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A green strategy for the synthesis of nonisocyanate polyester-urethanes (NIPHEUs) was developed. These NIPHEUs were synthesized by step growth polymerization combining sugar-derived dimethyl-2,5-furan dicarboxylate (DMFD) with polyhydroxylurethanes (PHUs) adducts bearing four hydroxyl groups. The later hydroxyl urethane tetraols (HU-tetraols) building blocks were prepared by aminolysis of glycerol carbonate with two different aliphatic diamines having different chain lengths, 8 and 12 carbons. Qualitative and quantitative NMR analyses of the HU-tetraols showed the presence of primary and secondary hydroxyl moieties at different ratios. Hence, in the polycondensation stage, the stoichiometry of the diester was varied from 1 to 6 equiv in order to tailor the structural features of the prepared NIPHEUs. The success of the chain extension through polycondensation was confirmed by FTIR and NMR analyses. Thermal analyses of these new polymers demonstrated satisfactory thermal stability, with onset degradation temperatures ranging from 170 to 220 °C where the main first degradation stage occurs. Their melting temperatures ranged between 93 and 110 °C and seem to be driven by the thermal behavior of HU-tetraol monomers. Surprisingly, preliminary results from thermal analyses revealed the occurrence of a striking thermal change in the NIPHEUs upon repetitive heating cycles. This behavior may be related to a thermal-induced bond exchange probably driven by transcarbamoylation reaction. Such interesting vitrimer-like behavior for this new type of NIPHEUs would be unique and should be confirmed by a deeper study before leading to a new range of functional green materials.A rigid chiral acyclic chelator H2CHXhox was synthesized and evaluated for Ga3+-based radiopharmaceutical applications; it was compared to the previously reported hexadentate H2hox to determine the effect of a backbone reinforced from adding a chiral 1S,2S-trans-cyclohexane on metal complex stability, kinetic inertness, and in vivo pharmacokinetics. NMR spectroscopy and theoretical calculation revealed that [Ga(CHXhox)]+ showed a very similar coordination geometry to that of [Ga(hox)]+, and only one isomer in solution was observed by NMR spectroscopy. Solution studies showed that the modification results in a significant improvement in the exceptionally high thermodynamic stability of [Ga(hox)]+ with a 1.56 log unit increase in stability constant (logKML = 35.91(1)). click here More importantly, H2CHXhox showed very fast Ga3+ complexation at physiological pH 7.4, and acid-assisted Ga3+ complex dissociation kinetic studies (pH 1) in comparison with H2hox revealed a 50-fold increase of the dissociation half-life time from 73 min to 58 h. Fluorescence microscopy imaging study confirmed its cellular uptake and accumulation in endoplasmic reticulum and mitochondria. MTT studies indicated a quite low cytotoxicity of [Ga(CHXhox)]+ over a large concentration range. Dynamic PET imaging studies showed no accumulation in muscle, lungs, bone, and brain, suggesting no release of free Ga3+ ions. [68Ga][Ga(CHXhox)]+ is cleared from the mouse via hepatobiliary and renal pathways. Compared to [68Ga][Ga(hox)]+, the increased lipophilicity of [68Ga][Ga(CHXhox)]+ enhanced heart and liver uptake and decreased kidney clearance. [67Ga][Ga(CHXhox)]+ SPECT/CT imaging and biodistribution study revealed good clearance from liver to gallbladder after 90 min and finally into feces after 5 h. No decomposition or transchelation was observed over the 5 h study. These results confirmed H2CHXhox to be an obvious improvement over H2hox and an excellent candidate in this new "ox" family for the development of radiopharmaceutical compounds.Molybdenum disulfide (MoS2) is traditionally grown at a high temperature and subsequently patterned to study its electronic properties or make devices. This method imposes severe limitations on the shape and size of MoS2 crystals that can be patterned precisely at required positions. Here, we describe a method of direct nanoscale patterning of MoS2 at room temperature by exposing a molybdenum thiocubane single-source precursor to a beam of electrons. Molybdenum thiocubanes with various alkylxanthate moieties [Mo4S4(ROCS2)6, where R = alkyl] were prepared using a "self-assembly" approach. Micro-Raman and micro-FTIR spectroscopic studies suggest that exposure to a relatively smaller dose of electrons results in the breakdown of xanthate moieties, leading to the formation of MoS2. High-resolution transmission electron micrographs suggest that the growth of MoS2 most likely happens along (100) planes. An electron-beam-induced chemical transformation of a molybdenum thiocubane resist was exploited to fabricate sub-10 nm MoS2 lines and dense dots as small as 13 nm with a pitch of 33 nm. Since this technique does not require the liftoff and etching steps, patterning of MoS2 with interesting shapes, sizes, and thicknesses potentially leading to tunable band gap is possible.Technological advances in wearable electronics have driven the necessity of a highly sensitive humidity sensor that can precisely detect physiological signals from the human body in real time. Herein, we introduce the anodic aluminum oxide (AAO)-assisted MoS2 honeycomb structure as a resistive humidity sensor with superior sensing performance. The unique honeycomb-like structure consists of MoS2 nanotubes, which can amplify the sensing performance because of their open pores and wider surface absorption sites. The formation of uniform MoS2 nanotubes inside the AAO membrane was manipulated by the number of vacuum filtration cycles of the (NH4)2MoS4 solution. The proposed humidity sensor exhibits an elevated sensitivity that is 2 orders of magnitudes higher than the MoS2 film-based humidity sensor at the relative humidity range of 20-85%. Moreover, the sensor showed significantly faster response and recovery times of 0.47 and 0.81 s. In addition, we demonstrate the multifunctional applications such as noncontact sensation of human fingertips, human breath, speech recognition, and regional sweat rate, which show its promising potential for the next-generation wearable sensors.
Website: https://www.selleckchem.com/products/protosappanin-b.html
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