Coauthored Publications with: Chen

Journal Article

Chen, B-J, Tsai P-Y, Huang T-K, Xia Z-H, Lin K-C, Chiou C-J, Sun B-J, Chang AHH.  2015.  Characterization of molecular channel in photodissociation of SOCl2 at 248 nm: Cl2 probing by cavity ring-down absorption spectroscopy. Physical Chemistry Chemical Physics. 17:7838-7847., Number 12 AbstractWebsite

A primary elimination channel of the chlorine molecule in the one-photon dissociation of SOCl2 at 248 nm was investigated using cavity ring-down absorption spectroscopy (CRDS). By means of spectral simulation, the ratio of the vibrational population in the v = 0, 1, and 2 levels was evaluated to be 1:(0.10 ± 0.02):(0.009 ± 0.005), corresponding to a Boltzmann vibrational temperature of 340 ± 30 K. The Cl2 molecular channel was obtained with a quantum yield of 0.4 ± 0.2 from the X1A′ ground state of SOCl2via internal conversion. The dissociation mechanism differs from a prior study where a smaller yield of <3% was obtained, initiated from the 21A′ excited state. Temperature-dependence measurements of the Cl2 fragment turn out to support our mechanism. With the aid of ab initio potential energy calculations, two dissociation routes to the molecular products were found, including one synchronous dissociation pathway via a three-center transition state (TS) and the other sequential dissociation pathway via a roaming-mediated isomerization TS. The latter mechanism with a lower energy barrier dominates the dissociation reaction. This journal is © the Owner Societies.
Chen, M-S, Fan H-F, Lin K-C.  2010.  Kinetic and thermodynamic investigation of rhodamine B adsorption at solid/solvent interfaces by use of evanescent-wave cavity ring-down spectroscopy. Analytical Chemistry. 82:868-877., Number 3 AbstractWebsite

Evanescent-wave cavity ring-down spectroscopy is applied to investigate the adsorption behavior of rhodamine B at three different interfaces. The adsorption equilibrium constant (Kads) and adsorption free energy of rhodamine B at the silica/methanol interface are determined to be (1.5 ± 0.2) × 104 M-1 and -23.8 ± 0.4 kJ/mol by use of a Langmuir isotherm model. A Langmuir-based kinetic model is also developed to determine the corresponding adsorption and desorption rate constants of (1.02 ± 0.03) × 102 M-1 s-1 and (7.1 ± 0.2) × 10-3 s-1, from which Kads is obtained to be (1.45 ± 0.09) × 104 M-1, in agreement with the value determined under equilibrium conditions. Similarly, when rhodamine B is at the chlorotrimethylsilane-immobilized silica/methanol interface, the adsorption and desorption rate constants are determined to be (1.7 ± 0.2) × 102 M-1 s-1 and (5.0 ± 1.0) × 10-3 s-1· The subsequent Kads is (3.6 ± 0.4) × 104 M-1, which is larger than that at the silica/methanol interface. The former adsorption is dominated by hydrophobic interaction, while the latter is subject to electrostatic attraction. When rhodamine B is at the silica/water interface, there exist three chemical forms, including zwitterion (R+B -), cation (RBH+), and lactone (RBL). A combination of double-layer and Langmuir competitive models is used to fit the adsorption isotherm as a function of solution pH, yielding Kads of (2.5 ± 0.2) × 104 M-1 and (1.1 ± 0.2) × 105 M-1 for R+B- and RBH +, respectively. RBL is considered to have the same Kads value as R+B-. © 2010 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.
Chen, Y-J, Tzeng H-Y, Fan H-F, Chen M-S, Huang J-S, Lin K-C.  2010.  Photoinduced electron transfer of oxazine 1/TiO2 nanoparticles at single molecule level by using confocal fluorescence microscopy. Langmuir. 26:9050-9060., Number 11 AbstractWebsite

Kinetics of photoinduced electron transfer (ET) from oxazine 1 dye to TiO2 nanoparticles (NPs) surface is studied at a single molecule level by using confocal fluorescence microscopy. Upon irradiation with a pulsed laser at 630 nm, the fluorescence lifetimes sampled among 100 different dye molecules are determined to yield an average lifetime of 2.9 ± 0.3 ns, which is close to the value of 3.0 ± 0.6 ns measured on the bare coverslip. The lifetime proximity suggests that most interfacial electron transfer (IFET) processes for the current system are inefficient, probably caused by physisorption between dye and the TiO2 film. However, there might exist some molecules which are quenched before fluorescing and fail to be detected. With the aid of autocorrelation analysis under a three-level energy system, the IFET kinetics of single dye molecules in the conduction band of TiO2 NPs is evaluated to be (1.0 ± 0.1)×104 s-1 averaged over 100 single molecules and the back ET rate constant is 4.7 ± 0.9 s-1. When a thicker TiO2 film is substituted, the resultant kinetic data do not make a significant difference. The trend of IFET efficacy agrees with the method of fluorescence lifetime measurements. The obtained forward ET rate constants are about ten times smaller than the photovoltage response measured in an assembled dye-sensitized solar cell. The discrepancy is discussed. The inhomogeneous and fluctuation characters for the IFET process are attributed to microenvironment variation for each single molecule. The obtained ET rates are much slower than the fluorescence relaxation. Such a small ET quantum yield is yet feasibly detectable at a single molecule level. © 2010 American Chemical Society.
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
Liu, C-Y, Tsai M-T, Tsai P-Y, Liu Y-T, Chen SY, Chang AHH, Lin K-C.  2011.  Gas-phase photodissociation of CH3CHBrCOCl at 248 nm: Detection of molecular fragments by time-resolved FT-IR spectroscopy. ChemPhysChem. 12:206-216., Number 1 AbstractWebsite

