基于乙二胺四乙酸酐和丁二胺的pH敏感水凝胶的合成与表征

以乙二胺四乙酸酐(EDTAD)和丁二胺(BDA)为原料,通过酸酐的N-酰化开环反应制备侧链含羧基的直链聚合物(pEDTAD-BDA);然后以二环己基碳二亚胺(DCC)活化pEDTAD-BDA中的羧基,以BDA为交联剂,制得单体间连接全部为酰胺键、侧链只含羧基的交联网络聚合物BDA-crosslinked-EDTAh-BDA。采用氢核磁共振(1H-NMR)、碳核磁共振(13C-NMR)和茚三酮显色法对pEDTAD-BDA的结构和数均分子量进行了表征。pH敏感性测试表明,BDA-crosslinked-pEDTAD-BDA在pH=12介质中的溶胀率约为pH=3和pH=7介质中溶胀率的5倍,表现出敏锐的pH响应性。该网络聚合物可望成为一种集完全可降解性、良好生物相容性和pH敏感性于一身的医用水凝胶材料。     

新型可生物降解两性pH敏感水凝胶的制备与性能研究

以乙二胺四乙酸酐(EDTAD)和丁二胺(BDA)为原料,通过酸酐的N-酰化开环反应得到侧链只含羧基的直链共聚物PEB-COOH,然后用N-羟基丁二酰亚胺(NHS)和二环己基碳二亚胺(DCC)活化PEB-COOH中的羧基,以重均分子量为500的氨基封端聚乙二醇(ATPEG500)为交联剂,制得单体间连接全部为酰胺键、侧链只含羧基的交联网络聚合物PEB-ATPEG500-COOH.pH敏感性测试表明,PEB-ATPEG500-COOH具有3个pH敏感范围,分别是pH=2～4、pH=6～7和pH=10～11,表现出明显的两性pH敏感性.研究了该水凝胶在37℃条件下分别在pH=2、7、11介质中的溶胀动力学,并对溶胀速率进行了详细分析.该网络聚合物可望成为一种集完全可降解性、pH敏感性和生物相容性于一身的新型两性pH敏感水凝胶.     

分步合成羧甲基纤维素/聚丙烯酸甲酯pH敏感互穿网络水凝胶及其表征

以羧甲基纤维素(CMC)、聚丙烯酸甲酯(PMA)为互穿物,N,N'-亚甲基双丙烯酰胺(MBA)为交联剂,过硫酸钾(KPS)为引发剂,采用互穿网络(IPN)聚合分步合成法在乙醇的水溶液中合成出具有互穿网络结构的水凝胶。通过红外光谱、扫描电镜、X射线衍射和热重分析等表征了聚合物的互穿网络结构。pH溶胀实验结果表明,该水凝胶具有比较明显的pH敏感性,当pH在8.0左右,复合水凝胶的溶胀率达到了最大值,且随着CMC/PMA复合水凝胶中2种组分比例的不同,溶胀率有明显的差异。     

新型胶原/聚丙烯酸互穿网络pH敏感水凝胶的制备及性能研究

以Bis为交联剂,采用互穿网络(IPN)技术制备胶原/聚丙烯酸pH敏感水凝胶.研究了不同配比的水凝胶的溶胀动力学、pH敏感性及pH溶胀-退胀特性,并利用傅里叶变换红外光谱法(FTIR)和差示量热扫描法(DSC)对其结构进行表征.结果显示:制备的水凝胶具有较快的溶胀速率,在13min时吸水率可达93%左右;水凝胶有明显的pH敏感性且pH溶胀-退胀可逆性良好.FTIR和DSC结果表明,在保持胶原三股螺旋结构的同时,材料间形成了互穿网络,材料的热稳定性显著提高,从而扩大了材料的应用范围.     

P(MMA-AN)的合成及其凝胶电解质的制备与性能

以甲基丙烯酸甲酯(MMA)和丙烯腈(AN)为单体,自由基引发聚合合成了聚(甲基丙烯酸甲酯-丙烯腈)[P(MMA-AN)]无规共聚物。采用红外光谱分析及元素分析法对共聚物的结构进行了表征。然后以此P(MMA-AN)无规共聚物为基体制备共聚物含量分别为30%、40%、50%(质量分数)的凝胶聚合物电解质(GPE)。采用交流阻抗法对其电性能进行表征。结果发现当MMA与AN投料比为1:3且共聚物在凝胶聚合物电解质中质量分数为30%时,GPE体系电导率达到最大值。     

