Differential scanning calorimetric examination of the degenerated human palmar aponeurosis in dupuytren disease

The Dupuytren contracture - degenerative shortening of the palmar aponeurosis - is a common disease of the hand in Europe. The aetiology of the degenerative changes in the collagen structures is still not clear. To describe the clinical manifestation of the disease we use an international classification according to Iselin. Our hypothesis was that in Dupuytren disease there is a clear pathological abnormality in the tissue elements building up the palmar aponeurosis, which is responsible for the disease, and could be monitored besides the classical histological methods by differential scanning calorimetry. The thermal denaturation of different parts of human samples was monitored by a SETARAM Micro DSC-II calorimeter. All the experiments were performed between 0 and 100°C. The heating rate was 0.3 K min⁻¹. DSC scans clearly demonstrated significant differences between the different types and conditions of samples (control: T _m=63°C and ΔH _cal=4.1 J g⁻¹, stage I.: T _m= 63°C and ΔH _cal=5.1 J g⁻¹, stage II.: T _m=64°C and ΔH _cal=5.2 J g⁻¹, stage III.: T _m=60°C and ΔH _cal=5.2 J g⁻¹, stage IV.: T _m=60.2°C and ΔH _cal=5.3 J g⁻¹). The heat capacity change between native and denatured states of aponeurosis samples increased with the degree of structural alterations indicating significant water loosing. These observations could be explained with the structural alterations caused by the biochemical processes. With our investigations we could demonstrate that DSC is a useful and well applicable method for the investigation of collagen tissue of the human aponeurosis. Our results may be of clinical relevance in the future i.e. in the choice of the optimal time of surgical therapy of different clinical level Dupuytren contractures.     

Light Modulates Electric Phenomena in Hornet Cuticle¶

In the cuticle of live social hornets, such as Vespa orientalis (Hymenoptera, Vespinae), endogenous electric effects are encountered, i.e. voltages of 100–200 mV under illumination and currents amounting to several microamperes on its subjection to darkness—clearly a process of charging and discharging. Of the various wavelengths of sunlight, UV was found to be the most contributory to the active cuticular voltage generation. Throughout the warm season of the yearthe–the active period in colonies of social hornets and wasps—colony members exit from the dark nest during the daytime and fly to the field under the hot sun for various foraging purposes, ultimately returning to the nest. Thus, each hornet, be it queen, worker or drone, probably undergoes daily cyclical process of electric charge and discharge in the exterior part of their integument, cuticle, which lasts up to 30–40 min. Such photoelectric phenomenon was detected in both live, ether‐anaesthetized hornets and dead hornets, albeit in the latter the electric values recorded were lower. The present study addresses the possible impact of the phenomenon on vespan daily life and also compares it with a parallel occurrence in electric fish.     

A new peptide from venom of the East-European hornet Vespa orientalis. Mass spectrometric de novo sequence

The de novo sequence of a new peptide from venom of the East-European hornet Vespa orientalis L. was determined by mass spectrometry. It was used as an example to show that time-of-flight mass spectrometry with an electrospray ion source can be used effectively to determine the amino-acid sequence of microquantities of peptides. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 49–51, January–February, 2008.     

Wax components of larval cocoon silk of the hornet Vespa analis Fabricius

Wax, 85% of which consists of orthorhombic crystals, has been found in the cocoon of the hornet Vespa analis Fabricius by means of high-resolution ¹³C solid-state nuclear magnetic resonance (NMR). GC–MS analysis revealed the major components of the wax in the cocoon were linear alkenes and alkanes with a total of 23 or 34 carbon atoms. At 40.7 °C a DSC absorption peak and a ¹³C NMR chemical shift change were observed and interpreted as the result of a crystal transition from the orthorhombic to rotator phase of the wax molecules. At 55.5 °C melting of the wax was observed. The amount of crystalline wax deposition varied with the part of the cocoon—crystalline wax was concentrated in the silk sleeve lining the inner wall of each comb cell but there was very little in the silk cap projecting from the end of each cell. Because the wax components of the larval cocoon were almost identical to those of the larval cuticle, despite a slight difference in the profiles, they might have come from the larval cuticle via direct body contact with the cocoon. Figure Cocoon of the hornet Vespa analis Fabricius     

