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2019
Sangili, A, Veerakumar P, Chen S-M, Rajkumar C, Lin K-C.  2019.  Voltammetric determination of vitamin B2 by using a highly porous carbon electrode modified with palladium-copper nanoparticles. Microchimica Acta. 186(5):299. AbstractWebsite

Palladium-copper nanoparticles were placed on activated carbon to give a nanocomposite for electrochemical sensing of riboflavin (vitamin B 2 ). The activated carbon was produced by pyrolysis of natural waste of pistachio nutshells after KOH activation and under a nitrogen atmosphere. The carbons possess a large surface area and micro/meso-porosity. The nanocomposite was characterized by a variety of techniques to confirm structures and morphology. A screen-printed electrode modified with the composite was examined by EIS, CV, DPV, and amperometry. The effects of pH value, scan rate, and stability of the modified electrode were studied. Under optimized conditions, vitamin B 2 displays a well-expressed oxidation peak at −0.15 V (vs. Ag/AgCl) in solutions with a pH value of 7.0. The voltammetric signal increases linearly in the 0.02 to 9 μM concentrations range and a lower detection limit of 7.6 pM. The sensor was successfully applied to the determination of vitamin B 2 even in the presence of other common vitamins and in (spiked) raw milk samples. [Figure not available: see fulltext.]. © 2019, Springer-Verlag GmbH Austria, part of Springer Nature.

2018
Dhenadhayalan, N, Lin T-W, Veerakumar P, Lin K-C.  2018.  Metal Nanoparticles Anchored on Rhenium Disulfide Nanosheets as Catalysts for the Reduction of Aromatic Nitro Compounds. ChemNanoMat. AbstractWebsite

Abstract The nanohybrids of noble metal (M=Ag, Au, Pd, Pt, and Ru) nanoparticle-decorated rhenium disulfide nanosheets (ReS2 NSs) were demonstrated as excellent catalysts towards the reduction of aromatic nitro compounds. The M/ReS2 nanohybrids were synthesized by facile hydrothermal method and characterization results proved that each metal nanoparticle was anchored on the ReS2 NSs. These nanohybrids exhibited superior catalytic performance towards the reduction of aromatic nitro compounds including 4-nitrophenol, 2-nitroaniline, and nitrobenzene. Interestingly, the Ru/ReS2 and Pd/ReS2 showed enhanced catalytic reduction compared to Ag/ReS2, Au/ReS2, and Pt/ReS2 and also showed significant catalytic stability due to metal nanoparticles anchored strongly on the surface of ReS2 NSs. Moreover, these M/ReS2 nanohybrids turned out to have much better catalytic performance compared to noble metal nanoparticle-based catalysts. A plausible reduction mechanism was proposed for each nitro compound. It was verified that the metal-nanoparticle-mediated hydrogen transfer was involved in the reduction of nitro compounds to amines. This report demonstrates the catalytic activities for metal nanoparticle-decorated ReS2 nanohybrids, which can serve as a paradigm to open up a future trend in the design of transition metal dichalcogenides nanohybrids as superior catalysts.

Veerakumar, P, Rajkumar C, Chen S-M, Thirumalraj B, Lin K-C.  2018.  Activated porous carbon supported rhenium composites as electrode materials for electrocatalytic and supercapacitor applications. Electrochimica Acta. 271:433-447. AbstractWebsite

In this study, we developed highly dispersed rhenium nanoparticles decorated on activated carbon (Re@CDACs). The activated carbons were derived from the biomass raw materials cardamom pods (Elettaria cardamomum L) via carbonization followed by activation with ZnCl2 at high temperature. The Re NPs synthesis was achieved by decomposition of [Re2(CO)10] complex via a facile microwave thermal reduction technique. The as-prepared Re@CDACs nanocomposites were characterized by a combination of state-of-the-art techniques. The Re@CDACs nanocomposites so prepared were utilized for electrocatalytic oxidation of sunset yellow (SY) and supercapacitor applications. The Re@CDACs-modified electrodes were found to show extraordinary electrochemical performance for sensitive and selective detection of SY with a wide linear range of 0.05–390 μM and a detection limit and sensitivity of 16 nM (S/N = 3) and 91.53 μA μM−1, respectively, surpassing other modified electrodes. Moreover, these Re@CDACs catalysts were also found to exhibit a higher specific capacitance of 181 F g-1 at a current density of 1.6 A g−1 in 1.0 M H2SO4 electrolyte. The specific capacitance retention of 90% was achieved after 2500 cycles at current density 2.0 A g−1. Therefore, we have demonstrated that the Re@CDACs nanocomposite materials could be used as a promising electrode material in electrochemical oxidation of SY and energy storage applications. © 2018

