Unusual degradation behavior of citric acid-crosslinked gelatin in vitro and in vivo

The aim of this study was to evaluate the biodegradability and biocompatibility of gelatin matrices designed for drug-eluting stents (DESs). The matrices were prepared by crosslinking alkali-treated gelatin (AlGelatin) with a citric acid-based crosslinker, trisuccinimidyl citrate (TSC), to form AlGelatin-TSC. The biodegradation behavior of the matrices was evaluated in vitro and in vivo. An in vitro enzymatic degradation test showed that AlGelatin-TSC prepared at a TSC concentration of 20 mM is the most stable in collagenase solution compared to AlGelatin-TSC prepared at TSC concentrations higher or lower than 20 mM. Then, AlGelatin-TSC were implanted subcutaneously in rats to evaluate their biodegradability and tissue reaction in vivo. Similar to the in vitro degradation behavior, AlGelatin-TSC with TSC concentration of 20 mM exhibited the lowest biodegradable rate in vivo among all AlGelatin-TSC. In addition, strong inflammation and calcification were not observed for AlGelatin-TSC at any TSC concentration. From an analysis of the crosslinking density of the resulting AlGelatin-TSC, the lowest biodegradability of AlGelatin-TSC with TSC concentration of 20 mM was due to the highest crosslinking density of the matrix. These results suggest that AlGelatin-TSC is suitable for use as matrices in DESs because of its excellent biocompatibility and biodegradability.     

基于儿茶酚交替共聚物的干湿态双高效胶黏剂材料

以多巴胺(DA)和双酚A型环氧树脂(BAER)进行氨基-环氧点击化学反应,合成了儿茶酚功能化交替共聚物聚(多巴胺-alt-双酚A型环氧)[P(DA-a-BAER)].以FeCl₃为交联剂,研究了交联剂用量对聚合物在干态及水下环境中黏接性能的影响.结果表明,该聚合物可以在干态及水下环境中对多种基材进行黏接.以不锈钢基材为例,在干态条件下,当Fe³⁺与儿茶酚基团的摩尔比为1:3时,黏接强度最高,为(3.03±0.68)MPa;在水下环境中,当Fe³⁺与儿茶酚基团的摩尔比为1:6时,黏接强度最高,为(0.65±0.10) MPa.拉曼光谱(Raman)和紫外-可见光吸收光谱(UV-Vis)分析结果表明,Fe³⁺与儿茶酚基团可通过配位交联和氧化交联的方式增大胶体强度,从而提高黏接强度.     

表面改性SUS316L不锈钢的电化学行为研究

分别以表面镀Rh,表面离子束增强沉积Ta2O5膜及溶胶凝胶法沉积TiO2膜对冠状动脉支架用材料SUS316L不锈钢进行表面改性.采用电化学方法研究了该表面改性试样在Tyrode's模拟人工体液中的电化学行为.结果表明,上述3种表面改性方法均可提高SUS316L不锈钢在模拟人工体液中的阳极极化性能.其中对于采用离子束增强法沉积的Ta2O5膜和溶胶凝胶法沉积的TiO2膜,因Ta和Ti上的d轨道空位已被氧的电子占据,不利于氢吸附,从而抑制了阴极的析氢过程.X射线衍射分析发现,3种改性方法在SUS316L不锈钢表面依次形成均匀而致密的Rh金属层,Ta2O5的无序膜层和TiO2晶态膜层,阻止了合金元素的溶解,改善不锈钢的电化学性能.     

硅烷偶联剂对不锈钢表面膜基结合强度的影响

运用拉伸法研究了硅烷偶联剂对316L不锈钢高分子涂层的结合强度的影响,并对硅烷偶联剂的含量、预处理时间及pH值等工艺条件进行了优化。采用ATRIR,XPS等技术表征了偶联剂提高膜基结合强度的机理。结果表明：硅烷偶联剂能够显著提高不锈钢与高分子涂层之间的结合强度,最佳的工艺条件为：偶联剂含量W=0．05,处理时间为10s,溶液的pH值为6。作用机理是：偶联剂一端与金属生成了Si-O-Me键。另一端与高分子相互缠绕形成了复杂的互穿网络结构。     

The effect of UV irradiation on the reduction of Au(III) ions adsorbed on manganese dioxide.

