Photolysis Dynamics Laser Chemistry Lab

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.

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.

Carbon mesoporous materials (CPMs) have great potential in the field of heterogeneous catalysis. Highly dispersed ruthenium nanoparticles (RuNPs) embedded in three dimensional (3D) CPMs as catalysts with a high surface area (1474 m2 g-1) were prepared by microwave-thermal reduction processes. Characterization technologies including X-ray diffraction (XRD), N2 adsorption/desorption isotherm measurements, field emission transmission electron microscopy (FE-TEM), thermogravimetric analysis (TGA), hydrogen temperature-programmed reduction (H2-TPR), Raman spectroscopy and 13C solid state cross polarization and magic angle spinning (13C CP/MAS) NMR spectroscopy were utilized to scrutinize the catalysts. It was revealed that the Ru/CPM catalysts exhibited a highly ordered 3D mesoporous structure and a large surface area and were widely used as catalysts for reduction reactions. Reduction of p-nitroaniline (p-NA) and crystal violet (CV) using NaBH4 with the use of this catalyst was studied by means of UV-vis spectroscopy. Here, NaBH4 acts as a hydrogen donor. This catalyst shows an excellent catalytic activity towards reduction of p-NA and CV dye at room temperature. Due to the promising properties of CPMs, they can be utilized to fabricate 3D carbon-based materials for a variety of novel applications. © The Royal Society of Chemistry 2015.

Acid-functionalized mesoporous carbons (AF-MPCs) have been synthesized and used as adsorbents for removal of an azo dye, Eriochrome Black-T (EBT), from aqueous solution. To generate acid surface functionalities, mesoporous carbons (MPCs) were treated with sulfuric acid. Characterization of the samples was analyzed by XRD, Raman spectra, N 2 adsorption-desorption, FE-TEM, TGA, and FT-IR studies. The adsorption studies were carried out under various parameters, such as pH, adsorbent dosage, contact time, initial dye concentration solution temperature, and salt concentration. The results showed that the EBT adsorption onto samples was affected by the pH of solution; the maximum EBT ion adsorption took place at pH 1; and the adsorption uptake was increased with an increase in the initial dye concentration. Moreover, the mechanism of adsorption was investigated using kinetic, diffusion, and isotherm models. The best fit was obtained by the Langmuir model with high correlation coefficients (R 2 = 0.9463) with a maximum monolayer adsorption capacity of 117.0 mg·g -1 . The adsorbed anionic EBT dye molecules were eluted by ethanol solvent with the recovery percentage of 98%. Moreover, this study demonstrates that AF-MPCs can be successfully used as a low-cost adsorbent for the removal of EBT from aqueous solutions. © 2019 American Chemical Society.

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

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.

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

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

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.

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.

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

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.

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.

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

Chicken feather-derived high-surface-area porous activated carbon (CFAC) material was prepared using chemical activation. A new composite composed of Ru-Pd nanoparticles supported on CFAC (Ru-Pd@CFAC) has been prepared by microwave-thermal reduction in the presence of the support. Characterization by XRD, Raman, BET, FE-SEM/TEM, FT-IR, TGA, XPS, HAADF-STEM-EDS, H2-chemisorption, H2-TPR, and ICP-AES was used to analyze the catalyst. This catalyst is found to be efficient for the reduction of hexavalent chromium (CrVI), potassium ferricyanide (K3[Fe(CN)6]), 4-nitrophenol (4-NP), and pendimethalin (PDM), at room temperature, and remains stable, even after several repeated runs. Moreover, it showed excellent catalytic activity compared with the monometallic counterparts. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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.

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

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

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.

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.

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.

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.

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.

A primary dissociation channel of Br 2 elimination is detected following a single-photon absorption of (COBr) 2 at 248 nm by using cavity ring-down absorption spectroscopy. The technique contains two laser beams propagating in a perpendicular configuration. The tunable laser beam along the axis of the ring-down cell probes the Br 2 fragment in the B 3Π + ou-X 1Σ g + transition. The measurements of laser energy- and pressure-dependence and addition of a Br scavenger are further carried out to rule out the probability of Br 2 contribution from a secondary reaction. By means of spectral simulation, the ratio of nascent vibrational population for v = 0, 1, and 2 levels is evaluated to be 1:(0.65 ± 0.09):(0.34 ± 0.07), corresponding to a Boltzmann vibrational temperature of 893 ± 31 K. The quantum yield of the ground state Br 2 elimination reaction is determined to be 0.11 ± 0.06. With the aid of ab initio potential energy calculations, the pathway of molecular elimination is proposed on the energetic ground state (COBr) 2 via internal conversion. A four-center dissociation mechanism is followed synchronously or sequentially yielding three fragments of Br 2 + 2CO. The resulting Br 2 is anticipated to be vibrationally hot. The measurement of a positive temperature effect supports the proposed mechanism. © 2011 American Institute of Physics.

Evanescent wave cavity ring-down absorption spectroscopy (EW-CRDS) is employed to study interaction and binding kinetics of DNA strands by using gold nanoparticles (Au NPs) as sensitive reporters. These Au NPs are connected to target DNA of study that hybridizes with the complementary DNA fixed on the silica surface. By the absorbance of Au NPs, the interaction between two DNA strands may be examined to yield an adsorption equilibrium constant of 2.2×1010M-1 using Langmuir fit. The binding efficiency that is affected by ion concentration, buffer pH and temperature is also examined. This approach is then applied to the label-free detection of the DNA mutation diseases using the sandwich hybridization assay. For monitoring a gene associated with sickle-cell anemia, the detection limit and the adsorption equilibrium constant is determined to be 1.2pM and (3.7±0.8)×1010M-1, distinct difference from the perfectly matched DNA sequence that yields the corresponding 0.5pM and (1.1±0.2)×1011M-1. The EW-CRDS method appears to have great potential for the investigation of the kinetics of a wide range of biological reactions. © 2014 Elsevier B.V.