Time-of-flight secondary ion mass spectrometric analysis of the interface between bone and titanium implants

Implant healing into bone tissue is a process where the mature bone grows towards and eventually fuses with the implant. In this study we investigated implant healing during 4 weeks with focus on the implant-tissue interface. Our main interest was to study the mineralization process around the implant. Titanium discs were implanted in rat tibia for 2 and 4 weeks. After implantation cross sections of bone and implant were made using a low-speed saw equipped with a diamond wafering blade. One section from each sample was stained with basic fuchsin and micrographed by light microscopy (LM). The other section was analyzed with imaging time-of-flight secondary ion mass spectrometry (TOF-SIMS) using a Bi(3)(+) cluster ion source. This ion source has recently been shown to enable identification of high-mass hydroxyapatite (HA) fragment ions (m/z 291-653) in bone samples. The LM images were used to identify areas suitable for TOF-SIMS analysis. Three areas were selected for mass spectral analysis, corresponding to interface region, bone and soft tissue, from which positive ion spectra were recorded. In the areas identified as bone, high-mass HA fragments ions were found after both 2 and 4 weeks. In the soft tissue area, no high-mass ions were found after 4 weeks. However, after 2 weeks HA-related ions were identified in mineralized spots in areas defined as soft tissue. After 4 but not after 2 weeks, high-mass HA fragment ions were found in the interface region. In conclusion, differences were observed regarding mineralization between 2 and 4 weeks of implantation and between different regions surrounding the implants. Imaging TOF-SIMS analysis using a Bi(3)(+) cluster as ion source enables identification of high-mass HA fragment ions at implant-tissue interfaces in bone. This technique might therefore be useful for biocompatibility assessment and for studying the mineralization process at implant surfaces.     

Experiences using IAEA Code of practice for radiation sterilization of tissue allografts: Validation and routine control

Problems of tissue allografts in using International Standard (ISO) 11137 for validation of radiation sterilization dose (RSD) are limited and low numbers of uniform samples per production batch, those are products obtained from one donor. Allograft is a graft transplanted between two different individuals of the same species. The minimum number of uniform samples needed for verification dose (VD) experiment at the selected sterility assurance level (SAL) per production batch according to the IAEA Code is 20, i.e., 10 for bio-burden determination and the remaining 10 for sterilization test. Three methods of the IAEA Code have been used for validation of RSD, i.e., method A1 that is a modification of method 1 of ISO 11137:1995, method B (ISO 13409:1996), and method C (AAMI TIR 27:2001). This paper describes VD experiments using uniform products obtained from one cadaver donor, i.e., cancellous bones, demineralized bone powders and amnion grafts from one life donor. Results of the verification dose experiments show that RSD is 15.4 kGy for cancellous and demineralized bone grafts and 19.2 kGy for amnion grafts according to method A1 and 25 kGy according to methods B and C.     

Ultra Compact Nanoporous Platinum Coating Improves Neural Recording

Neural electrodes are key tools for achieving a successful brain-computer interface and the electrodes should be small to minimize damage to neural tissue and obtain good spatial selectivity such as single unit recording. Here we show conventional platinum/tungsten neural probes can be coated with nanoporous Pt. Thanks to nanoporous Pt with the extremely small and uniform pores, L₂-ePt, the electrode impedance could be reduced by more than 2 orders of magnitude while the apparent area was almost the same. L₂-ePt coating enhanced neuronal recording of local field potential in monkeys, leading to facilitating implanted electrical devices in the nervous system.     

Complicity of degradable polymers in health-care applications

Polymeric biomaterials have revolutionized biomedical technology and related fields as biomaterials for health-care applications. Recent trend in polymeric medical technology has adapted a tendency to substitute degradable polymers instead of non-degradable synthetic polymers for the advancement of various health-care modalities. They have got considerable attention for their potential in various interdisciplinary arenas, which implies tissue engineering scaffolds, sustainable drug release, delivery agents, regenerative medicine, and development of life-saving devices, implants, dental products as well as in food technology. Various types of degradable polymers are been developed to date having stringent features applicable for various aspects in modern science. Thus, being the most renovative field of biomedicine and biomedical technology degradable polymers has gained substantial acceptance and appreciation recent times. This review critically underlines various degradative polymers and their subtypes, potential applications, types of degradation, and their possible effects in the biological system. Assessment of possible toxicological risks behind is an important criterion to be focused before validating any biomaterial safe for biomedical applications. Therefore various toxicological assessment strategies and their impact in biomedicine and technology were also included. In addition, the risk versus benefit assessment is also critically summarized.     

