Sulfonated magnetic sugarcane bagasse as an efficient natural polymer-based catalyst for the synthesis of nitrogen-containing heterocyclic rings in water

Molecular Diversity - A new species of catalysts that are prepared from biocompatible materials is demonstrated. Sulfonated magnetic sugarcane bagasse has been synthesized as a novel biodegradable...     

采用密度泛函理论与分子动力学对聚甲基丙烯酸甲酯双折射性的理论计算

双折射性是各种光学材料的重要性能之一,具有高双折射率的光学材料在诸多研究及工业领域的应用越来越广泛.然而,作为常用的光学薄膜及光波导材料之一的聚合物材料的双折射性通常却很弱,只能通过实验对其双折射率进行大致的表征,缺乏对其双折射率的系统性理论计算,从而限制了提高聚合物双折射性的研究.本文建立了从聚合物的单体分子结构到多分子链的系统性的双折射率理论计算方法,并借助此方法研究了导致聚合物弱双折射性的限制因素.以聚甲基丙烯酸甲酯(PMMA)为研究对象,运用密度泛函理论研究了其本征双折射率,这里的本征双折射率是指分子链完全取向时其单体单元的双折射率.计算结果表明其本征双折射率高达0.0738左右,并且通过计算给出了PMMA单体单元的平均双折射率色散曲线.采用分子动力学方法研究了该聚合物(包含20个分子链)的材料双折射率.理论计算结果表明,尽管该聚合物具有较大的本征双折射率,但是由于聚合物中分子链取向度极低,聚合物材料最终表现出来的双折射率只有0.00052.本文建立的研究方法及研究结果为研究增强聚合物材料双折射性提供了理论依据.     

Cellulosic fibre-reinforced green composites

Increased environmental awareness and societal needs serve as a catalyst for developing new eco-friendly materials like green composites. In the recent past, researchers have reported the results of their studies on green composites of different plant fibres and various biodegradable matrices. This article is an overview of the various aspects of green composites. Composites based on important biodegradable matrices like rubber, poly (lactic acid), poly(butylene succinate), poly(hydroxybutanoate) and soy-based matrices have been discussed. Special emphasis has been given to natural rubber-based green composites.     

Effect of degumming time on silkworm silk fibre for biodegradable polymer composites

Recently, many studies have been conducted on exploitation of natural materials for modern product development and bioengineering applications. Apart from plant-based materials (such as sisal, hemp, jute, bamboo and palm fibre), animal-based fibre is a kind of sustainable natural materials for making novel composites. Silkworm silk fibre extracted from cocoon has been well recognized as a promising material for bio-medical engineering applications because of its superior mechanical and bioresorbable properties. However, when producing silk fibre reinforced biodegradable/bioresorbable polymer composites, hydrophilic sericin has been found to cause poor interfacial bonding with most polymers and thus, it results in affecting the resultant properties of the composites. Besides, sericin layers on fibroin surface may also cause an adverse effect towards biocompatibility and hypersensitivity to silk for implant applications. Therefore, a proper pre-treatment should be done for sericin removal. Degumming is a surface modification process which allows a wide control of the silk fibre's properties, making the silk fibre possible to be used for the development and production of novel bio-composites with unique/specific mechanical and biodegradable properties. In this paper, a cleaner and environmentally friendly surface modification technique for tussah silk in polymer based composites is proposed. The effectiveness of different degumming parameters including degumming time and temperature on tussah silk is discussed through the analyses of their mechanical and morphological properties. Based on results obtained, it was found that the mechanical properties of tussah silk are affected by the degumming time due to the change of the fibre structure and fibroin alignment.     

