DSC analysis of human fat tissue in alcohol-induced avascular necrosis of the femoral head

Avascular necrosis of human femoral head (ANFH) causes incongruity in the joint that leads to disability in patients requires total hip arthroplasty (THA). Several etiological factors of ANFH have been proposed in the literature but there are cases of idiopathic origin. We observed macroscopic variation in quality of the subcutaneous fat tissue in patients with ANFH compared to patients with osteoarthritis or hip fracture during THA procedures. The samples were analysed by histology, gas chromatography (GC) and differential scanning calorimetry (DSC). Conclusion: the alteration in the fatty acid profile did not cause histological changes, however we could detect biochemical changes using DSC and GC.     

沙冬青抗冻蛋白热滞活性的DSC研究

在某些极地鱼类的血清以及某些昆虫和植物中 ,人们发现了一类特殊的物质 .它们的共同特点是能通过直接与冰晶核相互作用,抑制冰晶核的形成和生长,从而降低溶液冰点 .现已发现的这类抗冻物质都属于蛋白质,被统称为抗冻蛋白（ Antifreeze Proteins, AFPs） .抗冻蛋白能以非依数性形式大大降低溶液的冰点,但对熔点的影响很微弱,而且遵从依数性的原则,使冰点低于平衡态的熔点,溶液处于反常的非平衡相变状态 .这种冰点低于熔点的特性称为热滞 (Hysteresis).因此,抗冻蛋白也叫热滞蛋白或温度迟滞蛋白（ Thermal Hysteresis Proteins, …     

Differential Scanning Calorimetric and Circular Dichroistic Studies on Plant Antifreeze Proteins

Antifreeze protein (AFP) can lower the freezing point by inhibiting the growth of ice crystals. In this article, the thermal hysteresis activity (THA) of a plant AFP was measured with differential scanning calorimetry (DSC). As is shown, when the amount of ice in the sample was less than 5% THA of this AFP reached as high as 0.35°C. The secondary structure of this AFP was studied with circular dichroism (CD). The CD spectrum from 195to 240 nm indicated a well-defined secondary structure consisting 11% α-helix, 34%antiparallel β-sheet and 55% random coil. This revised version was published online in August 2006 with corrections to the Cover Date.     

Sensitivity of a planar micro-flame ionization detector

The sensitivity of a MEMS μFID with reduced fuel gas consumption for portable applications like mobile GC or THA is examined. It is shown that sensitivity depends on flame size and type of sample gas supply (either separate supply or premixed with the hydroxygen). In contrast to conventional FIDs, the sensitivity of the μFID increases with decreasing molecule size. The sensitivity to methane can be optimized up to conventional values. Measurements with the μFID as a second detector in a μGC module prove the additional functionality of such a system.     

Calorimetric studies on an insect antifreeze protein ApAFP752 from <Emphasis Type="Italic">Anatolica polita</Emphasis>

Many ectotherms organisms produce antifreeze proteins (AFPs), also known as thermal hysteresis proteins (THPs), which can lower the freezing temperature of body liquids without significantly affecting the melting point. In this article, thermal hysteresis activity (THA) of ApAFP752 from the desert beetle Anatolica polita was measured with differential scanning calorimetry (DSC). When the ice fraction was less than 25.3%, a delay in the onset temperature of refreezing was observed, indicating that the ApAFP752 solution has thermal hysteresis effect. When the amount of ice in the solution was less than 5.1%, THA of the ApAFP752 reached as high as 0.76 °C. THA of ApAFP752 was concentration-dependent. Hydrophilic ability of ApAFP752 was evaluated by thermal gravimetry (TG). The results of TG showed that ApAFP752 has strong hydrophilicity. The secondary structure of ApAFP752 was studied with circular dichroism (CD). The CD spectrum from 190 to 240 nm indicated a well-defined secondary structure consisting of 11.1% α-helix, 53.6% β-sheet, 8.3% turn, and 27.0% random coil.     

A new traceability scheme for the development of international system-traceable persistent organic pollutant reference materials by quantitative nuclear magnetic resonance

Quantitative nuclear magnetic resonance (qNMR) was used for the purity determination of neat compounds of persistent organic pollutants (POPs). qNMR is a unique quantitative method that is not only traceable to the International System of Units (SI), but it also does not require a standard of its own. The purities of the POP compounds determined in this work were traceable to a single certified reference material (CRM), which is extremely attractive for reference material producers. The purities observed by qNMR were equivalent to those observed by gas chromatography with flame ionization detection (GC/FID) or a differential scanning calorimetry (DSC) combined with a thermogravimetric analyzer (TGA). The uncertainties obtained by the qNMR method were comparable to being slightly larger than those observed by DSC.     