Dhenadhayalan, N, Sriram MI, Lin K-C.  2018.  Aptamer-based fluorogenic sensing of interferon-gamma probed with ReS2 and TiS2 nanosheets. Sensors and Actuators, B: Chemical. 258:929-936. AbstractWebsite

The fluorogenic aptamer sensing of interferon-gamma (IFN-γ) was scrutinized using two-dimensional (2D) ReS2 and TiS2 nanosheets (NSs) as a platform. The IFN-γ an important cytokine, functions as a bio-indicator to detect infectious diseases such as tuberculosis and human immunodeficiency virus. This 2D NSs based aptamer sensor was implemented to induce the fluorescence off/on resulting from an aptamer, in the absence or presence of a target to be probed. The fluorescence emitting from the aptamer is quenched by interacting with NSs, while the ensuing fluorescence is recovered upon addition of target. Such a fluorescence off/on mechanism was proposed based on the behavior of fluorescence resonance energy transfer (FRET) between the aptamer and NSs. The fluorescence response exhibits linearity as a function of target, and the detection limit of IFN-γ was evaluated to be 57.6 and 82.7 pM for ReS2 and TiS2 NSs, respectively, being comparable to or even better than those methods adopted for probing IFN-γ. The selectivity property was also characterized with various targets, exhibiting a very specific selectivity for IFN-γ. The findings reveal that the aptamer-transition metal dichalcogenides (TMD) NSs will be a great sensing pair to the development of aptamer-based biosensors. Moreover, the biocompatibility and sensing capability of IFN-γ was implemented in human embryonic kidney 293T (HEK) live cells. This is the first report to emerging fluorogenic sensing of IFN-γ aptamer with 2D TMD, showing a promising trend for future design of biosensors. © 2017 Elsevier B.V.

Paredes-Roibás, D, Balaganesh M, Kasai T, Gavira-Vallejo JM, Lin KC.  2018.  Cavity Ring-Down Absorption Spectroscopy: Optical Characterization of ICl Product in Photodissociation of CH2ICl at 248 nm. Journal of Physical Chemistry A. 122:8344-8353., Number 42 AbstractWebsite

Iodine monochloride (ICl) elimination from one-photon dissociation of CH2ICl at 248 nm is monitored by cavity ring-down absorption spectroscopy (CRDS). The spectrum of ICl is acquired in the transition of B3 0X1 + and is confirmed to result from a primary photodissociation, that is, CH2ICl + h→CH2 + ICl. The vibrational population ratio is determined with the aid of spectral simulation to be 1:(0.36 ± 0.10):(0.11 ± 0.05) for the vibrational levels = 0, 1, and 2 in the ground electronic state, corresponding to a Boltzmann-like vibrational temperature of 535 ± 69 K. The quantum yield of the ICl molecular channel for the reaction is obtained to be 0.052 ± 0.026 using a relative method in which the scheme CH2Br2 →CH2 + Br2 is adopted as the reference reaction. The ICl product contributed by the secondary collisions is minimized such that its quantum yield obtained is not overestimated. With the aid of the CCSD(T)//B3LYP/MIDI! level of theory, the ICl elimination from CH2ICl is evaluated to follow three pathways via either (1) a three-center transition state or (2) two isomerization transition states. However, the three-center concerted mechanism is verified to be unfavorable. © 2018 American Chemical Society.