Laser Raman spectroscopic investigations of biodegradable vehicle of active agents eluting LVM 316 stainless steel cardiovascular stents for in vivo degradation characteristics

Laser Raman spectroscopy is an effective tool for the study of biodegradable polymers, which play a vital role in the new developments in coronary implants such as stents. There is much excitement around the potential capabilities of synthetic biodegradable polymers and the effect they will have on the design and function of implanted devices. In the present investigation, heparin‐conjugated biodegradable copolymers were evaluated for their durability as drug‐eluting stent coatings. Laser Raman spectroscopic studies were carried out and spectra recorded and analyzed of explanted stents coated with different amounts of polymer alone, showing the existence of different levels at different quantities of polymer. The polymer was detected on every stent analyzed. On the stents coated with a thick layer of polymer, a firm layer of polymer still existed on the stent. In contrast, this layer was degraded and spread around on the stents coated with only a thin layer of the polymer. This indicates that the polymers used in the stents in the present investigation exhibit acceptable biodegradability. Such polymers can be used as efficient drug carriers, as these materials show good degradation after the stipulated period. Copyright © 2009 John Wiley & Sons, Ltd.     

New photopolymer with trifunctional monomer for holographic applications

New holographic recording materials based on photopolymerizable systems have contributed significantly to the recent growth of holographic applications. Previously, we reported that in photopolymerizable systems with a difunctional monomer, Ethylene Glycol DiMethAcrylate (EGDMA) improves the behaviour of the system and explains the role played by an eosin ester that has an oxo-oxime group in the production of amine initiator radicals. This comparative study was carried out in our laboratory using differential scanning photo-calorimetry and holography. The results of the new photosensitive recording materials for holography indicate that this system can be used for the formulation of very promising photopolymers that have a better performance. The aim of this study was to change the crosslinking monomer in order to increase the energetic sensitivity and discover the rest of the behavior. The new photo-polymerizable mixture contains PentaErythritol TriAcrylate (PETA) in a 1:1 ratio of volume and a 2-Hydroxy-Ethylene MethAcrylate monomer (HEMA). A diffraction efficiency of 80% is achieved with an energetic sensitivity of 3 J/cm² at 514 nm, and the spatial resolution is up to 2000 lines/mm.Part of this paper was presented at the IS&T/SPIE Symposium in Electronic Imaging, Science and Technology (Holographic Materials), February 5–10, San Jose, CA, USA     

Cellulose-based biocomposites: comparison of different multiphasic systems

Biocomposites (biodegradable composites) are obtained by blending biodegradable polymers and fillers. Since the main components are biodegradable, the composite as a whole is also expected to be biodegradable. This paper presents various biocomposites that have been elaborated with cellulose or lignocellulose fibers from diverse sources, with different lignin contents. This paper is targeted on the analysis of 'fiber–matrix' interactions of two types of biocomposites based on agropolymer (plasticized wheat starch) and biopolyester (polybutylene adipate-co-terephthalate), named APB and BPB, respectively. Processing and main properties of both biocomposites are shown and compared. Polyolefin-based composite (PPC), which is known to present very poor 'fiber–matrix' interactions, is used as a reference. Through the Young's modulus, mechanical properties have shown that the reinforcement, by increasing fiber content, is much more significant for APB compared to BPB. The evolution of chains mobility, evidenced through shift of T _g values, according to the increase in fiber content and thence in interfacial area, have shown that the fiber–matrix interactions are higher for APB. BPB presents intermediate values, higher than PPC ones. These results are in agreement with the analysis of the composite morphologies performed by SEM on cryogenic fractures. Finally, by determining the theoretical works of adhesion and the interfacial tensions from contact angle measurements, it is shown that these parameters are partially able to predict the level of interaction between the fibers and the matrix. We could show that the perspectives of such work seem to be of importance to tailor new materials with a controlled end-use.     

Preparation and Characterization of Nanocomposite Scaffolds Based on Polycaprolactone-Polyethylene Glycol/Methylene Diphenyl Diisocyanate/Diethylene Glycol and Nano-Bioactive Glass

Designing and fabricating nanocomposite scaffolds based on biodegradable polymers and bioactive materials are an important topic in the area of bone regeneration. A novel nanocomposite scaffold composed of polyurethane (BPU) and nano-bioactive glass (NBAG) was prepared. The effects of the NBAG content on the properties of the BPU/NBAG composite scaffolds, including the morphologies, porosity and compressive strength, were investigated. The BPU/NBAG composite scaffolds showed an interconnected pore structure with the pore size ranging from 50 to 500?μm for all samples. The porosity percent and swelling ability decreased with increasing NBAG content; however, the compressive strength was enhanced.     

