In Situ Crosslinked Biodegradable Hydrogels Based on Poly(Ethylene Glycol) and Poly(ε-Lysine) for Medical Application.

Hydrogels have emerged as promising biomaterials due to their excellent performance; however, their biocompatibility, biodegradability, and absorbability still require improvement to support a broader range of medical applications. This paper presents a new biofunctionalized hydrogel based on in situ crosslinking between maleimide-terminated four-arm-poly(ethylene glycol) (4-arm-PEG-Mal) and poly(ε-lysine) (ε-PL). The PEG/ε-PL hydrogels, named LG-n, were rapidly formed via amine/maleimide reaction by mixing 4-arm-PEG-Mal and ε-PL under physiological conditions.

Crosslinked Biodegradable Hybrid Hydrogels Based on Poly(ethylene glycol) and Gelatin for Drug Controlled Release.

A series of hybrid hydrogels of poly(ethylene glycol) (PEG) were synthesized using gelatin as a crosslinker and investigated for controlled delivery of the first-generation cephalosporin antibiotic, Cefazedone sodium (CFD). A commercially available 4-arm-PEG-OH was first modified to obtain four-arm-PEG-succinimidyl glutarate (4-arm-PEG-SG), which formed the gelatin-PEG composite hydrogels (SN) through crosslinking with gelatin. To regulate the drug delivery, SN hydrogels with various solid contents and crosslinking degrees were prepared.

PEG-crosslinked O-carboxymethyl chitosan films with degradability and antibacterial activity for food packaging.

This study developed a kind of PEG-crosslinked O-carboxymethyl chitosan (O-CMC-PEG) with various PEG content for food packaging. The crosslinking agent of isocyanate-terminated PEG was firstly synthesized by a simple condensation reaction between PEG and excess diisocyanate, then the crosslink between O-carboxymethyl chitosan (O-CMC) and crosslinking agent occurred under mild conditions to produce O-CMC-PEG with a crosslinked structure linked by urea bonds. FT-IR and H NMR techniques were utilized to confirm the chemical structures of the crosslinking agent and O-CMC-PEGs.

Cross-linked poly(ester urethane)/starch composite films with high starch content as sustainable food-packaging materials: Influence of cross-link density.

This study focused on the development of cross-linked poly(ester urethane)/starch (PEUST) composites containing 50 wt% starch content for food-packaging materials. The NCO-terminated poly(caprolactone-urethane) prepolymer (PCUP) was first synthesized through bulk condensation. Then, low-moisture starch (0.

Biomimetic and Multifunctional Hemostatic Hydrogel with Rapid Thermoresponsive Gelation and Robust Wet Adhesion for Emergency Hemostasis: A Rational Design Based on Photo-Cross-Linking Coordinated Hydrophilic-Hydrophobic Balance Strategies.

Uncontrolled bleeding in emergency situations is a great threat to both military and civilian lives, and an ideal hemostat for effectively controlling prehospital hemorrhage is urgently needed but still lacking. Although hemostatic hydrogels are promising for emergency hemostasis, they are currently challenged by either the mutual exclusion between a short gelation time and strong adhesive network or the insufficient functionality of ingredients and complicated operations for in situ curing. Herein, an extracellular matrix biopolymer-based and multifunctional hemostatic hydrogel that simultaneously integrates rapid thermoresponsive gelation, robust wet adhesion, and ease of use in emergencies is rationally engineered.

Enhanced hemocompatibility and antibacterial activity of biodegradable poly(ester-urethane) modified with quercetin and phosphorylcholine for durable blood-contacting applications.

This work developed innovative poly(ester-urethane) materials double-modified by quercetin (QC) and phosphorylcholine (PC) with improved antibacterial activity and hemocompatibility. The functional monomer of PC-diol was first synthesized a click reaction between 2-methacryloyloxyethyl phosphorylcholine and α-thioglycerol; the NCO-terminated prepolymer was subsequently prepared by a one-pot condensation method of PC-diol, poly(ε-caprolactone) diol, and excess isophorone diisocyanate; finally, the prepolymer was chain-extended with QC to produce the linear products (PEU-PQs). H NMR, FT-IR, and XPS techniques confirmed the successful introduction of PC and QC, and the in-depth characterization of the cast PEU-PQ films was carried out.

