle dimension of approximately 30 nm. The model ink dispersion is prepared using organic dyes (Disperse Yellow 232) and the amphiphilic block copolymer of PCL-b-PAA. The dispersion demonstrates near-Newtonian behavior, which is highly favorable for the application as inkjet ink. Furthermore, the ink dispersion displays a low viscosity, making it particularly suitable for visual communication design and printing purposes. Moreover, the ink dispersion demonstrates an unimodal distribution of the particle size, with an average diameter of approximately 500 nm. It retains exceptional stability of dispersion and even conducts a thermal aging treatment at 60 °C for 5 days. This work presents a facile and efficient synthetic strategy and molecular design of AB di-block copolymer-based dispersants for dye dispersions.

Synthesis of functional polyacrylamide (co)polymers by organocatalyzed post-polymerization modification of non-activated esters.

The broad application of polyacrylamides (PAMs) has greatly promoted the development of new synthetic methods to prepare PAM-based functional (co)polymers regarding their traditional preparation via the direct polymerization of various acrylamide monomers. Herein, we have explored the post-polymerization modification of the poly(2,2,2-trifluoroethyl acrylate) (PTFEA) homopolymer, a typical non-activated ester, and various amines using the organo-catalytic system involving 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,2,4-triazole (TA). The reaction kinetics (e.g., the optimized reaction solvent, temperature, time, initial molar ratio of amines to esters and the molar ratio of DBU to TA) were carefully studied with the modulus substrate of iso-propylamine as the formed poly(iso-propyl acrylamide) (PNIPAM) representing the most investigated PAM. The full and partial amidation of the esters in PTFEA could be precisely regulated just by controlling the kinetic conditions to give (co)polymers with designable compositions and structures. We have demonstrated that the poly(N-acryloyl pyrrolidine) obtained by the post-polymerization modification of non-activated ester and pyrrolidine exhibited a noticeable phase transition, which confirmed the robustness and versatility of the post-polymerization modification. The described method paves the way for the synthesis of various (co)polymers with amide side chains from readily available polymer precursors.

Recent Advances in Biodegradable and Biocompatible Synthetic Polymers Used in Skin Wound Healing.

The treatment of skin wounds caused by trauma and pathophysiological disorders has been a growing healthcare challenge, posing a great economic burden worldwide. The use of appropriate wound dressings can help to facilitate the repair and healing rate of defective skin. Natural polymer biomaterials such as collagen and hyaluronic acid with excellent biocompatibility have been shown to promote wound healing and the restoration of skin. However, the low mechanical properties and fast degradation rate have limited their applications. Skin wound dressings based on biodegradable and biocompatible synthetic polymers can not only overcome the shortcomings of natural polymer biomaterials but also possess favorable properties for applications in the treatment of skin wounds. Herein, we listed several biodegradable and biocompatible synthetic polymers used as wound dressing materials, such as PVA, PCL, PLA, PLGA, PU, and PEO/PEG, focusing on their composition, fabrication techniques, and functions promoting wound healing. Additionally, the future development prospects of synthetic biodegradable polymer-based wound dressings are put forward. Our review aims to provide new insights for the further development of wound dressings using synthetic biodegradable polymers.

Tough, Anti-Swelling Supramolecular Hydrogels Mediated by Surfactant-Polymer Interactions for Underwater Sensors.

It is a great challenge for traditional hydrogel-based sensors to be effective underwater due to unsatisfactory water resistance and insufficient wet adhesion. Herein, a tough supramolecular hydrogel aiming at underwater sensing is prepared by the modification of hydrophilic poly(acrylic acid) (PAA) with a small amount of hydrophobic lauryl methacrylate (LMA) in the presence of high concentrations of the cationic surfactant cetyltrimethylammonium bromide (CTAB). Owing to the synergistic effects of the electrostatic interactions and hydrophobic associations of CTAB with the P(AA-co-LMA) copolymer, the hydrogel with a water content of approximately 58.5 wt % demonstrates outstanding anti-swelling feature, superior tensile strength (≈1.6 MPa), large stretchability (>900%), rapid room-temperature self-recovery (≈3 min at 100% strain), and robust wet adhesion to diverse substrates. Moreover, the strain sensor based on the hydrogel displays keen sensitivity in a sensing range of 0-900% (gauge factor is 0.42, 3.44, 5.44, and 7.39 in the strain range of 0-100, 100-300, 300-500, and 500-900%, respectively) and pronounced stability both in air and underwater. Additionally, the hydrogel can be easily recycled by dissolving in anhydrous ethanol. This work provides a facile strategy to fabricate eco-friendly, tough supramolecular hydrogels for underwater sensing.

