scholarly journals Treatment of cartilage proteoglycan aggregate with hydrogen peroxide. Relationship between observed degradation products and those that occur naturally during aging

1987 ◽  
Vol 247 (2) ◽  
pp. 349-357 ◽  
Author(s):  
C R Roberts ◽  
J S Mort ◽  
P J Roughley

The effects of treatment of purified neonatal human articular-cartilage proteoglycan aggregate with H2O2 were studied. (1) Exposure of proteoglycan aggregate to H2O2 resulted in depolymerization of the aggregate and modification of the core protein of both the proteoglycan subunits and the link proteins. (2) Treatment of the proteoglycan aggregate with H2O2 rendered the proteoglycan subunits unable to interact with hyaluronic acid, with minimal change in their hydrodynamic size. (3) Specific cleavages of the neonatal link proteins occurred. The order in which the major products were generated and their electrophoretic mobilities resembled the pattern observed during human aging. (4) The proteolytic changes in the link proteins were inhibited in the presence of transition-metal-ion chelators, thiourea or tetramethylurea, suggesting that generation of hydroxyl radicals from H2O2 by trace transition-metal ions via a site-specific Fenton reaction may be responsible for the selective cleavages observed. (5) Cleavage of the link proteins in proteoglycan aggregates by H2O2 was shown to have a limited effect on the susceptibility of these proteins to cleavage by trypsin. (6) The relationship between these changes and those observed in cartilage during human aging suggests that some of the age-related changes in the structure of human cartilage proteoglycan aggregate may be the result of radical-mediated damage.

1986 ◽  
Vol 236 (1) ◽  
pp. 71-75 ◽  
Author(s):  
T T Glant ◽  
K Mikecz ◽  
P J Roughley ◽  
E Buzás ◽  
A R Poole

Monoclonal antibodies were prepared that recognize different age-related epitopes on proteoglycan subunits of high buoyant density isolated from human epiphysial and articular cartilages. Antibody EFG-4 (IgG1) recognizes a proteinase-sensitive segment associated with the core protein. Antibody BCD-4 (IgG1) reacts with keratan sulphate bound to core protein. Both epitopes are minimally expressed in foetal cartilage and increase with age after birth to become maximally expressed in adult cartilage by about 30 years of age. In contrast, monoclonal antibody alpha HFPG-846 (IgM) recognizes a core-protein-related epitope that is maximally expressed in young foetal cartilage, declines up to birth and thereafter and is almost absent after about 30 years of age. Antibody alpha HFPG-846 was used to isolate by immuno-affinity chromatography two subpopulations of proteoglycan subunits from a 16-year-old-human cartilage proteoglycan subunit preparation. Only the antibody-unbound population showed a significant reaction with antibodies EGF-4 and BCD-4. The amino acid and carbohydrate compositions of these proteoglycan fractions were different, and one (antibody-bound) resembled those of foetal and the other (antibody-unbound) resembled those of adult proteoglycans isolated from 24-27-week-old-foetal and 52-56-year-old-adult cartilage respectively. These observations demonstrate that human cartilages contain at least two chemically and immunochemically distinct populations of proteoglycans, the proportions and content of which are age-dependent. It is likely that these populations represent the products of different genes, though their heterogeneity may be compounded by the result of different post-translation modifications.


1978 ◽  
Vol 176 (3) ◽  
pp. 683-693 ◽  
Author(s):  
M T Bayliss ◽  
S Y Ali

1. Analysis of the purified proteoglycans extracted from normal human articular cartilage with 4M-guanidinium chloride showed that there was an age-related increase in their content of protein and keratan sulphate. 2. The hydrodynamic size of the dissociated proteoglycans also decreased with advancing age, but there was little change in the proportion that could aggregate. 3. Results suggested that some extracts of aged-human cartilage had an increased content of hyaluronic acid compared with specimens from younger patients. 4. Dissociated proteoglycans, from cartilage of all age groups, bind to hyaluronic acid and form aggregates in direct proportion to the hyaluronic acid concentration. 5. Electrophoretic heterogeneity of the dissociated proteoglycans was demonstrated on polyacrylamide/agarose gels. The number of proteoglycan species observed was also dependent on the age of the patient.


