Publications in the Year: 2020

Book Chapter

Veerakumar, P., DLNK-C.  2020.  Computational and experimental analysis of carbon functional nanomaterials. Abstract

Density functional theory (DFT) as one of molecular simulation techniques has been widely used to become rapidly a powerful tool for research and technology development for the past three decades. In particular, the DFT-based theoretical and fundamental knowledge have shed light on our understanding of the fundamental surface science, catalysis, sensors, materials science, and biology. Oxygen, nitrogen, boron, phosphorus, and sulfur are the most common heteroatoms introduced on the functional carbon nanomaterials surface with different surface functionalities. This book chapter aims to provide a pedagogical narrative of the DFT and relevant computational methods applied for surface chemistry, homogeneous/heterogeneous catalysis, and the fluorescence-based sensing properties of carbon nanomaterials. We overview several representative case studies associated with energy and chemicals production and discuss relevant principles of computationally driven carbon nanomaterials design.

Journal Article

Tso, C.-J., KLTK-C.  2020.  Roaming Dynamics and Conformational Memory in Photolysis of Formic Acid at 193 nm Using Time-resolved Fourier-transform Infrared Emission Spectroscopy. AbstractWebsite

In photodissociation of trans-formic acid (HCOOH) at 193 nm, we have observed two molecular channels of CO + H2O and CO2 + H2 by using 1 μs-resolved Fourier-transform infrared emission spectroscopy. With the aid of spectral simulation, the CO spectra are rotationally resolved for each vibrational state (v = 1–8). Each of the resulting vibrational and rotational population distributions is characteristic of two Boltzmann profiles with different temperatures, originating from either transition state pathway or OH-roaming to form the same CO + H2O products. The H2O roaming co-product is also spectrally simulated to understand the interplay with the CO product in the internal energy partitioning. Accordingly, this work has evaluated the internal energy disposal for the CO and H2O roaming products; especially the vibrational-state dependence of the roaming signature is reported for the first time. Further, given a 1 μs resolution, the temporal dependence of the CO/CO2 product ratio at v ≥ 1 rises from 3 to 10 of study, thereby characterizing the effect of conformational memory and well reconciling with the disputed results reported previously between absorption and emission methods. © 2020, The Author(s).

Veerakumar, P., MRGJLTBGS.  2020.  Paper flower-derived porous carbons with high-capacitance by chemical and physical activation for sustainable applications. AbstractWebsite

Porous carbon nanosheets were prepared by the carbonization of paper flower via chemical and physical activation. The structural properties of the as-prepared carbons were characterized using the techniques, such as X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), Raman spectroscopy, N2 sorption isotherms and X-ray photoelectron spectroscopy (XPS), while the related morphological analyses were conducted using scanning/transmission electron microscopy (SEM/TEM). The obtained carbons exhibit a high specific surface area up to 1801 m2 g−1 with a robust porous graphitic carbon layer structure, which provides the merits for potential application in energy storage and dye removal. We carried out potentiostatic and galvanostatic measurements using a three-electrode cell in 1.0 M H2SO4 aqueous electrolyte and achieved a specific capacitance of 118, 109.5, 101.7, 93.6, and 91.2 F g−1 at 1, 2, 4, 8 and 12 A g−1, respectively. The stability at 12 A g−1 was tested to reach 10,000 cycles with capacity retention of around 97.4%. We have demonstrated that the paper flower-derived carbons at activation temperature 800 °C (PFC-800) can be used as a promising electrode material in supercapacitor. PFC-800 can also serve as an efficient sunset yellow dye removal, showing the maximum adsorption capacity for sunset yellow (Q0, 273.6 mg g−1). © 2018 King Saud University

Lin, C.-H., WCLLKCSMSML-XK-.  2020.  Non-invasive and time-dependent blood-sugar monitoring via breath-derived CO2 correlation using gas chromatograph with a milli-whistle gas analyze. AbstractWebsite

A clear and positive correlation between the CO2 concentration and the blood-sugar level has been observed via a noninvasive and time-dependent monitoring of CO2 concentration from human breath, which is carried out by using a homemade gas chromatography (GC)/milli-whistle compact analyzer. The time-dependent sampling of the CO2 concentration correlated between 5.0 to 5.6% (1% = 104 ppm) in accordance with blood-sugar level variations of 80 to 110 mg/dL. The analytical method results in a rapid, continuous and non-invasive determination of blood-sugar level via measurement of the CO2 concentration exhaled from the lungs.

