Does decalcification alter the tissue sound speed of rabbit supraspinatus tendon insertion? In vitro measurement using scanning acoustic microscopy

Failure of the tendon or ligament insertions is one of the most common injuries in the Orthopaedic field. To elucidate the pathogenesis of those injuries, the authors had attempted to measure the tissue sound speed that could be correlated to its elasticity using scanning acoustic microscopy (SAM). For the application of SAM to tendon or ligament insertions, it was necessary to determine the role of decalcification in SAM measurements since mineralized tissues including bone or mineralized fibrocartilage were present at the insertion site. To assess whether decalcification alters the tissue sound speed or not, supraspinatus tendon insertion of six Japanese white rabbits were measured with SAM operating in the frequency range of 50-150 MHz. Right supraspinatus tendons attached to the humeral head were cut into two pieces at the center of the tendon. Then, they were fixed with 10% neutralized formalin for 12 h. In each specimen, medial half was not decalcified, while lateral half was decalcified with ethylene-diamine-tetra-acetic acid (EDTA). After embedding in paraffin, 5 microm thick specimens were prepared for the measurement using SAM. The mean sound speed in each histologic zone was evaluated, and subsequently compared to that measured in the undecalcified and the decalcified specimens. Mean sound speed of non-mineralized fibrocartilage was 1544 m/s in the undecalcified specimens, while the value of 1541 m/s was determined in the decalcified ones. On the other hand, it decreased 2-3% after decalcification in the mineralized tissue including mineralized fibrocartilage and bone (mineralized fibrocartilage: undecalcified = 1648 m/s, decalcified = 1604 m/s; bone: undecalcified = 1716 m/s, decalcified = 1677 m/s). However, no significant differences were found between the undecalcified and the decalcified specimens (non-mineralized fibrocartilage: p = 0.84, mineralized fibrocartilage: p = 0.35, bone: p = 0.28). These results indicate that SAM could be applied to determine the properties of the tendon or the ligament insertions after decalcification with EDTA. Although SAM is applicable only for in vitro experimental study, it is expected that these data will contribute to better understanding concerning the biomechanics of tendon or ligament insertions as well as the pathogenesis of their failure at a microscopic level.     

Uronic acid determination by high performance liquid chromatography with postcolumn fluorescence derivatization

To develop a fluorimetric high performance liquid chromatography (HPLC) technique for uronic acid microanalysis, a saline mobile phase and the postcolumn fluorimetric determination were combined. The detection limits of D-glucuronic, D-galacturonic and D-mannuronic acids were 7.19, 23.88 and 7.08 pmol, respectively. The proposed method was successfully applied to uronic acid microanalysis in a polysaccharide hydrolysate and a drink.     

Concerted proton-electron transfer in the oxidation of hydrogen-bonded phenols

Three phenols with pendant, hydrogen-bonded bases (HOAr-B) have been oxidized in MeCN with various one-electron oxidants. The bases are a primary amine (-CPh(2)NH(2)), an imidazole, and a pyridine. The product of chemical and quasi-reversible electrochemical oxidations in each case is the phenoxyl radical in which the phenolic proton has transferred to the base, (*)OAr-BH(+), a proton-coupled electron transfer (PCET) process. The redox potentials for these oxidations are lower than for other phenols, predominately from the driving force for proton movement. One-electron oxidation of the phenols occurs by a concerted proton-electron transfer (CPET) mechanism, based on thermochemical arguments, isotope effects, and DeltaDeltaG(++)/DeltaDeltaG degrees . The data rule out stepwise paths involving initial electron transfer to form the phenol radical cations [(*)(+)HOAr-B] or initial proton transfer to give the zwitterions [(-)OAr-BH(+)]. The rate constant for heterogeneous electron transfer from HOAr-NH(2) to a platinum electrode has been derived from electrochemical measurements. For oxidations of HOAr-NH(2), the dependence of the solution rate constants on driving force, on temperature, and on the nature of the oxidant, and the correspondence between the homogeneous and heterogeneous rate constants, are all consistent with the application of adiabatic Marcus theory. The CPET reorganization energies, lambda = 23-56 kcal mol(-)(1), are large in comparison with those for electron transfer reactions of aromatic compounds. The reactions are not highly non-adiabatic, based on minimum values of H(rp) derived from the temperature dependence of the rate constants. These are among the first detailed analyses of CPET reactions where the proton and electron move to different sites.     

Inside Back Cover: Integrated Soft Porosity and Electrical Properties of Conductive-on-Insulating Metal-Organic Framework Nanocrystals (Angew. Chem. Int. Ed. 35/2023)

A one-stone, two-bird method to integrate the soft porosity and electrical properties of distinct metal–organic frameworks (MOFs) into a single material involves the design of conductive-on-insulating MOF (cMOF-on-iMOF) heterostructures that allow for direct electrical control. Herein, we report the synthesis of cMOF-on-iMOF heterostructures using a seeded layer-by-layer method, in which the sorptive iMOF core is combined with chemiresistive cMOF shells. The resulting cMOF-on-iMOF heterostructures exhibit enhanced selective sorption of CO₂ compared to the pristine iMOF (298 K, 1 bar, S from 15.4 of ZIF-7 to 43.2–152.8). This enhancement is attributed to the porous interface formed by the hybridization of both frameworks at the molecular level. Furthermore, owing to the flexible structure of the iMOF core, the cMOF-on-iMOF heterostructures with semiconductive soft porous interfaces demonstrated high flexibility in sensing and electrical “shape memory” toward acetone and CO₂. This behavior was observed through the guest-induced structural changes of the iMOF core, as revealed by the operando synchrotron grazing incidence wide-angle X-ray scattering measurements.     

Porous Mn2+ Magnet with a Pt−Cl Framework: Correlation between Water Vapor Adsorption/Desorption and Slow Magnetic Relaxation

We report the water adsorption/desorption behavior and dynamic magnetic properties of the Pt−Cl chain complex [{[Pt(en)₂][PtCl₂(en)₂]}₃][{(MnCl₅)Cl₃}₂] ⋅ 12H₂O ( 1 ). Upon heating 1 in a vacuum, we obtained the dehydrated form [{[Pt(en)₂][PtCl₂(en)₂]}₃][{(MnCl₅)Cl₃}₂] ( 1DH ). The framework structures of 1 and 1DH are identical, and both complexes underwent slow magnetic relaxation. However, the magnetic relaxation times for 1DH were shorter than those for 1 , meaning that the dynamic magnetic properties were controlled upon water vapor adsorption/desorption. From detailed analyses of the dynamic magnetic behavior, a phonon-bottleneck effect contributes to the magnetic relaxation processes. We discuss the mechanism for the changes in the magnetic relaxation processes upon dehydration in terms of the heat capacity and thermal conductivity.     

Advancement of Electrochemical Thermoelectric Conversion with Molecular Technology

Thermocells are a thermoelectric conversion technology that utilizes the shift in an electrochemical equilibrium arising from a temperature difference. This technology has a long history; however, its low conversion efficiency impedes its practical usage. Recently, an increasing number of reports have shown drastic improvements in thermoelectric conversion efficiency, and thermocells could arguably represent an alternative to solid thermoelectric devices. In this Minireview, we regard thermocells as molecular systems consisting of successive molecular processes responding to a temperature change to achieve energy generation. Various molecular technologies have been applied to thermocells in recent years, and could stimulate diverse research fields, including supramolecular chemistry, physical chemistry, electrochemistry, and solid-state ionics. These research approaches will also provide novel methods for achieving a sustainable society in the future.