In situ-prepared poly(ether-ester)-based gel polymer electrolytes for high-performance lithium metal batteries.

Batteries based on an in situ-polymerized amorphous cross-linked poly(ether-ester) GPE exhibit high performance, which is attributed to the synergistic effect of the ether and ester segments of the GPE and the in situ-generated polymer electrolytes.

Hybrid Copolymerization of Ethylene Oxide and tert-Butyl Methacrylate with Organocatalyst.

Hybrid copolymerization of structurally different, reactivity and mechanism distinct monomers (e.g., cyclic and vinyl type monomers) is of great interest and challenge for both academic research and practical application. Herein, ethylene oxide-co-tert-butyl methacrylate-co-poly(ethylene glycol) benzyl methacrylate (EO-co-BMA-co-bPEO), a statistical copolymer was synthesized via hybrid copolymerization of EO and BMA using an uncharged, non-nucleophilic organobase t-BuP4 as the catalyst. Detailed characterizations indicate that hybrid copolymerization of ethylene oxide and vinyl monomer forms a statistical copolymer concurrently with the transesterification of tert-butyl group and oligomer PEO anions. The application of the copolymer as all solid lithium-ion battery polymer electrolyte was investigated by detecting the ionic conductivity (σ) with electrical impedance spectrum measurement.

Combined Approach of Compression Molding and Magnetic Attraction to Micropatterning of Magnetic Polydimethylsiloxane Composite Surfaces with Excellent Anti-Icing/Deicing Performance.

The accumulation of ice and contaminants on the surface of composite insulators will cause high energy consumption or even major hazards to power systems. In this work, the polydimethylsiloxane (PDMS) silicone rubber was modified by surface micropatterning and material compositing. Highly crosslinked poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) (PZS) was used to directly coat ferroferric oxide (Fe3O4) nanoparticles. The obtained core-shell Fe3O4@PZS microspheres were loaded with carbon nanotubes (CNTs) to get CNTs/Fe3O4@PZS as the photothermal magnetic filler. The PDMS/CNTs/Fe3O4@PZS surfaces with micronscale truncated cones were prepared via a combined method of compression molding and magnetic attraction. The 1H,1H,2H,2H-perfluorodecyltrichlorosilane-coated template and magnetic field can increase the height of the microstructure to ∼76 µm and maintain the contact angle of microstructured PDMS/CNTs/Fe3O4@PZS surfaces at a high level (∼152°). Compared with the flat PDMS surface, the micronscale truncated cones extend the freezing time from 4.5 to 11.5 min and also undermine the ice adhesion strength from ∼25 to ∼17 kPa for the microstructured PDMS/CNTs/Fe3O4@PZS surface. The temperature of the PDMS/CNTs/Fe3O4@PZS surface molded with magnetic attraction increases linearly with time and the internal magnetic fillers and achieves 280 °C in 10 s. The efficiency of temperature rise is increased by ∼46%, and hence the entire frozen water droplet can melt within 20 s. The strategy combining active deicing with passive anti-icing undoubtedly promotes the development of high efficiency anti-icing materials and can be applied on insulators to prevent icing flashover.

Studying the Ring-Opening Polymerization of 1,5-Dioxepan-2-one with Organocatalysts.

Three different organocatalysts, namely, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris (dimethylamino) phosphoranylidenamino]-2Λ5,4Λ5-catenadi(phosphazene) (t-BuP4), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), have been used as 1,5-dioxepan-2-one (DXO) ring-opening polymerization (ROP) catalysts at varied reaction conditions. 1H NMR spectra, size exclusion chromatography (SEC) characterizations, and kinetic studies prove that the (co)polymerizations are proceeded in a controlled manner with the three organocatalysts. It is deduced that t-BuP4 and DBU catalysts are in an initiator/chain end activated ROP mechanism and TBD is in a nucleophilic ROP mechanism.

PEGylation confers greatly extended half-life and attenuated immunogenicity to recombinant methioninase in primates.