An in vivo study of the host response to starch-based polymers and composites subcutaneously implanted in rats

Implant failure is one of the major concerns in the biomaterials field. Several factors have been related to the fail but in general these biomaterials do not exhibit comparable physical, chemical or biological properties to natural tissues and ultimately, these devices can lead to chronic inflammation and foreign-body reactions. Starch-based biodegradable materials and composites have shown promising properties for a wide range of biomedical applications as well as a reduced capacity to elicit a strong reaction from immune system cells in vitro. In this work, blends of corn starch with ethylene vinyl alcohol (SEVA-C), cellulose acetate (SCA) and polycaprolactone (SPCL), as well as hydroxyapatite (HA) reinforced starch-based composites, were investigated in vivo. The aim of the work was to assess the host response evoked for starch-based biomaterials, identifying the presence of key cell types. The tissues surrounding the implant were harvested together with the material and processed histologically for evaluation using immunohistochemistry. At implant retrieval there was no cellular exudate around the implants and no macroscopic signs of an inflammatory reaction in any of the animals. The histological analysis of the sectioned interface tissue after immunohistochemical staining using ED1, ED2, CD54, MHC class II and alpha/beta antibodies showed positively stained cells for all antibodies, except for alpha/beta for all the implantation periods, where it was different for the various polymers and for the period of implantation. SPCL and SCA composites were the materials that stimulated the greatest cellular tissue responses, but generally biodegradable starch-based materials did not induce a severe reaction for the studied implantation times, which contrasts with other types of degradable polymeric biomaterials.     

The metathetic degradation of polyisoprene and polybutadiene in block copolymers using Grubbs second generation catalyst

A degradation study of polystyrene-polybutadiene-polystyrene and polyisoprene-polystyrene-polyisoprene in both dichloromethane and hexane solvents is presented. Alternative solvents for metathetic degradation provide the potential for greener chemistry, better selectivity, and control over the products. The catalyst concentration and solvent selection both determine the products formed. The degradation of polyisoprene and polybutadiene in a particular solvent was controlled by the solubility of polyisoprene/polybutadiene, and by its solubility relative to polystyrene. A large difference in solubility between the polymers in the selected solvent provides an additional driving force for block separation, encouraging reaction close to the interface between different blocks. Furthermore, solubility of the block copolymer speeds the degradation reaction. This tailoring of the reaction mechanism yields a new control over the products of polymer degradation.     

Degradation issues of polymer materials used in railway field

Polymer materials used in railway field are degraded by environmental factors such as thermal, oxidative, photolytic, hydrolytic, and mechanical. The expected service life of the polymer materials used in railway field is approximately 20 years that is relatively long period for the polymer material; therefore, respective degradation factors should be well considered. Some of the degradation conditions indicate similar mechanism. The oxidative reaction was seen in every degradation conditions under air atmosphere. The hydrolytic reaction was mainly observed in chemical and biological degradations. The degradation behavior of the polymer material was analyzed by various methods. FTIR, thermal analysis (TG, DSC), and molecular weight determination were mainly applied for its purpose. However, the degradation mechanism of practical products made of polymer material was insufficiently studied and the exchange criteria of the products depended on the visual inspection without the suitable degradation analysis not only in the railway field but also in other commercial and industrial fields. In addition, most of the methods to analyze degradation of polymer material are performed on the standard specimen forms. For the installed product, some kinds of damage are generated through the sample collection process; therefore, the damaged products have to be exchanged for brand new ones or repaired totally to be used for more period. Moreover, it is hard to suspend the railway service for the degradation analysis of polymer products. From these backgrounds, the prospect of degradation analysis related to polymer materials used in railway field was proposed.     

