Stabilization of poly(lactic acid) by polycarbodiimide

Polycarbodiimide (CDI) was used to improve the thermal stability of poly(L-lactic acid) (PLA) during processing. The properties of PLA containing various amounts of CDI were characterized by GPC, DSC, rheology, and tensile tests. The results showed that an addition of CDI in an amount of 0.1-0.7 wt% with respect to PLA led to stabilization of PLA at even 210 degrees C for up to 30 min, as evidenced by much smaller changes in molecular weight. melt viscosity, and tensile strength and elongation compared to the blank PLA samples. In order to examine the possible stabilization mechanism, CDI was reacted with water, acetic acid, L-lactic acid, ethanol and low molecular weight PLA. The molecular structures of the reaction products were measured with FTIR.

Synthesis and characterisation of novel functional polyolefin containing sulfonic acid groups

The strong polar group, sulfonic acid, has successfully been introduced into ethylene/allylbenzene copolymers without degradation or crosslinking via chlorosulfonation reaction with chlorosulfonic acid as a chlorosulforiating agent in 1, 1,2,2-tetrachloroethane followed by hydrolysis. The degree of sulforiation (DS) can be easily controlled by changing the ratio of chlorosulfonic acid to the pendant phenyls of the copolymer. The microstructure of sulfonated copolymers were unambiguously revealed by H-1 NMR and H-1-H-1 COSY spectral analyses, which indicates that all the sulforiation reactions exclusively took place at the para-position of the aromatic rings.

Hollow DNA/PLL microcapsules with tunable degradation property as efficient dual drug delivery vehicles by alpha-chymotrypsin degradation

Hollow deoxyribonucleic acid (DNA)/poly-L-lysine (PLL) capsules were successfully fabricated through a layer-by-layer (LbL) self-assembly of DNA and PLL on porous CaCO3 microparticles, followed by removal of templates with ethylenediamine tetraacetic acid disodium salt (EDTA). The enzymatic degradation of the capsules in the presence of alpha-chymotrypsin was explored. The higher the enzyme concentration, the higher is the degradation rate of hollow capsules. in addition, glutaric dialdehyde (GA) cross-linking was found to be another way to manipulate degradation rate of hollow capsules.

Reactive compatibilization of LLDPE/PS blends with a new type of Lewis acid as catalyst

The reactive compatibilization of LLDPE/PS (50/50 wt%) was achieved by Friedel-Crafts alkylation reaction with a combined Lewis acids (Me3SiCl and InCl3 center dot 4H(2)O) as catalyst. The graft copolymer at the interface was characterized by Fourier transform infrared spectroscopy and the morphology of the blends was analysized by scanning electron microscopy. It was found that the combined Lewis acids had catalytic effect on Friedel-Crafts alkylation reaction between LLDPE and PS, and the catalytic effect was maximal when the molar ratio of InCl3 center dot 4H(2)O to Me3SiCl was 1:5. The graft copolymer LLDPE-g-PS was formed via the F-C reaction and worked as a tailor-made compatibilizer to reduce the interfacial tension. The mechanical properties of reactive blend with combined Lewis acids as catalyst was notably improved compared to that of physical LLDPE/PS blend and serious degradation had been decreased compared to the reactive blend system with AlCl3 as catalyst; we interpreted the above results in term of acidity of combined Lewis acids.

Synthesis of novel functional polyolefin containing carboxylic acid via Friedel-Crafts acylation reaction

The strong polar group, carboxylic acid, has triumphantly been introduced into ethylene and allylbenzene copolymers without obvious degradation or crosslinking via Friedel-Crafts (F-C) acylation reaction with glutaric anhydride (GA), succinic anhydride (SA) and phthalic anhydride (PA) in the presence of anhydrous aluminum chloride in carbon disulfide. Some important reaction parameters were examined in order to optimize the acylation process. In the optimum reaction conditions, almost all of the phenyls can be acylated with any anhydride. The microstructure of acylated copolymer was characterized by Fr-IR, H-1 NMR and H-1-H-1 COSY. All the peaks of acylated copolymers can be accurately attributed, which indicates that all the acylation reactions occur only at the para-positions of the substituent of the aromatic rings. The thermal behavior was studied by differential scanning calorimetry (DSC), showing that the melting temperatures (T(m)s) of acylated copolymers with GA firstly decrease slowly and then increase significantly with the increase of the amount of carboxyl acid groups.

