Novel calorimetric investigation of different degenerative disorders of the human hyaline cartilage

The purpose of this investigation was to further elucidate calorimetric properties of cartilage samples from femoral head necrosis and osteoarthritis from live surgeries. The natural course of this disease is one of steady progression with eventual collapse of the femoral head, followed by secondary osteoarthritis in the hip joint. All samples showed a clear denaturation peak on the calorimetric curve. Cartilage obtained from necrotic femoral head required the lowest amount of energy for decomposition. The use differential scanning calorimetry as part of thermal analysis was a reliable method for differentiating.     

New thermogravimetric protocol for the investigation of normal and damaged human hyaline cartilage

Osteoarthritis, although classically conceived of as a degenerative consequence of aging, is a disease with an increasingly well-characterized molecular pathophysiology. Pathologic changes in cartilage composition and molecular organization, as well as elevated water content, alter the exquisite balance of biomechanical properties. Much of what is known about changes in the extracellular matrix in osteoarthritis comes from animal models. Previously, thermogravimetric methods have not been used for compositional thermoanalytical study of normal and degenerative human hyaline cartilage. For this reason the research group established a sufficient new thermogravimetric protocol, which proved water content elevation contributing to disease progression.     

Thermal analysis of the osteoarthritic human hyaline cartilage

Summary Arthritis of major joints, especially osteoarthritis of the knee is a very frequent disease of human beings mainly in the developed countries. The pathology of osteoarthritis has been subject of many publications before, using a wide spectrum of different methods to evaluate degenerative changes of hyaline cartilage. The authors examined osteoarthritic human knee joint hyaline cartilage with differential scanning calorimetry. The different stages of cartilage degeneration have been verified by histological examinations. The research group demonstrated thermal differences between various stages of osteoarthritis. Besides explaining possible causes for experienced thermodynamic effects, the authors reflect upon future research ways and the possibilities of applying the method in practice.     

Novel calorimetric properties of human cartilage samples in rheumatoid arthritis

During recent years, knowledge of rheumatoid arthritis has increased, and management of the disease has improved. A limited number of papers have been published before on the subject of thermal analysis of degenerative cartilage but rheumatoid arthritis (RA) has not been studied previously. A new protocol had to be established before the investigation. The purpose of this study was to further characterize the altered metabolism in human RA cartilage that promotes disease progression. Previously, these methods have not been used for this purpose. The use of thermal analysis could be an effective method for controlling the relationship between biomarkers and disease progression.     

Characterization of human cartilage in degenerated spine disease with differential scanning calorimetry

The purpose of this study was to further characterize the altered metabolism spondylolisthesis that promotes disease progression. Degenerative human cartilage (intervertebral disc, facet joint and vertebral end-plate) was obtained during 15 posterior lumbar spine interbody fusion procedures performed at the University of Szeged. The thermal properties of samples were determined by differential scanning calorimetry (Mettler-Toledo DSC 821^e). Greatest change in the enthalpy was observed in the intervertebral disc samples: −1600.78 J g⁻¹. Denaturation caused by heating in the normal human hyaline cartilage needed −1493.31 J g⁻¹ energy. Characterization of the altered metabolism that promotes disease progression should lead to future treatment options.     

Calorimetric examination of the human meniscus

Meniscus degeneration is a very frequent disease of human beings mainly in the developed countries. The ability of the meniscus to participate in load bearing, shock absorption, joint lubrication, and joint stability depends on the maintenance of its structural integrity. Therefore the pathology of the degeneration has been subject of many publications before. These studies all agreed that the grade of the degeneration correlated with the patient’s age, weight, profession, and athletic activity [1]. These reviews also described the biochemical changes in the structure, too [2, 3]. In the current study authors examined degenerated human meniscus with differential scanning calorimetry and demonstrated thermal differences between healthy and intraoperatively removed pathological samples.     