Veerakumar, P, Panneer Muthuselvam I, Thanasekaran P, Lin K-C.  2018.  Low-cost palladium decorated on: M -aminophenol-formaldehyde-derived porous carbon spheres for the enhanced catalytic reduction of organic dyes. Inorganic Chemistry Frontiers. 5:354-363., Number 2 AbstractWebsite

We report the use of palladium nanoparticles (Pd NPs) immobilized on m-aminophenol/formaldehyde resin (APF)-derived porous carbon spheres (Pd@PCS) as heterogeneous catalysts for the reduction of organic dyes. The morphology, structure, surface compositions, and textural properties of PCS and the Pd@PCS catalyst were characterized fully to document the excellent catalytic efficiency of Pd@PCS composites. Pd NPs of mean particle size ca. 12 ± 0.8 nm were highly dispersed on the surface of PCSs, and possessed surface area and pore volume as high as 896.3 m2 g-1 and 0.934 cm3 g-1, respectively. Prepared catalysts were applied to the reduction of various organic dyes; high catalytic activity towards crystal violet, eosin yellow and sunset yellow was observed. More importantly, the catalysts could be recovered readily, and reused many times with good stability. Therefore, the robust material utilized for the treatment of containing organic dyes could be used widely for environmental applications. © 2018 the Partner Organisations.

Veerakumar, P, Maiyalagan T, Raj BGS, Guruprasad K, Jiang Z, Lin K-C.  2018.  Paper flower-derived porous carbons with high-capacitance by chemical and physical activation for sustainable applications. Arabian Journal of Chemistry. 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

Kasai, T, Che D-C, Tsai P-Y, Nakamura M, Muthiah B, Lin K-C.  2018.  Roaming and chaotic behaviors in collisional and photo-initiated molecular-beam reactions: a role of classical vs. quantum nonadiabatic dynamics. Rendiconti Lincei. 29:219-232., Number 2 AbstractWebsite

A new reaction scheme is proposed to account for roaming and chaotic behaviors in collisional and photo-initiated molecular-beam reactions, where nonadiabatic dynamics plays a key role and the collapse of superposition of wave functions is considered to be important in the beginning of the present scheme. Since the feature of molecular orbitals of reagents is crucial in reaction, we showed how to map out the spatial distribution of the relevant HOMO molecular orbitals of CH3Cl in the impact of fast electrons. We identified by experiment that the multiple overlap of nearby molecular orbitals affects even the vibrational motion of adjacent molecule DCl of the transient [ClDCl] chemical species. We also showed dynamical steric effects in the HBr + OH four-atom reaction as a manifestation of the nonadiabatic dynamics in complex systems. The roaming mechanism in the photo-initiated reaction of methyl formate is clarified in detail by experiment as well as the QCT trajectory calculation, where the conical intersection region plays an essential role. We suggest that two types of roaming trajectories coexist, i.e., deterministic and chaotic roaming trajectories based on classical trajectory calculations. To clarify the nonadiabatic dynamics in the roaming mechanism for non-collinear three-dimensional (3D) collisions, a new model of the 3D Polanyi rule is proposed as the extension of the well-established 2D Polanyi rule. In the 3D Polanyi rule, it is expected that the curvature and torsion of Frenet–Serret formulas in three-dimensional space would provide us key concepts in understanding reaction dynamics. © 2018, Accademia Nazionale dei Lincei.

Lin, K-C, Tsai P-Y, Chao M-H, Nakamura M, Kasai T, Lombardi A, Palazzetti F, Aquilanti V.  2018.  Roaming signature in photodissociation of carbonyl compounds. International Reviews in Physical Chemistry. 37:217-258., Number 2 AbstractWebsite

An alternative to the transition state (TS) pathway, the roaming route, which bypasses the minimum energy path but produces the same molecular products, was recently found in photodissociation dynamics. This account describes signatures of roaming in photodissociation of the carbonyl compounds, specifically methyl formate and aliphatic aldehydes. Methyl formate was promoted to the excited state, followed by internal conversion via a conical intersection. Then, the energetic precursor dissociated to fragments which proceeded along either TS or roaming path. In contrast to the lack of a roaming saddle point found in methyl formate, the structure of the roaming saddle point for each of a series of aliphatic aldehydes comprises two moieties that are weakly bound at a distance. As its size increases, the energy difference between the TS barrier and the roaming saddle point increases and the roaming pathway becomes increasingly dominant. Experimentally, the rotational-level dependence of the roaming route was measured with ion imaging, while the vibrational-state dependence was observed with time-resolved Fourier-transform infrared emission spectroscopy. The roaming signature was verified theoretically by quasi-classical trajectory (QCT) calculations. As an alternative to the QCT method, a multi-center impulsive model was developed to simulate the roaming scalar and vector properties. © 2018 Informa UK Limited, trading as Taylor & Francis Group.