1H pulsed NMR study of bombyx mori silk fibroin: Dynamics of fibroin and of absorbed water

The dynamical behavior of the Bombyx mori silk fibroin chain and of absorbed water in silk fiber, film, and powder has been studied by ¹H pulsed nuclear magnetic resonance (NMR). Segmental motions do not occur and only the rapid rotation of the methyl groups of alanine residues is observed from ?120 to 130°C. This is independent of the conformation or form of the silk fibroin samples. Magnetization of dry silk fibroin by the solid-echo method shows a single Gaussian decay, while two components are observed in the solid-echo signals of films containing 6–10 w/w% water. An immobile component with a T₂ value of 11 μs is attributed to silk fibroin, and the mobile component to bound water. The T₂ of the latter varies from 50 to 200 μs, depending on the sample. The dynamical behavior of water trapped in the film is discussed on the basis of these T₂ values.     

Thermal analysis of protein–metallic ion systems

Advanced thermal analysis methods, such as temperature modulated DSC (differential scanning calorimetry) and quasi-isothermal TMDSC were used to analyze the protein–metallic ion interactions in silk fibroin proteins. The precise heat capacities were measured and theoretically predicted in this study. To remove bound water and simplify the system, a thermal cycling treatment through both standard DSC and TMDSC was used to detect the underlying heat capacity and reveal the phase transitions of the silk–metallic salts system. Results show that K⁺ metallic salts play the role of plasticizer in silk fibroin proteins, which reduces the glass transition (T_g) of the pure silk protein and negatively affects its structural thermal stability. On the other hand, Ca²⁺ metallic salts act as an anti-plasticizer, and increase the glass transition and the thermal stability of the silk protein structure. This indicates that the thermal analysis methods offer a new pathway to study protein–metallic ion systems, yielding very fruitful information for the study of protein structures in the future.     

Mn4+掺杂Co3O4纳米纤维的静电纺丝法制备及其电化学性能

通过静电纺丝法制备Mn~(4+)掺杂的Co_3O_4复合纳米纤维,利用XRD、XPS、BET、SEM和电化学工作站等对材料的结构、成分、形貌和电化学性能进行表征与测试。研究发现,通过Mn~(4+)掺杂,Co_3O_4复合纳米纤维的电化学性能得到明显改善。当nCo∶nMn=20∶2时,相应的复合纤维具有较大比表面积68 m2·g-1,而且该样品呈现出清晰的氧化还原峰,在1 A·g-1的电流密度下,放电比电容量为585 F·g-1,这比纯Co_3O_4纳米纤维的416 F·g-1,有显著提高;循环500圈电容保持率达到82.6%,而纯Co_3O_4纳米纤维则是76.4%。     

富氮掺杂碳空心纳米笼协同钴镍硫化物提升超级电容器性能

采用简单的热解-硫化两步法成功制备了一种新型的富氮掺杂碳空心纳米笼(NC)负载双元金属硫化物纳米颗粒(CoNi_xS_y)的复合材料CoNi_xS_y/NC。该策略以丁二酮肟镍为镍源,增加了活性位点,同时前驱体ZIF-8@Ni-ZIF-67的核壳结构为空心碳纳米笼的构建提供了可能性。这种独特的负载多金属硫化物纳米颗粒的中空结构使CoNi_xS_y/NC作为电极材料时具有更多的活性位点、更高的导电性和结构稳定性,从而使其具有较高的比容量(1 A·g^-1时比容量为629.2 F·g^-1),优异的循环稳定性(1 A·g^-1下1 000次循环测试后容量保持率为93.4%)。当将其进一步组装成对称超级电容器后,在1 A·g^-1下可提供207.2 F·g^-1的比电容,1 000圈循环稳定后的容量保持率为85.36%。     

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.     

