This work aimed at elucidating the influence of zwitterionic hard segments on the structures and properties of shape memory polyurethanes (SMPUs). A series of zwitterionic SMPUs was successfully prepared with N-methyldiethanolamine (MDEA), 1,3-propanesultone (1,3-PS), 1,6-hexamethylene diisocyanate (HDI) and polyethylene glycol (PEG6000). The influence of MDEA-PS-based zwitterionic hard segment on structure, morphology, thermal property, shape memory property and cytocompatibility were systematically investigated. The results demonstrated that the PEG-based zwitterionic SMPUs (PEG-ZSMPUs) formed phase separation structure consisting of crystalline soft phase and amorphous hard phase. The MDEA-PS zwitterionic segments showed a tendency to form ionic clusters in hard segments, which served as reinforced net points. Shape memory analysis showed that zwitterionic PEG-ZSMPUs containing a high content of zwitterionic segments had thermal-induced shape memory effects. Finally, cytotoxic assays demonstrated that MDEA-PS zwitterionic segment improved the biocompatibility of PEG-ZSMPUs. The zwitterionic PEG-ZSMPUs could thus have a promising application in smart biomedical fields.

A pH-responsive hydrogel system was prepared by free radical polymerization of acrylamide and methyl acrylic acid in the presence of N-N'-methylene bisacrylamide. Sodium bicarbonate was further applied as a blowing agent, which afforded a porous hydrogel structure. The hydrogel system achieved a constant super swelling rate within simulated intestinal buffer (~4%/min) and remained relatively static within simulated gastric buffer (~0.8%/min). The hydrogel system was able to achieve matrix resilience greater than 30% under a relatively high strain of 40%. In addition, the hydrogel system demonstrated significant swelling properties in response to simulated intestinal environmental over 24 h, with contrasting characteristics in simulated gastric buffer. The hydrogel demonstrated type IV isotherm porosity characteristics, with remarkable MRI and SEM variations in gastric and intestinal simulated fluids. Drug loading was observed to be greater than 98% using theophylline as a prototype drug, evaluating its controlled release kinetics over 24 h. The hydrogel exhibited substantial pH-responsive activity, which could be used as a versatile platform for targeted release of gastric-sensitive therapeutics to the small intestine.

The emerging areas of polymer nanocomposites, as some are already in use in industrial applications and daily commodities, have the potential of offering new technologies with all manner of prominent capabilities. The incorporation of nanomaterials into polymeric matrix provides significant improvements, such as higher mechanical, thermal or electrical properties. In these materials, interface/interphase of components play a crucial role bringing additional features on the resulting nanocomposites. Among the various preparation strategies of such materials, an appealing strategy relies on the use of click chemistry concept as a multi-purpose toolbox for both fabrication and modulation of the material characteristics. This review aims to deliver new insights to the researchers of the field by noticing effective click chemistry-based methodologies on the preparation of polymer nanocomposites and their key applications such as optic, biomedical, coatings and sensor.

Micro-vascularization is a fast, energy-dependent process that is compromised by elevated glucose concentrations such as in diabetes mellitus disease. Here, we studied the effect of the physiological bioinorganic polymer, polyphosphate (polyP), on the reduced ATP content and impaired function of endothelial cells cultivated under "high glucose" (35 mM diabetes mellitus conditions) concentrations. This high-energy biopolymer has been shown to provide a source of metabolic energy, stored in its phosphoanhydride bonds. We show that exposure of human umbilical vein endothelial cells (HUVEC cells) to "high glucose" levels results in reduced cell viability, increased apoptotic cell death, and a decline in intracellular ATP level. As a consequence, the ability of HUVEC cells to form tube-like structures in the in vitro cell tube formation assay was almost completely abolished under "high glucose" conditions. Those cells were grown onto a physiological collagen scaffold (collagen/basement membrane extract). We demonstrate that these adverse effects of increased glucose levels can be reversed by administration of polyP to almost normal values. Using Na-polyP, complexed in a stoichiometric (molar) ratio to Ca2+ ions and in the physiological concentration range between 30 and 300 µM, an almost complete restoration of the reduced ATP pool of cells exposed to "high glucose" was found, as well as a normalization of the number of apoptotic cells and energy-dependent tube formation. It is concluded that the adverse effects on endothelial cells caused by the metabolic energy imbalance at elevated glucose concentrations can be counterbalanced by polyP, potentially opening new strategies for treatment of the micro-vascular complications in diabetic patients.