The effect of UV (ultraviolet) irradiation on the adsorption of Au(III) ions on manganese dioxide and their reduction to Au(0) (gold with 0 valence state) was investigated using XPS (X-ray photoelectron spectroscopy) and 197Au M?ssbauer spectroscopy. The UV irradiation accelerated the adsorption and the reduction. From the fact that the proportion of Au(0) estimated from Au 4f XPS spectra for surface analysis was significantly smaller than that from 197Au M?ssbauer spectra for bulk analysis, we deduced that Au(0) was interpenetrated to the inside of manganese dioxide (into deeper places than about 30 A) where XPS is impossible to detect. The content of surface hydroxyl groups on manganese dioxide also increased due to the UV irradiation. The relationship between the charge in the content of hydroxyl groups and the interpenetration of Au(0) is discussed.     

Modification of amorphous poly(ethylene terephthalate) surface by UV light and plasma for fabrication of an electrophoresis chip with an integrated gold microelectrode

Amorphous poly(ethylene terephthalate) (PET), which possess a low softening temperature (T(s)=75 degrees C), was exploited to fabricate the electrophoresis chip with an integrated gold electrode for amperometric detection, with emphases being focused on the PET surface modification via UV light and air plasma. Both UV irradiation and plasma treatment were found to be able to improve the surface wettability, enhance the supported electroosmotic flow (EOF), and increase thermal bonding strength of PET sheets, with the latter being more efficient and less time-consuming than the former in the surface modification. Upon treated with plasma for 2 min, the PET sheets could be thermally bonded at 65 degrees C. T-peer test showed that the bonding strength increased from 10 g/cm for native PET sheets to 1250 g/cm for the plasma treated sheets when chips were bonded at the softening point, Attenuated-total-internal-reflection spectrum showed that, after being exposed to the UV light, carboxylic groups site-selectively formed in the UV-exposed region on PET surface. These UV-induced carboxylic groups were further utilized as the scaffold for preparation of micro-gold electrode via electroless gold plating. By using this established UV-directed electroless plating and the plasma-assisted thermal bonding techniques, the full PET electrophoresis chip with an integrated micro-gold electrode could be fabricated in common chemistry laboratory without the need of clean rooms. The fabricated PET chips were demonstrated for separation and detection of model analytes of dopamine (DA) and catechol (CA). Satisfactory resolution of the two analytes was achieved within 40s, and detection limits of 0.87 microM and 1.28 microM for DA and CA were obtained, respectively.     

Surface graft polymerization of glycidyl methacrylate onto polyethylene and the adhesion with epoxy resin

Surface graft polymerization of glycidyl methacrylate (GMA) was carried out onto a high- density polyethylene (PE) sheet pretreated with corona to introduce peroxides onto the PE surface. Graft polymerization of GMA was effected by UV irradiation of the coronatreated PE in the presence of monomer solution without the use of any photosensitizer. The graft layer was found by staining the PE cross section to localize in the surface region of PE. The physical change in the PE surface was characterized by scanning electron microscopy, while the chemical changes due to the GMA graft polymerization were assessed by the dynamic contact angle, FT-IR, and x-ray photoelectron spectroscopy (XPS) measurement. The peroxide formation by corona exposure was confirmed by the XPS measurement after derivatization with SO₂. The epoxy groups introduced onto the PE surface by the GMA graft polymerization were reactive with water (in the presence of HCI) and amines. The adhesion between the GMA-grafted PE and an epoxy resin was studied by means of a shear strength test method. The GMA-grafted PE exhibited strong interfacial adhesion with the epoxy resin, compared to the original and corona-treated PE. The adhesion strength of the GMA-grafted PE was nearly two times higher than that of the corona-treated PE. This strongly suggests that the enhanced adhesion between the surface-grafted PE and the epoxy resin is ascribed to covalent bonding of the epoxy groups on the GMA-grafted surface to the amines in the epoxy resin. © 1995 John Wiley & Sons, Inc.     