Thermal and kinetic study of the ferroelectric phase transition in deuterated triglycine selenate

The specific heat and the enthalpy variation of a highly deuterated crystal of ferroelectric triglycine selenate have been measured around its first-order phase transition using the technique square modulated differential thermal analysis (SMDTA). The low temperature variation rate has allowed analyzing the kinetics of the phase transition. Due to an internal crack in the sample, the transition is carried out in two steps and an intermediate region where the transition is blocked and both phases coexist without transformation has been found. The latent heat on cooling (L _c=1.32±0.02 J g^–1) is higher than on heating (L _h=1.08±0.02 J g^–1) due to the thermal hysteresis and the great difference between the specific heat in both phases. Nevertheless, the enthalpy balance is fulfilled on heating and on cooling.     

Uncertainty of determination of palladium in road dust sample by inductively coupled plasma mass spectrometry

The determination of palladium in a road dust sample taken close to the highway (w _Pd=450 ng g⁻¹) was carried out by the ICP-MS method after sample decomposition by aqua-regia. Analyses were evaluated by two methods: external calibration accompanied with mathematical correction of spectral interferences (EC) and isotope dilution measurement after separation of Pd by extraction to dibutyl sulfide solution (ID). In both cases, the uncertainties and accuracy of results were investigated. Although in the case of ideally homogeneous sample the repeatability of EC results (11 ng g⁻¹ Pd) was somewhat lower than those of ID results (16 ng g⁻¹ Pd), the uncertainties of results of both techniques were almost the same and they reached the level of 19 ng g⁻¹ Pd. The main uncertainty source of the EC method is represented by the correction of spectral interferences. In case of real non-homogeneous sample, the main uncertainty component represents the soil sampling. The uncertainty of results (approx. 75 ng g⁻¹ Pd) only slightly exceeded the repeatability (approx. 70 ng g⁻¹ Pd). The accuracy of results was proven by analyses of CRM TDB–1 Diabas Rock (in case of ID) and by the standard addition method (in case of EC).     

Directly Suspended Droplet Three Liquid Phase Microextraction of Diclofenac Prior to LC

Directly suspended droplet liquid–liquid–liquid microextraction (LLLME) has been used to determine residues of diclofenac (2-[2-(2,6-dichlorophenyl) aminophenyl] ethanoic acid), in environmental water samples. In this technique a free suspended droplet of an aqueous solvent is delivered to the top-center position of an immiscible organic solvent floating on the top of an aqueous sample while being agitated by a stirring bar placed on the bottom of the sample cell. Recently, diclofenac was found as an environmental contaminant in sewage, surface, ground and drinking water samples. In the present work, diclofenac was extracted from water samples by LLLME and analysed by HPLC with UV detection at 281 nm. Factors such as organic solvent, extraction and back extraction times, stirring rate and the pH of acceptor and donor phases were optimized. Enrichment factor and detection limit (LOD, n = 7) were 102 and 0.1 μg L⁻¹, respectively. The linearity ranged from 0.5 to 2,000 μg⁻¹ with a %RSD (n = 5) of 7.2 at S/N = 3. All experiments were carried out at room temperature (22 ± 0.5 °C).     

Kinetics and mechanism of dehydration of kaolinite,muscovite and talc analyzed thermogravimetrically by the third-law method

