Evaluation of the shadowgraph method for the determination of mutual and thermal diffusivities.

The present work provides a systematic study on the influence of sample properties and experimental conditions on the reliable accessibility of Fick or mutual diffusion coefficients D11 and thermal diffusivities a in binary liquid mixtures using the shadowgraph method. For this, mixtures with varying magnitudes of the Soret coefficient ST and their optical contrast factors were studied at a temperature of 298.15 K and pressures between (0.1 and 0.65) MPa with varying magnitudes and orientations of the applied temperature and concentration gradients ∇T and ∇c. Experimental signals obtained in these investigations were analyzed with respect to the intensities of the signal contributions from non-equilibrium fluctuations (NEFs) in concentration and temperature, and the reliability of the determined D11 and a data was assessed by comparison to literature data. Larger signal intensities from NEFs and, therefore, a more reliable determination of diffusivities were given for sufficiently large magnitudes of ST, the optical contrast factors, and the applied ∇T and ∇c. At very small fluid layer thicknesses L ≤ 0.30 mm, the associated reduction of signal statistics outweighing the expected increase of signal intensities at larger magnitudes of ∇T and ∇c as well as the influence of confinement imposed limitations for the determination of diffusivities in some cases. Furthermore, an influence of the mixture composition on signal intensities from concentration-NEFs was identified, where too small mole fractions of one component can hinder the determination of D11 in mixtures with small magnitudes of the optical contrast factor (∂n/∂c)T,p.

Etomidate-induced hypokalemia in electronic cigarette users: two case reports and literature review.

Hypokalemia is a common clinical condition that can lead to muscle weakness, difficulty breathing, malignant arrhythmias, and even death. This report describes two cases of severe hypokalemia resulting from the use of electronic cigarettes containing etomidate, both accompanied by varying degrees of adrenal hyperplasia. In both cases, the patients were admitted to the hospital with lower limb weakness and difficulty walking. Relevant examinations revealed low blood potassium, low cortisol, high adrenocorticotropic hormone, low renin, and low aldosterone levels in the patients, with Case 2 also having significant hypertension. In both cases, adrenal CT scans showed thickening of the adrenal glands. After the delivery of potassium supplementation in both cases, blood potassium levels gradually returned to normal and muscle strength gradually improved. The case reports are followed by a review of the literature on etomidate and its related mechanisms of action with discussion of its association with hypokalemia.

Predictive value of angiopoietin-like protein 8 in metabolic dysfunction-associated fatty liver disease and its progression: A case-control study.

BACKGROUND: The prevalence of metabolic dysfunction-associated fatty liver disease (MAFLD) is rapidly increasing, currently affecting approximately 25% of the global population. Liver fibrosis represents a crucial stage in the development of MAFLD, with advanced liver fibrosis elevating the risks of cirrhosis and hepatocellular carcinoma. Simple serum markers are less effective in diagnosing liver fibrosis compared to more complex markers. However, imaging techniques like transient elastography face limitations in clinical application due to equipment and technical constraints. Consequently, it is imperative to identify a straightforward yet effective method for assessing MAFLD-associated liver fibrosis. AIM: To investigate the predictive value of angiopoietin-like protein 8 (ANGPTL8) in MAFLD and its progression. METHODS: We analyzed 160 patients who underwent abdominal ultrasonography in the Endocrinology Department, Xiaogan Central Hospital affiliated to Wuhan University of Science and Technology, during September 2021-July 2022. Using abdominal ultrasonography and MAFLD diagnostic criteria, among the 160 patients, 80 patients (50%) were diagnosed with MAFLD. The MAFLD group was divided into the liver fibrosis group (n = 23) and non-liver fibrosis group (n = 57) by using a cut-off fibrosis-4 index ≥ 1.45. Logistical regression was used to analyze the risk of MAFLD and the risk factors for its progression. Receiver operating characteristic curves were used to evaluate the predictive value of serum ANGPTL8 in MAFLD and its progression. RESULTS: Compared with non-MAFLD patients, MAFLD patients had higher serum ANGPTL8 and triglyceride-glucose (TyG) index (both P < 0.05). Serum ANGPTL8 (r = 0.576, P < 0.001) and TyG index (r = 0.473, P < 0.001) were positively correlated with MAFLD. Serum ANGPTL8 was a risk factor for MAFLD [odds ratio (OR): 1.123, 95% confidence interval (CI): 1.066-1.184, P < 0.001). Serum ANGPTL8 and ANGPTL8 + TyG index predicted MAFLD [area under the curve (AUC): 0.832 and 0.886, respectively; both P < 0.05]. Compared with MAFLD patients without fibrosis, those with fibrosis had higher serum ANGPTL8 and TyG index (both P < 0.05), and both parameters were positively correlated with MAFLD-associated fibrosis. Elevated serum ANGPTL8 (OR: 1.093, 95%CI: 1.044-1.144, P < 0.001) and TyG index (OR: 2.383, 95%CI: 1.199-4.736, P < 0.013) were risk factors for MAFLD-associated fibrosis. Serum ANGPTL8 and ANGPTL8 + TyG index predicted MAFLD-associated fibrosis (AUC: 0.812 and 0.835, respectively; both P < 0.05). CONCLUSION: The serum levels of ANGPTL8 are elevated and positively correlated with MAFLD. They can serve as predictors for the risk of MAFLD and liver fibrosis, with the ANGPTL8 + TyG index potentially exhibiting even higher predictive value.