Surface properties and photocatalytic activity of nanocrystalline titania films

In this work the efficiency and physicochemical details of a thin film produced by help of a microwave assisted sol gel technique is compared to different commercial powders (Degussa P25 and Hombikat UV100) deposited on glass substrates. Furthermore, a supercritical produced TiO₂ powder (SC 134) was included in the comparison.The prepared TiO₂ films were characterized using XRD, XPS, AFM, DSC and DLS. The photocatalytic activity was determined using stearic acid as a model compound. Investigation of the prepared films showed that the Degussa P25 film and the sol–gel film were the most photocatalytic active films. The activity of the films was found to be related to the crystallinity of the TiO₂ film and the amount of surface area and surface hydroxyl groups. Based on the XPS investigation of the films before and after UV irradiation it was suggested that the photocatalytic destruction of organic matter on TiO₂ films proceeds partly through formation of hydroxyl radicals which are formed from surface hydroxyl groups created by interactions between adsorbed water and vacancies on the TiO₂ surface. Furthermore a correlation between the amount of OH groups on the surface of the different TiO₂ films and the photocatalytic activity was found.     

Polyetheretherketone (PEEK) surface functionalization by low-energy ion-beam irradiation under a reactive O2 environment and its effect on the PEEK/copper adhesives

A low-energy Ar+ ion beam was used to modify the surface of a polyetheretherketone (PEEK) film. The modification reaction proceeded with or without oxygen gas injected during the irradiation. The surface functional groups of the modified PEEK were confirmed with X-ray photoelectron spectroscopy as increasing various oxygen-containing functional groups. The concentration of the functional groups varied rapidly with the irradiation time, reached a maximum value, and then slowly decreased. The surface morphology of PEEK was substantially changed by ion-beam irradiation. Surface smoothening occurred so that the surface roughness reached almost constant value after some irradiation time. The incorporation of functional groups on the PEEK surface and the surface topology change had opposite effects on the adhesion strength between PEEK and copper. Dominance of the former was evident because the lap-shear strength initially increased with the irradiation. The special surface features significantly enhanced the adhesion strength between the evaporated copper layer and the modified PEEK surface. However, the decrease in the surface roughness with a long time irradiation implies a decrease in adhesion strength due to a smaller contact area, and the shear strength due to topology change also slowly decreased after a long time irradiation.     

分子氧在锐钛矿型TiO2表面的光助吸附和光助脱附

本文采用真空-质谱技术研究了紫外线照射下分子氧在锐钛矿型TiO₂表面的吸附和脱附机理。氧光助吸附后,锐钛矿表面成为活化表面。活化表面的O₂^-(分子氧在锐钛矿表面的吸附态)在1.33×10^-3Pa的真空中,在能量大于锐钛矿禁带宽度2.9eV的紫外线照射下成为分子氧脱附,氧脱附后的表面在无紫外线照射的氧气氛中对分子氧有吸附作用,该O₂^-饱和吸附量大于相同氧压下紫外线照射下O₂的饱和吸附量。在氧压和光强度相同的条件下,O₂^-吸附量与表面羟基化程度呈线性关系。     

Improvement of the proton exchange membrane fuel cell (PEMFC) performance at low-humidity conditions by exposing anode in Ultraviolet light

External humidifying system is generally needed for the fully hydration of membrane and catalyst layer, but it is considered as a barrier to PEMFC all the time. In this study, ultraviolet (UV) light was served as external stimulus to increase the wettability of anode which consists of photo-sensitive hygroscopic materials titanium oxide (TiO₂). Under UV irradiation, water adsorbed on the photo-induced oxygen defects of TiO₂ and transformed into surface hydroxyl groups. The generated hydroxyl groups furthered the back diffusion and decreased the charge resistance, which improved the performance at the low-humidity condition. The problems on the introduction of excessive hygroscopic materials are avoided by the new method.     