By employing time-resolved Fourier transform infrared emission spectroscopy, the fragments HCl (v=1-3), HBr (v=1), and CO (v=1-3) are detected in one-photon dissociation of 2-bromopropionyl chloride (CH3CHBrCOCl) at 248 nm. Ar gas is added to induce internal conversion and to enhance the fragment yields. The time-resolved high-resolution spectra of HCl and CO were analyzed to determine the rovibrational energy deposition of 10.0A ±0.2 and 7.4A ±0.6 kcal mol-1, respectively, while the rotational energy in HBr is evaluated to be 0.9A ±0.1 kcal mol-1. The branching ratio of HCl(v>0)/HBr(v>0) is estimated to be 1:0.53. The bond selectivity of halide formation in the photolysis follows the same trend as the halogen atom elimination. The probability of HCl contribution from a hot Cl reaction with the precursor is negligible according to the measurements of HCl amount by adding an active reagent, Br2, in the system. The HCl elimination channel under Ar addition is verified to be slower by two orders of magnitude than the Cl elimination channel. With the aid of ab initio calculations, the observed fragments are dissociated from the hot ground state CH3CHBrCOCl. A two-body dissociation channel is favored leading to either HCl+CH3CBrCO or HBr+CH2CHCOCl, in which the CH 3CBrCO moiety may further undergo secondary dissociation to release CO. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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.
Chen, S-Y, Tsai P-Y, Lin H-C, Wu C-C, Lin K-C, Sun BJ, Chang AHH.  2011.  I2 molecular elimination in single-photon dissociation of CH2I2 at 248 nm by using cavity ring-down absorption spectroscopy. Journal of Chemical Physics. 134, Number 3 AbstractWebsite

Following single-photon dissociation of CH2I2 at 248 nm, I2 molecular elimination is detected by using cavity ring-down absorption spectroscopy. The technique comprises two laser beams propagating in a perpendicular configuration, in which a tunable laser beam along the axis of the ring-down cell probes the I2 fragment in the B 3 ou + - X 1 g + transition. The nascent vibrational populations for v 0, 1, and 2 levels are obtained with a population ratio of 1:(0.65 0.10):(0.30 0.05), corresponding to a Boltzmann-like vibrational temperature of 544 73 K. The quantum yield of the ground state I2 elimination reaction is determined to be 0.0040 0.0025. With the aid of ab initio potential energy calculations, the pathway of molecular elimination is proposed on the energetic ground state CH2I2 via internal conversion, followed by asynchronous three-center dissociation. A positive temperature effect supports the proposed mechanism. © 2011 American Institute of Physics.
Manavalan, S, Veerakumar P, Chen S-M, Murugan K, Lin K-C.  2019.  Binder-Free Modification of a Glassy Carbon Electrode by Using Porous Carbon for Voltammetric Determination of Nitro Isomers. ACS Omega. 4(5):8907-8918. AbstractWebsite

In this study, Liquidambar formosana tree leaves have been used as a renewable biomass precursor for preparing porous carbons (PCs). The PCs were produced by pyrolysis of natural waste of leaves after 10% KOH activation under a nitrogen atmosphere and characterized by a variety of state-of-the-art techniques. The PCs possess a large surface area, micro-/mesoporosity, and functional groups on its surface. A glassy carbon electrode modified with high PCs was explored as an efficient binder-free electrocatalyst material for the voltammetric determination of nitro isomers such as 3-nitroaniline (3-NA) and 4-nitroaniline (4-NA). Under optimal experimental conditions, the electrochemical detection of 3-NA and 4-NA was found to have a wide linear range of 0.2-115.6 and 0.5-120 μM and a low detection limit of 0.0551 and 0.0326 μM, respectively, with appreciable selectivity. This route not only enhanced the benefit from biomass wastes but also reduced the cost of producing electrode materials for electrochemical sensors. Additionally, the sensor was successfully applied in the determination of nitro isomers even in the presence of other common electroactive interference and real samples analysis (beverage and pineapple jam solutions). Therefore, the proposed method is simple, rapid, stable, sensitive, specific, reproducible, and cost-effective and can be applicable for real sample detection. © 2019 American Chemical Society.
Kao, M-J, Chen C-H, Tsai P-Y, Lim T-S, Lin K-C, Luh T-Y.  2011.  Hydrogen-bonding-induced one-handed helical polynorbornenes appended with chiral alaninegland. Macromolecular Chemistry and Physics. 212:2328-2338., Number 21 AbstractWebsite

Polynorbornenes appended with anthracene and chiral alanine linkers are synthesized. Hydrogen bonding between the adjacent bisamidic linkers brings adjacent anthracene chromophores in a more suitable orientation for exciton coupling and renders one-handed helical structures for these polymers. Excimer formation is observed from their emission spectra. Monoamidic linkers provide only one hydrogen bond, which would be less robust and result in much lower circular dichroic response. Hydrogen bonding between the adjacent chiral alanine linkers brings appended anthracene in a more suitable orientation for exciton coupling and excimer formation, rendering one-handed helical structures in polynorbornenes. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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.