Assemblies of four three-dimensional (3D) mixed-ligand coordination polymers (CPs) having formulas, {[Zn₂(bdc)₂(4-bpdh)]·C₂H₅OH·2H₂O}n (1), [Zn(bdc)(4-bpdh)]n (2), {[Zn₂(bdc)₂(4-bpdh)₂]·(4-bpdh)}n (3), and {[Zn(bdc)(4-bpdh)]·C₂H₅OH}n (4) (bdc2- = dianion of 1,4-benzenedicarboxylic acid, 4-bpdh = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene) have been synthesized and structurally characterized by single-crystal X-ray diffraction method. Structural determination reveals that the coordination numbers (geometry) of Zn(II) ions in 1, 2, 3, and 4 are five (distorted square-pyramidal (SP)), six (distorted octahedral (Oh)), five (trigonal-bipyramidal (TBP)), and four (tetrahedral (Td)), respectively, and are bridged by 4-bpdh with bis-monodentate coordination mode and bdc2- ligands with bis-bidentate in 1, chelating/bidentate in 2, bis-monodentate and bis-bidentate in 3, and bis-monodentate in 4, to generate two-fold interpenetrating 3D cube-like metal-organic framework (MOF) with pcu topology, non-interpenetrating 3D MOF, two-fold interpenetrating 3D rectangular-box-like MOF with pcu topology and five-fold interpenetrating diamondoid-like MOF with dia topology, respectively. These different intriguing architectures indicate that the coordination numbers and geometries of Zn(II) ions, coordination modes of bdc2- ligand, and guest molecules play important roles in the construction of MOFs and the formation of the structural topologies and interpenetrations. Thermal stabilities, and photoluminescence study of 1⁻4 were also studied in detail. The complexes exhibit ligands based photoluminescence properties at room temperature.

The biocide agent LAE (ethyl αN-lauroyl l-arginate chloride) was coupled with poly(γ-glutamic acid) (PGGA) to form stable ionic complexes with LAE:PGGA ratios of 1 and 0.5. The nanostructure adopted by these complexes and its response to thermal changes were examined in detail by Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) using synchrotron radiation in real time. A layered biphasic structure with LAE filling the space between the polypeptidic sheets was adopted in these complexes. The complexes were stable up to above 250 °C, non-water soluble, and were able to form consistent transparent films. The release of LAE from the complexes upon incubation in aqueous buffer was examined and found to depend on both pH and complex composition. The antibacterial activity of films made of these complexes against Gram-positive (L. monocytogenes and S. aureus) and Gram-negative (E. coli and S. enterica) bacteria was preliminary evaluated and was found to be very high against the formers and only moderate against the later. The bactericide activity displayed by the LAE·PGGA complexes was directly related with the amount of LAE that was released from the film to the environment.