An Imine-Based Porous 3D Covalent Organic Polymer as a New Sorbent for the Solid-Phase Extraction of Amphenicols from Water Sample.

In this paper, an imine-based porous 3D covalent organic polymer (COP) was synthesized via solvothermal condensation. The structure of the 3D COP was fully characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and powder X-ray diffractometry, thermogravimetric analysis, and Brunauer-Emmer-Teller (BET) nitrogen adsorption. This porous 3D COP was used as a new sorbent for the solid-phase extraction (SPE) of amphenicol drugs, including chloramphenicol (CAP), thiamphenicol (TAP), and florfenicol (FF) in aqueous solution.

Adsorption-Reaction Processes Between Gelatin and PDMS-E Emulsion Droplets.

In this work, the effects of droplet size and reaction time on the adsorption-reaction processes between gelatin and α-[3-(2,3-epoxypropoxy) propyl]-ω-butyl-polydimethylsiloxane (PDMS-E) emulsion droplets were studied. Gelatin molecules were only physically adsorbed on the surface of the PDMS-E droplet in the 0-75 min range, which was unrelated to the droplet size (100-1000 nm). For the small-size droplets (<410 nm), the physical adsorption proceeded over 75 min followed by agglomeration.

Facile Method for Surface-Grafted Chitooligosaccharide on Medical Segmented Poly(ester-urethane) Film to Improve Surface Biocompatibility.

In the paper, the chitooligosaccharide (CHO) was surface-grafted on the medical segmented poly(ester-urethane) (SPU) film by a facile two-step procedure to improve the surface biocompatibility. By chemical treatment of SPU film with hexamethylene diisocyanate under mild reaction condition, free -NCO groups were first introduced on the surface with high grafting density, which were then coupled with -NH groups of CHO to immobilize CHO on the SPU surface (SPU-CHO). The CHO-covered surface was characterized by FT-IR and water contact angle test.

Engineering a photosensitizer nanoplatform for amplified photodynamic immunotherapy via tumor microenvironment modulation.

Photosensitizer-based photodynamic therapy (PDT) can not only kill tumor cells by the generated cytotoxic reactive oxygen species (ROS), but also trigger immunogenic cell death (ICD) and activate an immune response for immunotherapy. However, such photodynamic immunotherapy suffers from major obstacles in the tumor microenvironment. The hypoxic microenvironment greatly weakens PDT, while the immunosuppressive tumor microenvironment caused by aberrant tumor blood vessels and indoleamine 2,3-dioxygenase (IDO) leads to a significant reduction in immunotherapy.

Facile preparation of medical segmented poly(ester-urethane) containing uniformly sized hard segments and phosphorylcholine groups for improved hemocompatibility.

In order to improve the hemocompatibility of durable medical-grade polyurethane, a novel series of segmented poly(ester-urethane)s containing uniformly sized hard segments and phosphorylcholine (PC) groups on the side chains (SPU-PCs) was prepared by a facile method. The 2-methacryloyloxyethyl phosphorylcholine (MPC) was first reacted with α-thioglycerol by Michael addition to give a diol compound (MPC-diol), then the SPU-PCs with various PC content were prepared by a one-step chain extension of the mixture of MPC-diol and poly(ε-caprolactone) diol (PCL-diol) with aliphatic diurethane diisocyanates (HBH). The chemical structures of MPC-diol and SPU-PCs were confirmed by H NMR and FT-IR, and the influences of PC content on the physicochemical properties of the SPU-PC films were studied.

A multifunctional gelatine-quaternary ammonium copolymer: An efficient material for reducing dye emission in leather tanning process by superior anionic dye adsorption.

Leather wastewater is one of the most polluting industrial emissions. The efficiency of wastewater remediation is limited by its complex composition. Herein, a novel strategy for designing modified gelatine with higher degree of quaternization (MG-2) is presented.

A mild method for surface-grafting MPC onto poly(ester-urethane) based on aliphatic diurethane diisocyanate with high grafting efficiency.