Veerakumar, P., MCPLSS-M.  2020.  Ultrafine Bi-Sn nanoparticles decorated on carbon aerogels for electrochemical simultaneous determination of dopamine (neurotransmitter) and clozapine (antipsychotic drug). AbstractWebsite

This present study describes the synthesis of ultrafine Bi-Sn nanoparticles decorated on carbon aerogels (Bi-Sn NP/CAG) as a nanocomposite for the electrochemical simultaneous determination of dopamine (DA) and clozapine (CLZ). The typical characterization techniques, such as XRD, Raman, BET, FT-IR, TGA, XPS, and FE-SEM/TEM, showed useful insights into the crystal phase and morphology of Bi-Sn NP/CAG. Integrated Bi-Sn NP/CAG built into a cost-effective screen printed carbon electrode (SPCE) offers a high electrochemical surface area (ECSA) compared to unmodified, Bi-Sn, and CAG/SPCEs, such that it favourably allowed the binding of DA and CLZ molecules onto the surface at the Bi-Sn/CAG, which was demonstrated by cyclic and differential pulse voltammetry techniques. As a result, the DA and CLZ sensing exhibited low detection limits (DL, 4.6 and 97.6 nM (S/N = 3)), and sensitivity (3.402 and 0.4 μA μM-1 cm-2) over a wide linear range (0.02-97.59 and 0.5-2092 μM), respectively. To go a step further, the Bi-Sn NP/CAG/SPCE was applied for the simultaneous determination of DA and CLZ which featured lower DL (23.1 and 31.3 nM (S/N = 3)), and sensitivity (0.4979 and 0.04 μA μM-1 cm-2) over a wide linear range (2-182 and 10-910 μM), respectively. The selectivity for DA and CLZ in the presence of a 10-fold concentration of their potentially interfering active species was demonstrated. Finally, this sensing methodology enables the rapid electrochemical determination of the amount of DA and CLZ in a rat brain region serum sample with successful recovery outcomes. © The Royal Society of Chemistry.

Veerakumar, P., LK-C.  2020.  An overview of palladium supported on carbon-based materials: Synthesis, characterization, and its catalytic activity for reduction of hexavalent chromium. AbstractWebsite

Palladium plays a pivotal role in most of the industrial heterogeneous catalysts, because of its unique properties such as well-defined structure, great intrinsic carrier, outstanding electronic, mechanical and thermal stability. The combination of palladium and various porous carbons (PCs) can widen the use of heterogeneous catalysts. This review highlights the advantages and limitations of carbon supported palladium-based heterogeneous catalyst in reduction of toxic hexavalent chromium (Cr(VI)). In addition, we address recent progress on synthesis routes for mono and bimetallic palladium nanoparticles supported by various carbon composites including graphene-based materials, carbon nanotubes, mesoporous carbons, and activated carbons. The related reaction mechanisms for the Cr(VI) reduction are also suggested. Finally, the challenge and perspective are proposed. © 2020

Vinothkumar, V., SCVLAS-M.  2020.  Sr-Doped NiO3 nanorods synthesized by a simple sonochemical method as excellent materials for voltammetric determination of quercetin. AbstractWebsite

The simple and novel surfactant-free synthesis of flower-like strontium-doped nickel oxide nanorods (SNO NRs) via a simple sonochemical co-precipitation method was used for electrochemical sensing of quercetin (QCT). The structure and morphology of the as-synthesized flower-like SNO NRs were characterized using various spectroscopic techniques. Then, CV, EIS, and DPV were used to examine their electrochemical properties. The effective loading concentration, pH, scan rate and stability of the SNO NR-modified electrodes were studied. Under optimized conditions, the electrochemical detection of QCT demonstrated a low detection potential of 0.3 V (vs. Ag/AgCl), and achieved a higher oxidation peak current compared to those of other modified electrodes in PB (pH 5.0). The voltammetric current response was found to linearly increase with an increasing concentration range from 0.01-68.53 μM, along with a low detection limit of 1.98 nM, and a high sensitivity of 2.1055 μA mM cm-2. The sensor also shows good selectivity and satisfactory recovery for real sample (apple and grape juice) analysis. © 2020 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