Dynamic mechanical analysis of the interphase in bacterial polyester/cellulose whiskers natural composites

Nanocomposite materials were prepared from an elastomeric poly(hydroxyoctanoate) (PHO) latex as a fully amorphous or semi-crystalline matrix using a colloidal suspension of hydrolyzed cellulose whiskers as natural and biodegradable filler. After stirring, the preparations were cast and evaporated. High performance materials were obtained from these systems, preserving the natural character of PHO. Interfacial phenomena were assumed to be noticeable owing to the high specific area of this filler. Dynamic mechanical analysis was performed on these systems to test the influence of the interphase on the molecular mobility of the amorphous phase. To quantify the distance away from the surface at which the molecular mobility is restricted, a physical model was used to predict the mechanical loss angle. This allows removal of the filler reinforcement effect keeping only the interfacial effect. It was shown that the local motion at the filler-matrix interface of amorphous PHO chains is strongly affected when an amorphous PHO was used as the matrix. No significant change was observed when a semi-crystalline PHO was used as the matrix. This result was ascribed to a possible trancrystallization phenomenon of semi-crystalline PHO in contact with cellulose whisker surface, which prevents any contact between amorphous PHO chains and filler surface.     

紫外光致聚合物和制造镭射玻璃的技术

本文论述了制造镭射玻璃的技术和材料。技术包括：清洗玻璃板；将紫外光致聚合物材料涂到玻璃板上；将镭射玻璃母版粘贴到涂有光致聚合物的玻璃板上；紫外光曝光固化；丝网印刷；真空镀膜；涂保护层。紫外光致聚合物材料是由光引发剂、单体、预聚体和其它添加剂组成。实验结果表明：此种镭射玻璃具有很高的抗酸、碱、热和紫外照射的能力     

Polylactic acid functionalization with maleic anhydride and its use as coupling agent in natural fiber biocomposites: a review

Abstract

Due to its renewability and biodegradability, biopolymers have developed interest in order to substitute oil-derived plastics. In particular, polylactic acid (PLA) is a promising biopolymer in terms of mechanical and biodegradable properties that is used for different applications. Nevertheless, PLA has some disadvantages like brittleness and processing instability. In order to overcome these drawbacks, it has been blended with natural fibers, leading to a fully biodegradable biocomposite material with enhanced properties. However, blending a hydrophobic biopolymer with hydrophilic fibers leads to poor interfacial adhesion producing interfacial voids, cavities and defects and consequently low performance properties. In this sense, this article reviews different strategies of biopolymer functionalization to improve compatibility in biocomposite materials. First, the effect of different parameters on biopolymers functionalization via melt and reactive extrusion processes is discussed. Finally, coupling efficiency of functionalized biopolymers is analyzed in terms of mechanical and thermal properties.     

In-vitro degradation behavior and biological properties of a novel maleated poly (D,L-lactide-co-glycolide) for biomedical applications

Synthesized biodegradable polymers with controlled degradability and good biological safety would be useful in biomedical applications. In this work a novel maleated poly(D,L-lactide-co-glycolide) (MPLGA) was melt copolymerized from maleic anhydride, D,L-lactide and glycolide monomers. The degradation behavior in phosphate-buffered solution (PBS) was investigated and the biological properties were studied by using fibroblastic cells cultured in an extract of MPLGA and by an in-vitro cell cytotoxicity test. The results indicated that the MPLGA was successfully obtained using the melt-copolymerization method. The maleic anhydride groups in the MPLGA led to a faster degradation in PBS than PLGA. Fibroblastic cells showed normal morphologies in MPLGA extracts, and the MPLGA materials showed no cell cytotoxicity. The in-vitro biological properties indicated that the obtained MPLGA had good biocompatibility and would be useful for medical applications.     

