Preparation of Cellulose Hydrogel Dressing with Evenly Dispersed Hydrophobic Drugs by Hydrogen Bonding and Encapsulation Methods

A transparent cellulose-based functional hydrogel dressing is prepared by hydrogen bonding interaction and encapsulation technique, which can uniformly disperse hydrophobic drugs and has the advantages of simple preparation, good biocompatibility, fast self-healing ability, and slow drug release. Menthol, which is insoluble and irritating, is used as a model drug, encapsulated by ethylenediamine-modified cyclodextrin, and then loaded onto a hydrogel dressing. The introduction of modified cyclodextrin not only improves the stability and solubility of menthol, but also makes the hydrophobic menthol uniformly dispersed in hydrophilic hydrogel dressing, and the large amount of hydrogen bonding can enable rapid hydrogel generation. In addition, the microstructure, swelling, biocompatibility and drug loading properties of the hydrogel are investigated, and the results show that the hydrogel has good prospects for application in the field of wound dressings.     

Facile synthesis and antibacterial evaluation of poly(acrylamide‐co‐(β‐cyclodextrin))/silver nanocomposite

Hydrogel/silver nanocomposites have shown immense potential in many biological applications. In this article, a facile method to synthesize poly(acrylamide‐co‐(β‐cyclodextrin))/silver nanocomposites is reported. The silver nanoparticles were in situ synthesized accompanying with the formation of poly(acrylamide‐co‐(β‐cyclodextrin)) hydrogel by gamma irradiation without additional reducing and stabilizing agents. In addition, the nanocomposites were prepared under ambient conditions. The formation of silver nanoparticles was confirmed by ultraviolet used to characterize the structure and composition of the synthetic nanocomposites. Transmission electron microscope verified the formation and homogeneous distribution of silver nanoparticles in the hydrogel matrix. The hybrid hydrogel exhibited excellent water‐swelling properties, which could be controlled by varying the mass ratio of acrylamide (AM) to β‐cyclodextrin (β‐CD) in the hydrogel. Furthermore, the poly(acrylamide‐co‐(β‐cyclodextrin))/silver nanocomposites were found to be effective in inhibiting the growth of both Gram‐negative Escherichia coli and Gram‐positive Staphylococcus aureus. POLYM. COMPOS., 37:1480–1487, 2016. © 2014 Society of Plastics Engineers     

Effect of sodium dodecyl sulfate on shape-memory properties of side-chain crystalline hydrogel via micellar copolymerization

A chemical shape-memory hydrogel containing crystalline structure is prepared via micellar copolymerization of hydrophilic monomer acrylamide (AM) and hydrophobic monomer octadecyl acrylate (C18) in a sodium dodecyl sulfate (SDS) solution. The influence of SDS on the shape-memory behavior of hydrogel investigated by differential scanning calorimetry (DSC) and Temperature-dependent X-ray indicate that the melting and crystallization peaks derived from the thermal properties of C18 units is different from peaks corresponding to the pure SDS. In addition, the microstructure evolution information of hydrogels dose not change upon heating process, regardless of the presence or absence of SDS. Therefore, only the hydrophobic associations formed by C18 blocks play a decisive role in the shape memory function of hydrogel system. The difference between the transition process (from temporary shape to permanent shape) of hydrogel with and without SDS at different temperature is because that the hydrophobic region of side chain crystallization of SDS-free hydrogel may escape the restriction of SDS and become more sensitive to temperature, they can preferentially return to their initial shape under the same time and temperature than SDS-containing gels. Whether SDS exists only affect the speed of shape memory behavior, but not the microstructure evolution of hydrogel system.     