Chemical nature of adhesion: Plasma modified styrene-butadiene elastomer and polyurethane adhesive joints

A study of the mechanism of gluing between plasma-modified styrene-butadiene elastomer (SBS) surfaces and polyurethane (PU) adhesives is presented in this paper. The plasma treatment was carried out employing low-pressure O₂ plasma generated by an RF discharge (13.56 MHz). FTIR-ATR spectroscopy and peel tests were utilized to characterize the SBS surfaces before and after the plasma treatment. It was found that hydroxyl groups are mainly created on the SBS surface by the plasma treatment and their concentration reveals very good linear correlation with the peel strength of the SBS-PU joints. The grafting of phenyl isocyanate (analog of the PU curing agent) into the plasma-treated SBS surface was also investigated. The process was performed at 353 K, that is at temperature in which the adhesive-bonded joints were made. It was shown that all hydroxyl groups on the SBS surface react with isocyanate groups forming carbamate bonds. The results obtained in this work strongly confirm the conception of the adhesion by chemical bonding between SBS and PU.     

Immobilization of Tris-(8-hydroxyquinoline) aluminum onto P4VP polymer thin films by UV irradiation cross-linking

We report a novel method for the immobilization of Tris-(8-hydroxyquinoline) aluminum (Alq₃) onto poly(4-vinylpyridine) (P4VP) thin polymer films by UV irradiation cross-linking. The polymer films were prepared by spin-coating of P4VP onto cleaned silicon wafer surface followed by UV irradiation. The thicknesses of the polymer thin films were measured by ellipsometry with different irradiation times. The immobilization of Alq₃, orientation and the surface activity were followed using photoluminescence and UV-visible spectroscopy. The surface morphology was investigated by using field emission scanning electron microscopy and atomic force microscopy. Patterning of Alq₃ on P4VP film was obtained using photolithography technique. Our experimental results show that the cross-linked P4VP thin film is a universal surface modifier.     

紫外线预照射对TiO2上三氯乙烯气相光催化氧化反应的影响

 用紫外线照射法对TiO2光催化剂进行了预处理,并利用热重分析比较了预照射法和高温加热法对TiO2上三氯乙烯气相光催化氧化反应的影响. 结果表明,紫外线预照射可加快三氯乙烯的气相光催化反应. 这可能是紫外线预照射使TiO2 的表面状态和表面结构发生了变化,使催化剂表面活性基团羟基自由基的量增加所致.     

由亲水和疏水硅胶制备的Co/Ru/SiO2催化剂的表征及催化性能研究

以亲水硅胶Degussa A300和疏水硅胶Degussa R106作为催化剂载体,采用等体积浸渍法制备了一系列钴基催化剂。利用MS、XRD、BET、FT-IR、TPR等手段考察了载体热稳定性,催化剂表面物相结构和还原性能等物化性能。结果表明,载体表面有机基团对催化剂中Co3O4尺寸大小有影响,有机基团对载体表面羟基的取代使得金属钴与载体的作用力减弱,有利于金属团聚为较大的颗粒。费-托反应结果表明,亲水硅胶性制得的催化剂通过后处理引入甲基后,造成催化剂活性下降,C18+的选择性下降,但使烃分布集中在C5～C18,这是由于表面甲基的空间位阻作用不利于反应中的吸附过程和链增长过程。由疏水载体制备的催化剂虽然钴颗粒较大,但是由于催化剂制备过程中部分有机基团的烧结,对催化剂活性产生了较大的负面影响,使催化活性降低,重质烃选择性明显降低。     

Selective photochemical functionalization of surfactant-dispersed single wall carbon nanotubes in water

Ultraviolet (UV) irradiation of single wall carbon nanotubes (SWCNTs) individually dispersed in surfactants leads to diameter and type-selective photohydroxylation of the nanotubes. Photohydroxylation of first semiconductor and then small diameter metallic SWCNTs was confirmed after 254 nm UV irradiation in acidic, neutral, and basic aqueous solutions at ambient and elevated temperatures. The increased oxygen content of the SWCNTs after UV irradiation, as detected by X-ray photoelectron spectroscopy, suggests that SWCNTs were hydroxylated by reaction with water. Attenuated total reflectance Fourier transform infrared analysis provides evidence of hydroxyl functional groups on their surface. This photochemical reaction is impeded by molecular oxygen and appears to involve a reactive intermediate generated in the vicinity of semiconducting SWCNTs. This represents a noncontaminating selective reaction in the liquid phase that uses an intrinsic property of the tubes.     