DSC measurement of cartilage destruction caused by septic arthritis

Summary Treatment of a bacterial arthritis is a challenging task for a clinician as inadequate therapy can cause cartilage destruction and can result in severe osteoarthritis of the affected joint. The development of cartilage destruction in septic arthritis is not known in details. The aim of this study was to follow this process by calorimetric method. We induced experimental septic arthritis in knee joints of seven New Zealand rabbits by single inocculation of Staphylococcus aureusOKI 112001 culture (1.5 mL 8·10⁸±5% c.f.u.). The first rabbit died on the 11^thday. At that time all the other subjects were made overslept and samples were isolated from the cartilage of the femurs for calorimetric measurement. The DSC scans clearly demonstrated the development of infective structural destruction in cartilage from the first to the tenth day of incubation. In case of healthy control the melting temperatures (T_m) were: 49.7, 55 and 63.4°C and the total calorimetric enthalpy change (ΔH) was 0.55 J g^-1. After the first day the enthalpy decreased (0.375 J g^-1), the first two transition temperature shifted towards higher temperature: 57 and 63.15°C. Up to the fourth day the effect of infection culminated with T_mof 49.3, 55.9, 59.4, 62.8°C and further decrease of the ΔH. At the fifth day the effect of infection is culminated in two separable thermal denaturation events (with 55 and 63.3°C T_ms) with high jump in ΔHindicating the dramatic change of the structure of rabbit cartilage, so this time elapsed seems to be critical from the point of view of practical clinical relevance too. Between the 7^thand 11^thdays practically we had same melting temperatures (50 and 63°C) with low (~0.24 J g^-1) enthalpy.     

Differential scanning calorimetric examination of the tracheal cartilage after primary reconstruction with differential suturing techniques

Summary Resection and subsequent end-to-end anastomosis of the windpipe is a tried-and-tested acceptable method for the surgical treatment of segmental defects. There are a variety of different techniques for tracheal end-to-end anastomosis, but controversial reports highlight the fact that the suturing technique of the anastomosis is still subject of debate. We aimed to show the postoperative effects of the continuous and simple interrupted suturing technique respectively on the tracheal cartilage using differential scanning calorimetry. Transsection and subsequent reanastomosis of the cervical trachea was performed in 14 adult beagle dogs. The trachea was anastomized with continuous or simple interrupted sutures respectively depict no change in microcirculation after the resection of the trachea, but significant decrease following the completion the anastomosis with continuous sutures. Conventional histological analysis did not show any marked postoperative change in the tracheal cartilage but our DSC scans clearly demonstrated the differences between the intact cartilages and the ones involved in the anastomosis.     

Differential scanning calorimetric examination of the tracheal cartilage after primary reconstruction with continuos sutures: A preliminary study

Acquired upper airway stenosis is usually associated with a complex of pathological conditions at the high tracheal and the subglottic levels. Reported reconstructive techniques include widening of the airways by incorporation of grafts, segmental resection, and anastomosis or combined procedures. Progress in anaesthesia, surgical techniques, and understanding of the pathophysiology of the trachea has made primary tracheal reconstruction a safe operative procedure, although there are no reports observing its acute effect on the tracheal cartilage. Differential scanning calorimetry (DSC) is a well-established method for the demonstration of thermal consequences of local and global conformational changes in biological systems, including hyaline cartilage, but it has never been applied for the investigation of tracheal cartilage. According to the present study, the thermograms may prove the presence of structural changes of the cartilage after primary reconstruction in the short-term follow up (smaller melting temperature and calorimetric enthalpy in the operated dog). The differences were clearly demonstrated between the intact cartilages and the ones involved in the anastomosis.     

Thermal analysis of the cruciate ligaments of the human knee

Summary Cruciate ligaments of the knee joint are important structures very often affected by the degenerative process in case of osteoarthritis. One of the most controversial issues in knee arthroplasty practice nowadays is the role of the posterior cruciate ligament. With foregoing studies authors have demonstrated the feasibility of DSC in the investigation of the musculoskeletal system. With current study authors established the thermal behaviour of healthy cruciate ligaments and detected the alterations in case of osteoarthritis. By establishing the DSC scans of the normal ligaments authors demonstrated clear differences between the posterior and anterior ligament. In addition alterations between normal and arthritic samples could be detected both in terms of changes in total enthalpy and heat capacity. Calorimetric findings have been verified by histological examinations as well.     