Chemometric processing of pharmaceutical essential oil fingerprints -- comparison of GC, HPLC, TLC, IR spectroscopy, and differential scanning calorimetry

Fifteen essential oils of pharmaceutical grade were fingerprinted by five techniques: TLC, GC, HPLC, attenuated total reflectance FTIR spectroscopy, and differential scanning calorimetry (DSC). Denoising and baseline removal was found to be a crucial step for correct comparative analysis. Standardization of the signal was not necessary in the presented case; however, it should be considered and checked in each case. Due to small variance explained by first two principal components (below 50%) and outlying observations, the main analysis was performed by Euclidean dendrograms. It was found that almost all techniques besides DSC find real chemical similarities; however, DSC can be used as an additional tool. The similarities among the five techniques were also compared and discussed.     

Differential scanning calorimetry (DSC) analysis of human plasma in different psoriasis stages

Psoriasis vulgaris is a chronic autoimmune, inflammatory and proliferative skin disease. Recently, there is a need for new methods to detect and to monitor this dermatological syndrome at any stage. The application of differential scanning calorimetry (DSC) should be as a new diagnostic method for psoriasis detection and monitoring using human plasma. We aimed to detect blood plasma components with DSC in psoriasis patients. The study included 18 white adults (eight men and ten women; median age 55.7 years) who had underwent a full skin examination for psoriasis. According to the psoriasis area severity index (PASI) we selected them into three groups: PASI: 0 (symptomless), PASI: 1–6 (minimal symptoms), PASI: >7 (symptoms). According to medical treatment human blood plasma samples were collected from healthy controls, patients without or with therapy, and were analyzed by DSC technique. In this preliminary study we observed that thermal changes (T _m, calorimetric enthalpy) in blood plasma showed closed correlation with psoriasis severity and medical treatment. Further studies are needed to elucidate these relationships, but our application of the DSC method has provided a potential new tool for the early diagnosis and monitoring of psoriasis patients.     

Thermal Degradation of Glutamate Polymers

Thermal properties of precipitated samples and films of poly-γ-benzyl-L-glutamate (PBG) and poly-L-glutamic acid (PGA) have been studied using TGA, DSC, and pyrolysis. The PBG film was identified as that described by McKinnon and Tobolsky as “form C” (“film A” of Uematsu et al.) using IR, dielectric relaxation, and DSC data. The PGA film is α-helical (IR) and was further characterized by dielectric relaxation measurements. With the exception of water loss at ～110° from PGA, TGA and DSC measurements reveal only incomplete endotherms corresponding to decomposition. Volatile decomposition products were trapped and identified using combined GC/IR and GC/MS techniques. Identified products were as follows: from PGB–CO₂, NH₃, H₂O, toluene, benzaldehyde, benzyl alcohol, and benzoic acid; from PGA–CO₂, NH₃, CH₃OH, acetone, and H₂O. Only minor differences were noted in GC traces of the total volatile decomposition products in air or in nitrogen streams. No evidence for retained solvent in cast films was obtained.     

Influence of oxidative injury and monitoring of blood plasma by DSC on patients with psoriasis

Oxidative stress induced by oxygen free radicals (OFRs) is a casual factor in psoriasis. Our aim was to detect the oxidative stress parameters and blood plasma changes with differential scanning calorimetry (DSC) in psoriatic patients. The study included untreated (n = 39) and treated (retinoids, methotrexate, biologic response modifiers; n = 33) white adult patients from both sex. To monitor oxidative stress concentration of malondialdehyde (MDA), reduced glutathione and sulfhydryl groups, production of OFRs, and activity of myeloperoxidase (MPO), superoxide dismutase, and catalase were measured. Denaturation of plasma components was detected in SETARAM Micro DSC-II calorimeter. Total production of OFRs and MPO activity, and the concentration of MDA were significantly increased both in untreated patients with moderate and severe symptoms and in all drug-treated groups compared with controls (p < 0.001). All of the scavengers and antioxidants were significantly decreased in untreated patients and better preserved after retinoid and biological therapy. DSC scans of blood plasma showed melting temperature a characteristic parameter to follow the severity of disease. The calorimetric enthalpy is exhibiting a moderate decrease with the progression of the inflammation. These findings suggest that an imbalance exists between pro-oxidants and antioxidants in untreated severe psoriatic patients. All drug therapy reduced the changes, mainly the biologic response modifiers. Similarly, DSC showed differences between untreated and conventional systemic drug treatment.     