Modulating the Coordination Environment of Carbon-Dot-Supported Fe Single-Atom Nanozymes for Enhanced Tumor Therapy.

Herein, carbon dot (CD)-supported Fe single-atom nanozymes with high content of pyrrolic N and ultrasmall size (ph-CDs-Fe SAzyme) are fabricated by a phenanthroline-mediated ligand-assisted strategy. Compared with phenanthroline-free nanozymes (CDs-Fe SAzyme), ph-CDs-Fe SAzyme exhibit higher peroxidase (POD)-like activity due to their structure similar to that of ferriporphyrin in natural POD. Aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analyses show that metal Fe is dispersed in ph-CDs-Fe SAzyme as single atoms. Steady-state kinetic studies show that the maximum velocity (Vmax ) and turnover number (kcat ) of H2 O2  homolytic cleavage catalyzed by ph-CDs-Fe SAzyme are 3.0 and 6.2 more than those of the reaction catalyzed by CDs-Fe SAzyme. Density functional theory (DFT) calculations show that the energy barrier of the reaction catalyzed by ph-CDs-Fe SAzyme is lower than that catalyzed by CDs-Fe SAzyme. Antitumor efficacy experiments show that ph-CDs-Fe SAzyme can efficiently inhibit the growth of tumor cells both in vitro and in vivo by synergistic chemodynamic and photothermal effects. Here a new paradigm is provided for the development of efficient antitumor therapeutic approaches based on SAzyme with POD-like activity.

Selenophene Substitution Enabled High-Performance n-Type Polymeric Mixed Ionic-Electronic Conductors for Organic Electrochemical Transistors and Glucose Sensors.

High-performance n-type polymeric mixed ionic-electronic conductors (PMIECs) are essential for realizing organic electrochemical transistors (OECTs)-based low-power complementary circuits and biosensors, but their development still remains a great challenge. Herein, by devising two novel n-type polymers (f-BTI2g-SVSCN and f-BSeI2g-SVSCN) containing varying selenophene contents together with their thiophene-based counterpart as the control, it is demonstrated that gradually increasing selenophene loading in polymer backbones can simultaneously yield lowered lowest unoccupied molecular orbital levels, boosted charge-transport properties, and improved ion-uptake capabilities. Therefore, a remarkable volumetric capacitance (C*) of 387.2 F cm-3 and a state-of-the-art OECT electron mobility (µe,OECT ) of 0.48 cm2 V-1 s-1 are synchronously achieved for f-BSeI2g-SVSCN having the highest selenophene content, yielding an unprecedented geometry-normalized transconductance (gm,norm ) of 71.4 S cm-1 and record figure of merit (µC*) value of 191.2 F cm-1 V-1 s-1 for n-type OECTs. Thanks to such excellent performance of f-BSeI2g-SVSCN-based OECTs, a glucose sensor with a remarkably low detection limit of 10 nMm and decent selectivity is further implemented, demonstrating the power of selenophene substitution strategy in enabling high-performance n-type PMIECs for biosensing applications.

Multi-Selenophene Incorporated Thiazole Imide-Based n-Type Polymers for High-Performance Organic Thermoelectrics.