Calorimetric study of myoglobin embedded in trehalose-water matrixes

It has been suggested that in ‘dry’ protein-trehalose-water systems, water-mediated hydrogen bond network, whose strength increases by drying, anchors the protein to its surroundings. To further characterize this effect, we performed a DSC study on low-water myoglobin-trehalose systems. The denaturation temperature resulted to increase by decreasing hydration, and linearly correlated to the glass transition temperature of both the ternary protein-water-trehalose and the binary water-trehalose systems. Further measurements are being performed to investigate eventual differences among different saccharides.     

Differential Scanning Calorimetric Analysis of Composted Materials From Different Sources

Differential scanning calorimetry (DSC) was applied to the study of material composted from sawdust, used coffee, farmyard manure and the organic fraction of domestic solid waste. Composting trials were carried out in Morocco and samples were collected after different periods of composting. The results obtained provided evidence that sawdust substrate is not a suitable source for composting due to the high content of lignin; samples from used coffee are characterized by a degree of aromaticity that is lower and a functional group heterogeneity that is higher than those of organic wastes from manure and the organic fraction of domestic wastes. The latter organic waste substrates appear to be easily degraded and humified and to give DSC curves that at the end of composting are vary close to those of native soil humic acids. This revised version was published online in July 2006 with corrections to the Cover Date.     

Calorimetric and rheological properties of wheat flour suspensions and doughs: Effects of wheat types and milling procedure

Three types of wheat were submitted to two different milling procedures, giving rise to six flours which differed by some physico-chemical characteristics such as particle size, level of damaged starch and protein content. Differential scanning calorimetry was used for monitoring heat-induced structural changes in flour aqueous dispersions 80% water and in doughs 45% water. Differences between the thermal behaviour of the flour dispersions and doughs were explained mainly by differences in protein content. This result was confirmed after partial substitution of flour by gluten. Dynamic mechanical analysis performed at 20°C on the flour doughs indicated, as expected, a linear increase in the elastic modulus with increasing protein content. The results did not bring any evidence that, under these experimental conditions, starch damage might affect gluten hydration.This revised version was published online in November 2005 with corrections to the Cover Date.     

TA of pval hydrogel cross-linked by chemical and eb irradiation process used as artificial articular cartilage

Hydrogels, in general, can be used as a compliant surface in prosthesis of human synovial joints due to their biocompatible characteristics. In this work, different hydrogels were prepared from two aqueous solutions of PVAL (15 and 20 mass/mass%) by chemical reactions using citric acid as a cross-linking agent and by electron beam (EB) irradiation with doses from 25 to 100 kGy. The hydrogels were evaluated by their mechanical properties through indentation creep test, thermal properties by differential scanning calorimetry (DSC), and also equilibrium water content (EWC). This revised version was published online in August 2006 with corrections to the Cover Date.     

Calorimetric study of thermal decomposition of lithium hexafluorophosphate

Enthalpy of formation of lithium hexafluorophosphate was calculated based on the differential scanning calorimetry study of heat capacity and thermal decomposition. It was found that thermal decomposition of LiPF₆ proceeds at normal pressure in the temperature range 450-550 K. Enthalpy of LiPF₆ decomposition is Δ_d H(LiPF₆, c, 298.15 K)= 84.27±1.34 kJ mole^-1. Enthalpy of formation of lithium hexafluorophosphate from elements in standard state is Δ_f H ⁰(LiPF₆,c, 298.15 K) = -2296±3 kJ mol^-1. This revised version was published online in July 2006 with corrections to the Cover Date.     