Summary The third-law method has been applied to determine the enthalpies, Δ_rH_T⁰, for dehydration reactions of kaolinite, muscovite and talc. The Δ_rH_T⁰values measured in the equimolar (in high vacuum) and isobaric (in the presence of water vapour) modes (980±15, 3710±39 and 2793±34 kJ mol^-1, for kaolinite, muscovite and talc, respectively) practically coincide if to take into account the strong self-cooling effect in vacuum. This fact strongly supports the mechanism of dissociative evaporation of these compounds in accordance with the reactions (primary stages): Al₂O₃·2SiO₂·2H₂O(s)→Al₂O₃(g)↓+2SiO₂(g)↓+2H₂O(g); K₂O·3Al₂O₃·6SiO₂·2H₂O(s) →K₂O(g)↓+3Al₂O₃(g)↓+6SiO₂(g)↓+2H₂O(g) and 3MgO·4SiO₂·H₂O(s) →3MgO(g)↓+4SiO₂(g)↓+H₂O(g). The values of the Eparameter deduced from these data for equimolar and isobaric modes of dehydration are as follows: 196 and 327 kJ mol^-1for kaolinite, 309 and 371 kJ mol^-1for muscovite and 349 and 399 kJ mol^-1for talc. These values are in agreement with quite a few early results reported in the literature in 1960s.     

一种家蚕茧衍生具有蜂窝状结构的钴-锰共掺杂碳材料双功能电解水催化剂

通过一步碳化石墨化过程,由家蚕茧制得了一种具有蜂窝状结构的氮钴锰共掺杂碳材料。该材料具有蜂窝状结构和高比表面积,同时由于暴露的钴-锰活性位点以及富含的吡啶氮和石墨氮,3%钴-锰/蚕茧的碳材料(3%Co-Mn/SCC)显示了高析氢反应活性,其初始电位和10 m A·cm~(-2)过电位分别只有121和155 m V,Tafel斜率为130 m V·dec~(-1),并且在酸性条件下具有很好的稳定性。与此同时,2%Co-Mn/SCC在碱性条件下表现出优异的析氧反应催化性能,具有较低的初始电位,Tafel斜率为143 m V·dec~(-1)。     

介孔碳/石墨烯复合材料的制备及其醌类改性电容性能

首先利用硬模板法制备出介孔碳/石墨烯复合材料,然后向复合材料中引入具有赝电容活性的醌类分子进一步增大材料的电容性能。研究结果表明,负载30%(w/w)叔丁基氢醌的介孔碳/石墨烯复合材料具有最佳的电容性能,在电流密度为0.5 A·g~(-1)时,比电容值为355 F·g~(-1);当电流密度高达30 A·g~(-1)时,其比电容值高达226 F·g~(-1),比电容保持率为64%,表现出良好的速率特性。     

泡沫镍负载NiMoO4/NiMoS4复合材料的制备及其电化学性能

以泡沫镍作为基底,采用水热法原位生长出具有片状结构的NiMoO₄活性材料,然后通过水热硫化制备出NiMoO₄/NiMoS₄复合材料,研究了水热时间和硫脲添加量对样品形貌和电化学性能的影响。电化学结果表明,NiMoO₄/NiMoS₄电极在电流密度为1A·g^-1时,比电容为1560.7F·g^-1,在电流密度为40A·g^-1时循环2000次后,比电容仍为初始比电容的76.7%。将NiMoO₄/NiMoS₄电极材料与活性炭(AC)分别作为正、负极组装的非对称超级电容器(ASC)在400W·kg^-1的功率密度下可提供29.0Wh·kg^-1的能量密度。     

泡沫镍负载NiMoO4/NiMoS4复合材料的制备及其电化学性能

以泡沫镍作为基底，采用水热法原位生长出具有片状结构的NiMoO₄活性材料，然后通过水热硫化制备出NiMoO₄/NiMoS₄复合材料，研究了水热时间和硫脲添加量对样品形貌和电化学性能的影响。电化学结果表明，NiMoO₄/NiMoS₄电极在电流密度为 1 A·g^-1时，比电容为 1 560.7 F·g^-1，在电流密度为 40 A·g^-1时循环 2 000次后，比电容仍为初始比电容的 76.7%。将 NiMoO₄/NiMoS₄电极材料与活性炭(AC)分别作为正、负极组装的非对称超级电容器(ASC)在 400 W·kg^-1的功率密度下可提供 29.0 Wh·kg^-1的能量密度。     

Development of a highly precise ID-ICP-SFMS method for analysis of low concentrations of lead in rice flour reference materials

