For graphene oxide (GO) composite hydrogels, a two-dimensional GO material is introduced into them, whose special structure is used to improve their properties. GO contains abundant oxygen-containing functional groups, which can improve the mechanical properties of hydrogels and support the application needs. Especially, the unique-conjugated structure of GO can endow or enhance the stimulation response of hydrogels. Therefore, GO composite hydrogels have a great potential in the field of wearable devices. We referred to the works published in recent years, and reviewed from these aspects: (a) structure of GO; (b) factors affecting the mechanical properties of the composite hydrogel, including hydrogen bond, ionic bond, coordination bond and physical crosslinking; (c) stimuli and signals; (d) challenges. Finally, we summarized the research progress of GO composite hydrogels in the field of wearable devices, and put forward some prospects.

본 연구에서는, 주위 산도나 근적외선과 같은 외부에서 주어지는 자극에 의하여 내부 탑재 약물의 방출을 조절할 수 있는, 자극 응답성 키토산(Cs) 하이드로겔를 합성하고 그것의 특성과 성능을 조사하였다. 우선 Cs와 carbic anhydride의 개 환반응에 의하여 노르보닐(Nb) 작용기가 도입된 Cs 유도체(Cs-Nb) 를 합성하였으며, methyltetrazine-amine과 selenolactone의 반응에 의하여 테트라진 (Tz) 작용기가 양 말단에 도입된 가교제(Se-Tz)를 합성하였다. Cs-Se 하 이드로겔은 CS-Nb와 Se-Tz 사이의 클릭반응에 의하여 빠르게 형성할 수 있었으며, Nb/Tz 반응 몰비 변화로서 가교도를 조절하였다. 하이드로겔의 가교도와 용액의 산도가 낮을수록 하이드로겔의 팽윤도가 높아졌으며, 하이드로겔의 내부구조가 다공성을 가짐을 SEM 단면 분석 결과 확인할 수 있었다. Ciprofloxacin hydrochloride monohydrate 약물을 탑재한 하이드로겔은 pH 5.2의 PBS용액에서 pH 3.7에 비하여 높은 약물 방출을 나타내었다. 또한 근적외선 조사에 의하여 약물 방출을 빠르게 유도할 수 있었다.

목적: 이 연구에서는 도파민이 적용된 히알루론산 가교 하이드로겔을 제조하고 항산화 활성을 조사하였다. 방법: 먼저 히알루론산과 p(HEMA)로 구성된 상호침투고분자구조로 후처리 한 p(HEMA) 기반 하이드로겔을 제조하였다. 다음으로 아마이드 결합반응을 통해 도파민이 적용된 항산화 하이드로겔을 제조하였다. 항산화 활성의 평가는 ABTS 와 DDPH 라디칼 소거능 방법을 사용하였다. 결과: 도파민이 적용된 하이드로겔은 유의한 항산화 활성을 나타내었다. 히알루론산의 가교는 하이드로겔 표면의 습윤성을 개선시킨 반면에 도파민이 적용된 하이드로겔은 대조군과 비교하여 유의한 차이를 나타내지 못했다. 도파민이 적용된 하이드로겔은 높은 광투율을 나타내었다. (>88%) 결론: 도파민이 결합된 히알루론산의 가교에 기초한 항산화 하이드로겔의 개발이 안의료 및 생물의학 재질 개발에 도움을 줄 수 있을 것으로 사료된다.

