Comparison of human blood serum DSC profiles in aqueous and PBS buffer solutions

Journal of Thermal Analysis and Calorimetry - The results of studies of physiological fluids by differential scanning calorimetry (DSC) for the purpose of diagnosis and monitoring of diseases are...     

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Modification of Polylactide Nonwovens with Carbon Nanotubes and Ladder Poly(silsesquioxane)

Electrospun nonwovens of poly(L-lactide) (PLLA) modified with multiwall carbon nanotubes (MWCNT) and linear ladder-like poly(silsesquioxane) with methoxycarbonyl side groups (LPSQ-COOMe) were obtained. MWCNT and LPSQ-COOMe were added to the polymer solution before the electrospinning. In addition, nonwovens of PLLA grafted to modified MWCNT were electrospun. All modified nonwovens exhibited higher tensile strength than the neat PLA nonwoven. The addition of 10 wt.% of LPSQ-COOMe and 0.1 wt.% of MWCNT to PLLA increased the tensile strength of the nonwovens 2.4 times, improving also the elongation at the maximum stress.     

Radical processes initiated by ionizing radiation in PEEK and their macroscopic consequences

Poly (ether ether ketone) was irradiated with gamma rays or electron beam to investigate the radical process. The generated paramagnetic species were observed by electron spin resonance spectroscopy at ambient temperature and in liquid nitrogen. The effect of microwave power on saturation of the particular spectra and thermal annealing effects were determined. The following radicals were identified: radical anion, phenoxyl radical, and phenylperoxy radical. Despite the fact that the intermediates were formed as a result of backbone cleavage causing degradation, the macroscopic features were almost unaffected by irradiation up to dose of 1500 kGy.     

Transformable H-bonds and conformation in compressed glucose

In response to external stimuli the α-d-glucose molecule extensively transforms its H-bonding pattern and conformation. High-pressure reverses the linear compressibility and changes the hierarchy of intermolecular interactions in crystalline α-d-glucose. At 5.40(2) GPa it undergoes an isostructural phase transition rearranging the OH···O hydrogen bonds, promoting the role of CH···O contacts and eliminating voids in the structure. Such monotonic and abrupt transformations may be characteristic of sugars and polysaccharides.     

Dicyclohexylammonium bromoacetate: a low molecular mass organogelator with a one‐dimensional secondary ammonium monocarboxylate (SAM) synthon

The asymmetric unit of the title salt, C₁₂H₂₄N⁺·C₂H₂BrO₂⁻, contains a dicyclohexylammonium cation connected to a bromoacetate anion by means of an N—H...O hydrogen bond. In the crystal, the ion pairs assemble via N—H...O interactions, forming zigzag infinite chains parallel to the c axis with the (...H—N—H...O—C—O...)_n motif that is considered to be a prerequisite for ensuring gelation properties of secondary ammonium monocarboxylate salts. The title salt was characterized by FT–IR, X‐ray powder diffraction (XRPD), TG–DTA and ¹H NMR spectroscopy in solution. Gelation experiments revealed that dicyclohexylammonium bromoacetate forms molecular gels with dimethylformamide and dimethyl sulfoxide. Scanning electron microscopy (SEM) was used to reveal morphological features of dried gels.     

Blood serum DSC analysis of well-trained men response to CrossFit training and green tea extract supplementation

Differential scanning calorimetry (DSC) has been used for the detection of post-exercise changes in blood serum resulting from participation in the CrossFit (CF) training combined with green tea extract (GTE) supplementation. Blood samples from 20 well-trained men were collected at rest, immediately post-exercise and after 1 h of recovery in two trials: first before and second after CF training combined with GTE or placebo administration in the supplemented (S) and control (C) groups, respectively. Selected muscle damage biomarkers have been compared in different phases of the experiment. A significant increase in blood lactate content has been observed post-exercise in both trials in both participants’ groups. The opposite trends have been noted for the C and S groups in creatine kinase (CK) activity changes recorded during the first to the second trial: an increase in CK for the control and a decrease for the supplemented group in all phases of the experiment: pre-exercise, post-exercise and after recovery. In the second trial, all CK values for the S group have been found significantly lower than the corresponding values recorded in the C group. These results suggest a mitigate effect of GTE supplementation on post-training muscle damage. DSC results did not reveal clear effects of training nor GTE supplementation on serum denaturation transition. However, interesting dependences of thermodynamic parameters describing this transition have been observed in different phases of the experiment. Statistically significant negative correlations have been found between post-training VO_2max and post-exercise thermodynamic parameters associated with haptoglobin contribution to serum denaturation transition.