pH敏感性水凝胶P(MAPOSS-co-AA)的制备及药物缓释性能

以丙烯酸(AA)和七苯基甲基丙烯酰氧基笼型倍半硅氧烷(MAPOSS)为单体,以偶氮二异丁腈为催化剂,N,N-亚甲基丙烯酰胺为交联剂,通过自由基溶液聚合法,制备了具有pH敏感性的有机-无机共聚水凝胶P(MAPOSS-co-AA)。采用傅里叶变换红外光谱、X射线衍射和扫描电子显微镜对P(MAPOSS-co-AA)水凝胶的结构和溶胀后的形态进行了表征,并对其溶胀性能、药物缓释性能进行了研究。结果表明,XRD图中MAPOSS峰的消失说明MAPOSS均匀地分散在水凝胶交联网络中;与常规聚丙烯酸(PAA)水凝胶相比,MAPOSS的加入明显降低了其吸水能力,即P(MAPOSS-co-AA)水凝胶在模拟肠液(SIF)中溶胀后的孔径明显小于PAA水凝胶,但其pH敏感性不变,即随着pH值的增加,水凝胶的吸水能力增强,溶胀比增加;同时P(MAPOSS-co-AA)水凝胶作为茶碱的药物缓释体系,明显改善了茶碱在模拟胃液(SGF)和SIF中的释放性能,降低了茶碱在SIF中的释放速率。     

含二硫键铵盐交联水凝胶的制备及其性能研究

以N,N-二乙丙烯酰胺(DEAAm)和甲基丙烯酸二乙基氨基乙酯(DEAM)为单体通过自由基聚合合成线性共聚物。通过线性聚合物与交联剂CL1中的叔胺基团形成季碱结构,获得具有网络结构的氧化还原敏感型阳离子水凝胶(p DEAAm-co-p DEAM-CL1)。通过红外光谱(FT-IR)、核磁(1H NMR)对交联剂CL1结构进行表征,通过FT-IR和扫描电镜(SEM)对聚合物结构和表面形态进行表征。研究了水凝胶在不同介质中的溶胀和降解情况。结果表明该水凝胶在PBS溶液中具有显著的溶胀现象,在不同的还原性介质中,则表现出溶胀的同时,也表现出不同程度的降解,具有显著的氧化还原敏感性。     

温度敏感性P(NtBA-co-AAm)聚合物和水凝胶的合成及表征

以N-叔丁基丙烯酰胺(Nt BA)和丙烯酰胺(AAm)为反应单体,过硫酸铵(APS)为引发剂,在50℃时通过自由基聚合反应合成了具有温度敏感性的聚(N-叔丁基聚丙烯酰胺-co-丙烯酰胺)(P(Nt BA-co-AAm))线型聚合物及水凝胶。为提高凝胶的溶胀性能,以硅胶微粒和聚乙二醇400(PEG400)为造孔剂,合成了一系列大孔P(Nt BA-co-AAm)水凝胶。用差热分析仪分析了P(Nt BA-co-AAm)共聚物的热力学性能,通过红外光谱、扫描电镜表征了P(Nt BA-co-AAm)凝胶的结构。研究了进料中单体配比和交联剂用量对水凝胶溶胀性能的影响以及不同温度下水凝胶的溶胀动力学。结果表明,进料中Nt BA与AAm的摩尔比越高,共聚物及水凝胶的相转变温度越低;增加交联剂的用量,水凝胶的溶胀率降低;大孔凝胶的溶胀率和去溶胀率较传统凝胶有较大提高,同时对外界温度变化的响应更迅速。     

UV固化含氟聚丙烯酸酯的制备

以甲基丙烯酸十二氟庚酯、丙烯酸-2-乙基己酯、甲基丙烯酸羟乙酯、苯乙烯为聚合单体,偶氮二异丁腈为引发剂,通过溶液聚合制得了含氟羟基聚丙烯酸酯共聚物(PGHES),以含异氰酸酯的不饱和单体HIp与共聚物PGHES侧链上的羟基反应制得光敏性含氟聚丙烯酸酯(U-PGHES)。用傅立叶红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)表征聚合物结构;用凝胶渗透色谱(GPC)及差示扫描量热仪(DSC)表征聚合物分子量及玻璃化转变温度;用光学接触角测量仪测量了聚合物固化膜接触角并计算得到表面能。结果表明,固化膜表面能随U-PGHES中含氟量的增加而降低,当含氟量达到9%时,表面能降低趋缓。     