Gene transfection of hyperbranched PEI grafted by hydrophobic amino acid segment PBLG

The complex copolymer of hyperbranched polyethylenimine (PEI) with hydrophobic poly(gamma-benzyl L-glutamate) segment (PBLG) at their chain ends was synthesized. This water-soluble copolymer PEI-PBLG (PP) was characterized for DNA complexation (gel retardation assay, particle size, DNA release and DNase I protection), cell viability and in vitro transfection efficiency. The experiments showed that PP can effectively condense pDNA into particles. Size measurement of the complexes particles indicated that PP/DNA tended to form smaller nanoparticles than those of PEI/DNA, which was caused by the hydrophobic PBLG segments compressing the PP/DNA complex particles in aqueous solution. The representative average size of PP/DNA complex prepared using plasmid DNA (pEGFP-N1, pDNA) was about 96 nm. The condensed pDNA in the PP/pDNA complexes was significantly protected from enzymatic degradation by DNase1. Cytotoxicity studies by MTT colorimetric assays suggested that the PP had much lower toxicity than PEI. The in vitro transfection efficiency of PP/pDNA complexes improved a lot in HeLa cells, Vero cells and 293T cells as compared to that of PEI25K by the expression of Green Fluorescent Protein (GFP) as determined by flow cytometry. Thus, the water-soluble PP copolymer showed considerable potential as carriers for gene delivery.

Chemical effects of cationic surfactant and anionic surfactant used in organically modified montmorillonites on degradation and fire retardancy of polyamide 12 nanocomposites

Three kinds of organically modified Na+-montmorillonites (OMMTs), including two kinds of octadecylammonium modified montmorillonite with different contents of octadecylammonium and a kind of sodium dodecylsulfonate (SDSo) modified montmorillonite, were used to prepare polyamide 12 (PA12)/OMMT nanocomposites. Effects of the modifiers on degradation and fire retardancy of PA12/OMMT nanocomposites were investigated. Acid sites formed in cationic surfactant modified MMT via Hoffman decomposition could accelerate degradation of PA12 at high temperature. However, catalytic effect of the acid sites on carbonization of the degradation products promoted char barrier formation, which reduced heat release rate (HRR). Higher content of cationic surfactant in OMMT is beneficial to fire retardancy of PA12 nanocomposites and the dispersion states of OMMT have assistant effects. In contrast, Na+-montmorillonite (Na-MMT) and anionic surfactant modified MMT (a-MMT) could not form acid sites on the MMT layers; in this case, fire retardancy of PA12/Na-MMT appears to have no improvement and PA12/a-MMT appears to have limited improvement.

Enzymatic degradation of poly(L-lactide) and poly (epsilon-caprolactone) electrospun fibers

Poly(L-lactide) (PLLA) and poly(epsilon-caprolactone) (PCL) ultrafine fibers were prepared by electrospinning. The influence of cationic and anionic surfactants on their enzymatic degradation behavior was investigated by measuring weight loss, molecular weight, crystallinity, and melting temperature of the fibers as a function of degradation time. Under the catalysis of proteinase K, the PLLA fibers containing the anionic surfactant sodium docecyl sulfate (SDS) exhibited a faster degradation rate than those containing cationic surfactant triethylbenzylammonium chloride (TEBAC), indicating that surface electric charge on the fibers is a critical factor for an enzymatic degradation. Similarly, TEBAC-containing PCL fibers exhibited a 47% weight loss within 8.5 h whereas SDS-containing PCL fibers showed little degradation in the presence of lipase PS. By analyzing the charge status of proteinase K and lipase PS under the experimental conditions, the importance of the surface charges of the fibers and their interactions with the charges on the enzymes were revealed. Consequently, a "two-step" degradation mechanism was proposed: (1) the enzyme approaches the fiber surface; (2) the enzyme initiates hydrolysis of the polymer.

Salt-assisted acid hydrolysis of chitosan to oligomers under microwave irradiation

The effect of inorganic salts such as sodium chloride on the hydrolysis of chitosan in a microwave field was investigated. While it is known that microwave heating is a convenient way to obtain a wide range of products of different molecular weights only by changing the reaction time and/or the radiation power, the addition of some inorganic salts was shown to effectively accelerate the degradation of chitosan under microwave irradiation. The molecular weight of the degraded chitosan obtained by microwave irradiation was considerably lower than that obtained by traditional heating. Moreover, the molecular weight of degraded chitosan obtained by microwave irradiation assisted under the conditions of added salt was considerably lower than that obtained by microwave irradiation without added salt. Furthermore, the effect of ionic strength of the added salts was not linked with the change of molecular weight. FTIR spectral analyses demonstrated that a significantly shorter time was required to obtain a satisfactory molecular weight by the microwave irradiation-assisted inorganic salt method than by microwave irradiation without inorganic salts and conventional technology. (C) 2005 Elsevier Ltd. All rights reserved.