Developing polymers with high electrical conductivity (σ) after n-doping is a great challenge for the advance of the field of organic thermoelectrics (OTEs). Herein, we report a series of thiazole imide-based n-type polymers by gradually increasing selenophene content in polymeric backbone. Thanks to the strong intramolecular noncovalent N⋅⋅⋅S interaction and enhanced intermolecular Se⋅⋅⋅Se interaction, with the increase of selenophene content, the polymers show gradually lowered LUMOs, more planar backbone, and improved film crystallinity versus the selenophene-free analogue. Consequently, polymer PDTzSI-Se with the highest selenophene content achieves a champion σ of 164.0 S cm-1 and a power factor of 49.0 µW m-1 K-2 in the series when applied in OTEs after n-doping. The σ value is the highest one for n-type donor-acceptor OTE materials reported to date. Our work indicates that selenophene substitution is a powerful strategy for developing high-performance n-type OTE materials and selenophene incorporated thiazole imides offer an excellent platform in enabling n-type polymers with high backbone coplanarity, deep-lying LUMO and enhanced mobility/conductivity.

Heterodyne dynamic light scattering for the characterization of particle dispersions.

Particle self-diffusivities in unimodal and bimodal aqueous dispersions are characterized by dynamic light scattering (DLS) applying a heterodyne detection scheme. For unimodal dispersions close to infinite dilution, it could be evidenced that pure homodyne conditions cannot be realized, leading to an increasing underestimation of diffusivity with a decreasing concentration. Even for bimodal dispersions and neglecting any local oscillator field, the coherent superposition of scattered light from different particle species hinders a clear assignment of the measured signals and their evaluation for diffusivity. In this case, the impact of a cross term on the determined diffusivities cannot be neglected. The results emphasize that the use of a heterodyne detection scheme in DLS experiments is a key aspect for an accurate determination of particle diffusivities in low-concentrated unimodal and bimodal dispersions.

Diffusion of gold nanoparticles in porous silica monoliths determined by dynamic light scattering.

HYPOTHESIS: The applicability of the dynamic light scattering method for the determination of particle diffusivity under confinement without applying refractive index matching was not adequately explored so far. The confinement effect on particle diffusion in a porous material which is relevant for particle chromatography has also not yet been fully characterized. EXPERIMENTS: Dynamic light scattering experiments were performed for unimodal dispersions of 11-mercaptoundecanoic acid-capped gold nanoparticles. Diffusion coefficients of gold nanoparticles in porous silica monoliths were determined without limiting refractive index matching fluids. Comparative experiments were also performed with the same nanoparticles and porous silica monolith but applying refractive index matching. FINDINGS: Two distinct diffusivities could be determined inside the porous silica monolith, both smaller than that in free media, showing a slowing-down of the diffusion processes of nanoparticles under confinement. While the larger diffusivity can be related to the slightly slowed-down diffusion of particles in the bulk of the pores and in the necks connecting individual pores, the smaller diffusivity might be related to the diffusion of particles near the pore walls. It shows that the dynamic light scattering method with a heterodyne detection scheme can be used as a reliable and competitive tool for determining particle diffusion under confinement.

Study on the thermal decomposition mechanism of Mg(NO3)2·6H2O from the perspective of resource utilization of magnesium slag.

The magnesium slag (magnesium nitrate hydrate Mg(NO3)2·6H2O) produced in the nitric acid leaching process of laterite nickel ore can be effectively recycled by thermal decomposition. To this end, this study placed great emphasis on disclosing the thermal decomposition mechanism of Mg(NO3)2·6H2O. Firstly, thermal decomposition paths of Mg(NO3)2·6H2O were revealed through Thermogravimetry-Mass Spectrometry, Differential Scanning Calorimetry and powder X-ray diffraction. It was found that the thermal decomposition of Mg(NO3)2·6H2O was a multistep endothermic reaction involving two dehydration stages and one denitration stage. The two dehydration stages were characterized by the evolution of H2O, with the formation of magnesium nitrate dihydrate and anhydrous magnesium nitrate. The denitration stage was characterized by the simultaneous evolution of O2 and NO2, with the formation of MgO. The conventional kinetic analysis was not suitable for describing such complex multistep reaction behaviour. Thus, the kinetic rate data (dα/dt-T) for the overall reaction were separated into those for three contributing stages by mathematical peak deconvolution. Then, the complete kinetic interpretations of the separated reaction stages for Mg(NO3)2·6H2O pyrolysis were achieved by the Friedman method and the master plots method. Finally, the original experimental α-T curves were successfully simulated using the resulting kinetic triplets.