Methionine depletion by recombinant methioninase (rMETase) has been demonstrated previously to be highly effective in tumor-bearing mouse models. However, the therapeutic potential of rMETase has been limited by its short plasma half-life and immunologic effects, including high antibody production in mice and monkeys and anaphylactic reactions in monkeys. To overcome these limits of rMETase, the enzyme has been coupled to methoxypolyethylene glycol succinimidyl glutarate (MEGC-PEG-5000). In this study, we evaluated the pharmacokinetics, antigenicity and toxicity of MEGC-PEG-rMETase in Macaca fascicularis monkeys using an escalating-dose strategy. Dose ranging studies at 1,000, 4,000, and 8,000 units/kg i.v. determined that a single dose of 4,000 units/kg was sufficient to reduce plasma methionine to <5 micromol/L for 12 hours. Pharmacokinetic analysis with the single 4,000 units/kg dose showed that MEGC-PEG-rMETase holoenzyme activity was eliminated with a biological half-life of 1.3 hours, and the MEGC-PEG-rMETase apoenzyme was eliminated with a biological half-life of 90 hours, an approximately 36-fold increase compared with non-PEGylated rMETase. A single dose at 2,000 units/kg of MEGC-PEG-rMETase resulted in an apoenzyme half-life of 143 hours. A seven-day i.v. administration of 4,000 units/kg every 12 hours resulted in a steady-state depletion of plasma methionine to <5 micromol/L. The only manifest toxicity was decreased food intake and slight weight loss. Red cell values and hemoglobin declined transiently during treatment but recovered after cessation of treatment. Subsequent challenges on days 29, 50 and, 71 did not result in any immunologic reactions. This result is in contrast to non-PEGylated rMETase, which elicited anaphylactic reactions in monkeys. Anti-MEGC-PEG-rMETase antibodies (at 10(-2)) were found on day 29, and these increased to 10(-3) to 10(4) on day 71, 100 to 1,000-fold less than antibodies elicited by naked rMETase. Although anti-MEGC-PEG-rMETase antibodies were produced, no neutralizing antibody was identified, and each challenge dose was effective in depleting plasma methionine levels. The results of the present study demonstrate that PEGylation greatly prolongs serum half-life of the rMETase apoenzyme and eliminated anaphylactic reactions. The results indicate a profile with respect to serum half-life, toxicity, and antigenicity that suggest clinical potential of MEGC-PEG-rMETase.

Cationic polycarbonate-grafted superparamagnetic nanoparticles with synergistic dual-modality antimicrobial activity.

We report a new class of antimicrobial nanomaterials with biodegradable cationic polycarbonates grafted on superparamagnetic nanoparticles. Our results have shown that end-functionalized cationic polycarbonates, synthesized by organocatalytic ring opening polymerization, can be grafted onto superparamagnetic MnFe2O4 nanoparticles via ligand exchange. In comparison with the individual building blocks, the core-shell hybrid nanoparticles led to improved antimicrobial activities in two ways: first, the cationic polycarbonates in a brush form afforded a greater charge density than that of free polymer chains, resulting in stronger interactions with bacterial surfaces. Second, the structural integration of the "soft" polycarbonate shell and the "hard" superparamagnetic core in the hybrid nanoparticles brings about a synergistic action of membrane disruption by the cationic shell and magnetic hyperthermia by the nanoparticle core. The combination of two physical killing mechanisms holds great promise in fighting against a broad spectrum of bacterial pathogens.

Large-Size CH3NH3PbBr3 Single Crystal: Growth and In Situ Characterization of the Photophysics Properties.

We reported a facile single-solution fabrication method to grow large-scale CH3NH3PbBr3 hybrid perovskite single crystal at room temperature. The obtained single crystal in this experiment was 14 × 14 mm. The sample's in situ photophysics properties under dark and illumination, including the surface morphology, work function, surface current distribution, microcosmic I-V curves, as well as the polarization behavior, were in situ characterized by integrated utilization of a scanning probe microscopy, respectively. Piezoresponse force microscopy (PFM) phase angles indicated the existence of "polarization" in CH3NH3PbBr3 lattice. Interestingly, the "polarization effect" was enhanced by the plus light source. Moreover, a surface potential shift as large as 200 mV was observed under the condition of the illumination on and off. This research is proposed to provide an opportunity to take a fresh look at the architectural design and photovoltaic performance origin of the hybrid perovskite solar cells.

Computational Study of the Cation-Modified GSH Peptide Interactions With Perovskite-Type BFO-(111) Membranes Under Aqueous Conditions.

We elucidated a number of facets regarding glutathione (GSH)-bismuth ferrite (BiFeO3, BFO) interactions and reactivity that have previously remained unexplored on a molecular level. In this approach, the cation-modified reduced GSH (or oxidised glutathione (GS·)) formed on the (111)-oriented BiFeO3 membrane (namely BFO-(111)) can serve as an efficient quencher, and the luminescence mechanism is explained in aqueous conditions. Notably, we suggest the use of Fe(2+)↓ ion as an electron donor and K(+) ion as an electron acceptor to exert a "gluing" effect on the glutamic acid (Glu) and glycine (Gly) side chains, producing an exposed sulfhydryl (-SH) configuration. This method may enable the rational design of a convenient platform for biosensors.