Veerakumar, P, Salamalai K, Thanasekaran P, Lin K-C.  2018.  Simple Preparation of Porous Carbon-Supported Ruthenium: Propitious Catalytic Activity in the Reduction of Ferrocyanate(III) and a Cationic Dye. ACS Omega. 3:12609-12621., Number 10 AbstractWebsite

The present study involves the synthesis, characterization, and catalytic application of ruthenium nanoparticles (Ru NPs) supported on plastic-derived carbons (PDCs) synthesized from plastic wastes (soft drink bottles) as an alternative carbon source. PDCs have been further activated with CO2 and characterized by various analytical techniques. The catalytic activity of Ru@PDC for the reduction of potassium hexacyanoferrate(III), (K3[Fe(CN)6]), and new fuchsin (NF) dye by NaBH4 was performed under mild conditions. The PDCs had spherical morphology with an average size of 0.5 μm, and the Ru NP (5 ± 0.2 nm) loading (4.01 wt %) into the PDC provided high catalytic performance for catalytic reduction of ferrocyanate(III) and NF dye. This catalyst can be recycled more than six times with only a minor loss of its catalytic activity. In addition, the stability and reusability of the Ru@PDC catalyst are also discussed. Copyright © 2018 American Chemical Society.

Veerakumar, P, Rajkumar C, Chen S-M, Thirumalraj B, Lin K-C.  2018.  Ultrathin 2D graphitic carbon nitride nanosheets decorated with silver nanoparticles for electrochemical sensing of quercetin. Journal of Electroanalytical Chemistry. 826:207-216. AbstractWebsite

In this work, we describe a facile fabrication of silver nanoparticles decorated on porous ultrathin two dimensional (2D) graphitic carbon nitride nanosheets (AgNPs@g-CN) via chemical approach, which was characterized by various analytical techniques including cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry. As expected, the AgNPs@g-CN modified glassy carbon electrode (AgNPs@g-CN/GCE) exhibited remarkable electrocatalytic activity towards the detection of quercetin (QCR) with a wide linear range from 1.0 × 10−8 to 1.2 × 10−4 mol L−1 and a lower detection limit of 6.0 × 10−9 mol L−1. Besides, the amperometric results revealed that the peak current for QCR could not affect upon the sequential additions of electroactive interfering species such as metal ions (300 μM), biomolecules (100 μM), and other flavonoids (50 μM) indicating the selectivity of the proposed sensor. Moreover, the AgNPs@g-CN modified electrode displayed higher stability and reproducibility towards the detection of QCR. The AgNPs@g-CN/GCE could also be used to detect QCR in green apple (GA) samples with satisfactory recoveries for practical applications. The concepts behind the novel architecture to modify electrodes can be potentially harnessed in other electrochemical sensors and photocatalysis applications. © 2018 Elsevier B.V.

2017
Chao, M-H, Lin Y-T, Dhenadhayalan N, Lee H-L, Lee H-Y, Lin K-C.  2017.  3D Probed Lipid Dynamics in Small Unilamellar Vesicles. Small. 13, Number 13 AbstractWebsite

Single-molecule fluorescence correlation spectroscopy overcomes the resolution barrier of optical microscopy (10≈–20 nm) and is utilized to look into lipid dynamics in small unilamellar vesicles (SUVs; diameter < 100 nm). The fluorescence trajectories of lipid-like tracer 1,1′-dioctadecyl-3,3,3′,3′-tetramethylindodicarbocyanine (DiD) in the membrane bilayers are acquired at a single-molecule level. The autocorrelation analysis yields the kinetic information on lipid organization, oxygen transport, and lateral diffusion in SUVs' membrane. First, the isomerization feasibility may be restricted by the addition of cholesterols, which form structure conjugation with DiD chromophore. Second, the oxygen transport is prevented from the ultrasmall cluster and cholesterol-rich regions, whereas it can pass through the membrane region with liquid-disordered phase (Ld) and defects. Third, by analyzing 2D spectra correlating the lipid diffusion coefficient and triplet-state lifetime, the heterogeneity in lipid bilayer can be precisely visualized such as lipid domain with different phases, the defects of lipid packing, and DiD-induced “bouquet” ultrasmall clusters. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Lin, K-C, Nakamura M, Yang, S. J, Kasai T, Che D-C, Lombardi A, Palazzetti F, Aquilanti V.  2017.  Angular distribution of bromine atomic photofragment in oriented 2-bromobutane via hexapole state selector. AIP Conference Proceedings. 1906 Abstract

In this work, an asymmetric top molecule 2-bromobutane has been successfully oriented by using hexapole state selector combined with orientation field, followed by detection of the bromine atomic photofragment distribution in the photolysis. The photofragment is produced in both the ground Br (2P3/2) and the excited Br (2P1/2) electronic states and both channels are studied by the slice imaging technique, revealing new features in the stereodynamic vectorial properties with respect to previous investigations on non-oriented molecules. © 2017 Author(s).