Molecules ◽  
2021 ◽  
Vol 26 (18) ◽  
pp. 5541
Author(s):  
Daniel Koch ◽  
Mohamed Chaker ◽  
Manabu Ihara ◽  
Sergei Manzhos

Description of redox reactions is critically important for understanding and rational design of materials for electrochemical technologies, including metal-ion batteries, catalytic surfaces, or redox-flow cells. Most of these technologies utilize redox-active transition metal compounds due to their rich chemistry and their beneficial physical and chemical properties for these types of applications. A century since its introduction, the concept of formal oxidation states (FOS) is still widely used for rationalization of the mechanisms of redox reactions, but there exists a well-documented discrepancy between FOS and the electron density-derived charge states of transition metal ions in their bulk and molecular compounds. We summarize our findings and those of others which suggest that density-driven descriptors are, in certain cases, better suited to characterize the mechanism of redox reactions, especially when anion redox is involved, which is the blind spot of the FOS ansatz.


1988 ◽  
Vol 58 (4) ◽  
pp. 198-210 ◽  
Author(s):  
James W. Rucker ◽  
David M. Cates

Peracetic acid can be catalyzed to bleach cotton fibers at temperatures as low as 30°C by incorporating 2,2î-bipyridine in the bleach solution. Treatment of the fibers with HCl prior to bleaching reduces bleaching effectiveness by removing trace transition metal ions from the fibers. Sorption of individual ions (Cr+3 Mn+2, Fe+2, Fe+3 Co+2, Ni+2, Cu+2, and Zn+2) by HCl treated cotton fibers prior to bleaching indicates that the ferrous ion produces the greatest catalytic effect, and it is only effective when the metal ion is in the fiber as opposed to in solution. Ferrous ions in the fibers sorb 2,2î-bipyridine from solution to form the tris-2,2î-bipyridine ferrous ion complex that is associated with the fibers, and it is the trischelate associated with the fibers that catalyzes bleaching. The effects of pH, temperature, and concentrations of 2,2î-bipyridine, sodium lauryl sulfate, and transition metal ions (in the fibers and in solution) on bleaching effectiveness and peracetic acid decomposition have been studied, and a bleaching mechanism is proposed.


1982 ◽  
Vol 35 (7) ◽  
pp. 1335 ◽  
Author(s):  
M Chatterjee ◽  
D Ganguli

The exchange behaviour of some divalent transition metal ions M2+ (Zn2+, Cu2+, Ni2+, Co2+, Mn2+) in a zeolite NaX (SiO2/Al2O3 2.75) was studied at intermediate stages before equilibrium. The equivalent counter ion supply in the solution, given by the equivalent ratio of the two counter ions 2M2+/Na+, was found to be critical in determining the saturation level of exchange. The series of relative abilities of exchange was very similar to the well known selectivity series at equilibrium. It is suggested that water exchange of the metal ions in solution could be one of the factors controlling the relative ease of ion exchange.


2006 ◽  
Vol 957 ◽  
Author(s):  
Shubra Singh ◽  
N Rama ◽  
M.S. Ramachandra Rao

ABSTRACTThe effect of doping of transition metal ions (Fe and Co) on transport properties of ZnO has been studied in both bulk and thin films. The solubility limit of these ions have been found to be higher in thin films compared to bulk. Optical measurements reveal the presence of Fe in both 2+ and 3+ state. Co is believed to be in 2+ states. Electrical resistivity measurements show that while for bulk Fe doped ZnO samples there is a decrease in resistivity compared to undoped ZnO, it increases for bulk Co doped ZnO samples. However, thin film samples of both types of doped compounds show a decrease in resistivity compared to undoped ZnO. This difference in bulk and thin film behaviour has been explained on the basis of experimental results.


2004 ◽  
Vol 847 ◽  
Author(s):  
Bridget Ingham ◽  
S. V. Chong ◽  
Jeff L. Tallon

ABSTRACTLayered organic-inorganic hybrid materials based on tungsten oxide as the inorganic framework have been synthesised to include transition metal ions. The resulting materials have been characterised using a number of techniques. X-ray diffraction shows an interlayer expansion with increasing alkyl length. Infrared vibrational spectra of manganese tungstate compounds indicate the organic amine molecules are neutrally charged, and the inorganic framework is unaltered as one varies the organic intercalate. The magnetic behaviour of the materials has also been explored using a SQUID magnetometer. In the manganese tungstate hybrids an antiferromagnetic (AF) transition is observed, which decreases in temperature as the inorganic interlayer spacing is increased. A nickel tungstate hybrid sample, on the other hand, displays a ferromagnetic transition, which we attribute to a canted AF phase below 15 K. In all cases studied, the behaviour can be mapped to an effective moment (Peff) per transition metal ion, which agrees well with theoretical and literature values for other transition metal oxides.


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