Employing neural density functionals to generate potential energy surfaces.

CONTEXT: With the union of machine learning (ML) and quantum chemistry, amid the debate between machine-learned functionals and human-designed functionals in density functional theory (DFT), this paper aims to demonstrate the generation of potential energy surfaces using computations with machine-learned density functional approximation (ML-DFA). A recent research trend is the application of ML in quantum sciences in the design of density functionals such as DeepMind's Deep Learning model (DeepMind21, DM21). Though science reported the state-of-the-art performance of DM21, the opportunity to utilize DeepMind's pretrained DM21 neural networks in computations in quantum chemistry has not yet been tapped. So far in the literature, the Deep Learning density functionals (DM21) have not been applied to generate potential energy surfaces. While the superior accuracy of DM21 has been reported, there is still a scarcity of publications that apply DM21 in calculations in the field. In this context, for the first time in literature, neural density functionals inferring 2D potential energy surfaces (ML-DFA-PES) based on machine-learned DFA-based computational method is contributed in this paper. This paper reports the ML-DFA-generated PES for C4H8, H2O, H2, and H2+ by employing a pretrained DM21m TensorFlow model with cc-pVDZ basis set. In addition, we also analyze the long-range behavior of DM21 based PES to investigate the ability to describe a system at long ranges. Furthermore, we compare PES diagrams from DM21 with popular DFT functionals (b3lyp/ PW6B95) and CCSD(T). METHODS: In this method, 2D potential energy surfaces are obtained using a method that relies upon the neural network's ability to accurately learn the mapping between 3D electron density and exchange-correlation potential. By inserting Deep Learning inference in DFT with a pretrained neural network, self-consistent field (SCF) energy at different geometries along the coordinates of interest is computed, and then, potential energy surfaces are plotted. In this method, first, the electron density is computed mathematically, and this computed 3D electron density is used as a ML feature vector to predict the exchange correlation potential as a ML inference computed by a forward pass of pre-trained DM21 TensorFlow computational graph, followed by the computation of self-consistent field energy at multiple geometries, and then, SCF energies at different bond lengths/angles are plotted as 2D PES. We implement this in a python source code using frameworks such as PySCF and DM21. This paper contributes this implementation in open source. The source code and DM21-DFA-based PES are contributed at https://sites.google.com/view/MLfunctionals-DeepMind-PES .

Simple sonochemical synthesis of novel grass-like vanadium disulfide: A viable non-enzymatic electrochemical sensor for the detection of hydrogen peroxide.

Design and fabrication of novel inorganic nanomaterials for the low-level detection of food preservative chemicals significant is of interest to the researchers. In the present work, we have developed a novel grass-like vanadium disulfide (GL-VS2) through a simple sonochemical method without surfactants or templates. As-prepared VS2 was used as an electrocatalyst for reduction of hydrogen peroxide (H2O2). The crystalline nature, surface morphology, elemental compositions and binding energy of the as-prepared VS2 were analyzed by X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The electrochemical studies show that the GL-VS2 modified glassy carbon electrode (GL-VS2/GCE) has a superior electrocatalytic activity and lower-reduction potential than the response observed for unmodified GCE. Furthermore, the GL-VS2/GCE displayed a wide linear response range (0.1-260 µM), high sensitivity (0.23 µA µM-1 cm-2), lower detection limit (26 nM) and excellent selectivity for detection of H2O2. The fabricated GL-VS2/GCE showed excellent practical ability for detection of H2O2 in milk and urine samples, revealing the real-time practical applicability of the sensor in food contaminants.

The design of novel visible light driven Ag/CdO as smart nanocomposite for photodegradation of different dye contaminants.

In this paper, we report a novel visible light driven Ag/CdO photocatalyst, fabricated for the first time via one pot hydrothermal method and further applied for the photodegradation of two important exemplar water contaminants, Malachite green and Acid Orange 7. The microstructure, composition and optical properties of Ag/CdO nanocomposites were thoroughly investigated by various techniques. Scanning electron microscopy clearly shows that Ag NPs were strongly embedded between the CdO nanoparticles. Among the series of synthesized Ag/CdO nanocomposites, (5%) Ag/CdO nanocomposite possesses enhanced photocatalytic activity. This result was attributed to the synergistic effect between Ag and CdO, and mainly Ag NPs can act as an electron trap site, which could reduce the recombination of the electron-hole and induce the visible light absorption. The active species trapping experiments implicate OH and O2- radicals as the respective primary and secondary reactive species responsible for oxidative photodegradation of organic pollutants. On the basis of the results, a possible photocatalytic mechanism has also been proposed.