Camellia sinensis, which is obtained from green tea extract (GTE), has been widely used in therapy owing to the antioxidant, chemoprotective, and anti-inflammatory activities of its chemical components. However, GTE is an unstable compound, and may undergo reactions that lead to a reduction or loss of its effectiveness and even its degradation. Hence, an attractive approach to overcome this problem to protect the GTE is its incorporation into liquid crystalline systems (LCS) that are drug delivery nanostructured systems with different rheological properties, since LCS have both fluid liquid and crystalline solid properties. Therefore, the aim of this study was to develop and characterize GTE-loaded LCS composed of polyoxypropylene (5) polyoxyethylene (20) cetyl alcohol, avocado oil, and water (F25E, F29E, and F32E) with different rheological properties and to determine their anti-inflammatory efficacy. Polarized light microscopy revealed that the formulations F25, F29, and F32 showed hexagonal, cubic, and lamellar liquid crystalline mesophases, respectively. Rheological studies showed that F32 is a viscous Newtonian liquid, while F25 and F29 are dilatant and pseudoplastic non-Newtonian fluids, respectively. All GTE-loaded LCS behaved as pseudoplastic with thixotropy; furthermore, the presence of GTE increased the S values and decreased the n values, especially in F29, indicating that this LCS has the most organized structure. Mechanical and bioadhesive properties of GTE-unloaded and -loaded LCS corroborated the rheological data, showing that F29 had the highest mechanical and bioadhesive values. Finally, in vivo inflammation assay revealed that the less elastic and consistent LCS, F25E and F32E presented statistically the same anti-inflammatory activity compared to the positive control, decreasing significantly the paw edema after 4 h; whereas, the most structured and elastic LCS, F29E, strongly limited the potential effects of GTE. Thereby, the development of drug delivery systems with suitable rheological properties may enhance GTE bioavailability, enabling its administration via the skin for the treatment of inflammation.

The development of new antifouling paints requires understanding the parameters involved in antifouling activity and to develop new analytical tools for their evaluation. A series of biodegradable poly(ε-caprolactone-co-δ-valerolactone) copolymers varying by molecular weight and composition were synthesized, characterized and formulated as antifouling paints. The physico-chemical properties such as hydration, degradation, erosion and lixiviation of paints were studied. Microfouling (bacteria and microalgae) was observed by microscopic observations in a short delay, whereas macrofouling colonization was observed by visual inspection during one year. The antifouling activity of paints was modified by varying the composition and molecular weight of copolymer. The crystallinity appears to play a major role in antifouling activity, however the involvement of other properties such as hydration, degradation or erosion remains difficult to understand. Confocal laser scanning and scanning electron microscopes were used for the evaluation of antifouling paints. Results show that microalgae seem to be a pertinent indicator of antifouling activity.

Diblock copolymers consisting of a hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) block and either a cationic or anionic block were prepared from (3-(methacrylamido)propyl)trimethylammonium chloride (MAPTAC) or sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS). Polymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization using a PMPC macro-chain transfer agent. The degree of polymerization for PMPC, cationic PMAPTAC, and anionic PAMPS blocks was 20, 190, and 196, respectively. Combining two solutions of oppositely charged diblock copolymers, PMPC-b-PMAPTAC and PMPC-b-PAMPS, led to the spontaneous formation of polyion complex vesicles (PICsomes). The PICsomes were characterized using ¹H NMR, static abd dynamic light scattering, transmittance electron microscopy (TEM), and atomic force microscopy. Maximum hydrodynamic radius (Rh) for the PICsome was observed at a neutral charge balance of the cationic and anionic diblock copolymers. The Rh value and aggregation number (Nagg) of PICsomes in 0.1 M NaCl was 78.0 nm and 7770, respectively. A spherical hollow vesicle structure was observed in TEM images. The hydrodynamic size of the PICsomes increased with concentration of the diblock copolymer solutions before mixing. Thus, the size of the PICsomes can be controlled by selecting an appropriate preparation method.