Dhenadhayalan, N., LK-C.  2020.  Photochemically Synthesized Ruthenium Nanoparticle-Decorated Carbon-Dot Nanochains: An Efficient Catalyst for Synergistic Redox Reactions. AbstractWebsite

Ruthenium nanoparticle (NP)-decorated carbon dots (Ru/C-dots) were fabricated as a potential catalyst in the application of both oxidation and reduction. The photochemical method was used to synthesize Ru/C-dot nanohybrids. The as-prepared Ru/C-dots exhibited a core-shell-based nanochain structure, in which the spherical nature of C-dots further evolved to a layer structure to homogeneously encapsulate Ru NPs. Such Ru/C-dots have excellent catalytic properties, which were demonstrated in the oxidation of flavonoids and concomitantly reduction of inorganic complex and organic dyes, each yielding a high catalytic rate constant. We also proposed an appropriate catalytic mechanism for each reaction. Higher catalytic activity was achieved by the synergistic effect of the encapsulated Ru NPs and the C-dots layer. Further, this nanohybrid was successfully applied to inspect a real aqueous sample. We anticipated that Ru/C-dots nanohybrid may open up a broad platform for the design of efficient multifunctional catalysts. Copyright © 2020 American Chemical Society.

Veerakumar, P., SCLAS-M.  2020.  Ultrafine gold nanoparticle embedded poly(diallyldimethylammonium chloride)-graphene oxide hydrogels for voltammetric determination of an antimicrobial drug (metronidazole). AbstractWebsite

In this work, gold nanoparticle (Au NP) decorated poly(diallyldimethylammonium chloride) (PDDA) functionalized graphene hydrogel (Au NP@PDDA/GH) nanocomposites were fabricated. The resulting materials were characterized by a variety of analytical and spectroscopic techniques. Electrochemical performances of the prepared composites were examined by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and linear sweep voltammetry (LSV). The Au NPs were decorated uniformly and densely on the GO@PDDA composite material based on the electrostatic attraction and this new hierarchical nanostructure can provide a more favourable microenvironment for electron transfer. Under the optimized conditions, the Au NP@PDDA/GH nanocomposite was used as a novel sensing probe for metronidazole (MZ) which was found to have the concentration range of 0.4-656.4 μM with a correlation coefficient (0.999, limit of detection (LOD) based on (LOD = 3k/∂) of 0.097 μM), and a sensitivity of 4.286 μA μM−1. With satisfactory selectivity, reproducibility, and stability, the nanostructure we proposed offered an alternative for electrode fabrication and MZ sensing. Au NP@PDDA/GH was also applied to the reduction of MZ and pharmacy tablets by NaBH4under ambient conditions. Thus, Au NP@PDDA/GH application provides simplicity, reliability, durability, and low cost benefits. © The Royal Society of Chemistry 2020.

  2020.  Three-dimensional zinc oxide nanostars anchored on graphene oxide for voltammetric determination of methyl parathion. AbstractWebsite

The two-step microwave method was used to synthesize zinc oxide nanostars linked to graphene oxide (GO) nanosheets. The material was used to modify a screen printed carbon electrode (SPCE) and then explored as a binder-free electrocatalyst for the electrochemical determination of methyl parathion (MP). The morphology and crystallinity of the material were characterized by various techniques. The modified SPCE shows extraordinary electrochemical performances for sensitive determination of MP. Figures of merit include (a) a wide linear dynamic range (0.03–670 μM), (b) a low detection limit (1.2 nM; at S/N = 3), (c) a comparably low working voltage (−0.69 V vs. Ag/AgCl); and (d) an excellent sensitivity (16.5 μA μM−1 cm−2) that surpasses other modified electrodes. The sensor was successfully applied to the determination of MP, even in the presence of other common electroactive interference, in (spiked) fruits and vegetables. [Figure not available: see fulltext.]. © 2019, Springer-Verlag GmbH Austria, part of Springer Nature.

