Thermo-, pH- and glucose-responsive polymeric nanoparticles are of great interest in developing a self-regulated drug delivery system. The novel core-shell nanoparticles were synthesized by self-assembly of a phenylboronic acid-based block copolymer poly-(N-isopropylacrylamide)-block-poly(3-acrylamidophenylboronic acid) (PNIPAM₁₃₆-b-PAPBA₁₆) and a fluorescent complex glucosamine-poly(N-isopropylacrylamide)/Eu(III) (GA-PNIPAM)/Eu(III) based on the cross-linking between PBA- and GA-containing blocks in this work. The nanoparticles can be tuned via thermo-induced collapse or glucose-induced swelling at appropriate pH and temperatures; they had an average kinetic radius was about 80nm, and which showed excellent fluorescence. MTT assays revealed the nanocarriers had no significant cytotoxic response of the micelle when it was observed in the cell line over the concentration range from 0.1 to 1000 μg/ml at any exposure times. GRAPHICAL ABSTRACT

Stimuli-responsive luminescent hybrid nanoparticles consisting of a magnetite Fe₃O₄ core and a hydrophilic outer shell were synthesized. The shell was a thermo-responsive Eu(III) complex shell, which was synthesized as follows: first, 3-Methacryloxypropyl-trimethoxysilane (MEMO)-co-poly(N-isopropylacrylamide) (NIPAM) (MEMO-co-PNIPAM) copolymer was prepared by free radical polymerization. Subsequently, the copolymer chelated with Europium(III) ions to form a luminescent polymeric layer. Finally, the polymeric shell was grafted onto the Fe₃O₄ nanoparticles surface through chemical action. The sizes of fabricated nanoparticles with core–shell structure were controlled at about 30-45 nm. The as-synthesized nanocomposite particles had excellent fluorescence performance and thermo-responsive behavior, which possessed high color purity and produced red-emission at 613 nm. The lower critical solution temperature (LCST) of thermo-sensitive magnetic nanoparticles was at around 37–38 °C. Cell viability assays suggested that these nanoparticles showed excellent biocompatibility and fluorescence-intensity in vitro.

A series of thermo- and light-responsive copolymers of poly (N-isopropylacrylamide) (PNIPAM) and 6-[4-(4-methoxy phenyl azo)-phenoxyl-hexyl methacrylate) (AzoMA) (PNIPAM-b-PAzoMA) were synthesized via reversible addition–fragmentation chain transfer (RAFT) radical polymerization. The resulting copolymers had a narrow molecular weight distribution range of 1.06–1.24, in which M_n changed regularly with the monomer concentration. Subsequently, the diblock copolymers were successfully modified on the surface of iron oxide nanoparticles through the interaction between the chemical bonds to prepare Fe₃O₄@(PNIPAM-b-PAzoMA) nanoparticles. The size of fabricated nanoparticles with excellent thermo-sensitivity and photo-sensitivity was controlled at about 40–50 nm. Cell viability assays suggested that the nanoparticles showed no significant cytotoxicity and potential drug delivery in the tumor microenvironment.

Chitosan (CS) has been extensively studied in wound care for its intrinsic hemostatic and antibacterial properties. However, CS has limiting hemostasis applications on account of its drawbacks such as poor adhesion in humid environments and water solubility at neutral pH. CS-based biomaterials, inspired by mussel-adhesive proteins, serve as a suggested platform by biomedical science. The reports show that the mussel-inspired CS-based hemostatic structure has negligible toxicity and excellent adhesiveness. Biomedicine has witnessed significant progress in the development of these hemostatic materials. This review summarizes the methods for the modification of CS by mussel-inspired chemistry. Moreover, the general method for preparation of mussel-inspired CS-based biomaterials is briefly discussed in this review. This work is expected to give a better understanding of opportunities and challenges of the mussel-inspired strategy for the functionalization of CS-based biomaterials in hemostasis and wound healing. This review is hoped to provide an important perspective on the preparation of mussel-inspired CS-based hemostatic materials.

This contribution reports the syntheses, structural analyses and properties of europium (Eu³⁺)- and terbium (Tb³⁺)-based coordination complexes of poly(N-isopropyl,N-methylacrylamide-stat-N,N-dimethylacrylamide) (poly(iPMAm-stat-DMAm)) copolymer, named as poly-Eu(III) and poly-Tb(III), respectively. In greater detail, poly(iPMAm₈₅-stat-DMAm₁₅) is first prepared by random copolymerization of N-isopropyl,N-methylacrylamide (iPMAm) and N,N-dimethylacrylamide (DMAm) via group transfer polymerization (GTP). Next, poly(iPMAm₈₅-stat-DMAm₁₅) is used as the polymer matrix for chelating with Eu³⁺ and Tb³⁺ cations at its side amide groups, to produce poly-Eu(III) and poly-Tb(III). Their structural characterizations by FT-IR spectroscopy and XPS confirm the formation of polymeric complexes. The study on their fluorescence emission characteristics and luminescence lifetime demonstrates that Poly-Eu(III) shows four strong emission peaks at 578, 593, 622, and 651 nm, which are responsible for the electron transitions from the excited ⁵D₀ state to the multiplet ⁷F_J (J = 0, 1, 2, 3) states, respectively, and poly-Tb(III) also displays four emission peaks at 489, 545, 588, and 654 nm, mainly due to the electron transitions of ⁵D₄ → ⁷F_i (i = 6, 5, 4, 3). The luminescence lifetimes of poly-Eu(III) (τ_poly-Eu(III)) and poly-Tb(III) (τ_poly-Tb(III)) are determined to be 4.57 and 7.50 ms, respectively. In addition, in aqueous solutions, poly-Eu(III) and poly-Tb(III) are found to exhibit thermoresponsivity, with their cloud temperatures (T_cs) locating around 36.4 and 36.8 °C, respectively. Finally, the cytotoxicity study on the human colon carcinoma cells LoVo and DLD1 suggests that the luminescent Eu³⁺ and Tb³⁺ in the chelated state with poly(iPMAm-stat-DMAm) show much better biocompatibility and lower toxicity than their inorganic salts.

Regioselective modification of d-glucosamine (2-amino-2-deoxy-d-glucopyranose, GA) through C-1 and C-2 positions to synthesized thermo-responsive D-Glucosamine-poly(N-iso-propylacrylamide) (PNIPAM) via atom transfer radical polymerization (ATRP) was investigated for the first time. Two different schemes of the synthesis for GA derivatives (GA-PNIPAM (i) and (ii)) with well-defined structures using 3,4,6-tri-o-acetyl-2-deoxy-2-phthalimido-β-d-glucopyranose and 1,3,4,6-tetra-o-acetyl-2-amino-2-deoxy-β-d-glucopyranose intermediates were examined. The GA-PNIPAM (ii) had an amino at C-2 position, while there was a hydroxyl in GA-PNIPAM (i) at this position. Both the resulting oligomers (i) and (ii) had a narrow dispersity, and no significant cytotoxic response of copolymers (i) and (ii) was observed in the cell line over the concentration range from 0.1 μg/mL to 1000 μg/mL at any of the exposure times. In addition, it was discovered that GA-PNIPAM (i) and (ii) inhibited the proliferation of Human Hepatocellular Carcinoma Cells HepG2 as the concentration and the time changed, and the inhibitory activity of polymer (ii) was higher than that of he (i). The results suggest that the GA-PNIPAM polymers show excellent biocompatibility in vitro.