DFT and two-dimensional correlation analysis methods for evaluating the Pu(3+)-Pu(4+) electronic transition of plutonium-doped zircon.

Understanding how plutonium (Pu) doping affects the crystalline zircon structure is very important for risk management. However, so far, there have been only a very limited number of reports of the quantitative simulation of the effects of the Pu charge and concentration on the phase transition. In this study, we used density functional theory (DFT), virtual crystal approximation (VCA), and two-dimensional correlation analysis (2D-CA) techniques to calculate the origins of the structural and electronic transitions of Zr1-cPucSiO4 over a wide range of Pu doping concentrations (c=0-10mol%). The calculations indicated that the low-angular-momentum Pu-fxy-shell electron excites an inner-shell O-2s(2) orbital to create an oxygen defect (VO-s) below c=2.8mol%. This oxygen defect then captures a low-angular-momentum Zr-5p(6)5s(2) electron to form an sp hybrid orbital, which exhibits a stable phase structure. When c>2.8mol%, each accumulated VO-p defect captures a high-angular-momentum Zr-4dz electron and two Si-pz electrons to create delocalized Si(4+)→Si(2+) charge disproportionation. Therefore, we suggest that the optimal amount of Pu cannot exceed 7.5mol% because of the formation of a mixture of ZrO8 polyhedral and SiO4 tetrahedral phases with the orientation (10-1). This study offers new perspective on the development of highly stable zircon-based solid solution materials.

First principles simulation of temperature dependent electronic transition of FM-AFM phase BFO.

Understanding how temperature affects the electronic transitions of BFO is important for design of BiFeO3 (BFO)-based temperature-sensitive device. Hitherto, however, there have been only very limited reports of the quantitative simulation. Here, we used density functional theory (DFT) and two-dimensional correlation analysis (2D-CA) techniques to calculate the systematic variations in electronic transitions of BFO crystal, over a range of temperature (50~1500 K). The results suggest that the heat accumulation accelerates the O-2p(4) orbital splitting, inducing the Fe(3+)-3d(5) → Fe(2+)-3d(5)d(0) charge disproportionation. The origin is observed as the temperature-dependent electron transfer process changes from threefold degeneracy to twofold degeneracy. Additionally, the crystallographic orientation (111) can be used to control the 2p-hole-induced electronic transition as O → unoccupied Fe(3+)-3d(5), in comparison to the O → Bi-6p(3) + Fe(3+)-3d(5)d(0) on the orientations (001) and (101). This study offers new perspective on the improvement of BFO-based temperature-sensitive device.

Poly(l-lactide-co-2-(2-methoxyethoxy)ethyl methacrylate): a biodegradable polymer with protein resistance.

We have synthesized poly(l-lactide-co-2-(2-methoxyethoxy)ethyl methacrylate) (LA-co-MEO2MA) containing both degradable and protein resistant units via hybrid copolymerization with (1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phophoranylidenamino]-2Λ5,Λ5-catenadi(phosphazene) (t-BuP4) as the catalyst. Nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC) show that LA-co-MEO2MA is a random copolymer. The studies of quartz crystal microbalance with dissipation (QCM-D) demonstrate that the copolymer enzymaticlly degrades much faster than poly(l-lactide) (PLA) homopolymer due to its lower crystallinity. We have also investigated the adsorption of bovine serum albumin (BSA), lysozyme or fibrinogen on a LA-co-MEO2MA surface in real time by use of QCM-D and surface plasmon resonance (SPR). Our studies reveal that the polymer is protein resistant depending on MEO2MA content. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay experiments demonstrate that the polymer has a low cytotoxicity.

Computational investigation on the new high energy density material of aluminum enriched 1, 1-diamino-2, 2-dinitroethylene.

Aluminum enriched 1, 1-diamino-2, 2-dinitroethylene (Al-FOX-7) crystal, as a new high energy density material (HEDM), was designed and investigated using grand canonical monte carlo (GCMC), NVT+NPT-molecular dynamics (MD) and GGA-PBE-density functional theory (DFT) methods. The results show that, Al atoms break out H-bond of functional group of FOX-7 crystal, and form new Al-H and Al-O bonds. Their atomic content (x) influences the surface electronic states, friction sensitivities and cj detonation properties of Al-FOX-7 crystals. While x is 4 atoms, the crystal has the highest friction sensitivities and cj detonation temperatures, which are about 1.5 times to that of FOX-7 crystal.