Preparation and characterization of bottle‐brush polymer via host−guest self‐assembly between β‐cyclodextrin and adamantane

Supramolecular assemblies with a bottle‐brush structure are obtained by inclusion complexation between β‐cyclodextrin and adamantane. β‐cyclodextrin‐modified chitosan is synthesized via the aldimine condensation reaction between β‐cyclodextrin monoaldehyde and chitosan as the host. The guest is prepared through the esterification reaction between methoxypoly(ethylene glycol) and 1‐adamantanecarboxylic acid chloride. The supramolecular assemblies are formed through the inclusion of adamantane‐modified methoxypoly(ethylene glycol) into the β‐cyclodextrin cavity on the chitosan chain. Fourier transform infrared and ¹H NMR spectra were used to prove that the host, guest and assemblies were successfully obtained. UV?visible spectra were employed to confirm the formation of assemblies. Furthermore, the size of the particles in the assembled solution, the change before and after self‐assembly, and the effect of the addition of competitive molecules were studied by dynamic light scattering measurements. The results indicate that supramolecular assemblies have formed successfully which might be used to realize the biomimetic structure of the articular cartilage proteoglycan. © 2014 Society of Chemical Industry     

Antifouling enhancement of PVDF membrane tethered with polyampholyte hydrogel layers

The preparation and property of antifouling poly(vinylidene fluoride) (PVDF) membrane tethered with polyampholyte hydrogel layers were described in this work. In fabricating these membranes, the [2‐(methacryloyloxy)ethyl] trimethylammonium chloride and 2‐acrylamide‐2‐methyl propane sulfonic acid monomers were grafted onto the alkali‐treated PVDF membrane to yield polyampholyte hydrogel layers via radical copolymerization with N,N′‐methylenebisacrylamide as crosslinking agent. The analyses of fourier transform infrared attenuated total reflection spectroscopy and X‐ray photoelectron spectroscopy confirm the covalent immobilization of polyampholyte hydrogel layer on PVDF membrane surface. The grafting density of polyampholyte hydrogel layer increases with the crosslinking agent growing. Especially for the membrane with a high grafting density, a hydrogel layer can be observed obviously, which results in the complete coverage of membrane pores. Because of the hydrophilic characteristic of grafted layer, the modified membranes show much lower protein adsorption than pristine PVDF membrane. Cycle filtration tests indicate that both the reversible and irreversible membrane fouling is alleviated after the incorporation of polyampholyte hydrogel layer into the PVDF membrane. This work provides an effective pathway of covalently tethering hydrogel onto the hydrophobic membrane surface to achieve fouling resistance. POLYM. ENG. SCI., 55:1367–1373, 2015. © 2015 Society of Plastics Engineers     

Preparation and characterization of a temperature‐sensitive nonwoven poly(propylene) with increased affinity for guest molecules

A temperature‐sensitive hydrogel with the capability of inclusion complex formation with guest molecules was successfully grafted onto the surface of nonwoven polypropylene (nonwoven PP). This was carried out by the use of N‐isopropylacrylamide monomer and a modified cyclodextrin (acrylamidomethyl‐β‐cyclodextrin (β‐CD‐NMA)). Fourier‐transform infra red (FT‐IR) and elemental analyses confirmed the presence of poly(N‐isopropylacrylamide) (PNIPAAm) and β‐CD‐NMA components on the surface of the textile. Equilibrium swelling ratio measurements showed that the grafted hydrogel maintained its temperature‐sensitive property compared to a nongrafted hydrogel. The effect of β‐CD‐NMA and crosslink agent concentrations on the grafting yield was studied. The β‐CD‐NMA content into the PNIPPAM‐ β‐CD‐NMA grafted nonwoven PP (PNIPAAm‐β‐CD‐NMA‐PP) was estimated by FT‐IR through a new procedure. The estimated amounts of β‐CD‐NMA in PNIPAAm‐β‐CD‐NMA‐PP were determined to be 0.9, 1.9 mg g^?1 for 0.019M and 0.049M concentrations of β‐CD‐NMA in monomer solution, respectively. The PNIPAAm‐β‐CD‐NMA‐PP showed a remarkable increase in absorbance affinity of 8‐anilino‐1‐naphthalenesulfonic acid ammonium salt at 20°C from 0.93 to 3.33 µmol g^?1 compared to PNIPAAm‐PP. Furthermore, the results showed a temperature‐sensitive loading affinity for PNIPAAm‐β‐CD‐NMA‐PP in absorbance of guest molecules due to the presence of β‐CD‐NMA. The use of hydrophobic guest molecules such as fragrance oils and antibiotics in modified fabrics can provide new applications in textile and pharmaceutical industry. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40497.     