Lee, T.-Y., JTLCVSTPK.  2020.  Carbon dot nanoparticles exert inhibitory effects on human platelets and reduce mortality in mice with acute pulmonary thromboembolism. AbstractWebsite

The inhibition of platelet activation is considered a potential therapeutic strategy for the treatment of arterial thrombotic diseases; therefore, maintaining platelets in their inactive state has garnered much attention. In recent years, nanoparticles have emerged as important players in modern medicine, but potential interactions between them and platelets remain to be extensively investigated. Herein, we synthesized a new type of carbon dot (CDOT) nanoparticle and investigated its potential as a new antiplatelet agent. This nanoparticle exerted a potent inhibitory effect in collagen-stimulated human platelet aggregation. Further, it did not induce cytotoxic effects, as evidenced in a lactate dehydrogenase assay, and inhibited collagen-activated protein kinase C (PKC) activation and Akt (protein kinase B), c-Jun N-terminal kinase (JNK), and p38 mitogen-activated protein kinase (MAPK) phosphorylation. The bleeding time, a major side-effect of using antiplatelet agents, was unaffected in CDOT-treated mice. Moreover, our CDOT could reduce mortality in mice with ADP-induced acute pulmonary thromboembolism. Overall, CDOT is effective against platelet activation in vitro via reduction of the phospholipase C/PKC cascade, consequently suppressing the activation of MAPK. Accordingly, this study affords the validation that CDOT has the potential to serve as a therapeutic agent for the treatment of arterial thromboembolic disorders. © 2020 by the authors.

Veerakumar, P., SMTLASP.  2020.  Research Progress on Porous Carbon Supported Metal/Metal Oxide Nanomaterials for Supercapacitor Electrode Applications. AbstractWebsite

Recently, transition metal/metal oxides (TMMOs) decorated on porous carbons (PCs) have been intensively focused on designing rational electrode materials for the promising future specific category of electrochemical energy storage and conversion technologies. In particular, TMMO incorporation with PC structures has become very attractive in the area of supercapacitors (SCs) mainly caused by their large accessible surface areas (SSA), together with the suitable pore size distributions (PSD), high electrical conductivity, and rapid redox reactions reversibly on the surface. The transportation of ions, as well as electrons in the bulk of electrodes, is fast as a result of optimal contact between electrodes and electrolytes at the electrode-electrolyte interface, thereby generating high specific capacities (Csp) of these PCs with TMMOs. We report a survey regarding recent advances in the fabrication and synthesis of TMMOs decorated on PCs with some physical characteristics and their applications for electrochemical capacitors. Some future trends and prospects for further development of the subject nanocomposites in application to next-generation supercapacitors are discussed. © 2020 American Chemical Society.

Dhenadhayalan, N., LSK-CTA.  2020.  Recent Advances in Functionalized Carbon Dots toward the Design of Efficient Materials for Sensing and Catalysis Applications. AbstractWebsite

Since the past decade, enormous research efforts have been devoted to the detection/degradation and quantification of environmental toxic pollutants and biologically important molecules due to their ubiquitous necessity in the fields of environmental protection and human health. These fields of sensor and catalysis are advanced to a new era after emerging of nanomaterials, especially, carbon nanomaterials including graphene, carbon nanotube, carbon dots (C-dots), etc. Among them, the C-dots in the carbon family are rapidly boosted in the aspect of synthesis and application due to their superior properties of chemical and photostability, highly fluorescent with tunable, non/low-toxicity, and biocompatibility. The C-dot-based functional materials have shown great potential in sensor and catalysis fields for the detection/degradation of environmental pollutants. The major advantage of C-dots is that they can be easily prepared from numerous biomass/waste materials which are inexpensive and environment-friendly and are suitable for a developing trend of sustainable materials. This review is devoted to the recent development (since 2017) in the synthesis of biomass- and chemical-derived C-dots as well as diverse functionalization of C-dots. Their capability as a sensor and catalyst and respective mechanism are summarized. The future perspectives of C-dots are also discussed.

