Compositionally Graded Organic–Inorganic Nanocomposites for Enhanced Thermoelectric Performance

AbstractThermoelectric generators (TEGs) operate in the presence of a temperature gradient, where the constituent thermoelectric (TE) material converts heat into electricity via the Seebeck effect. However, TE materials are characterized by a thermoelectric figure of merit (ZT) and/or power factor (PF), which often has a strong dependence on temperature. Thus, a single TE material spanning a given temperature range is unlikely to have an optimal ZT or PF across the entire range, leading to inefficient TEG performance. Compositionally graded organic–inorganic nanocomposites are demonstrated, where the composition of the TE nanocomposite can be systematically tuned along the length of the TEG, in order to optimize the PF along the applied temperature gradient. The nanocomposite composition is dynamically tuned by an aerosol‐jet printing method with controlled in situ mixing capability, thus enabling the realization of such compositionally graded thermoelectric composites (CG‐TECs). It is shown how CG‐TECs can be realized by varying the loading weight percentage of Bi2Te3 nanoparticles or Sb2Te3 nanoflakes within an organic conducting matrix using bespoke solution‐processable inks. The enhanced energy harvesting capability of these CG‐TECs from low‐grade waste heat (&lt;100 °C) is demonstrated, highlighting the improvement in output power over single‐component TEGs.</jats:p

L-2-hydroxyglutarate production arises from non-canonical enzyme function at acidic pH

The metabolite 2-hydroxyglutarate (2HG) can be produced as either a D(R)- or L(S)- enantiomer, each of which inhibits alpha-ketoglutarate (αKG)-dependent enzymes involved in diverse biologic processes. Oncogenic mutations in isocitrate dehydrogenase produce D-2HG, which causes a pathologic blockade in cell differentiation. On the other hand, oxygen limitation leads to accumulation of L-2HG, which can facilitate physiologic adaptation to hypoxic stress in both normal and malignant cells. Here we demonstrate that purified lactate dehydrogenase (LDH) and malate dehydrogenase (MDH) catalyze stereospecific production of L-2HG via ‘promiscuous’ reduction of the alternative substrate αKG. Acidic pH enhances production of L-2HG by promoting a protonated form of αKG that binds to a key residue in the substrate-binding pocket of LDHA. Acid-enhanced production of L-2HG leads to stabilization of hypoxia-inducible factor 1 alpha (HIF-1α) in normoxia. These findings offer insights into mechanisms whereby microenvironmental factors influence production of metabolites that alter cell fate and function

Thermophysical and Forced Convection Studies on (Alumina + Menthol)-Based Deep Eutectic Solvents for Their Use as a Heat Transfer Fluid

The current work reports the thermophysical and flow measurements of novel thermal solvents based on deep eutectic solvents (DESs) and alumina-based nanoparticle-dispersed deep eutectic solvents (NDDESs) for its use as a potential solar energy storage medium. The DESs were synthesized using a hydrogen bond donor (i.e., oleic acid) and a hydrogen bond acceptor (i.e., dl-menthol) by using the COSMO-SAC-predicted equimolar ratio at a temperature of 350.15 K. Thereafter, NDDESs or nanofluids were formed by dispersing different volume fractions (0.001, 0.005, 0.0075, and 0.01) of Al2O3 nanoparticles in the DESs. The optimum volume fraction (0.005) of Al2O3 nanoparticles was selected through their thermophysical properties (density, viscosity, thermal conductivity, and specific heat capacity) and its agglomeration or stability behavior. As expected, NDDESs with a 0.005 volume fraction gave a higher enhancement in thermal conductivity, viscosity, heat capacity, and density as compared to DESs. To evaluate the heat transfer coefficient, forced convection experiments were conducted in a circular test section for both DESs and NDDESs under laminar conditions (Re = 124, 186, and 250). The enhancement of the local heat transfer coefficient was found to be higher when compared to their thermophysical properties. This was due to the nanoparticle migration resulting in a non-uniform distribution of both thermal conductivity and viscosity fields, which was inherently found to reduce the thermal boundary layer thickness. In the final section, the heat transfer coefficient and the Nusselt number were also validated with COMSOL Multiphysics simulations

Reductive carboxylation supports redox homeostasis during anchorage-independent growth

Epithelial cells receive growth and survival stimuli through their attachment to an extracellular matrix (ECM)(1). Overcoming the addiction to ECM-induced signals is required for anchorage-independent growth, a property of most malignant cells(2). Detachment from ECM is associated with enhanced reactive oxygen species (ROS) due to altered glucose metabolism(2). Here we identify an unconventional pathway that supports redox homeostasis and growth during adaptation to anchorage independence. We observed that detachment from monolayer culture and growth as anchorage-independent tumor spheroids was accompanied by changes in both glucose and glutamine metabolism. Specifically, oxidation of both nutrients was suppressed in spheroids, whereas reductive formation of citrate from glutamine was enhanced. Reductive glutamine metabolism was highly dependent on cytosolic isocitrate dehydrogenase-1 (IDH1), because the activity was suppressed in cells homozygous null for IDH1 or treated with an IDH1 inhibitor. This activity occurred in absence of hypoxia, a well-known inducer of reductive metabolism. Rather, IDH1 mitigated mitochondrial ROS in spheroids, and suppressing IDH1 reduced spheroid growth through a mechanism requiring mitochondrial ROS. Isotope tracing revealed that in spheroids, isocitrate/citrate produced reductively in the cytosol could enter the mitochondria and participate in oxidative metabolism, including oxidation by IDH2. This generates NADPH in the mitochondria, enabling cells to mitigate mitochondrial ROS and maximize growth. Neither IDH1 nor IDH2 was necessary for monolayer growth, but deleting either one enhanced mitochondrial ROS and reduced spheroid size, as did deletion of the mitochondrial citrate transporter protein. Together, the data indicate that adaptation to anchorage independence requires a fundamental change in citrate metabolism, initiated by IDH1-dependent reductive carboxylation and culminating in suppression of mitochondrial ROS