Calorimetric and Thermal Investigation of Metal Derivatives of 6-aminopicolinic Acid

The comparison of thermal and calorimetric properties of metal derivatives of 6-aminopicolinic acid (APH) is presented. The salts and complexes of APH with Cr(III), Cd(II), Cu(II), Ni(II), Pb(II), Co(II)and Ag(I) have been studied by TG-DTA and DSC methods up to 1200°C in a nitrogen atmosphere. Decomposition processes are proposed. The decarboxylation, deamination and carbonation of the organic fragments of molecules take place. The compounds decompose to metal or to metal oxides. The values of the transition enthalpy were determinated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Calorimetric study of blends of poly(butylene terephthalate) and liquid crystalline copolyester

A calorimetric study of blends of poly(ethylene terephthalate-co-p-oxybenzoate), PET/PHB, with poly(butylene terephthalate), PBT has been carried out in the form of as-spun and drawn fibres. DSC melting and crystallization results show that PBT is compatible with LCP and the crystallization of PBT decreases by the addition of LCP in the matrix. The crystallization behaviour of blend fibres is investigated as a function of temperature of crystallization. A detailed analysis of the crystallization course has been made utilizing the Avrami expression. The isothermal calorimetric measurements provide evidence of decrease of rate of crystallization of PBT on addition of the liquid crystalline component up to about 50% by weight. The values of the Avrami exponents change in the temperature range from 200° to 215°C. Dimensionality changes in crystallization could be due to LCP mesophase-transition.     

Calorimetric study and thermal analysis of berberine sulphate

The heat capacities of berberine sulphate [(C₂₀H₁₈NO₄)₂SO₄·3H₂O] were measured from 80 to 390 K by means of an automated adiabatic calorimeter. Smoothed heat capacities, H _T-H _298.15 and S _T-S _298.15 were calculated. The loss of crystalline water started at about 339.3±0.2 K, and its peak temperature was 365.8±0.6 K. The peak temperature of decomposition for berberine sulphate was at about 391.4±0.4 K by DSC curve. TG-DTG analysis of this material was carried out in temperature range from 310 to 970 K. TG and DSC curves show that there is no melting in the whole heating process. This revised version was published online in August 2006 with corrections to the Cover Date.     

Calorimetric characterization of grass during its decomposition

Grass is cultivated for bioenergy purposes yet and expected to play a more prominent role as a source of renewable energy in the future. Understanding its burning characteristics is thus crucial to optimize the energetic efficiency. The aim of this study was to reveal the effect of i) microbial decomposition and ii) enzymatic depolymerisation of grass on its thermal behaviour. Thermal characteristics of grass during the course of aerobic decomposition and of fresh samples after treatment by enzymatic hydrolysis were measured by differential scanning calorimetry (DSC). Heat of reaction, 50% burnoff values and positions and areas of peaks were taken as indicators for the thermal behaviour. An increase in biochemical stability of the grass during 140 days of decomposition was indicated by an exponential mass loss and decreasing specific CO₂ respiration rates. Parameters representing the thermal stability of the materials coincided with this pattern. The relative contribution of the thermolabile fraction decreased, and 50% burnoff values increased almost steadily during decomposition from 366 to 407°C. These thermal stability parameters are thus indicators for biochemical degradation. However, peak temperatures of the individual peaks continuously decreased during decomposition. A comparison of composted and fresh, cellulase-treated samples without long-term microbial decomposition indicated that enzymatic depolymerisation rather than microbial consumption of the plant tissue led to the observed decrease in peak temperatures.     

Calorimetric determinations and theoretical calculations of polymorphs of thalidomide

The analysis of the thermograms of thalidomide obtained for the two reported polymorphs and β by differential scanning calorimetry (DSC) shows some inconsistencies that are discussed in the present work. The conception of a new polymorph form, named β^*, allowed us to explain the observed thermal behavior more satisfactorily. This new polymorph shows enantiotropy with both and β polymorphs, reflected in the unique endotherm obtained in the DSC-thermograms, when a heating rate of 10 °C/min is applied. Several additional experiments, such as re-melting of both polymorph forms, showed that there is indeed a new polymorph with an endotherm located between the endotherms of and β. IR, Raman, and powder X-ray permit us to characterize the isolated compound, resulting from the re-melting of both polymorph forms. Mechanical calculations were performed to elucidate the conformations of each polymorph, and ab initio quantum chemical calculations were performed to determine the energy of the more stable conformers and the spatial cell energy for both polymorphs and β. These results suggested a possible conformation for the newly discovered polymorph β^*.