하이드로겔은 다량의 물과 화장품용 성분들을 함유할 수 있는 천연고분자 구조를 가지고 있으며 내부의 친수성기들이 활성성분을 다량 함유하고 효과적으로 전달할 수 있는 구조체를 형성할 수 있어 화장품 소재로 즐겨 사용되고 있다. 화장품용 하이드로겔에 첨가하는 소재로 셀룰로오스가 많이 이용되고 있는데 파우더 형태의 셀룰로오스와 면섬유 및 셀룰라아제를 처리한 면섬유와 같이 다양한 형태의 셀룰로오스를 하이드로겔에 적용했을 경우 하이드로겔의 물성변화 및 외관변화를 조사해 보았다. 일반적으로 사용되는 셀룰로오스 파우더를 하이드로겔에 첨가하였을 경우 예상과 달리 하이드로겔의 인장강도가 상당히 저하되는 결과를 보였다. 첨가하지 않았을 때 대비 0.1%와 0.3%의 셀룰로오스 파우더를 첨가한 시료는 각각 10%, 14%의 인장강도 저하현상을 보였다. 이와는 다르게 면섬유를 0.1 ~ 0.3% 첨가하였을 경우 하이드로겔의 강도가 약 20% 증가함을 보였다. 그러나 길이가 긴 면섬유는 뻣뻣하여 하이드로겔에 혼합시 분산성에 문제를 보였다. 이를 해결하기 위하여 면에 셀룰라아제를 처리함으로써 효소-분해 반응을 통해 섬유의 유연성을 증가시킬 수 있었다. 또한 효소 처리된 면섬유를 하이드로겔에 첨가하여 보습성의 변화를 조사한 결과 셀룰라아제를 처리한 면섬유를 함유한 하이드로겔은 처리하지 않은 면섬유-하이드로겔 대비 380% 증가된 보습성을 보였으며 또한 혼합 가공시 우수한 분산성을 보였다.

This study investigated the physical properties of polymers and antimicrobial activities of organic acids on Listeria monocytogenes to develop hydrogels. κ-carrageenan (1, 2, and 3%), carboxymethylcellulose (CMC; 1, 3, and 5%), and agar (1.5 and 3%) were mixed with cross-linkers (Na+, K+, Ca2+, and Al3+) or each other by stirring or heating to form cross-linkage, and their physical properties (hardness, elasticity, and swelling) were measured. The hydrogels formulated with organic acid (1, 3, and 5%) were analyzed by spot assay against L. monocytogenes. κ-carrageenan formed hydrogels with high hardness without other cross-linkers, but they had low elasticity. The elasticity was improved by mixing with other cross-linkers such as K+ or other polymer, especially in 3% κ-carrageenan. CMC hydrogel was formed by adding cross-linkers Al3+, Na+, or Ca2+, especially in 5% CMC. Thus, stickiness and swelling for selected hydrogel formulations (two of κ-carrageenan hydrogels and three of CMC hydrogels) were measured. Among the selected hydrogels, most of them showed appropriate hardness, but only 3% κ-carrageenan-contained hydrogels maintained their shapes from swelling. Hence, 3% κ-carrageenan+0.2% KCl and 3% κ-carrageenan+1% alginate+0.2% KCl+0.2% CaCl2 were selected to be formulated with lactic acid, and showed antilisterial activity. These results indicate that 3% κ-carrageenan hydrogels formulated with lactic acid can be used to control L. monocytogenes on food surface.

The water-swollen hydrogels containing silicone or fluorine were prepared by copolymerization of 2-hydroxy ethyl methacylate (HEMA) with 3-(trimethoxysilyl)propyl methacrylate(SM) or 2,2,2-trifluoroethyl acrylate(FA). When the content of SM or FA increased in copolymers, there was tendency of water absorbance to decrease, whereas contact angles to increase. The hydrogels containing FA showed 2 ~ 4% higher water content and 4 ~ 5% lower contact angles compared to that of SM. Tensile strengths decreased as the content of SM increased. However, FA exhibited strength of 2.2 Mpa/cm2 which is similar to 2.3 Mpa/cm2 of B. FA, which implies comparatively low adherence, hence, showed better protein resistance properties than SM-based hydrogel. The photo-polymerization was also applied instead of thermal polymerization to enhance the energy efficiency. As a result, the reaction yield reached over 95% within 1 minute.