Veerakumar, P, Thanasekaran P, Lin K-C, Liu S-B.  2017.  Biomass Derived Sheet-like Carbon/Palladium Nanocomposite: An Excellent Opportunity for Reduction of Toxic Hexavalent Chromium. ACS Sustainable Chemistry and Engineering. 5:5302-5312., Number 6 AbstractWebsite

Palladium nanoparticles (Pd NPs) immobilized on a garlic skin-derived activated carbons (GACs) is reported. The morphology, structure, surface compositions, and textural properties of the GACs and Pd@GAC catalyst were investigated by a variety of physicochemical characterization techniques, which revealed a dispersion of Pd NPs with average particle size of ca. 21 nm on sheet-like graphitized GACs with surface areas and pore volumes as high as 1836 m2 g-1 and 0.89 cm3 g-1, respectively. As a result, the Pd@GAC with a Pd loading of ca. 1-2 wt% exhibited superior activity for catalytic reduction of toxic Cr(VI) to Cr(III) surpassing most metal-based catalysts reported in the literature. As evidenced by a comprehensive UV-vis spectrophotometric study, the eco-friendly Pd@GAC catalyst reported herein, which can be facilely prepared with biowaste feedstocks, also showed excellent catalytic performances for efficient reduction of Cr(VI) with extraordinary stability and recyclability over at least five repeated catalytic test cycles. © 2017 American Chemical Society.

Huang, T-K, Chen B-J, Lin K-C, Lin L, Sun B-J, Chang AHH.  2017.  Cl2 Elimination in 248 nm Photolysis of (COCl)2 Probed with Cavity Ring-Down Absorption Spectroscopy. Journal of Physical Chemistry A. 121:2888-2895., Number 15 AbstractWebsite

Cavity ring-down absorption spectroscopy (CRDS) is employed to investigate one-photon dissociation of (COCl)2 at 248 nm obtaining a primary Cl2 elimination channel. A ratio of vibrational population is estimated to be 1:(0.12 ± 0.03):(0.011 ± 0.003) for the v = 0, 1, and 2 levels. The quantum yield of Cl2 molecular channel is obtained to be 0.8 ± 0.4 initiated from the X̃ 1Ag ground state surface (COCl)2 via internal conversion. The obtained total quantum yield is attributed to both primary ((COCl)2 + hν → 2CO + Cl2) and secondary reactions (dominated by Cl + COCl → Cl2 + CO). The former is estimated to share a yield of >0.14, while the latter contributes up to 0.66. The photodissociation pathway to the molecular products is calculated to proceed via a four-center transition state (TS) from which Cl2 is eliminated synchronously. Installation of the mirrors with reflectivity of 99.995% in the CRDS apparatus prolongs the ring-down time to 70 μs, thus allowing for the contribution from 17% up to 66% of the total Cl2 yield from secondary reaction depending on the reaction temperature. Despite uncertainty in determining the product yield, the primary Cl2 dissociation channel eliminated from (COCl)2 is observed for the first time. © 2017 American Chemical Society.

Veerakumar, P, Thanasekaran P, Lu K-L, Lin K-C, Rajagopal S.  2017.  Computational Studies of Versatile Heterogeneous Palladium-Catalyzed Suzuki, Heck, and Sonogashira Coupling Reactions. ACS Sustainable Chemistry and Engineering. 5:8475-8490., Number 10 AbstractWebsite

This perspective focuses on the mechanistic insights and complexity, which are difficult to acquire from pure experimental techniques, of the computational studies of Pd-catalyzed Suzuki, Heck, and Sonogashira carbon-carbon bond-forming reactions. These reactions consist of three fundamental steps including oxidative addition (OA), transmetalation (TM), and reductive elimination (RE) for the generation of carbon-carbon bonds from the bond-forming reactions of aryl halides (R1X) and organometallic species (R2M). Computational studies of these coupling reactions allow us to understand specific reaction pathways in the analysis of OA (resolving the linkage between coordination number and selectivity in Suzuki reaction), TM (the function of the base in the Suzuki reaction and various mechanistic options in the Sonogashira reaction), and RE (way of efficient β-hydride elimination in the Heck reaction). In addition, the reaction pathways and complexities in the full catalytic cycle of each reaction along with the future perspective are also discussed. © 2017 American Chemical Society.