Solid-phase extraction and gas chromatographic-mass spectrometric identification of degradation products from enhanced environmentally degradable polyethylene

A solid-phase extraction (SPE) method using unbonded silica (Si) and silica bonded with octadecyl (C₁₈) or aminopropyl (NH₂) groups was developed to separate into five fractions the highly complex mixture of low-molecular-mass degradation products formed from degradable polymers. Application of the method to polyethylene modified with starch and/or a pro-oxidant system, degraded for 30 weeks in water at 95°C, enabled the identification by GC-MS of over three times as many products as when the sample was prepared by liquid-liquid extraction. Over 60 degradation products were identified in each sample; mainly dicarboxylic acids, monocarboxylic acids and n-alkanes. In addition, several lactones, aldehydes and alcohols were detected.     

可降解PET/PEG共聚物的合成

利用聚合物法通过熔融缩聚直接合成了可降解的PET／PEG共聚物，通过红外光谱、色质联用分析对聚合反应机理进行了研究，讨论了聚合条件对聚合物分子量的影响，测定了聚合物的体外降解。     

Degradation of cellulose at the wet-dry interface: I—study of the depolymerization

The degradation of cellulose in paper due to the formation of a tideline at the wet-dry interface when paper is suspended in water was explored. SEC/MALS was used to assess the molar mass, while ICP/MS, SEM/EDS and CE/UV provided a qualitative and quantitative analysis of the elements and inorganic ions present in the paper. Immediately after the formation of the tideline, no significant depolymerization was observed at the wet-dry interface, despite the accumulation of water soluble brown and/or fluorescent degradation compounds and salts containing sodium, chlorine, sulfur and calcium. Various artificial aging configurations were applied to the paper with tidelines to evaluate the effect of the material accumulated at the wet-dry interface on the long-term stability of paper. The decrease in the molar mass of cellulose (above, at and below the tideline) differed depending on the type of aging, i.e. whether the entire sheet of paper was aged or whether small amounts of paper from the different areas were sampled and aged, individually or together, which evidences a complex degradation pathway. In the former aging configuration the material accumulated in the tideline affected the degradation of the tideline area to the same extent or more than the other areas. When the different areas of the paper sheet were sampled and aged together, it was found that the presence of the tideline clearly affected the degradation of the other paper areas. Conversely, in that case, cellulose within the tidelines was the least degraded. The area below the tideline, through which the water migrated, showed the most significant degradation.     

Degradable polyesters through chain linking for packaging and biomedical applications

The major route to convert lactic acid to high-molecular-weight polymers is ring-opening polymerization of lactide. We have investigated alternative synthesis routes based on oligomerization and chain linking to produce high-molecular-weight thermoplastic degradable polymers cost-effectively. Chain linking also offers new possibilities to prepare degradable polyesters for biomedical applications by extending the range of polymer properties achievable. In this paper, we briefly review different chain linking techniques used in our laboratory. Typically, lactic acid prepolymers with molecular weights of around 3,000-15,000 g x mol(-1) have been prepared by direct polycondensation. Hydroxyl terminated oligomers have been chain linked by using diisocyanate coupling agents, preferably 1,4-butane diisocyanate, forming poly(ester-urethanes). Poly(ester-amides) have been prepared by using 2,2'-bis(2-oxazoline) as coupling agent for carboxylic acid telechelic oligomers. Chain linking by end functionalization has been used in the preparation of poly(ester-anhydrides). In addition, a variety of crosslinked degradable polymers and copolymers have been synthesized through different crosslinking routes, by using methacrylic, itaconic or maleic double bonds or triethoxysilane moieties. A biodegradation test and ecotoxicological evaluation of the degradation products were carried out in addition to hydrolysis tests. Lactic acid based chain linked polymers were biodegradable and the degradation products were harmless. In hydrolysis tests, enzymatic degradation was pronounced in the chain linked poly(epsilon-caprolactone).     

治理塑料废弃物新技术途径探讨--专论可降解塑料的研究开发

综述了可降解塑料的研究开发现状及其进展。可降解塑料的降解时控性研究，合成，加工工艺改进以及降低成本的研究，可控光－生物降解的合成降解性研究和一次性使用塑料实用性研究，仍是今后需要深入探讨的重要研究课题。     

Facile synthesis of functional polyperoxides by radical alternating copolymerization of 1,3‐dienes with oxygen