Characterization of shape memory behaviour of CTBN-epoxy resin system

The temperature-responsive poly(vinyl alcohol)/ poly(N-isopropylacrylamide) hydrogel was prepared as a drug delivery carrier. The vitamin B12 release behavior of hydrogel was controlled by direct oxyfluorination. The oxyfluorination of hydrogel changed the surface characteristics to have hydrophilic functional groups. On the other hand, the hydrophobicity of hydrogel increased by fluorination treatment due to the induced hydrophobic functional groups. C-O bond and C-F bond were mainly formed by oxyfluorination and fluorination, respectively. The surface morphology showed the significant variation depending on the oxyfluorination conditions. Both swelling ratio and drug release rate were strongly dependent on the oxyfluorination conditions. The swelling of hydrogel increased further by the surface modification with oxyfluorination in a higher oxygen content to give more hydrophilic properties. The drug release from hydrogel also increased as more hydrophilic functional groups were introduced by oxyfluorination because the favorable affinity at the interface resulted in a higher swelling ratio. On the other hand, the relatively low swelling ratio and slower drug release from hydrogel were observed with more hydrophobic functional groups introduced by fluorination.     

疏水改性温敏水凝胶的合成及应用研究进展

N-异丙基丙烯酰胺（NIPAM）类水凝胶是典型的温敏水凝胶,通常含有亲水性酰胺基和疏水性异丙基,具有随温度变化而发生可逆溶胀/收缩的特殊性质,作为一种新型的智能材料得到广泛的应用。本文主要论述了NIPAM类疏水改性温敏水凝胶的合成,在骨架中引入疏水单体可以改善其疏水特性,同时提高其温度敏感性,使其在药物释放、物质分离及生物医用材料等领域具有独特的应用价值。目前对疏水改性温敏水凝胶的理论研究尚浅,仍需拓展其在实际方面的应用,今后可考虑改善疏水单体的官能团结构提高疏水性能,合成更具温度响应性和环境友好性的智能温敏水凝胶,拓展其在催化、水处理、生物化工等领域的广泛应用。     

Switch-peptides: design and characterization of controllable super-amyloid-forming host-guest peptides as tools for identifying anti-amyloid agents

Several amyloid-forming proteins are characterized by the presence of hydrophobic and highly amyloidogenic core sequences that play critical roles in the initiation and progression of amyloid fibril formation. Therefore targeting these sequences represents a viable strategy for identifying candidate molecules that could interfere with amyloid formation and toxicity of the parent proteins. However, the highly amyloidogenic and insoluble nature of these sequences has hampered efforts to develop high-throughput fibrillization assays. Here we describe the design and characterization of host-guest switch peptides that can be used for in vitro mechanistic and screening studies that are aimed at discovering aggregation inhibitors that target highly amyloidogenic sequences. These model systems are based on a host-guest system where the amyloidogenic sequence (guest peptide) is flanked by two beta-sheet-promoting (Leu-Ser)(n) oligomers as host sequences. Two host-guest peptides were prepared by using the hydrophobic core of Abeta comprising residues 14-24 (HQKLVFFAEDV) as the guest peptide with switch elements inserted within (peptide 1) or at the N and C termini of the guest peptide (peptide 2). Both model peptides can be triggered to undergo rapid self-assembly and amyloid formation in a highly controllable manner and their fibrillization kinetics is tuneable by manipulating solution conditions (for example, peptide concentration and pH). The fibrillization of both peptides reproduces many features of the full-length Abeta peptides and can be inhibited by known inhibitors of Abeta fibril formation. Our results suggest that this approach can be extended to other amyloid proteins and should facilitate the discovery of small-molecule aggregation inhibitors and the development of more efficacious anti-amyloid agents to treat and/or reverse the pathogenesis of neurodegenerative and systemic amyloid diseases.     