The aim of this work is to provide a new kind of polyurethane with improved surface blood compatibility for long-term blood-contacting biomaterials. In the study, an aliphatic poly(ester-urethane) (H-PEU) with uniform-size hard segments was synthesized by one-step chain extension of poly(ε-caprolactone) (PCL) with diurethane diisocyanate (HBH), and biomimetic phosphorylcholine (PC) groups were immobilized onto the film surface with high grafting efficiency by three-step chemical treatments under mild reaction conditions. The H-PEU film was firstly treated with 1,6-hexanediisocyanate (HDI) to introduce -NCO groups on the surface (H-PEU-NCO) through an allophanate reaction; the -NCO groups were then coupled via a condensation reaction with one of -NH groups of tris(2-aminoethyl)amine (TAEA) to immobilize -NH on the surface (H-PEU-NH); finally, the double bond of 2-methacryloyloxyethyl phosphorylcholine (MPC) reacted with -NH by Michael addition reaction to obtain MPC-grafted H-PEU (H-PEU-MPC).

Degradable Poly(ether-ester-urethane)s Based on Well-Defined Aliphatic Diurethane Diisocyanate with Excellent Shape Recovery Properties at Body Temperature for Biomedical Application.

The aim of this study is to offer a new class of degradable shape-memory poly(ether-ester-urethane)s (SMPEEUs) based on poly(ether-ester) (PECL) and well-defined aliphatic diurethane diisocyanate (HBH) for further biomedical application. The prepolymers of PECLs were synthesized through bulk ring-opening polymerization using ε-caprolactone as the monomer and poly(ethylene glycol) as the initiator. By chain extension of PECL with HBH, SMPEEUs with varying PEG content were prepared.

Synthesis and properties of biodegradable poly(ester-urethane)s based on poly(ε-caprolactone) and aliphatic diurethane diisocyanate for long-term implant application: effect of uniform-size hard segment content.

In this article, a series of medical poly(ester-urethane)s (PEUs) with varying uniform-size hard segment content were prepared one-step chain extension of poly(-caprolactone)s with aliphatic urethane diisocyanate, and the corresponding films were obtained by solvent evaporation technique. The chemical structures of polymers were confirmed by H NMR, FT-IR and GPC. The effect of uniform-size hard segment content on the physicochemical properties of PEU films, including thermal properties, mechanical properties, crystallization behavior, water-swelling behavior and degradability, was extensively researched.

Preparation, Physicochemical Properties, and Hemocompatibility of the Composites Based on Biodegradable Poly(Ether-Ester-Urethane) and Phosphorylcholine-Containing Copolymer.

To improve the hemocompatibility of the biodegradable medical poly(ether-ester-urethane) (PEEU), containing uniform-size aliphatic hard segments that was prepared in our lab, a copolymer containing phosphorylcholine (PC) groups was blended with the PEEU. The PC-copolymer of poly(MPC-co-EHMA) (PMEH) was first obtained by copolymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) and 2-ethylhexyl methacrylate (EHMA), and then dissolved in mixed solvent of ethanol/chloroform to obtain a homogeneous solution. The composite films (PMPU) with varying PMEH content were prepared by solvent evaporation method.

Preparation of Compositional Gradient Polymeric Films Based on Gradient Mesh Template.

In this paper, a template-filling method was found to prepare composition gradient gelatin films by incorporating α-[3-(2,3-epoxypropoxy) propyl]-ω-butyl-polydimethylsiloxane (PDMS⁻E) grafted gelatin (PGG) into a gradient gelatin mesh template. The method can be used to prepare other composition gradient biopolymer films. Gradient mesh template prepared by the methacrylic anhydride cross-linked gelatin under temperature gradient field.

Preparation, Physicochemical Properties and Hemocompatibility of Biodegradable Chitooligosaccharide-Based Polyurethane.

The purpose of this study was to develop a process to achieve biodegradable chitooligosaccharide-based polyurethane (CPU) with improved hemocompatibility and mechanical properties. A series of CPUs with varying chitooligosaccharide (COS) content were prepared according to the conventional two-step method. First, the prepolymer was synthesized from poly(ε-caprolactone) (PCL) and uniform-size diurethane diisocyanates (HBH).