Tryptophan degradation in irritable bowel syndrome: evidence of indoleamine 2,3-dioxygenase activation in a male cohort

Background: Irritable bowel syndrome (IBS) is a common disorder that affects 10–15% of the population. Although characterised by a lack of reliable biological markers, the disease state is increasingly viewed as a disorder of the brain-gut axis. In particular, accumulating evidence points to the involvement of both the central and peripheral serotonergic systems in disease symptomatology. Furthermore, altered tryptophan metabolism and indoleamine 2,3-dioxygenase (IDO) activity are hallmarks of many stress-related disorders. The kynurenine pathway of tryptophan degradation may serve to link these findings to the low level immune activation recently described in IBS. In this study, we investigated tryptophan degradation in a male IBS cohort (n = 10) and control subjects (n = 26). Methods: Plasma samples were obtained from patients and healthy controls. Tryptophan and its metabolites were measured by high performance liquid chromatography (HPLC) and neopterin, a sensitive marker of immune activation, was measured using a commercially available ELISA assay. Results: Both kynurenine levels and the kynurenine:tryptophan ratio were significantly increased in the IBS cohort compared with healthy controls. Neopterin was also increased in the IBS subjects and the concentration of the neuroprotective metabolite kynurenic acid was decreased, as was the kynurenic acid:kynurenine ratio. Conclusion: These findings suggest that the activity of IDO, the immunoresponsive enzyme which is responsible for the degradation of tryptophan along this pathway, is enhanced in IBS patients relative to controls. This study provides novel evidence for an immune-mediated degradation of tryptophan in a male IBS population and identifies the kynurenine pathway as a potential source of biomarkers in this debilitating condition.

Simulation chamber studies of the atmospheric degradation of naphthalene, 1-nitronaphthalene and phthaldialdehyde

A detailed series of simulation chamber experiments has been performed on the atmospheric degradation pathways of the primary air pollutant naphthalene and two of its photooxidation products, phthaldialdehyde and 1-nitronaphthalene. The measured yields of secondary organic aerosol (SOA) arising from the photooxidation of naphthalene varied from 6-20%, depending on the concentrations of naphthalene and nitrogen oxides as well as relative humidity. A range of carbonyls, nitro-compounds, phenols and carboxylic acids were identified among the gas- and particle-phase products. On-line analysis of the chemical composition of naphthalene SOA was performed using aerosol time-of-flight mass spectrometry (ATOFMS) for the first time. The results indicate that enhanced formation of carboxylic acids may contribute to the observed increase in SOA yields at higher relative humidity. The photolysis of phthaldialdehyde and 1-nitronaphthalene was investigated using natural light at the European Photoreactor (EUPHORE) in Valencia, Spain. The photolysis rate coefficients were measured directly and used to confirm that photolysis is the major atmospheric loss process for these compounds. For phthaldialdehyde, the main gas-phase products were phthalide and phthalic anhydride. SOA yields in the range 2-11% were observed, with phthalic acid and dihydroxyphthalic acid identified among the particle phase products. The photolysis of 1-nitronaphthalene yielded nitric oxide and a naphthoxy radical which reacted to form several products. SOA yields in the range 57-71% were observed, with 1,4-naphthoquinone, 1-naphthol and 1,4-naphthalenediol identified in the particle phase. On-line analysis of the SOA generated in an indoor chamber using ATOFMS provided evidence for the formation of high-molecular-weight products. Further investigations revealed that these products are oxygenated polycyclic compounds most likely produced from the dimerization of naphthoxy radicals. These results of this work indicate that naphthalene is a potentially large source of SOA in urban areas and should be included in atmospheric models. The kinetic and mechanistic information could be combined with existing literature data to produce an overall degradation mechanism for naphthalene suitable for inclusion in photochemical models that are used to predict the effect of emissions on air quality.

The Trim39 ubiquitin ligase inhibits APC/CCdh1-mediated degradation of the Bax activator MOAP-1.

Proapoptotic Bcl-2 family members, such as Bax, promote release of cytochrome c from mitochondria, leading to caspase activation and cell death. It was previously reported that modulator of apoptosis protein 1 (MOAP-1), an enhancer of Bax activation induced by DNA damage, is stabilized by Trim39, a protein of unknown function. In this paper, we show that MOAP-1 is a novel substrate of the anaphase-promoting complex (APC/C(Cdh1)) ubiquitin ligase. The influence of Trim39 on MOAP-1 levels stems from the ability of Trim39 (a RING domain E3 ligase) to directly inhibit APC/C(Cdh1)-mediated protein ubiquitylation. Accordingly, small interfering ribonucleic acid-mediated knockdown of Cdh1 stabilized MOAP-1, thereby enhancing etoposide-induced Bax activation and apoptosis. These data identify Trim39 as a novel APC/C regulator and provide an unexpected link between the APC/C and apoptotic regulation via MOAP-1.