Prospective for biodegradable microstructured optical fibers

We report fabrication of a novel microstructured optical fiber made of biodegradable and water soluble materials that features approximately 1 dB/cm transmission loss. Two cellulose butyrate tubes separated with hydroxypropyl cellulose powder were codrawn into a porous double-core fiber offering integration of optical, microfluidic, and potentially drug release functionalities.     

叶黄素聚集体吸收光谱的实验分析与理论模拟

分子聚集体表现出单分子所不具备的特有功能,利用吸收光谱对聚集体分子结构特性的研究是理解其电子和能量转移功能的基础。实验中利用紫外-可见分光光度计,检测了叶黄素在乙醇溶液中的单体吸收谱和在1∶1乙醇水溶液中的聚集体吸收谱。并通过对叶黄素单体吸收谱的高斯分解,获得了激发态的振动能级结构参数。理论上采用时间相关函数描述的吸收谱线和Frenkel激子模型,通过模拟单分子吸收光谱,获得了叶黄素分子的激发能、特征模振动频率、Huang-Phys因子等参数。再利用这些参数进行了聚集体分子光谱的模拟,分析了叶黄素聚集体的分子结构影响光谱变化的原因。结果表明,(1) 分子间的相互作用是决定吸收光谱峰位移动的主要原因,实验中叶黄素H-聚集体的吸收光谱较单体蓝移了77 nm,模拟显示相互作用在2 000 cm-1附近;(2) 聚集体分子个数越多,聚集协作效应越大,吸收光谱半高宽变小,同时吸收峰进一步蓝移;(3) 环境的无序度对吸收光谱的半高宽也存在较大的影响,无序度越大,吸收光谱半高宽越大。实验结果为进一步研究聚集体在生物系统和材料系统中的功能提供了理论依据。     

Nanoscale surface of carbon nanotube fibers for medical applications: Structure and chemistry revealed by TOF-SIMS analysis

Surface structure and related chemistry understanding is a vital element in the design of high biocompatible materials since adsorption and adhesion of biological components are involved. These features are even more important in the case of nanostructured materials such as carbon nanotubes (CNTs) fibers. In our preliminary work we synthesised CNTs based fibers for medical applications. This new hybrid system combines polyvinyl alcohol (PVA) with CNTs and polylactic-co-glycolic acid (PLGA), a biodegradable copolymer. The surface properties of this material are investigated in order to guarantee a biocompatible response. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) was found to be an ideal tool for fiber characterisation owing to its capacity to provide chemical specificity combined with detection limits beyond the reach of techniques previously used. Complementary morphological information is provided by atomic force microscopy (AFM). The corroboration of both data enables us to define the chemistry and structure of this new formulation.     

Structure‐Property Relationships for Model Heterocyclic Polymer Networks: Effect of Monomer Functionality

The effect of initial monomer functionality on the final properties of densely cross‐linked heterocyclic polymer networks (HPN) was evaluated from comparative studies of the viscoelastic behavior and enthalpy relaxation in the glass transition range of polyisocyanurates prepared from a bifunctional monomer D (1,6‐hexamethylene diisocyanate, HDI) and a trifunctional monomer T (the isocyanurate of HDI). Quantitative analysis of these data suggested that an HPN prepared from the monomer T was chemically more heterogeneous and possessed a lower effective network density (presumably, as a result of a lower mobility of the initial monomer T compared to monomer D).     