A Mild Method for Surface-Grafting PEG Onto Segmented Poly(Ester-Urethane) Film with High Grafting Density for Biomedical Purpose.

In the paper, poly(ethylene glycol) (PEG) was grafted on the surface of poly(ester-urethane) (SPEU) film with high grafting density for biomedical purposes. The PEG-surface-grafted SPEU (SPEU-PEG) was prepared by a three-step chemical treatment under mild-reaction conditions. Firstly, the SPEU film surface was treated with 1,6-hexanediisocyanate to introduce -NCO groups on the surface with high density (5.

Tailored graphene oxide-doxorubicin nanovehicles via near-infrared dye-lactobionic acid conjugates for chemo-photothermal therapy.

Graphene oxide (GO), as a drug delivery carrier, has attracted considerable attention because of its interesting properties. However, GO tends to aggregate in aqueous solution. Amphiphilic molecules are usually necessary to stabilize GO.

Reaction Kinetics at PDMS-E Emulsion Droplet-Gelatin Interface.

In this work, interfacial reaction kinetics between α-[3-(2,3-epoxypropoxy)propyl]-ω-butyl-polydimethylsiloxane emulsion droplets with different sizes and gelatin was studied. The results of amino conversion rate determination show that the reaction proceeded in two steps. Fluorescence spectra analysis indicates that step 1 (0-2 h) should be the adsorption of gelatin on droplet surface.

Electrostatic and hydrophobic controlled self-assembly of PDMS-E grafted gelatin for self-cleaning application.

Understanding the assembly mechanisms of supramolecular architectures in nature is essential for the design and synthesis of novel biomaterials. In the work, self-assembly of gelatin-mono epoxy terminated polydimethylsiloxane polymer (PGG) controlled by electrostatic and hydrophobic interactions between gelatin and sodium dodecyl sulfate (SDS) was investigated in suit. Confocal laser scanning microscopy, circular dichroism spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were conducted to reveal the structure evolution of PGG at a molecular level with the increment of SDS concentration, including micro-sized sphere, core-shell and multi-layer structure.

Synthesis of a novel biomedical poly(ester urethane) based on aliphatic uniform-size diisocyanate and the blood compatibility of PEG-grafted surfaces.

The purpose of this study is to offer a novel kind of polyurethane with improved surface blood compatibility for long-term implant biomaterials. In this work, the aliphatic poly(ester-urethane) (PEU) with uniform-size hard segments was prepared and the PEU surface was grafted with hydrophilic poly(ethylene glycol) (PEG). The PEU was obtained by chain-extension of poly(ɛ-caprolactone) (PCL) with isocyanate-terminated urethane triblock.

Photo-cross-linked biodegradable hydrogels based on n-arm-poly(ethylene glycol), poly(ε-caprolactone) and/or methacrylic acid for controlled drug release.

In this paper, a novel kind of photo-cross-linked biodegradable hydrogels based on n-arm-poly(ethylene glycol) ( n = 2, 3, and 4) and poly(ɛ-caprolactone) was prepared by ultraviolet-initiated free radical polymerization. The resulting n-arm-poly(ethylene glycol)-poly(ɛ-caprolactone) and n-arm-poly(ethylene glycol)-poly(ɛ-caprolactone) acrylate (n-arm-PEG-PCL-AC, macromer) were characterized by proton nuclear magnetic resonance and fourier transform infrared spectra. The influences of arm numbers and concentration of macromer on the properties of hydrogel were researched systematically, and the results showed that the gelation time, equilibrium swelling ratio, in vitro degradation, and drug release rate decreased with the increase of arm numbers and concentration of macromer.

Scale Effect on the Interface Reaction between PDMS-E Emulsion Droplets and Gelatin.

In this study, the scale effect on the interface reaction between PDMS-E emulsion droplets and gelatin was studied systematically. The monodisperse α-[3-(2,3-epoxy-propoxy)propyl]-ω-butyl-polydimethylsiloxane (PDMS-E) emulsion droplets on different scales were prepared using a Shirasu porous glass (SPG) membrane with a 0.5 μm pore size.