Differential scanning calorimetry to measure the purity of polycyclic aromatic hydrocarbons

The application of differential scanning calorimetry (DSC) for purity determination is well documented in literature and is used amongst others in the analysis of pure organic crystalline compounds. The aim of this work is to examine whether the DSC method for purity determination consistently produces values for the purity of polycyclic aromatic hydrocarbons (PAHs) which are sufficiently accurate as required for the certification of reference materials. For this purpose, 34 different existing PAH certified reference materials were tested. The DSC results are shown to be consistent with the results obtained by other methods assessing the organic impurities content in PAHs, like gas chromatography (GC), high performance liquid chromatography (HPLC) and mass spectrometry. Significant differences between the measured values and the certified purity values were observed only in a limited number of cases.     

Role of differential scanning calorimetry (DSC) in the staging of COPD

Chronic obstructive pulmonary disease (COPD) is an imminent public health catastrophe. A proper severity marker is desperately needed to reflect the progress of the disease in a stage-specific manner (GOLD I–IV/A–D). The aim of the study was testing the applicability of thermodynamic analysis of blood, identifying different stages of COPD patients against each other and healthy controls. Sera from 63 COPD patients were investigated using differential scanning calorimetry (DSC). Patients formed four groups according to their GOLD severity stages, and smoking or ex-smoking subgroups were further analysed. In total, 18 GOLD A, 17 GOLD B, 16 GOLD C and 12 GOLD D patients’ DSC characteristics were investigated. Nine healthy sera (smoker and non-smoker controls) were evaluated using the same methodology. Enthalpy and melting parameters of severe COPD patients are significantly different from those in the early stages and from healthy subjects. There are clearly visible trends in both features in all stages as COPD progresses. The thermal denaturation parameters are significantly different between the smokers and non-smokers in advanced COPD stages (C&D). Healthy controls do not differ significantly according to their smoking status. The new thermophysical method described here has a potential to be applicable as a stage and/or symptom score of the individual COPD patients. Longitudinal studies are needed to monitor DSC changes of the same patients during progression and/or stagnation.     

Comparative methods in the determination of wax content and pour points of crude oils

In this research, differential scanning calorimetry (DSC) and gas chromatography is used to determine the wax content of fourteen crude oils of different sources. Different empirical equations were applied to compare the wax content of crude oils. For the fourteen crude oil samples with the wax content ranging from 7.5 to 43.8 mass%, it was observed that the results of empirical equations were in good agreement with those determined by DSC and GC. Accordingly, a correlation between ASTM pour point and the temperature at which 2 mass% of wax has precipitated out from crude oil is developed.     

Elliptic crack behavior emanating from the cement mantle of the total hip prosthesis

Damage accumulation and failure in the cement polymethylmethacrylate (PMMA) is the most prominent in a cemented total hip arthroplasty (THA) leading to eventual implant loosening. In this study, we used the three-dimensional finite element method (FEM) to analyze and calculate the three modes (I, II and III) of the stress intensity factor (SIF) of elliptic crack in the cement mantle for different sizes, orientation and location of crack according to different patient activities. From obtained results, we show that the opening crack mode is proportional to the stress applied on the damaged part (compression or traction). The risk of crack failure in the anterior region of the proximal part is more important and causes a danger of fracture of cement whose the value of the SIF reached exceeds the intrinsic resistance of the material. The study of the daily patient activities shows us that the climbing stairs represents the maximum value of SIF.     

Synthesis and Characterization of Polymeric Materials from Vegetable Oils

Although the petrochemical polymers have revolutionized the technological development, the intensive use of these materials have contributed to the global pollution. In this context, researches involving ecofriendliness materials are growing up, as well as, a current interest in developing materials from inexpensive and renewable resources, such as vegetable oils. In this work, is described the synthesis of polymeric materials by thermal polymerization from linseed oil (Linum usitatissimum L.) and passion fruit oil (Passiflora edulis) and their characterization by gas chromatographic (GC), Fourier transform infrared (FTIR) spectroscopy, solubility in organic solvents, thermogravimetry (TG), differential scanning calorimetry (DSC) and Raman spectroscopy. The TG curve shows that those polymeric materials present two stages of decomposition. DSC plots of the vegetable oils showed some endothermic and exothermic transitions which are not present in the DSC curves corresponding to oil-based polymers. The Raman spectra of the polymers indicate declining of absorbance in the region of CC stretching (∼1600 cm⁻¹). This absorption was used to estimate the degree of polymerization (79% and 67.5% for linseed and passion fruit oils, respectively).     