Interaction of ester functional groups with aluminum oxide surfaces studied using infrared reflection absorption spectroscopy

The bonding of two types of ester group-containing molecules with a set of different oxide layers on aluminum has been investigated using infrared reflection absorption spectroscopy. The different oxide layers were made by giving typical surface treatments to the aluminum substrate. The purpose of the investigation was to find out what type of ester-oxide bond is formed and whether this is influenced by changes in the composition and chemistry of the oxide. The extent by which these bonded ester molecules resisted disbondment in water or substitution by molecules capable of chemisorption was also investigated. The ester groups were found to show hydrogen bonding with hydroxyls on the oxide surfaces through their carbonyl oxygens. For all oxides, the ester groups showed the same nu(C = O) carbonyl stretching vibration after adsorption, indicating very similar bonding occurs. However, the oxides showed differences in the amount of molecules bonded to the oxide surface, and a clear relation was observed with the hydroxyl concentration present on the oxide surface, which was determined from XPS measurements. The two compounds showed differences in the free to bonded nu(C = O) infrared peak shift, indicating differences in bonding strength with the oxide surface between the two types of molecules. The bonding of the ester groups with the oxide surfaces was found to be not stable in the presence of water and also not in the presence of a compound capable of chemisorption with the aluminum oxide surface.     

High damping and mechanical properties of hydrogen-bonded polyethylene materials with variable contents of hydroxyls: Effect of hydrogen bonding density

Hydrogen bonding is considered to have significant effect on the interaction between polymeric chains and on the viscoelasticity of the polymeric materials. In this paper, we attempt to discuss the relationship between hydrogen bonding density and damping behavior and mechanical properties of polyethylene-based polymeric materials. For this reason, a series of pendant chain hydrogen bonding polymers(PCHBP) with different hydrogen bonding density(HBD) were prepared by quantitatively changing the content of pendent hydroxyl groups on the main chain of polyethylene. It was found that PCHBP with low HBD showed similar properties to polyethylene, indicating that the property of the materials was dependent mainly on the structure of the main chain. However, PCHBP with high HBD exhibited two tanδ peaks and a platform of loss modulus as well as a high storage modulus(about 400 MPa) at the second tanδ peak temperature, demonstrating that a polymeric material with high strength and damping properties was obtained. More importantly, the maximum of loss modulus showed a linear increase with the HBD, indicating that a higher HBD greatly improved the damping properties of the polymeric materials.     

酸法纳米纤维素模板剂合成介孔TiO2及光催化活性

以生物可再生资源的酸法纳米纤维素为模板剂,四氯化钛为钛源,采用液相水解-沉淀法制备了具有介孔结构的TiO2光催化剂。采用低温N2物理吸附-脱附、透射电镜(TEM)、X射线衍射(XRD)、热重-量热扫描(TG/DSC)、傅里叶变换红外(FTIR)、X射线光电子能谱(XPS)等对介孔TiO2进行了表征,并以甲基橙为模型物,考察了介孔TiO2光催化活性。结果表明,以酸法纳米纤维素为模板剂合成的TiO2光催化活性显著提高,且具有良好的孔隙结构,平均孔径5.03 nm、总孔容积0.35 cm3.g-1、比表面积192m2.g-1;纤维素模板剂合成的TiO2表面羟基数量降低;纤维素长链分子结构之间的羟基与TiO2表面羟基的键合,可有效限制TiO2前驱体的生长和团聚,并抑制锐钛矿相TiO2向金红石相转变。     

Diffusion of Formaldehyde on Rutile TiO2(110) Assisted by Surface Hydroxyl Groups

As the photo-dissociation product of methanol on the TiO₂(110) surface,the diffusion and desorption processes of formaldehyde (HCHO) were investigated by using scanning tunneling microscope (STM) and density functional theory (DFT).The molecular-level images revealed the HCHO molecules could diffuse and desorb on the surface at 80 K under UV laser irradiation.The diffusion was found to be mediated by hydrogen adatoms nearby,which were produced from photodissociation of methanol.Diffusion of HCHO was significantly decreased when there was only one H adatom near the HCHO molecule.Furthermore,single HCHO molecule adsorbed on the bare TiO₂(110) surface was quite stable,little photo-desorption was observed during laser irradiation.The mechanism of hydroxyl groups assisted diffusion of formaldehyde was also investigated using theoretical calculations.