Cyano-Functionalized n-Type Polymer with High Electron Mobility for High-Performance Organic Electrochemical Transistors.

n-Type organic mixed ionic-electronic conductors (OMIECs) with high electron mobility are scarce and highly challenging to develop. As a result, the figure-of-merit (µC*) of n-type organic electrochemical transistors (OECTs) lags far behind the p-type analogs, restraining the development of OECT-based low-power complementary circuits and biosensors. Here, two n-type donor-acceptor (D-A) polymers based on fused bithiophene imide dimer f-BTI2 as the acceptor unit and thienylene-vinylene-thienylene (TVT) as the donor co-unit are reported. The cyanation of TVT enables polymer f-BTI2g-TVTCN with simultaneously enhanced ion-uptake ability, film structural order, and charge-transport property. As a result, it is able to obtain a high volumetric capacitance (C*) of 170 ± 22 F cm-3 and a record OECT electron mobility (µe,OECT ) of 0.24 cm2 V-1 s-1 for f-BTI2g-TVTCN, subsequently achieving a state-of-the-art µC* of 41.3 F cm-1 V-1 s-1 and geometry-normalized transconductance (gm,norm ) of 12.8 S cm-1 in n-type accumulation-mode OECTs. In contrast, only a moderate µC* of 1.50 F cm-1 V-1 s-1 is measured for the non-cyanated polymer f-BTI2g-TVT. These remarkable results demonstrate the great power of cyano functionalization of polymer semiconductors in developing n-type OMIECs with substantial electron mobility in aqueous environment for high-performance n-type OECTs.

A Nanosensor Based on a Metal-Insulator-Metal Bus Waveguide with a Stub Coupled with a Racetrack Ring Resonator.

A nanostructure comprising the metal-insulator-metal (MIM) bus waveguide with a stub coupled with a racetrack ring resonator is designed. The spectral characteristics of the proposed structure are analyzed via the finite element method (FEM). The results show that there is a sharp Fano resonance profile and electromagnetically induced transparency (EIT)-like effect, which are excited by a coupling between the MIM bus waveguide with a stub and the racetrack ring resonator. The normalized HZ field is affected by the displacement of the ring from the stub x greatly. The influence of the geometric parameters of the sensor design on the sensing performance is discussed. The sensitivity of the proposed structure can reach 1774 nm/RIU with a figure of merit of 61. The proposed structure has potential in nanophotonic sensing applications.

Mutual and Thermal Diffusivities as well as Fluid-Phase Equilibria of Mixtures of 1-Hexanol and Carbon Dioxide.

This work contributes to an improved understanding of the fluid-phase behavior and diffusion processes in mixtures of 1-hexanol and carbon dioxide (CO2) at temperatures around the upper critical end point (UCEP) of the system. Raman spectroscopy and dynamic light scattering were used to determine the composition at saturation conditions as well as Fick and thermal diffusivities. An acceleration of the Fick diffusive process up to CO2 mole fractions of about 0.2 was found, followed by a strong slowing-down approaching vapor-liquid-liquid equilibrium or critical conditions. The acceleration of the Fick diffusive process vanished at temperatures much higher than the UCEP. Experimental Fick diffusivity data were compared with predictions from equilibrium molecular dynamics simulations and excess Gibbs energy calculations using interaction parameters from the literature. Both theoretical methods were not able to predict that the thermodynamic factor is equal to zero at the spinodal composition, stressing the need for new methodologies under such conditions. Thus, new sets of temperature-dependent interaction parameters were developed for the nonrandom two-liquid model, which improve the prediction of the Fick diffusion coefficient considerably. The link between the Fick diffusion coefficient and the nonrandomness of the liquid phases is also discussed.

Diffusivities in 1-Alcohols Containing Dissolved H2, He, N2, CO, or CO2 Close to Infinite Dilution.