Hydrogen bonding induced enhancement for constructing anisotropic sugarcane composite hydrogels

Anisotropic hydrogels are appealing with their merits of similar biochemical and structural properties to the biological tissues. However, the mechanical properties of current anisotropic hydrogels need to be further improved. Herein, three kinds of novel anisotropic poly(2-hydroxyethyl methacrylate) (pHEMA), poly(acrylamide) (pAM), and poly(acrylamide-co-acrylic acid) (p[AM-co-AA]) sugarcane composite hydrogels were prepared successfully by filling the hydrogel monomer precursor into porous aligned sugarcane nanofibers network and then performing subsequent free radical polymerization. The hydrogel matrix and sugarcane nanofibers network were combined closely together through hydrogen bonding interaction. The anisotropic sugarcane composite hydrogels exhibit good flexibility and elastic recovery properties upon encountering mechanical crimping and twisting. In typical case, the as-prepared pHEMA sugarcane composite hydrogel can exhibit high anisotropic tensile strength of 2.37 and 0.54 MPa, while differential tear strength of 0.36 and 0.78 N/mm, along the parallel and vertical nanofibers directions. Finally, anisotropic lubrication behaviors were found and investigated systematically for those three kinds of sugarcane composite hydrogels when water was used as lubricant. Our current work proposes a simple and universal strategy for developing bioinspired anisotropic functional composite matters such as artificial skin, flexible sensor, and cartilage lubrication materials.     

Improvement of physical characteristics of petroleum waxes by using nano-structured materials

Layered double hydroxides (LDHs) are a class of synthetic two-dimensional nano-structured anionic clays whose structure can be described as nano-layered ordered material. This study aims to use nano-layered materials as a host for organic guests having required functional groups such as azo-compounds to alter LDH surface properties from hydrophilic to hydrophobic and increase sorption capacity for sulfur and aromatic compounds through constructing nano-hybrid material. A large anionic pigment (phenyl azobenzoic sodium salt) has been intercalated into Zn-Al LDH and a complex system of supra-molecular host-guest interactions was formed.We have examined the unusual bi-functionality effects caused by hybridization for removing sulfur and aromatic compounds from petroleum waxes. Results clearly indicated that nano-layered material decreased sulfur content and mono-aromatic compounds of heavy slack wax. In the same run, it completely removed di-aromatic compounds. In the same trend, the nano-hybrid material showed high efficiency for removing aromatic and sulfur compounds from crude petrolatum. This leads to an improvement for the physical properties of heavy slack wax and crude petrolatum.     

环糊精介入与TiO_2光催化应用研究进展

环糊精特有的结构可以对疏水客体分子进行主-客体包合,它介入到TiO2光催化过程中,可以增加TiO2光催化材料对疏水客体的吸附,加快被包合客体底物分子的传质效率,增大化学反应动力学常数,提高TiO2的光催化降解活性。其对有机疏水底物分子的选择性识别包合作用,有望解决TiO2对高毒性不可生物降解污染物催化选择性低及催化活性不高的难题。根据近年来公开发表的国内外相关文献,对环糊精介入的TiO2光催化应用研究进行简要评述。     

Physically Linked PVA/P(AAm‐co‐SMA) Hydrogels: Tough,Fast Recovery,Antifatigue, and Self‐Healing Soft Materials

The application of traditional chemically crosslinked hydrogels is often limited by poor mechanical properties because of their own inhomogeneous network and irreversible crosslinking bonds. Herein, physical interactions are applied to crosslink the interpenetrating network hydrogel, i.e., hydrogen bonding and crystalline domain for polyvinyl alcohol network, and hydrophobic interaction inside micelle for poly (acrylamide‐co‐stearyl methyl acrylate) [P(AAm‐co‐SMA)] network. In this gel network system, reversible energy dissipation mechanism is realized by dissociation and reassociation of weak interactions including hydrogen bonding and hydrophobic interaction inside the micelle. Strong crystalline domains serve as permanent crosslinking interactions to maintain network integrity under large extension. As a result, the synergy of weak and strong interactions leads to tough, antifatigue, fast recovery, and self‐healing properties of the hydrogel. This proposed strategy of achieving versatile hydrogels can broaden the use of hydrogels into load‐bearing applications.     