Che, D.-C., NCLKAPMH-P.  2020.  UV Photodissociation of Halothane in a Focused Molecular Beam: Space-Speed Slice Imaging of Competitive Bond Breaking into Spin-Orbit-Selected Chlorine and Bromine Atoms. AbstractWebsite

A molecular beam of halothane (2-bromo-2-chloro-1,1,1-trifluoroethane) is focused by a hexapolar electrostatic field and photolyzed by UV laser radiation at 234 nm. Angular and speed distributions of chlorine and bromine photofragments emitted from halothane are measured for both spin-orbit states independently. Although the dissociation energy of the C-Cl bond is larger than that of C-Br, the relative yield of Cl to Br was found to be approximately 2. Measured speed and angular distributions of atomic fragments show distinct kinetic energy release and scattering characteristics: for bromine, observed fast and aligned fragments exhibit a signature of a direct mode of dissociation for the C-Br bond, via the electronically excited potential energy surface denoted nσ*(C-Br), of repulsive nature; for chlorine, a variation in the features is observed for the dissociation pathway through nσ*(C-Cl), from a modality similar to the bromine case, leading to fragments with appreciable kinetic energy release and pronounced directionality, to a modality involving slow products, nearly isotopically distributed. The origin of this behavior can be attributed to nonadiabatic interaction operating between the nσ*(C-Br) and nσ*(C-Cl) surfaces. These results are not only relevant for a detailed understanding of adiabatic versus diabatic coupling mechanisms in the manifold of excited states populated by photon absorption, but they also point out the possibility of selectively inducing specific dissociation pathways, even when involving energetically unfavorable outcomes, such as, in this case, the prevailing rupture of the stronger C-Cl bond against that of the weaker C-Br bond. Copyright © 2020 American Chemical Society.

Veerakumar, P., SCPLAS-M.  2020.  Fabrication of Platinum-Rhenium Nanoparticle-Decorated Porous Carbons: Voltammetric Sensing of Furazolidone. AbstractWebsite

This study discusses the prospect of using biomass waste material, such as Cassia fistula (golden shower) fruit, as a carbon precursor in the development of new carbon material for the sustainable electrochemical sensor application. We successfully synthesized platinum-rhenium nanoparticles decorated on a porous activated carbon (Pt-Re NP/PAC) nanocomposite through the incorporation of metal precursors such as platinum(II) acetylacetonate (Pt(acac)2) and dirhenium decacarbonyl (Re2(CO)10) via a facile thermal reduction process. A variety of physicochemical and electrochemical methods were employed to characterize the morphology, structural, and electrochemical properties of the Pt-Re NP/PAC material. We then looked into the analytical behavior and applications of GCE modified with Pt-Re NP/PAC (Pt-Re NP/PAC/GCE) for the determination of furazolidone (chemotherapy drug) by employing different voltammetric techniques. The influence of experimental conditions such as scan rate, pH, accumulation time, amount of the modifier, and sample concentration on the peak current of the furazolidone was studied. The proposed drug sensor exhibited a wide linear range (WLR) for furazolidone in 0.05 M phosphate-buffered saline (PBS, pH 7.0) from 1.0 to 299 μM with a limit of detection (LOD) of 75.5 nM and appreciable sensitivity (5.52 μA μM-1 cm-2) which were calculated from linear sweep voltammetry (LSV). In addition, these analytical parameters including WLR, sensitivity, and LOD were estimated to be 0.2-117.7 μM, 19.20 μA μM-1 cm-2, and 20.8 nM and were obtained using differential pulse voltammetry (DPV). Therefore, the prepared Pt-Re NP/PAC modified sensor could be a potential candidate for the determination of furazolidone in pharmaceutical formulation, human urine, and blood serum samples, and the results are appreciable. Copyright © 2020 American Chemical Society.