双重敏感性两亲性聚己内酯混合胶束的合成

合成了两亲性嵌段共聚物聚己内酯(ε-己内酯)-b-聚甲基丙烯酸二乙胺基乙酯和聚乙二醇-二硫键-聚己内酯,用核磁氢谱和凝胶渗透色谱对聚合物的结构及分子量进行了表征。用溶剂挥发法制备了聚合物胶束,用动态光散射以及扫描电镜对胶束结构及性质进行了表征。结果显示,两种聚合物自身可以形成胶束,也可以形成混合胶束;形成的混合胶束粒径在pH小于5.5或pH大于6.5时基本保持稳定,且前者稍大于后者,而在10mmol/L的二硫苏糖醇(DTT)的还原条件下,胶束发生破坏并产生团聚,体现了混合胶束的pH敏感性和还原敏感性,期望能够作为新的药物载体。     

PEG derived hydrogel: A novel synthesis route under mild condition

PEG derived hydrogels were synthesized by a novel synthesis route under mild condition. First, we synthesized a soluble linear copolymer by amino-terminated polyethylene glycol ATPEG and Pyromellitic dianhydride (PMDA), named by p (ATPEG-co-PMDA). The copolymer with imide rings on the main chain can be soluble in most of solvents. Then, the imide-rings of the copolymer were open by amino groups of Butanediamine (BDA) under ambient condition to form cross-linking network. The cross-linking network can form in few minutes. The p (ATPEG-co-PMDA) and gels were characterized by ¹³ C NMR and FTIR. The gels swelled significantly in water, and co-continuous porous structure was observed by scanning electron microscopy. The ring-opening cross-linked reaction of p(ATPEG-co-PMDA) provided a simple, versatile approach to hydrogel network under mild condition without initiator, which have potential as biomaterials to apply in biomedical region.     

How big data and analytics reshape the wearable device market – the context of e-health

The wearable device can be a key link between health care and big data and analytics (BDA). The benefits of BDA in health care have been widely acknowledged, but the uncertainty of the implementation of BDA has led some firms to hesitate in adopting this technology. In this research, we are keen to answer the key questions of whether the wearable device firms would adopt the BDA strategy, and how much effort they would put into it. We propose a competition model between the wearable device firms with and without BDA strategies, and consider the consumer’s preference towards BDA and network effects. Our model demonstrates that the investment on BDA directly affects the firm’s equilibrium price, market share and profit and at the same time, this strategy also affects the rival’s performances. When the firm with BDA strategy adopts different competition strategy: conservative or expansive, the outcomes of market are different. We also find that different market structures, fully covered and partially covered, have different impacts on the firms’ competition when the consumers have heterogeneous preference on BDA strategy.     

An amidated carboxymethylcellulose hydrogel for cartilage regeneration

An amidic derivative of carboxymethylcellulose was synthesized (CMCA). The new polysaccharide was obtained by converting a large percentage of carboxylic groups ( approximately 50%) of carboxymethylcellulose into amidic groups rendering the macromolecule quite similar to hyaluronan. Then, the polysaccharide (CMCA) was crosslinked. The behavior of CMCA hydrogel towards normal human articular chondrocytes (NHAC) was in vitro studied monitoring the cell proliferation and synthesis of extra cellular matrix (ECM) components and compared with a hyaluronan based hydrogel (Hyal). An extracellular matrix rich in cartilage-specific collagen and proteoglycans was secreted in the presence of hydrogels. The injectability of the new hydrogels was also analysed. An experimental in vivo model was realized to study the effect of CMCA and Hyal hydrogels in the treatment of surgically created partial thickness chondral defects in the rabbit knee. The preliminary results pointed out that CMCA hydrogel could be considered as a potential compound for cartilage regeneration.     

A soft tissue adhesive based on aldehyde-sodium alginate and amino-carboxymethyl chitosan preparation through the Schiff reaction

Sodium alginate and carboxymethyl chitosan have been extensively applied in tissue engineering and other relative fields due to their low price and excellent biocompatibility. In this paper, we oxidized sodium alginate with sodium periodate to convert 1,2-hydroxyl groups into aldehyde groups to get aldehyde-sodium alginate (ASA). Carboxymethyl chitosan was modified with ethylenediamine (ED) in the presence of water-soluble N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC) to introduce additional amino groups to get amino-carboxymethyl chitosan (A-CS). Upon mixing the A-SA and A-CS aqueous solutions together, a gel rapidly formed based on the Schiff’s base reaction between aldehyde groups in A-SA and amino groups in A-CS. FTIR analysis confirmed the characteristic peak of Schiff’s base group in the hydrogel. It was confirmed that the gelation time be dependent on the aldehyde group content in A-SA and amino group content in A-CS. The fasted hydrogel formation takes place within 10 min. The data of bonding strength and cytotoxicity measurement also showed that the hydrogel had good adhesion and biocompatibility. All these results support that this gel has the potential as soft tissue adhesive.     