Samples of polymer polyethylene terephthalate were exposed to a weakly ionized gaseous plasma to modify the polymer surface properties for better cell cultivation. The gases used for treatment were sulfur dioxide and oxygen of various partial pressures. Plasma was created by an electrodeless radio frequency discharge at a total pressure of 60 Pa. X-ray photoelectron spectroscopy showed weak functionalization of the samples' surfaces with the sulfur, with a concentration around 2.5 at %, whereas the oxygen concentration remained at the level of untreated samples, except when the gas mixture with oxygen concentration above 90% was used. Atomic force microscopy revealed highly altered morphology of plasma-treated samples; however, at high oxygen partial pressures this morphology vanished. The samples were then incubated with human umbilical vein endothelial cells. Biological tests to determine endothelialization and possible toxicity of the plasma-treated polyethylene terephthalate samples were performed. Cell metabolic activity (MTT) and in vitro toxic effects of unknown compounds (TOX) were assayed to determine the biocompatibility of the treated substrates. The biocompatibility demonstrated a well-pronounced maximum versus gas composition which correlated well with development of the surface morphology.

Poly(vinyl alcohol)/hyaluronic acid cryogels loaded with methotrexate were studied. The physical⁻chemical characterization of cryogels was performed by FT-IR spectroscopy, scanning electron microscopy, differential scanning calorimetry and dynamic mechanical thermal analysis. Acute toxicity and haematological parameters were determined by "in vivo" tests. The biocompatibility tests proved that the obtained cryogels showed significantly decreased toxicity and are biocompatible. The pH-responsiveness of the swelling behaviour and of the methotrexate release from the poly(vinyl alcohol)/hyaluronic acid (PVA/HA) cryogels were studied in a pH interval of 2⁻7.4. A significant change in properties was found at pH 5.5 specific for treatment of affected skin in psoriasis disease.

Patients of diabetes mellitus urgently need noninvasive and continuous glucose monitoring in daily point-of-care. As the tear glucose concentration has a positive correlation with that in blood, the hydrogel colloidal crystal integrated into contact lens possesses promising potential for noninvasive monitoring of glucose in tears. This paper presents a new glucose-responsive sensor, which consists a crystalline colloidal array (CCA) embedded in hydrogel matrix, attached onto a rigid gas permeable (RGP) contact lens. This novel sensing lens is able to selectively diffract visible light, whose wavelength shifts between 567 and 468 nm according to the alternation of the glucose concentration between 0 and 50 mM and its visible color change between reddish yellow, green, and blue. The detection limit of responsive glucose concentration can be reduced to 0.05 mM. Its combination with a contact lens endows it with excellent biocompatibility and portability, which shows great possibility for it to push the development of glucose-detecting devices into new era.

We report on a versatile and easy approach to micro-pattern gold nanoparticles (Au NPs) on 8-arm poly(ethylene glycol)-vinyl sulfone thiol (8PEG-VS-SH) hydrogels, and the application of these patterned Au NPs stripes in controlling cell adhesion. Firstly, the Au NPs were patterned on silicon wafers, and then they were transferred onto reactive, multifunctional 8PEG-VS-SH hydrogels. The patterned, micrometer-sized Au NPs stripes with variable spacings ranging from 20 μm to 50 μm were created by our recently developed micro-contact deprinting method. For this micro-contact deprinting approach, four different PEG-based stamp materials have been tested and it was found that the triblock copolymer PEG-PPG-PEG-(3BC) stamp established the best transfer efficiency and has been used in the ongoing work. After the successful creation of micro-patterns of Au NPs stripes on silicon, the patterns can be transferred conveniently and accurately to 8PEG-VS-SH hydrogel films. Subsequently these Au NPs patterns on 8PEG-VS-SH hydrogels have been investigated in cell culture with murine fibroblasts (L-929). The cells have been observed to adhere to and spread on those nano-patterned micro-lines in a remarkably selective and ordered manner.