Kasai, T, Lin K-C.  2017.  Coordinate Analysis for Interpreting the Decoherence in the Coherent NO with Ar Collision: A Physico-mathematical Picture Using the Stereographic Projection and the Cusp Catastrophe. Journal of the Chinese Chemical Society. 64:25-35., Number 1 AbstractWebsite

We present here a physico-mathematical picture for explaining the unexpectedly large decoherence cross-section (almost 10 times larger than its gas-kinematic cross-section) recently observed by Ureña and coworkers in their scattering experiment involving a coherent NO beam with Ar gas. The present topological picture consists of a stereographic projection and the cusp catastrophe theory of Thom, and we find that this model enables us to clarify the origin of the collisional decoherence. From the view of the stereographic projection, we can naturally introduce the wave property originating from the singular point at the “North pole” on the circumference S1 coordinate corresponding to a critical point for the collisional decoherence (condition 1). This picture also predicts the sudden changes of wave-phase collapse due to network interaction in the many-body system (condition 2). Thus it is hoped that the model proposed by Ureña et al. based on the dipole-induced dipole interaction in the NO + Ar system could be modified through this picture by including interactions with many Ar atoms in the environment. One way to fill the gap between the single-pair interaction picture and the multiple interaction one would be to employ theoretical calculations by use of the density matrix theory with and without adding the second Ar atom to the NO–Ar system. The cusp catastrophe theory reinforces the necessity of some cooperative network interaction between the coherent NO molecule and many neighboring Ar atoms and provides a qualitative scenario in which the whole system leads to a sudden change of the collisional decoherence of NO as a function of the control parameters (a, b). At this stage, the present physico-mathematical picture cannot give any specific values of the decoherence distance by the theory itself, but it clearly provides us a new topological concept for clarifying the origin of collisional decoherence which is strongly connected with the complexity of the system. Thus it gives us a global guide map toward further clarification of the collisional decoherence phenomenon with the aid of more sophisticated quantum mechanical calculations in the future. © 2016 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Veerakumar, P, Tharini J, Ramakrishnan M, Panneer Muthuselvam I, Lin K-C.  2017.  Graphene Oxide Nanosheets as An Efficient and Reusable Sorbents for Eosin Yellow Dye Removal from Aqueous Solutions. ChemistrySelect. 2:3598-3607., Number 13 AbstractWebsite

In this study, 2D graphene oxide nanosheets (GONS) were synthesized and characterized by XRD, Raman, SEM, FE-SEM, TEM, XPS, TGA, UV-vis and FTIR spectral techniques. The efficiency of eosin yellow (EY) dye adsorption on the GONS under various experimental parameters such as contact time, pH and temperature was investigated. Adsorption kinetic data were characterized appropriately using pseudo second-order-kinetics and intraparticle diffusion methods. Free energy of adsorption (ΔG0), enthalpy (ΔH0), entropy (ΔS0) changes, activation energy and Arrhenius factors were also calculated. The endothermic and spontaneous nature of the adsorption process was confirmed by the positive value of the enthalpy change (ΔH0) and the negative value of free energy change (ΔG0). The adsorption mechanism was investigated by FTIR spectra of GONS before and after adsorption of EY dye molecules. The remarkable adsorption capacity of EY onto the GONS can be attributed to the various adsorption interaction mechanisms such as hydrogen bonding, π-π electron, and electrostatic interactions. The maximum adsorption capacity for EY was calculated to be 217.33 mg g-1. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Kasai, T, Muthiah B, Lin K-C.  2017.  Role of cooperative network interaction in transition region of roaming reactions: Non-equilibrium steady state vs. thermal equilibrium reaction scheme. AIP Conference Proceedings. 1906 Abstract