We have developed a facile synthesis of degradable polyperoxides by the radical alternating copolymerization of 1,3‐diene monomers with molecular oxygen at an atmospheric pressure. In this review, the synthesis, the degradation behavior, and the applications of functional polyperoxides are summarized. The alkyl sorbates as the conjugated 1,3‐dienes gave a regiospecific alternating copolymer by exclusive 5,4‐addition during polymerization and the resulting polyperoxides decomposed by the homolysis of a peroxy linkage followed by successive β‐scissions. The preference of 5,4‐addition was well rationalized by theoretical calculations. The degradation of the polyperoxides occurred with various stimuli, such as heating, UV irradiation, a redox reaction with amines, and an enzyme reaction. The various functional polyperoxides were synthesized by following two methods, one is the direct copolymerization of functional 1,3‐dienes, and the other is the functionalization of the precursor polyperoxides. Water soluble polyperoxides were also prepared, and the LCST behavior and the application to a drug carrier in the drug delivery system were investigated. In order to design various types of degradable polymers and gels we developed a method for the introduction of dienyl groups into the precursor polymers. The resulting dienyl‐functionalized polymers were used for the degradable gels. The degradable branched copolymers showed a microphase‐separated structure, which changed owing to the degradation of the polyperoxide segments. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 000–000; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900009     

Architecture‐controlled synthesis of redox‐degradable hyperbranched polyglycerol block copolymers and the structural implications of their degradation

We have successfully synthesized a series of redox‐degradable hyperbranched polyglycerols using a disulfide containing monomer, 2‐((2‐(oxiran‐2‐ylmethoxy)ethyl)disulfanyl) ethan‐1‐ol (SSG), to yield PSSG homopolymers and hyperbranched block copolymers, P(G‐b‐SSG) and P(SSG‐b‐G), containing nondegradable glycerol (G) monomers. Using these polymers, we have explored the structures of the hyperbranched block copolymers and their related degradation products. Furthermore, side reaction such as reduction of disulfide bond during the polymerization was investigated by employing the free thiol titration experiments. We elucidated the structures of the degradation products with respect to the architecture of the hyperbranched block copolymer under redox conditions using ¹H NMR and GPC measurements. For example, the degradation products of P(G‐b‐SSG) and P(SSG‐b‐G) are clearly different, demonstrating the clear distinction between linear and hyperbranched block copolymers. We anticipate that this study will extend the structural diversity of PG based polymers and aid the understanding of the structures of degradable hyperbranched PG systems. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1752–1761     

A resorbable calcium-deficient hydroxyapatite hydrogel composite for osseous regeneration

It was previously discovered that the unique structure and chemistry of bacterial cellulose (BC) permits the formation of calcium-deficient hydroxyapatite (CdHAP) nanocrystallites under aqueous conditions at ambient pH and temperature. In this study, BC was chemically modified via a limited periodate oxidation reaction to render the composite degradable and thus more suitable for bone regeneration. While native BC does not degrade in mammalian systems, periodate oxidation yields dialdehyde cellulose which breaks down at physiological pH. The composite was characterized by tensile testing, X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. X-ray diffraction showed that oxidized BC retains its structure and could biomimetically form CdHAP. Degradation behavior was analyzed by incubating the samples in simulated physiological fluid (pH 7.4) at 37 °C under static and dynamic conditions. The oxidized BC and oxidized BC-CdHAP composites both lost significant mass after exposure to the simulated physiological environment. Examination of the incubation solutions by UV–Vis spectrophotometric analysis demonstrated that, while native BC released only small amounts of soluble cellulose fragments, oxidized cellulose releases carbonyl containing degradation products as well as soluble cellulose fragments. By entrapping CdHAP in a degradable hydrogel carrier, this composite should elicit bone regeneration then resorb over time to be replaced by new osseous tissue.     

Hydrophilic Quaternary Ammonium Ionenes—Is There an Influence of Backbone Flexibility and Topology on Antibacterial Properties?

The antimicrobial properties of polycations are strongly affected by the structural features such as the backbone flexibility and topology (isomerism) through the polymer ability to attain proper conformation in interaction with the cell membrane. In this paper, a synthesis and biocidal properties evaluation of ionenes characterized by different backbone topology (isomerism) and flexibility are presented. The findings reveal influence of variation in topology on activity against different microorganisms, and general positive effect of improved flexibility. Furthermore, one of the obtained ionenes displays degradable properties in near physiological environment (phosphate‐buffered saline pH 7.4, 37 °C). The degradation proceeds via Hofmann elimination reaction and the products are not of acidic character. For the first time a new class of degradable ionenes with a high antimicrobial potential is presented.     