The top-performing linear poly(β-amino ester) (LPAE), poly(5-amino-1-pentanol-co-1,4-butanediol diacrylate) (C32), has demonstrated gene transfection efficiency comparable to viral-mediated gene delivery. Herein, we report the synthesis of a series of highly branched poly(5-amino-1-pentanol-co-1,4-butanediol diacrylate) (HC32) and explore how the branching structure influences the performance of C32 in gene transfection. HC32 were synthesized by an "A2 + B3 + C2" Michal addition strategy. Gaussia luciferase (Gluciferase) and green fluorescent protein (GFP) coding plasmid DNA were used as reporter genes and the gene transfection efficiency was evaluated in human cervical cancer cell line (HeLa) and human recessive dystrophic epidermolysis bullosa keratinocyte (RDEBK) cells. We found that the optimal branching structure led to a much higher gene transfection efficiency in comparison to its linear counterpart and commercial reagents, while preserving high cell viability in both cell types. The branching strategy affected DNA binding, proton buffering capacity and degradation of polymers as well as size, zeta potential, stability, and DNA release rate of polyplexes significantly. Polymer degradation and DNA release rate played pivotal parts in achieving the high gene transfection efficiency of HC32-103 polymers, providing new insights for the development of poly(β-amino ester)s-based gene delivery vectors.

Today, none of the wound dressings available on the market is fully capable of reproducing all the features of native skin. Herein, an asymmetric electrospun membrane was produced to mimic both layers of skin. It comprises a top dense layer (manufactured with polycaprolactone) that was designed to provide mechanical support to the wound and a bottom porous layer (composed of chitosan and Aloe Vera) aimed to improve the bactericidal activity of the membrane and ultimately the healing process. The results obtained revealed that the produced asymmetric membranes displayed a porosity, wettability, as well as mechanical properties similar to those presented by the native skin. Fibroblast cells were able to adhere, spread, and proliferate on the surface of the membranes and the intrinsic structure of the two layers of the membrane is capable of avoiding the invasion of microorganisms while conferring bioactive properties. Such data reveals the potential of these asymmetric membranes, in the near future, to be applied as wound dressings.

Because of the complex mechanisms mediating cancer onset, prognosis, and metastatic behavior, different therapeutic approaches targeting these mechanisms have been investigated. Recent advancements in nanocarrier-based drug and gene delivery methods have encouraged scientific groups to investigate various novel therapeutic techniques. In this study, a poly(amidoamine) (PAMAM) polymer-based gene carrier containing the cathepsin B-enzyme sensitive sequence (glycine-phenylalanine-leucine-glycine, GFLG) was evaluated to determine transfection efficiency. Following the GFLG sequence, the surface of PAMAM generation 4 (G4) was conjugated with histidine (H) and arginine (R) for improved endosomal escape and cellular uptake, respectively. The successful synthesis of G4-GLFG-H-R was confirmed by ¹H-nuclear magnetic resonance spectroscopy. The polyplex composed of G4-GLFG-H-R and pDNA was simulated by the enzyme cathepsin B and induced endosomal escape of pDNA, which was confirmed by gel electrophoresis. Compared with the G4 control, enzyme-sensitive G4-GLFG-H-R showed higher transfection efficiency and lower cytotoxicity in HeLa cells. These results demonstrated that G4-GLFG-H-R may be a highly potent and efficient carrier for gene therapy applications.

The implantation of biomedical devices, including collagen-based implants, evokes an inflammatory response. Despite inflammation playing an important role in the early stages of wound healing, excessive and non-resolving inflammation may lead to the poor performance of biomaterial implants in some patients. Therefore, steps should be taken to control the level and duration of an inflammatory response. In this study, oxygen and nitrogen gas plasmas were employed to modify the surface of collagen film, with a view to modifying the surface properties of a substrate in order to induce changes to the inflammatory response, whilst maintaining the mechanical integrity of the underlying collagen film. The effects of cold plasma treatment and resultant changes to surface properties on the non-specific inflammatory response of the immune system was investigated in vitro in direct contact cell culture by the measurement of protein expression and cytokine production after one and four days of human peripheral blood mononuclear cell (PBMC) culture. The results indicated that compared to oxygen plasma, nitrogen plasma treatment produced an anti-inflammatory effect on the collagen film by reducing the initial activation of monocytes and macrophages, which led to a lower production of pro-inflammatory cytokines IL-1β and TNFα, and higher production of anti-inflammatory cytokine IL-10. This was attributed to the combination of the amino chemical group and the significant reduction in roughness associated with the introduction of the nitrogen plasma treatment, which had an effect on the levels of activation of the adherent cell population.