Stimuli-responsive biomaterials that alter their function through sensing local molecular cues may enable technological advances in the fields of drug delivery, gene delivery, actuators, biosensors, and tissue engineering. In this research, pH-responsive hydrogel which is comprised of dimethylaminoethyl methacylate (DMAEMA) and 2-hydroxyethyl methacrylate (HEMA) was synthesized for the effective delivery of doxorubicin (Dox) to breast cancer cells. Cancer and tumor tissues show a lower extracellular pH than normal tissues. DMAEMA/HEMA hydrogels showed significant sensitivity by small pH changes and each formulation of hydrogels was examined by scanning electron microscopy, mechanical test, equilibrium mass swelling, controlled Dox release, and cytotoxicity. High swelling ratios and Dox release were obtained at low pH buffer condition, low cross-linker concentration, and high content of DMAEMA. Dox release was accelerated to 67.3% at pH 5.5 for 6-h incubation at 37oC, while it was limited to 13.8% at pH7.4 at the same time and temperature. Cell toxicity results to breast cancer cells indicate that pH-responsive DMAEMA/HEMA hydrogels may be used as an efficient matrix for anti-cancer drug delivery with various transporting manners. Also, pH-responsive DMAEMA/HEMA hydrogels may be useful in therapeutic treatment which is required a triggered release at low pH range such as gene delivery, ischemia, and diabetic ketoacidosis.

Three dimensional self-assembled graphene hydrogels were easily fabricated by electron beam irradiation (EBI) using an aqueous solution of wool/poly(vinyl alcohol) and graphene oxide (GO). After exposure to various levels of EBI radiation, the highly porous, self-assembled, wool-based graphene hydrogels were characterized using scanning electron microscopy and Fourier-transform infrared spectroscopy; to determine the gel fraction, degree of swelling, gel strength, kinetics-of-swelling analyses and removal of hexavalent chromium (Cr(VI)) from the aqueous solution. X-ray diffraction results confirmed that EBI played a significantly important role in reducing GO to graphene. The adsorption equilibrium of Cr(VI) was reached within 80 min and the adsorption capacity was dramatically increased as the acidity of the initial solution was decreased from pH 5 to 2. Changes in ionic strength did not exert much effect on the adsorption behavior.

A drug delivery system (DDS) was prepared with a temperature and pH-responsive hydrogel. Poly(vinyl alcohol) (PVA)/poly(acrylic acid) (PAAc)/poly(N-isopropylacrylamide) (PNIPAAm)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by radical polymerization for the temperature and pH-responsive hydrogels. MWCNTs were employed to improve both the thermal conductivity and mechanical properties of the PVA/PAAc/PNIPAAm/MWCNT nanocomposite hydrogels. Various amounts of MWCNTs (0, 0.5, 1 and 3 wt%) were added to the nanocomposite hydrogels. PVA/PAAc/PNIPAAm/MWCNT nanocomposite hydrogels were characterized with a scanning electron microscope. The mechanical properties were measured with a universal testing machine. Swelling and releasing properties of nanocomposite hydrogels were investigated at various temperatures and pHs. Temperature and pH-responsive release behavior was found to be dependent on the content of MWCNTs in nanocomposite hydrogels.

Poly(vinyl alcohol) (PVA) composites with various graphite oxide (GO) contents (0 to 10 wt%) were prepared by sonicating the mixture of PVA and GO, followed by crosslinking with glutaraldehyde. GO was pre-treated with oxyfluorination (O2:F2 = 8:2) in order to modify the surface of GO to allow it to carry hydrophilic functional groups. PVA/GO composite hydrogels were characterized by scanning electron microscopy and Fourier-transform infrared spectrometer (FT-IR). The morphology of the PVA/GO composite hydrogels and the variations in soluble gel portion were investigated under various GO contents and UV irradiation doses. The variation in the chemical structure of photo degraded PVA/GO composite hydrogels was studied by FT-IR. The photochemical stability of PVA/GO composite hydrogels under UV irradiation was found to improve noticeably with increasing content of uniformly dispersed GO.