This paper proposes a new type of roaming mechanism. We find a signature of trajectory with chaotic behavior in the action-angle diagram of the H + H2 reaction on a LEP surface, namely the trajectory is found to be very sensitive to the initial angle variable which corresponds to the phase of the H2 vibration. The trajectory pattern switches from the direct to the complex forming mechanism, and vice versa, in the angle range (0 ∼ π). In the complex forming angle range, trajectories switch from reactive to non-reactive randomly and suddenly, as the result, we cannot predict the collision pattern from the initial conditions. Therefore, we may classify such trajectory as a new type of roaming with chaotic behavior, and it is different from the ordinary trajectory with deterministic behavior. This chaotic behavior could be due cooperative nearby network interaction (CNN effect). We also suggest that the KPP (Kolmogorow-Petrovsky-Piskounov) equation is useful to estimate the density gradient of the activated reagents, so that one can evaluate the branching ratio to various exit channels, such as triple fragmentation, tight transition state, or the roaming channel with the aid of the present classical trajectory calculation. © 2017 Author(s).

Veerakumar, P, Dhenadhayalan N, Lin K-C, Liu S-B.  2017.  Silver Nanoparticles Modified Graphitic Carbon Nitride Nanosheets as a Significant Bifunctional Material for Practical Applications. ChemistrySelect. 2:1398-1408., Number 4 AbstractWebsite

Amine-functionalized graphitic carbon nitride (NH2/GCN) nanosheets photoluminescence, catalytic properties and excellent water dispersion stability were prepared and characterized by a variety of different analytical and spectroscopic techniques. The well-dispersed NH2/GCN nanosheets were found to exhibit remarkable pH sensing sensitivity at an ambient temperature with desirable broad detection range (1 ≤ pH ≤ 12). Moreover, upon incorporating silver nanoparticles (Ag NPs), the Ag-NH2/GCN nanocomposites showed excellent performances for catalytic reduction of 4-nitrophenol (4-NP) in NaBH4 with a superior rate constant (k) of 0.1594 s-1 within as short as 30 s. The NH2/GCN and Ag-NH2/GCN nanocomposites reported herein therefore render prospective applications as sensitive pH and practical catalytic applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Nakamura, M, Yang, S. J, Lin K-C, Kasai T, Che D-C, Lombardi A, Palazzetti F, Aquilanti V.  2017.  Stereodirectional images of molecules oriented by a variable-voltage hexapolar field: Fragmentation channels of 2-bromobutane electronically excited at two photolysis wavelengths. Journal of Chemical Physics. 147, Number 1 AbstractWebsite

The asymmetric-top molecule 2-bromobutane is oriented by means of a hexapole state selector; the angular distribution of the bromine atom photofragment, for the two fine-structure components, is acquired by velocity-map ion imaging. The molecular beam, spatially oriented along the time-of-flight axis, is intersected with a linearly polarized laser, whose polarization is tilted by 45° with respect to the detector surface. To obtain the mixing ratio of the perpendicular and parallel transitions, the fragment ion images and angular distributions can be appropriately simulated to give insight on the population mechanism of the specific electronic state involved at each selected excitation wavelength. The photofragment images obtained at 238.6 nm yielded an asymmetry factor β1 of 0.67, indicative of the extent of molecular orientation, and an anisotropy parameter β2 of 1.03, which is a signature of a prevailing parallel transition along the C-Br axis. When the photolysis wavelength is tuned to 254.1 nm, the corresponding angular distribution is less asymmetric (β1 = 0.24) and the obtained small value β2 = 0.12 is a characteristic of a predominantly perpendicular transition. The photofragment angular distributions are also affected by hexapole voltage, especially regarding the asymmetry factor, and this aspect provides information on the effect of molecular orientation. © 2017 Author(s).

Wu, PY, Huang HH, Lin KC, Tzeng WB.  2017.  Two-color resonant two-photon ionization and mass-analyzed threshold ionization spectroscopy of 4-chlorostyrene. Chemical Physics Letters. 682:34-37. AbstractWebsite

The first electronic excitation and adiabatic ionization energies of 35Cl and 37Cl 4-chlorostyrene were similar, with values of 33,977 ± 2 and 67,972 ± 5 cm−1, respectively. The general features in the obtained vibronic and cation spectra of the two isotopologues were similar. A frequency shift of 1–5 cm−1 was observed on many active vibrations of the 35Cl and 37Cl isotopologues of 4-chlorostyrene in the S1 and D0 states. This frequency difference at each mode may reflect the degree of Cl atom involvement in the overall vibration. © 2017 Elsevier B.V.