Microwave digestion and isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-SFMS) has been applied to the determination of Pb in rice flour. In order to achieve highly precise determination of low concentrations of Pb, the digestion blank for Pb was reduced to 0.21 ng g⁻¹ after optimization of the digestion conditions, in which 20 mL analysis solution was obtained after digestion of 0.5 g rice flour. The observed value of Pb in a non-fat milk powder certified reference material (CRM), NIST SRM 1549, was 16.8 ± 0.8 ng g⁻¹ (mean ± expanded uncertainty, k = 2; n = 5), which agreed with the certified value of 19 ± 3 ng g⁻¹ and indicated the effectiveness of the method. Analytical results for Pb in three brown rice flour CRMs, NIST SRM 1568a, NIES CRM 10-a, and NIES CRM 10-b, were 7.32 ± 0.24 ng g⁻¹ (n = 5), 1010 ± 10 ng g⁻¹ (n = 5), and 1250 ± 20 ng g⁻¹ (n = 5), respectively. The concentration of Pb in a candidate white rice flour reference material (RM) sample prepared by the National Metrology Institute of Japan (NMIJ) was observed to be 4.36 ± 0.28 ng g⁻¹ (n = 10 bottles). Figure Digestion blank of Pb was carefully reduced to approximately 0.2 ng g^-1 which permitted the highly precise determination of Pb at low ng g^-1 level in foodstuff samples by ID-SFMS     

Specific surface of two hydrated cements differing in strength

Specific surface, S, of CSH-gel particles of disordered layered structure, was studied by water sorption/retention in two cement pastes differing in strength, i.e. C-33 (weaker) and C-43 (stronger), w/c=0.4. Hydration time in liquid phase was t _h=1 and 6 months, followed by hydration in water vapour either on increasing stepwise the relative humidity, RH=0.5→0.95→1.0 (WS) or on its lowering in an inverse order (WR). Specific surface was estimated from evaporable (sorbed) water content, EV (110°C), assuming a bi- and three-molecular sorbed water layer at RH=0.5 or 0.95, respectively (WS). On WR it was three- and three- to four-molecular (50 to 75%), respectively, causing a hysteresis of sorption isotherm. At RH=0.5 the S increased with cement strength from 146 m² g^-1 (C-33, 1 m) to 166 m² g^-1 (C-43, 1 m) and with hydration time to 163 (C-33, 6 m) and to 204 m² g^-1 (C-43, 6 m). At RH=1.0 (and 0.95), higher S-value were measured but these differences were smaller: S amounted to 190-200 m² g^-1 in C-33 (1 and 6 m) and 198-210 m² g-1 in C-43 (1 and 6 m). Thus no collapse occurred on air drying of paste C-43 (6 m). This revised version was published online in July 2006 with corrections to the Cover Date.     

Calorimetric determination of activated carbons in aqueous solutions

The interactions among five samples of activated carbons, obtained from different lignocellulosic materials with different degrees of activation of approximately 20% and aqueous solutions of phenol and 4-nitro phenol are studied by means of the determination of immersion enthalpies. It is established that the obtained activated carbons are of a basic character and show values for the pH at the point of zero charge, pH_PZC, that range from 7.4 to 9.7 and, in all cases, higher total basicity contents than the values obtained for total acidity. The immersion heat of the activated carbons in CCl₄ and water is determined obtaining values which are higher for CCl₄ immersion and vary from 31.4 to 48.6 J g⁻¹. The hydrophobic factor, hf, it is calculated from the relation between of the immersion heat of the activated carbons in CCl₄ and the immersion heat in water, the obtained values were 2.98 and 6.75, which are greater than 1 due to the greater values obtained in CCl₄ when compared to the values obtained in water. Immersion enthalpies in phenol solution range from 7.6 to 13.9 J g⁻¹ and for the case of 4-nitro phenol such enthalpies range from 12.7 to 20.5 J g⁻¹; all the 5 samples studied showed a higher value for the heat of immersion in aqueous solutions of 4-nitro phenol.