A selective electrochemical sensor for caffeic acid and photocatalyst for metronidazole drug pollutant - A dual role by rod-like SrV2O6.

In the present study, well-defined one-dimensional (1D) rod-like strontium vanadate (SrV2O6) was prepared by simple hydrothermal method without using any other surfactants/templates. The successful formation of rod-like SrV2O6 was confirmed by various analytical and spectroscopic techniques. Interestingly, for the first time the dual role of as-prepared rod-like SrV2O6 were employed as an electrochemical sensor for the detection of caffeic acid (CA) as well as visible light active photocatalyst for the degradation of metronidazole (MNZ) antibiotic drug. As an electrochemical sensor, the SrV2O6 modified glassy carbon electrode (GCE) demonstrated a superior electrocatalytic activity for the detection of CA by chronoamperometry and cyclic voltammetry (CVs). In addition, the electrochemical sensor exhibited a good current response for CA with excellent selectivity, wide linear response range, lower detection limit and sensitivity of 0.01-207 µM, 4 nM and 2.064 µA µM-1cm-2, respectively. On the other hand, as-synthesized rod-like SrV2O6 showed highly efficient and versatile photocatalytic performances for the degradation of MNZ, which degrades above 98% of MNZ solution under visible light irradiation within 60 min. The obtained results evidenced that the improvement of rod-like SrV2O6 might be a resourceful electrocatalyst and photocatalyst material in the probable applications of environmental and biomedical applications.

Construction of novel Pd/CeO2/g-C3N4 nanocomposites as efficient visible-light photocatalysts for hexavalent chromium detoxification.

In this study, we report a series of novel palladium nanoparticles (Pd) supported cerium oxide (CeO2)/graphitic carbon nitride (g-C3N4) nanocomposites, fabricated via the simple strategy, which were used for the detoxification of toxic hexavalent chromium to benign trivalent chromium under visible light irradiation. The synthesized Pd/CeO2/g-C3N4 nanocomposites were characterized by various tools including powder X-ray diffraction (PXRD), fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (DRS/UV-vis), high resolution transmission electron microscopy (HRTEM), and energy dispersive X-ray spectra (EDS). The wrapping with surface of graphitic carbon nitride nanosheets can efficiently promote the interface charge separation and transmission over the ternary photocatalyst, which was studied by photoluminescence spectra (PL) analysis and electrochemical impedance spectroscopy (EIS) spectra. The obtained 3% Pd/CeO2/g-C3N4 nanocomposite photocatalyst exhibit an excellent photocatalytic performance when compared to other single and composite counter parts. The 3% Pd/CeO2/g-C3N4 exhibits a strong synergistic effect which arises due to the interactions between palladium nanoparticles, CeO2 and graphitic carbon nitride resulting in the lower recombination of photo-induced charge carriers with enhanced photocatalytic activity. This work implies that the synergistic Pd/CeO2/g-C3N4 nanocomposites would be a new kind of high-efficiency visible-light-driven photocatalysts materials for the detoxification of public safety and security.

Evaluation of a new electrochemical sensor for selective detection of non-enzymatic hydrogen peroxide based on hierarchical nanostructures of zirconium molybdate.

The construction and characterization of selective and sensitive non-enzymatic hydrogen peroxide (H2O2) electrochemical sensor based on sphere-like zirconium molybdate (ZrMo2O8) nanostructure are reported for the first time. The sphere-like ZrMo2O8 were prepared via a simple hydrothermal route followed by annealing process. The structural and morphological properties were investigated by various analytical and spectroscopic techniques such as XRD, Raman, SEM, EDX, TEM, and XPS analysis. Furthermore, the electrochemical properties were investigated by cyclic voltammetry and amperometric techniques. The obtained results displayed that the prepared ZrMo2O8 materials hold excellent-crystallinity, well-defined sphere-like formation and demonstrated superior electrochemical properties. Interestingly, the electrochemical H2O2 sensor was constructed based on ZrMo2O8 nanostructure on the glassy carbon electrode exhibited wide linear response ranges, good sensitivity and lower detection limit (LOD). The estimated sensitivity, wide linear ranges and LOD of the fabricated electrochemical sensor was 2.584µAµM-1cm-2, 0.05-523, 543-3053µM and 0.01µM respectively. The proposed sensor had excellent selectivity even in the presence of biologically co-interfering substances such as uric acid, dopamine, ascorbic acid and glucose. This effortless, fast, inexpensive technique for constructing a modified electrode is a gorgeous approach to the growth of new sensors.