In vitro and in vivo degradation of an injectable bone repair composite

In vitro and in vivo degradation behaviors of an injectable bone regeneration composite (IBRC) which comprised of nano-hydroxyapatite/collagen (nHAC) particles in alginate hydrogel carrier were investigated. In vitro degradation quantitative testing indicated that the alginate had a faster degradation rate in simulated body fluid (SBF) than in deionized water at 37 °C. Similarly, IBRC also had a higher degradation rate in SBF than in deionized water at 37 °C, which was evaluated by alginate molecular weight measurement, mechanical properties test and degradation kinetics evaluation. But molecular weight of alginate degraded slower in IBRC than that in aqueous solution. In vitro results showed that degradation medium SBF had influence on degradation of alginate molecules. In the in vivo degradation study, surprisingly, there was no obvious decreasing of molecular weight of alginate from 0 to 8 weeks. IBRC degraded mostly after 24 weeks implantation and was replaced by connective tissue. No fibrous capsule and acute inflammatory reaction were found during the observed 24 weeks after IBRC implantation. There is only a mild short-term inflammatory response in rat dorsum muscle. These results indicated that IBRC had a controllable degradability and biocompatibility. Therefore, IBRC may be a promising degradable material for bone repair and bone tissue engineering.     

二氧化钛纳米粒子和纳米管的合成、表征及对硝基苯的光催化性能研究

采用水热合成法, 通过改变反应条件, 控制反应参数, 成功地合成了粒径可控的球形TiO2纳米粒子和长径比、比表面积均比较大的纳米管. 用XRD, TEM, SAED和BET等手段对产物进行了表征. 为了测试产物的光催化性能, 以高浓度的硝基苯(NB)溶液为模拟水样, 进行了一系列提高降解效率的优化实验和光催化降解的对比实验. 通过对硝基苯溶液初始浓度、TiO2加入量和降解体系pH值等条件的考察, 得出硝基苯溶液的质量浓度为300 mg/L, TiO2的加入量为0.4 g/L, 体系的pH值为6~7时, 降解效果最好; 通过对比实验发现, 由于纳米管的大比表面积, 使得其光催化性能明显优于球形纳米粒子, 3 h后的降解率达到90%以上, 3.5 h左右硝基苯几乎被完全降解.     

Determination of rice herbicides, their transformation products and clofibric acid using on-line solid-phase extraction followed by liquid chromatography with diode array and atmospheric pressure chemical ionization mass spectrometric detection

A simultaneous method for the trace determination of acidic, neutral herbicides and their transformation products in estuarine waters has been developed through an on-line solid-phase extraction method followed by liquid chromatography with diode array and mass spectrometric detection. An atmospheric pressure chemical ionization (APCI) interface was used in the negative ionization mode after optimization of the main APCI parameters. Limits of detection ranged from 0.1 to 0.02 ng/ml for 50 ml of acidified estuarine waters preconcentrated into polymeric precolumns and using time-scheduled selected ion monitoring mode. Two degradation products of the acidic herbicides (4-chloro-2-methylphenol and 2,4-dichlorophenol) did not show good signal response using APCI-MS at the concentration studied due to the higher fragmentor voltage needed for their determination. For molinate and the major degradation product of propanil, 3,4-dichloroaniline, positive ion mode was needed for APCI-MS detection. The proposed method was applied to the determination of herbicides in drainage waters from rice fields of the Delta del Ebro (Spain). During the 3-month monitoring of the herbicides, 8-hydroxybentazone and 4-chloro-2-methylphenoxyacetic acid were successively found in those samples.     

Polyurethane microporous membranes as pericardial substitutes

Pericardial substitutes were prepared from stable and degradable segmented polyurethanes and/or polyurethane/polyhydroxybutyrate composites.Polyurethane membranes implanted as pericardial substitute in the rabbit, did not activate adhesion and epicardial reaction over 3 months.Polyurethane/polyhydroxybutyrate membranes induced minimal adhesion or epicardial reaction, yet stimulated the growth of epithelium on the polymeric substrate and reduced the incidence of infection.