Fire retardant synergism between melamine and triphenyl phosphate in poly(butylene terephthalate)

The fire retardant efficiency of melamine (MA) and triphenyl phosphate (TPP) in poly(butylene terephthalate) (PBT) was studied by the limiting oxygen index (LOI) and the UL94 test. On adding 10 wt. % MA and 20 wt. % TPP, LOI increased from 20.9 to 26.6 and the UL94 V-0 rating was achieved. SEM and DSC analyses show that the fire retardants are compatible with PBT and facilitate crystallization of PBT. The occurrence of an interaction between MA + TPP and PBT was elucidated by TGA, dynamic FTIR, and pyrolysis/GC/MS. MA + TPP changes the degradation path of PBT and modifies the compositions of the gas and condensed-phase products.     

Gas chromatographic and differential scanning calorimetric studies of new bonded silicas in connection with transition phenomena

Summary In order to give a molecular interpretation to the phase transition observed with densely bonded octadecyl-silicas in reversed phase liquid chromatography (RPLC) as well as in gas chromatography (GC), nine new bonded silicas were prepared including grafts with polar groups at the extremities of long spacers (18 carbon atoms). The interpretation is simplified by using large-pore macroporous substrates and inverse GC in conjunction with differential scanning calorimetry (DSC) as the test method. A phase transition is observed in almost all cases, but the temperature range is lower and more extended in comparison to the dimethyloctadecyl reference silica. An interpretation of the phase transition is given, based on the folding of the chains and the resulting autodensification of the layer.     

Differential sacnning calorimetric examination of the human intervertebral disc: establishment of calorimetric standards of different stages of degeneration

Intervertebral disc (IVD) degeneration is a common orthopaedic disorder with significant social and economic impact. The major pathological changes occur in the structure of anulus fibrosus (AF) and nucleus pulposus (NP). According to previous reports differential sacnning calorimetric (DSC) proved to be a suitable method for the demonstration of thermal consequences of local and global conformational changes in the structure of the human intervertebral discs. According to the present study, the DSC results clearly proved that definitive differences are present between the stages of disc degeneration in calorimetric measures. The structural differences between the stages could be also demonstrated by histology.     

The differences in thermal profiles between normal and leukemic cells exposed to anticancer drug evaluated by differential scanning calorimetry

Chronic lymphocytic leukemia (CLL) is a heterogenous disease with an imbalance between apoptosis and cell proliferation. Therefore, the main goal in CLL therapy is to induce apoptosis and effectively support this process in transformed B lymphocytes. In the current study, we have compared differential scanning calorimetry (DSC) profiles of nuclei isolated from CLL cells and normal mononuclear cells exposed to cladribine or fludarabine combined with mafosfamide (CM; FM), and additionally to CM combined with monoclonal antibody—rituximab (RCM) for 48 h, as well as in culture medium only (controls). Under current study, the mononuclear cells from peripheral blood (PBMCs) of healthy individuals have been included. The obtained results have shown the presence of thermal transition at 95 ± 5 °C in most of nuclear preparations (92.2 %) isolated from blood of CLL patients. This thermal characteristic parameter was changed after drug exposure, however, to a different extent. These thermal changes were accompanied by the decrease of cell viability, an elevation of apoptosis rate and the changes in expression/proteolysis of poly(ADP-ribose)polymerase-1—main marker of apoptosis. Importantly, in DSC profiles of nuclear preparations of PBMCs from blood of healthy donors exposed to investigated drug combinations and control CLL cells, the lack of such changes was observed. Our results confirmed that DSC technique complemented with other biological approaches could be helpful in tailoring therapy for CLL patients.     

The determination of total and unbound midazolam in human plasma. A comparison of high performance liquid chromatography, gas chromatography and gas chromatography/mass spectrometry

Midazolam concentrations in patients' plasma was determined after extraction with high performance liquid chromatography (HPLC), gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). GC was selected for routine plasma assays in terms of selectivity, simplicity, precision, accuracy and sensitivity (0.02 microgram/mL); HPLC analysis was less sensitive (0.1 microgram/mL) than GC; GC/MS was used for analysis validation. Plasma protein binding of midazolam was determined by GC in patients' plasma after in vitro incubation with midazolam, ultrafiltration and extraction; 5% of the drug was unbound to plasma proteins. Midazolam distribution in lipoprotein fractions separated by ultracentrifugation of plasma obtained from patients on prolonged midazolam treatment was also assayed by GC.