Green synthesis of a novel flower-like cerium vanadate microstructure for electrochemical detection of tryptophan in food and biological samples.

In this present investigation, we introduced a novel electrochemical sensor for the detection of tryptophan (TRP) based on green pompoms flower-like cerium vanadate (CeVO4). The flower-like CeVO4 microstructure was prepared by the simple hydrothermal treatment with the assistance of urea for the first time. The as-prepared flower-like CeVO4 microstructure was characterized by various analytical and spectroscopic techniques such as X-ray diffraction, Raman spectroscopy fourier transform infrared spectroscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy studies. The electrochemical properties are evaluated by the cyclic voltammetry (CV) and differential pulse voltammetry (DPV). As an electrochemical sensor, the green pompoms flower-like CeVO4 modified glassy carbon electrode (GCE) displayed an excellent electrocatalytic activity for the detection of TRP. The obtained electrochemical results revealed that the oxidation of TRP, exhibited a lower potential and higher anodic peak current when compared to unmodified GCE. These results were suggested that the flower-like CeVO4/GCE have a good electrocatalytic activity towards the TRP oxidation. The flower-like CeVO4 sensor exhibited the wide linear concentration range and low detection limit of 0.1-94µM and 0.024µM respectively. Finally, the proposed sensor was successfully applied to the determination of TRP in real sample analysis such as food and biological samples with satisfied recoveries.

A highly sensitive and selective electrochemical determination of non-steroidal prostate anti-cancer drug nilutamide based on f-MWCNT in tablet and human blood serum sample.

A novel electrochemical sensor based on the functionalized multiwalled carbon nanotube (f-MWCNT) was successfully developed for the sensitive and selective determination of non-steroidal prostate anti-cancer drug nilutamide in tablet and blood serum samples. The f-MWCNT was prepared by the simple reflux method and characterized by the scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, X-ray powder diffraction (XRD) and fourier transform infrared spectroscopy (FT-IR). Interestingly, the f-MWCNT was exhibited a superior electrocatalytic activity towards the anti-cancer drug nilutamide when compared with pristine MWCNT and unmodified electrodes. Besides, the electrochemical sensor was revealed an excellent current response for the determination of nilutamide with wide linear ranges (0.01-21µM and 28-535µM), high sensitivity (11.023 and 1.412µA µM-1cm2) and very low detection limit (LOD) 0.2nM. The developed electrochemical sensor was showed an excellent selectivity even in the presence of electrochemically active biological substances and nitro aromatic compounds. Moreover, it manifested a good reproducibility and stability. In addition, the f-MWCNT modified glassy carbon electrode (GCE) sensor was successfully applied for the detection of nilutamide in tablet and blood serum sample.

Fabrication of potato-like silver molybdate microstructures for photocatalytic degradation of chronic toxicity ciprofloxacin and highly selective electrochemical detection of H2O2.

In the present work, potato-like silver molybdate (Ag2MoO4) microstructures were synthesized through a simple hydrothermal method. The microstructures of Ag2MoO4 were characterized by various analytical and spectroscopic techniques such as XRD, FTIR, Raman, SEM, EDX and XPS. Interestingly, the as-prepared Ag2MoO4 showed excellent photocatalytic and electrocatalytic activity for the degradation of ciprofloxacin (CIP) and electrochemical detection of hydrogen peroxide (H2O2), respectively. The ultraviolet-visible (UV-Vis) spectroscopy results revealed that the potato-like Ag2MoO4 microstructures could offer a high photocatalytic activity towards the degradation of CIP under UV-light illumination, leads to rapid degradation within 40 min with a degradation rate of above 98%. In addition, the cyclic voltammetry (CV) and amperometry studies were realized that the electrochemical performance of Ag2MoO4 modified electrode toward H2O2 detection. Our H2O2 sensor shows a wide linear range and lower detection limit of 0.04-240 µM and 0.03 µM, respectively. The Ag2MoO4 modified electrode exhibits a high selectivity towards the detection of H2O2 in the presence of different biological interferences. These results suggested that the development of potato-like Ag2MoO4 microstructure could be an efficient photocatalyst as well as electrocatalyst in the potential application of environmental, biomedical and pharmaceutical samples.