Sodium Alginate/Carboxyl-Functionalized Graphene Composite Hydrogel Via Neodymium Ions Coordination

A facile method for the preparation of sodium alginate(SA)/carboxyl-functionalized graphene(G-COOH)composite hydrogel was developed. Based on the coordination ability of lanthanide ions to the carboxyl groups, a series of hydrogel derived from different ratios of SA and G-COOH was fabricated by neodymium(Nd~(3+)) ions coordination. A relatively uniform layered structure was recorded by SEM at the interior of SA/G-COOH hydrogel. Several parameters such as water content, swelling ratio(SR), tensile test and solvent resistance were also investigated. The SA/G-COOH composite hydrogel showed excellent mechanical strength, and the tensile strength of SA/G-COOH composite hydrogel reaches 53.72 MPa at high water content. Due to the coordination ability of Nd~(3+) ions, the hydrogel also exhibited an excellent solvent resistance and stability.     

Big data analytics business value and firm performance: linking with environmental context

Previous studies, grounded on the resource based view, have already explored the relationship between the business value that Big Data Analytics (BDA) can bring to firm performance. However, the role played by the environmental characteristics in which companies operate has not been investigated in the literature. We inform the theory, in that direction, via the integration of the contingency theory to the resource based view theory of the firm. This original and integrative model examines the moderating influence of environmental features on the relationship between BDA business value and firm performance. The combination of survey data and secondary financial data on a representative sample of medium and large companies makes possible the statistical validation of our research model. The results offer evidence that BDA business value leads to higher firm performance, namely financial performance, market performance and customer satisfaction. More original is the demonstration that this relationship is stronger in munificent environments, while the dynamism of the environment does not have any moderating effect on the performance of BDA solutions. It means that managers working for firms in markets with a growing demand are in the best position to profit from BDA.     

High ionic strength glucose-sensing photonic crystal

We demonstrate a colorimetric glucose recognition material consisting of a crystalline colloidal array embedded within a polyacrylamide-poly(ethylene glycol) (PEG) hydrogel, or a polyacrylamide-15-crown-5 hydrogel, with pendent phenylboronic acid groups. We utilize a new molecular recognition motif, in which boronic acid and PEG (or crown ether) functional groups are prepositioned in a photonic crystal hydrogel, such that glucose self-assembles these functional groups into a supramolecular complex. The formation of the complex results in an increase in the hydrogel cross-linking, which for physiologically relevant glucose concentration blue shifts the photonic crystal diffraction. The visually evident diffraction color shifts across the visible spectral region over physiologically important glucose concentration ranges. These materials respond to glucose at physiological ionic strengths and pH values and are selective in their mode of response for glucose over galactose, mannose, and fructose. Thus, we have developed a new recognition motif for glucose that shows promise for the fabrication of noninvasive or minimally invasive in vivo glucose sensing for patients with diabetes mellitus.     

Thermometric sensing of nitrofurantoin by noncovalently imprinted polymers containing two complementary functional monomers

Molecularly imprinted polymers (MIPs) for nitrofurantoin (NFT) recognition addressing in parallel of two complementary functional groups were created using a noncovalent imprinting approach. Specific tailor-made functional monomers were synthesized: a diaminopyridine derivative as the receptor for the imide residue and three (thio)urea derivatives for the interaction with the nitro group of NFT. A significantly improved binding of NFT to the new MIPs was revealed from the imprinting factor, efficiency of binding, affinity constants and maximum binding number as compared to previously reported MIPs, which addressed either the imide or the nitro residue. Substances possessing only one functionality (either the imide group or nitro group) showed significantly weaker binding to the new imprinted polymers than NFT. However, the compounds lacking both functionalities binds extremely weak to all imprinted polymers. The new imprinted polymers were applied in a flow-through thermistor in organic solvent for the first time. The MIP-thermistor allows the detection of NFT down to a concentration of 5 μM in acetonitrile + 0.2% dimethyl sulfoxide (DMSO). The imprinting factor of 3.91 at 0.1 mM of NFT as obtained by thermistor measurements is well comparable to the value obtained by batch binding experiments.