Use of β‐cyclodextrin in an antimigration coating for polyester fabric

When β‐cyclodextrin was adopted as a dye catcher, the degree of dye migration onto adjacent fabrics as well as onto the coated surface was greatly reduced, while other physical properties, such as waterproofness and breathability, remained unaffected. When acetylation of β‐cyclodextrin was carried out, its solubility in an organic solvent, including methyl ethyl ketone and toluene, was greatly improved. Hence, it provided a smoother coated surface and an excellent antimigration effect in a direct‐coating system. These results confirm that β‐cyclodextrin is an effective dye catcher in a polyurethane‐based coating system, in which it prevents the migration of the dyes from coated polyester fabrics onto adjacent surfaces. The solubility of cyclodextrin can be optimised by a chemical modification of its cyclodextrin‐hydroxyl groups. Hence, this host–guest interaction demonstrates a universal and effective platform for antimigration coating systems.     

Synthesis and characterization of polysaccharide hydrogel based on hydrophobic interactions

Hydrogels based on hydrophobic, or micellar interactions, are physically crosslinked hydrogels which are an attempt to overcome the poor mechanical properties of traditional, chemically crosslinked gels, such as low shear strength. We have prepared a polysaccharide-based hydrogel with physical crosslinks via hydrophobic interactions. In this work, we have synthesized hydrogel by grafting a hydrophobic moiety dioctylamine onto hydrophilic precursor carboxymethyl cellulose (CMC) through an amide bond formation, where ~33% of the carboxyl group in CMC was reacted with dioctylamine. The thermosensitive hydrogel can arrest 100 mL of deionized water per gram of gelator within few seconds. It showed the moderate rheological property. The hydrogel is nontoxic and does not show any adverse to human hemoglobin. It is a CMC based a unique gelator with high biocompatibility represent to be useful materials for biomedical application. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47665.     

Photocurrent generators derived from non-covalently assembled soft-matter molecular system

It is rather difficult to design a multilayer photocurrent generator system on the ITO electrode, however, the preparation of thin film with high surface concentration of donor units is indispensable in order to achieve high conversion efficiency. The polymer film of porphyrin bearing pyroles on the electrode was prepared by the potential sweep method. It was indicated that the self-aggregation can be suppressed by encapsulation of the porphyrin unit in the cavity of macro-cyclic host molecule, cyclodextrin. We established the non-equilibrium host-guest system with porphyrins and cyclodextrins for the first time. The photocurrent density and the quantum yield in the porphyrin-cyclodextrin system are remarkably improved. It was demonstrated that the high quantum yield, perhaps 25 times larger, arises from the isolation of the porphyrin unit by cyclodextrin through host-guest interactions.     

The preparation of pH-sensitive hydrogel based on host-guest and electrostatic interactions and its drug release studies in vitro

A new self-assembly strategy called the synthesis of an amphiphilic crosslinking agent for electrostatic and host-guest is used to prepare a new cellulose-based pH-responsive hydrogel. The amphiphilic crosslinking agent could be encapsulated by poly β-cyclodextrin (β-CDP) through host-guest interaction and be meanwhile attracted by carboxyl groups through electrostatic interaction, then, forming a three-dimensional (3D) gel network structure. Additionally, the linear β-CDP part of the remaining hydrophobic cavity can be equipped with hydrophobic drug molecules to achieve the function of hydrogel expansion. ¹H NMR was used to characterize the synthesized amphiphilic crosslinking agent N,N-dimethyl-1-adamantanamine (DM-AD). FTIR, SEM to characterize the synthesized β-CDP. SEM was used to observe the surface to characterize the prepared hydrogel. The swelling of the gel was measured in aqueous solution, and the swelling kinetic equation was fitted. Meanwhile, the in vitro release of ibuprofen (IBU) in hydrogels was studied. The gel showed a sustained release effect in drug release, and the IBU is hardly released in the gastric juice but is easily released in the intestines. Within 240–1350 min, the release of the drug from the hydrogel conforms to the Korsmeyer and Peppas model, which is a non-Fickian diffusion mechanism. Within 240–1350 min, the drug is released from the hydrogel conforms to the Higuchi model. Furthermore, the gel has the ability of self-healing and self-degradation under acid conditions.     