Multi-walled carbon nanotube (MWCNT)/poly(vinyl alcohol) (PVA) nanocomposite hydrogels were prepared by freezingthawing method for the electro-responsive transdermal drug delivery. MWCNTs were used as the functional ingredient to improve both mechanical and electrical properties of MWCNT/PVA nanocomposite hydrogels. The morphology of nanocomposites revealed the uniform distribution of MWCNTs and the good interfacial contact. The compression moduli of hydrogel matrices increased greatly from 40 to 1500 kPa by forming MWCNT/PVA nanocomposites. The swelling ratio of MWCNT/PVA nanocomposites decreased as the content of MWCNTs increased under no electric voltage applied. However, the swelling ratio of MWCNT/PVA nanocomposites increased as the content of MWCNTs increased under electric voltage applied and the applied electric voltage increased. The drug was released in the electro-responsive manner through the skin due to the electro-sensitive swelling characteristics of MWCNT/PVA nanocomposite hydrogels.

The alginate-based hydrogel was prepared as a pH-sensitive drug delivery system. To enhance the drug loading capacity, activated carbon was introduced as a drug absorbent. The iron oxide was incorporated into the alginate matrix for the magnetic transferring to the target organ. The activated carbon and iron-oxide were dispersed uniformly in the alginate hydrogel. The drug release from the alginate/activated carbon composite hydrogel was carried out in various pH conditions with vitamin B12 and Lactobacillus lamnosers as model drugs. The fast and sustainable release of drug was observed in the basic condition due to the pH-sensitive solubility of alginate. The novel drug delivery system having pH-sensitive release property and magnetic movement to target place was developed by using the alginate/activated carbon composite magnetic hydrogels.

Superporous Hydrogels (SPHs) have been extensively investigated for various biomedical applications due to their fast swelling and superabsorbent properties. In this study, glycol chitosan that is one of most abundant natural polymers was used as a cross-linking agent instead of bisacrylamide (BIS), which is a broadly used crosslinking agent for preparation of SPHs. Glycol chitosan was modified to have reactive vinyl groups by chemical conjugation with glycidyl methacrylate (GMA). The vinyl group-containing glycol chitosan (GC-GMA) was characterized by FT-IR and 1H-NMR measurements. SPHs have been prepared in various synthetic conditions to establish the optimum synthetic process for making superporous structure, where the inner pores are interconnected to each other to form a open channel structure. Various SPHs with different GC-GMA contents have been successfully prepared and have been observed to show faster swelling properties than other conventional SPHs. From the study on the swelling behavior of SPHs, the GC-GMA content is considered to be an important factor for controlling their swelling properties.

We manufactured PVA-derived hydrogels using a foam generation technique that has been widely used to prepare colloidal gas aphrons(CGA). These gels were differentiated to the conventional gels such as for medical or pharmaceutical applications, which have tiny pores and some crystalline structure. Rather these should be used in de-pollution devices or adhesion of cells or biomolecules. The crosslinkers used in this work were amino acid, organic acid, sugars and lipids(vitamins). The structures of the gels were observed in a scanned electron microscope. Amino acids gels showed remarkably higher swelling ratios probably because their typical functional groups help constructing a highly crosslinked network along with hydrogen bonds. Boric acid and starch would catalyze dehydration while structuring to result in much lower water content and accordingly high gel content, leading to less elastic, hard gels. Bulky materials such as ascorbic acid or starch produced, in general, large pores in the matrices and also nicotinamide, having large hydrophobic patches was likely to enlarge pore size of its gels as well since the hydrophobicity would expel water molecules, thus leading to reduced swelling. Hydrophilicity(or hydrophobicity), functional groups which are involved in the reaction or physical linkage, and bulkiness of crosslinkers were found to be more critical to gel's crosslinking structure and its density than molecular weights that seemed to be closely related to pore sizes. Microscopic observation revealed that pores were more or less homogeneous and their average sizes were 20 μm for methionine, 10-15 μm for citric acid, 50-70 μm for L-ascorbic acid, 30-40 μm for nicotinamide, and 70-80 μm for starch. Also a sensory test showed that amino acid and glucose gels were more elastic meanwhile acid and nicotinamide gels turned out to be brittle or non-elastic at their high concentrations. The elasticity of a gel was reasonably correlated with its water content or swelling ratio. In addition, the PVA gel including 20% ascorbic acid showed fair ability of cell adherence as 0.257mg/g-hydrogel and completely degraded phenanthrene(10 mM) in 240 h.