The literature describes that the most efficient cell penetration takes place at 200⁻500 µm depth of the scaffold. Many different scaffold fabrication techniques were described to reach these guidelines. One such technique is solvent casting particulate leaching (SC/PL). The main advantage of this technique is its simplicity and cost efficiency, while its main disadvantage is the scaffold thickness, which is usually not less than 3000 µm. Thus, the scaffold thickness is usually far from the requirements for functional tissue reconstruction. In this paper, we report a successful fabrication of the microporous polyurethane thin layer (MPTL) of 1 mm thick, which was produced using SC/PL technique combined with phase separation (PS). The obtained MPTL was highly porous (82%), had pore size in the range of 65⁻426 µm and scaffold average pore size was equal to 154 ± 3 µm. Thus, it can be considered a suitable scaffold for tissue engineering purpose, according to the morphology criterion. Polyurethane (PUR) processing into MPTL scaffold caused significant decrease of contact angle from 78 ± 4° to 56 ± 6° and obtained MPTL had suitable hydrophilic characteristic for mammalian cells growth and tissue regeneration. Mechanical properties of MPTL were comparable to the properties of native tissues. As evidenced by biotechnological examination the MPTL were highly biocompatible with no observed apparent toxicity on mouse embryonic NIH 3T3 fibroblast cells. Performed studies indicated that obtained MPTL may be suitable scaffold candidate for soft TE purposes such as blood vessels.

Functional p-aramid fibers that can express antimicrobial activity were produced by simple processing of silver nanoparticles (AgNPs), which are well known as antimicrobial agents, by using glycidyltrimethylammonium chloride (GTAC), a quaternary ammonium salt. P-aramid fibers were treated with GTAC by the pad-dry-cure process and put into an Ag colloid solution for reactions at 40 °C for 90 min to prepare GTAC/AgNPs-treated p-aramid fibers. Through these processes, GTAC was used as a substitute for existing cross-linking agents. The changes in the degree of attachment of AgNPs to the surface of p-aramid fibers were determined using a scanning electron microscope according to parameters such as GTAC concentration, Ag colloid concentration, and reaction temperature. Through this study, the following results were obtained: (i) The tensile strength of AgNPs/GTAC-treated p-aramid fibers was found to be about 80% of that of untreated p-aramid fibers; (ii) Thermogravimetric analysis showed that the thermal stability of p-aramid fibers did not change much after GTAC/AgNPs treatment and (iii) Antimicrobial activity analysis showed that AgNPs/GTAC-treated p-aramid fibers exhibited superior antibacterial properties compared to untreated p-aramid fibers, which may or may not be the effect of GTAC or AgNPs, or both.

Low molecular weight polyethylenimine (1800 Da, also referred to as oligoethylenimines, OEI) was modified with amino acids, including two aromatic amino acids (tryptophan, phenylalanine) and an aliphatic amino acid (leucine). The substitution degree of amino acids could be controlled by adjusting the feeding mole ratio of the reactants. Fluorescence spectroscopy and circular dichroism experiments demonstrated that the indole ring of tryptophan may intercalate into the DNA base pairs and contribute to efficient DNA condensation. In vitro gene expression results revealed that the modified OEIs (OEI-AAs) may provide higher transfection efficiency even than high molecular weight polyethylenimine (25 kDa, PEI), especially the aromatic tryptophan substituted OEI. Moreover, OEI-AAs exhibited excellent serum tolerance, and up to 137 times higher transfection efficiency than PEI 25 kDa that was obtained in the presence of serum. The cytotoxicity of OEI-AAs is much lower than PEI 25 kDa. This study may afford a new method for the development of low molecular weight oligomeric non-viral gene vectors with both high efficiency and biocompatibility.