Mass Spectrometric Evaluation of β-Cyclodextrins as Potential Hosts for Titanocene Dichloride

Bent metallocene dichlorides (Cp₂MCl₂, M = Ti, Mo, Nb, …) have found interest as anti-cancer drugs in order to overcome the drawbacks associated with platinum-based therapeutics. However, they suffer from poor hydrolytic stability at physiological pH. A promising approach to improve their hydrolytic stability is the formation of host-guest complexes with macrocyclic structures, such as cyclodextrins. In this work, we utilized nanoelectrospray ionization tandem mass spectrometry to probe the interaction of titanocene dichloride with β-cyclodextrin. Unlike the non-covalent binding of phenylalanine and oxaliplatin to β-cyclodextrin, the mixture of titanocene and β-cyclodextrin led to signals assigned as [βCD + Cp₂Ti–H]⁺, indicating a covalent character of the interaction. This finding is supported by titanated cyclodextrin fragment ions occurring from collisional activation. Employing di- and trimethylated β-cyclodextrins as hosts enabled the elucidation of the influence of the cyclodextrin hydroxy groups on the interaction with guest structures. Masking of the hydroxy groups was found to impair the covalent interaction and enabling the encapsulation of the guest structure within the hydrophobic cavity of the cyclodextrin. Findings are further supported by breakdown curves obtained by gas-phase dissociation of the various complexes.     

PCEC hydrogel used on sustained‐release hyaluronic acid delivery with lubrication effect

Injection of bionic synovial fluid (BSF) is a conventional method to improve the lubricity of artificial joints, but BSF cannot maintain long due to the dilution and degradation of BSF in human body. To prolong the effectiveness of hyaluronic acid (HA), which is the major component of BSF, this study applies a temperature‐sensitive poly(?‐caprolactone)–poly(ethylene glycol)–poly(?‐caprolactone) (PCEC) hydrogel loaded with HA to achieve long‐term lubrication. In addition, Fourier transform infrared, nuclear magnetic resonance analysis, X‐ray diffraction, scanning electron microscopy (SEM), and gel permeation chromatography spectra were used to analyze the structure of the synthetic hydrogel. Rheological test and test tube inverting method were used to characterize the thermosensitivity. The lubrication properties of the released solution were characterized by UV–vis, tribological tests, SEM, and 3D laser confocal scanning microscope. The experimental results reveal that the triblock PCEC hydrogel contains both hydrophilic block and hydrophobic block, and both PCEC and PCEC/HA hydrogels have phase‐changed effect when the temperature increases from room temperature to body temperature. Moreover, the friction coefficient of the released solution from PCEC/HA hydrogel is approximatively 38% lower than that of phosphate buffer saline. And the ability of shear resistance and creep recovery of PCEC/HA hydrogel are better than that of PCEC hydrogel. This study provides an effective approach to achieve long‐time lubrication effect for artificial joints. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46228.     

Approach to Obtain Electrospun Hydrophilic Fibers and Prevent Fiber Necking

Solution electrospinning of a blend containing a hydrophobic polymer with a hydrophilic functional polymer as an additive is a simple and straight‐forward route to obtain functional and hydrophilic fibers accompanied by the mechanical properties of the hydrophobic polymer. However, this process of thermodynamically unfavored surface segregation of the hydrophilic additive is not well understood. To understand the process the dependencies of the surface hydrophilization on type of hydrophilic polymers, the solvent, and the process, using poly(caprolactone) (PCL) as the matrix polymer is explored. The results show that hydrophilic fibers can be obtained using different additive hydrophilic polymers. The combination of polymer blends which show this effect can be predicted using the Flory–Huggins interaction parameter. In addition mechanical and micromechanical properties of PCL fibers blended with NCO‐terminated star‐shaped poly(ethylene glycol) (sPEG‐NCO) as additive are investigated. In this context blending with sPEG‐NCO turns out to be a powerful tool to prevent fiber necking rendering this method an interesting candidate for tissue engineering application, where it is mandatory to retain the surface properties under mechanical stress.