Quantitative ToF-SIMS studies of protein drug release from biodegradable polymer drug delivery membranes

Biodegradable polymers are of interest in developing strategies to control protein drug delivery. The protein that was used in this study is Keratinocyte Growth Factor (KGF) which is a protein involved in the re-epithelialization process. The protein is stabilized in the biodegradable polymer matrix during formulation and over the course of polymer degradation with the use of an ionic surfactant Aerosol-OT (AOT) which will encapsulate the protein in an aqueous environment. The release kinetics of the protein from the surface of these materials requires precise timing which is a crucial factor in the efficacy of this drug delivery system.Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used in the same capacity to identify the molecular ion peak of the surfactant and polymer and use this to determine surface concentration. In the polymer matrix, the surfactant molecular ion peak was observed in the positive and negative mode at m/z 467 and 421, respectively. These peaks were determined to be [AOT + Na⁺] and [AOT − Na⁺]. These methods are used to identify the surfactant and protein from the polymer matrix and are used to measure the rate of surface accumulation. The second step was to compare this accumulation rate with the release rate of the protein into an aqueous solution during the degradation of the biodegradable film. This rate is compared to that from fluorescence spectroscopy measurements using the protein autofluorescence from that released into aqueous solution [C.M. Mahoney, J. Yu, A. Fahey, J.A.J. Gardella, SIMS depth profiling of polymer blends with protein based drugs, Appl. Surf. Sci. 252 (2006), 6609-6614.].     

Biodegradable nanocomposite magnetite stent for implant-assisted magnetic drug targeting

This study shows, for the first time, the fabrication of a biodegradable polymer nanocomposite magnetic stent and the feasibility of its use in implant-assisted-magnetic drug targeting (IA-MDT). The nanocomposite magnetic stent was made from PLGA, a biodegradable copolymer, and iron oxide nanopowder via melt mixing and extrusion into fibers. Degradation and dynamic mechanical thermal analyses showed that the addition of the iron oxide nanopowder increased the polymer’s glass transition temperature (T_g) and its modulus but had no notable effect on its degradation rate in PBS buffer solution. IA-MDT in vitro experiments were carried out with the nanocomposite magnetic fiber molded into a stent coil. These stent prototypes were used in the presence of a homogeneous magnetic field of 0.3 T to capture 100 nm magnetic drug carrier particles (MDCPs) from an aqueous solution. Increasing the amount of magnetite in the stent nanocomposite (0, 10 and 40 w/w%) resulted in an increase in the MDCP capture efficiency (CE). Reducing the MDCP concentrations (0.75 and 1.5 mg/mL) in the flowing fluid and increasing the fluid velocities (20 and 40 mL/min) both resulted in decrease in the MDCP CE. These results show that the particle capture performance of PLGA-based, magnetic nanocomposite stents are similar to those exhibited by a variety of different non-polymeric magnetic stent materials studied previously.     

Thermophysical properties of fluorinated acrylate homopolymers: Mixing and phase separation

The thermophysical properties of fluorinated acrylate homopolymers are investigated by differential scanning calorimetry (DSC) and optical microscopy and discussed in terms of relative lengths of the fluorinated chain and the hydrocarbon spacer between the acrylate moiety and the fluorinated chain. These compounds exhibit an intrinsic microphase-separation (Isotropic+Isotropic morphology) occurring between the fluorinated chains and the acrylate polymer backbone. It is shown that the enthalpy of mixing is a function of the length of the lateral fluorocarbon chains. The thermophysical behaviour of these materials may be regarded as demixed systems exhibiting an Upper Critical Solution Temperature. The photopolymerization process of one of the monomer is studied by isothermal photocalorimetry. High acrylate double-bond conversion and fast curing rates were obtained thus demonstrating the promising use of these materials for coating and film processing applications using UV-curing techniques. Received 30 January 2002     

Application of In-Line Fiber-Optic Raman Spectroscopy to Monitoring Emulsion Polymerization Reactions

INTRODUCTION

Emulsion polymerization has a large number of applications in the chemical and process industry. It is one of the predominant processes for the commercial manufacture of polymeric materials used in paints, adhesives, and synthetic rubbers etc. Raman spectroscopy has been identified as a promising tool for monitoring the aqueous emulsion polymerization processes as it provides direct information about the changes in the double bond content from the monomer as the polymerization reaction progresses.