D-Amino acid peptide residualizing agents bearing N-hydroxysuccinimido- and maleimido-functional groups and their application for trastuzumab radioiodination.

INTRODUCTION: Proteins that undergo receptor-mediated endocytosis are subject to lysosomal degradation, requiring radioiodination methods that minimize loss of radioactivity from tumor cells after this process occurs. To accomplish this, we developed the residualizing radioiodination agent N(ϵ)-(3-[(*)I]iodobenzoyl)-Lys(5)-N(α)-maleimido-Gly(1)-D-GEEEK (Mal-D-GEEEK-[(*)I]IB), which enhanced tumor uptake but also increased kidney activity and necessitates generation of sulfhydryl moieties on the protein. The purpose of the current study was to synthesize and evaluate a new D-amino acid based agent that might avoid these potential problems. METHODS: N(α)-(3-iodobenzoyl)-(5-succinimidyloxycarbonyl)-D-EEEG (NHS-IB-D-EEEG), which contains 3 D-glutamates to provide negative charge and a N-hydroxysuccinimide function to permit conjugation to unmodified proteins, and the corresponding tin precursor were produced by solid phase peptide synthesis and subsequent conjugation with appropriate reagents. Radioiodination of the anti-HER2 antibody trastuzumab using NHS-IB-D-EEEG and Mal-D-GEEEK-IB was compared. Paired-label internalization assays on BT474 breast carcinoma cells and biodistribution studies in athymic mice bearing BT474M1 xenografts were performed to evaluate the two radioiodinated D-peptide trastuzumab conjugates. RESULTS: NHS-[(131)I]IB-D-EEEG was produced in 53.8%±13.4% and conjugated to trastuzumab in 39.5%±7.6% yield. Paired-label internalization assays with trastuzumab-NHS-[(131)I]IB-D-EEEG and trastuzumab-Mal-D-GEEEK-[(125)I]IB demonstrated similar intracellular trapping for both conjugates at 1h ((131)I, 84.4%±6.1%; (125)I, 88.6%±5.2%) through 24h ((131)I, 60.7%±6.8%; (125)I, 64.9%±6.9%). In the biodistribution experiment, tumor uptake peaked at 48 h (trastuzumab-NHS-[(131)I]IB-D-EEEG, 29.8%±3.6%ID/g; trastuzumab-Mal-D-GEEEK-[(125)I]IB, 45.3%±5.3%ID/g) and was significantly higher for (125)I at all time points. In general, normal tissue levels were lower for trastuzumab-NHS-[(131)I]IB-D-EEEG, with the differences being greatest in kidneys ((131)I, 2.2%±0.4%ID/g; (125)I, 16.9%±2.8%ID/g at 144 h). CONCLUSION: NHS-[(131)I]IB-D-EEEG warrants further evaluation as a residualizing radioiodination agent for labeling internalizing antibodies/fragments, particularly for applications where excessive renal accumulation could be problematic.

Assessment of the degradation of Aspirin by Differential Scanning Calorimetry (DSC)

Purpose. To study thermal stability of Aspirin and define thermal events that are associated with the thermal degradation of aspirin. Methods. Experiments were performed using a DSC 823e (Mettler Toledo, Swiss). Aspirin is prone to thermal degradation upon exposure to high temperatures. The melting point of aspirin is 140.1±0.4ºC (DSC). Aspirin has been examined by heating samples to 120ºC, 155ºC and 185ºC with subsequent cooling to -55ºC and a final heating to 155ºC. Although different heating and cooling ranges have been used, only results obtained at a rate of 10ºC/min will be presented. All runs where conducted in hermetically sealed pans. Results. Upon heating the sample to 120ºC no significant thermal event can be detected. After cooling the sample and reheating a glass transition can be observed at ~-8ºC, followed by the melting of aspirin at ~139ºC. By heating the sample to 155ºC melting of aspirin has been detected at ~139ºC. On cooling and subsequent heating a glass transition occurs at ~-32ºC, together with a broad crystallisation (onset at ~38ºC and peak maximum at ~57ºC) followed by a broad melting with an onset at 94ºC and peak maximum at ~112ºC. Finally, by heating the sample to 185ºC melting at ~ 139ºC was observed, and upon cooling and reheating a glass transition was detected at ~-26ºC and no further events could be recorded. Conclusions. This research demonstrates that the degradation steps of Aspirin depend on the thermal treatment. The main degradation products of different thermal treatments are currently unknown it is clear that acetic acid, which is one of the degradation products, acts as an antiplasticiser by lowering the glass transition temperature. In addition, due to the presence of the degradation products in liquid form (observed by hot stage microscopy), Aspirin is still present in the sample and recrystallises during the second heating step and melts at much lower temperatures.