Dhenadhayalan, N, Yadav K, Sriram MI, Lee H-L, Lin K-C.  2017.  Ultra-sensitive DNA sensing of a prostate-specific antigen based on 2D nanosheets in live cells. Nanoscale. 9:12087-12095., Number 33 AbstractWebsite

Herein, we report ultra-sensitive sensing of a prostate-specific antigen (PSA), which is used as a biomarker to detect prostate cancer, using a molybdenum series (MoO3, MoS2, and MoSe2) of two-dimensional nanosheets (2D NSs). Moreover, the design of a 2D NS-based PSA aptamer sensor system was demonstrated based on a fluorescence turn-on mechanism in the presence of a target. The 2D NSs acted as an excellent sensing platform in which the PSA aptamer was adsorbed on the NSs and subsequent energy transfer between them led to fluorescence quenching of the aptamer. The detection limit of PSA was achieved to be 13 pM for MoO3 NSs, whereas the MoS2 and MoSe2 systems exhibited a detection limit of 72 and 157 pM, respectively. To the best of our knowledge, this is the first report on the ultra-sensitive detection of a 2D NS-based aptamer sensor. The in vitro bioimaging measurements were performed using confocal fluorescence microscopy. Herein, PSA detection was successfully demonstrated in human embryonic kidney 293T (HEK) live cells. Moreover, the MoO3, MoS2, and MoSe2 NSs exhibit excellent biocompatibility and low toxicity; thus, these 2D NSs can be used as a promising sensor platform to detect prostate cancer. This journal is © The Royal Society of Chemistry.

Veerakumar, P, Thanasekaran P, Lin K-C, Liu S-B.  2017.  Well-dispersed rhenium nanoparticles on three-dimensional carbon nanostructures: Efficient catalysts for the reduction of aromatic nitro compounds. Journal of Colloid and Interface Science. 506:271-282. AbstractWebsite

Rhenium nanoparticles (ReNPs) supported on ordered mesoporous carbon (OMC) as a catalyst (Re/OMC) through a solvent-evaporation induced self-assembly (ELSA) method were prepared. The synthesized heterogonous catalyst was fully characterized using X-ray diffraction, field emission transmission electron microscopy, N2 sorption, metal dispersion, thermogravimetric analysis, Raman, Fourier-transform infrared, and X-ray photon spectroscopies. In addition, the catalyst was applied to reduce the aromatic nitro compounds (ANCs) for the first time in aqueous media and the reactions were monitored by following the intensity changes in the UV–vis absorption spectra with respect to time. This method provides the advantages of obtaining a high rate constant (k), green reaction conditions, simple methodology, easy separation and easy workup procedures. Moreover, the catalyst can be easily recovered by centrifugation, recycled several times and reused without any loss of activity. The higher activity of this catalyst was attributed to higher dispersion and smaller particle size of ReNPs as observed from FE-TEM and XRD results. © 2017

2016
Veerakumar, P, Panneer Muthuselvam I, Hung C-T, Lin K-C, Chou F-C, Liu S-B.  2016.  Biomass-Derived Activated Carbon Supported Fe3O4 Nanoparticles as Recyclable Catalysts for Reduction of Nitroarenes. ACS Sustainable Chemistry and Engineering. 4:6772-6782., Number 12 AbstractWebsite

Highly porous beetroot-derived activated carbons incorporated with well-dispered magnetite nanoparticles (Fe3O4 NPs; average size ca. 3.8 ± 0.5 nm) were fabricated via a microwave-assisted synthesis route. The magnetic Fe3O4@BRAC catalysts so-fabricated were characterized by a variety of diffent physicochemical teniques, viz. XRD, FE-TEM, VSM, gas physisorption/chemisorption, TGA, XPS, Raman, ICP-AES, and FT-IR spectroscopy. The as-prepared catalysts were exploited for heterogeneous-phase reduction of a series of nitroaromatics (RNO2; R = H, OH, NH2, CH3, and COOH) under KOH as a base, isopropyl alcohol acting as a hydrogen donor as well as solvent and also tested with other solvents. The reaction system not only exhibits excellent activity with high anilines yield but also represents a green and durable catalytic process, which facilitates facile operation, easy separation, and catalyst recycle. © 2016 American Chemical Society.