The influence of the strength of intermolecular interactions on mass diffusive processes remains poorly understood for mixtures of associative liquids with dissolved gases. For contributing to a fundamental understanding of the interplay between liquid structures and mass diffusivities in such systems, dynamic light scattering, Raman spectroscopy, and molecular dynamics simulations were used in this work. As model systems, binary mixtures consisting of the gases hydrogen, helium, nitrogen, carbon monoxide, or carbon dioxide dissolved in ethanol, 1-hexanol, or 1-decanol were selected. Experiments and simulations were performed at macroscopic thermodynamic equilibrium close to infinite dilution of solute for temperatures between 303 and 423 K. The Fick diffusion coefficients and self-diffusivities of the gas solutes increase with increasing temperature, decreasing alkyl chain length of the 1-alcohols, and decreasing molar mass of the solutes except for helium and hydrogen showing the opposite behavior. The analysis of the liquid structure of the mixtures showed that the fraction of hydrogen-bonded alcohol molecules decreases with increasing alkyl chain length and temperature. From the obtained structure-property relationships, a new correlation was developed to predict mass diffusivities in binary mixtures consisting of n-alkanes or 1-alcohols with dissolved gases close to infinite dilution within 10% on average.

Influence of Liquid Structure on Fickian Diffusion in Binary Mixtures of n-Hexane and Carbon Dioxide Probed by Dynamic Light Scattering, Raman Spectroscopy, and Molecular Dynamics Simulations.

This study contributes to a fundamental understanding of how the liquid structure in a model system consisting of weakly associative n-hexane ( n-C6H14) and carbon dioxide (CO2) influences the Fickian diffusion process. For this, the benefits of light scattering experiments and molecular dynamics (MD) simulations at macroscopic thermodynamic equilibrium were combined synergistically. Our reference Fickian diffusivities measured by dynamic light scattering (DLS) revealed an unusual trend with increasing CO2 mole fractions up to about 70 mol %, which agrees with our simulation results. The molecular impacts on the Fickian diffusion were analyzed by MD simulations, where kinetic contributions related to the Maxwell-Stefan (MS) diffusivity and structural contributions quantified by the thermodynamic factor were studied separately. Both the MS diffusivity and the thermodynamic factor indicate the deceleration of Fickian diffusion compared to an ideal mixture behavior. Computed radial distribution functions as well as a significant blue-shift of the CH stretching modes of n-C6H14 identified by Raman spectroscopy show that the slowing down of the diffusion is caused by a structural organization in the binary mixtures over a broad concentration range in the form of self-associated n-C6H14 and CO2 domains. These networks start to form close to the infinite dilution limits and seem to have their largest extent at a solute-solvent transition point at about 70 mol % CO2. The current results not only improve the general understanding of mass diffusion in liquids but also serve to develop sound prediction models for Fick diffusivities.

Enhanced thermoelectric performance of a chalcopyrite compound CuIn3Se5-xTex (x = 0~0.5) through crystal structure engineering.

In this work the chalcopyrite CuIn3Se5-xTex (x = 0~0.5) with space group through isoelectronic substitution of Te for Se have been prepared, and the crystal structure dilation has been observed with increasing Te content. This substitution allows the anion position displacement ∆u = 0.25-u to be zero at x ≈ 0.15. However, the material at x = 0.1 (∆u = 0.15 × 10-3), which is the critical Te content, presents the best thermoelectric (TE) performance with dimensionless figure of merit ZT = 0.4 at 930 K. As x value increases from 0.1, the quality factor B, which informs about how large a ZT can be expected for any given material, decreases, and the TE performance degrades gradually due to the reduction in nH and enhancement in κL. Combining with the ZTs from several chalcopyrite compounds, it is believable that the best thermoelectric performance can be achieved at a certain ∆u value (∆u ≠ 0) for a specific space group if their crystal structures can be engineered.

Engineering Band Structure via the Site Preference of Pb(2+) in the In(+) Site for Enhanced Thermoelectric Performance of In6Se7.

Although binary In-Se based alloys have in recent years gained interest as thermoelectric (TE) candidates, little attention has been paid to In6Se7-based compounds. Substituting Pb in In6Se7, preference for Pb(2+) in the In(+) site has been observed, allowing Fermi level (Fr) shift toward the conduction band, where the localized state conduction becomes dominant. Consequently, the Hall carrier concentration (nH) has been significantly enhanced with the highest nH value being about 2-3 orders of magnitude higher than that of the Pb-free sample. Meanwhile, the lattice thermal conductivity (κL) tends to be reduced as the nH value increases, owing to an increased phonon scattering on carriers. As a result, a significantly enhanced TE performance has been achieved with the highest TE figure of merit (ZT) of 0.4 at ∼850 K. This ZT value is 27 times that of intrinsic In6Se7 (ZT = 0.015 at 640 K), which proves a successful band structure engineering through site preference of Pb in In6Se7.