Order Rate Constants Research Articles

Carbon Dioxide Insertion into Bridging Iron Hydrides: Kinetic and Mechanistic Studies.

The reduction of CO2 to formic acid by transition metal hydrides is a potential pathway to access reactive C1 compounds. To date, no kinetic study has been reported for insertion of a bridging hydride in a weak-field ligated complex into CO2; such centers have relevance to metalloenzymes that catalyze this reaction. Herein, we report the kinetic study of the reaction of a tri(μ-hydride)triiron(II/II/II) cluster supported by a tris(β-diketimine) cyclophane (1) with CO2 monitored by 1H-NMR and temperature-controlled UV-vis spectroscopy. We found that 1 reacts with CO2 to traverse the reported monoformate (1-CO 2 ) and a diformate complex (1-2CO 2 ) at 298 K in toluene, and ultimately yields the triformate species (1-3CO 2 ) at elevated temperature. The second order rate constant, H/D kinetic isotope effect, ∆H ‡,and ∆S ‡for formation of 1-CO 2 were determined as 8.4(3)×10-4 M-1·s-1, 1.08(9), 11(1) kcal·mol-1, and -3(1)×10 cal·mol-1·K-1, respectively at 298 K. These parameters suggest that CO2 coordination to the iron centers does not coordinate prior to the rate controlling step whereas Fe-H bond cleavage does.

Development of a rate law for arsenite oxidation by manganese oxides

Abstract Arsenite (As(III)), may be rapidly oxidized to arsenate (As(V)) by manganese oxides over a wide range of pH. Interestingly, pseudo-first order rate constants for Mn(IV) oxides (MnO2) reported in the literature differ by orders of magnitude, mainly due to the fact that experimental conditions have not been normalized and surface passivation may hinder the reaction rate. As a result, a formal kinetic rate law for the oxidation of As(III) by MnO2 does not exist. In this study, a comprehensive rate law that describes the abiotic oxidation of As(III) by vernadite (δ-MnO2) was developed by systematically varying pH and the concentrations of δ-MnO2 and As(III). Experiments were performed with excess δ-MnO2 compared to As(III) in buffered solutions with an ionic strength typical of freshwater environments to reflect the geochemical conditions of most environments. The half-life of the pseudo-first order reaction is less than three minutes in all experiments. Results show the initial reaction rate is proportional to the concentrations of δ-MnO2 and As(III) and independent of pH in the pH range 4–9. However, below pH 6 and above pH 8 the pseudo-first order rate constant is slightly lower due to the protonation of the surface δ-MnO2 and the deprotonation of As(III). Overall, the reaction follows a first order rate law with respect to As(III) and effective surface sites of δ-MnO2 and zeroth order with respect to pH. The overall second order rate constant, k, was calculated to be 0.36 ± 0.11 L h−1 m−2. This rate constant is comparable to the vast majority of rate constants derived from previously published data when using the effective surface sites of MnO2 as reactive species only, indicating the most influential factors of As(III) oxidation by MnO2 are constrained in the developed rate law. Based on the present experiments, the oxidation of As(III) by MnO2 is proposed to proceed as one two-electron transfer reaction between As(III) and Mn(IV) to eventually form As(V) and Mn2+ species. Two steps of one-electron transfer, however, may be possible though it is likely that both Mn(IV) and Mn(III) species are ultimately reduced to Mn2+. Comproportionation of Mn2+ and Mn(IV) to Mn(III) does not seem to be important on the time scale of these experiments.

Hydrodesulphurization of dibenzothiophene on NiMoS catalysts: Impact of the carbon support on the reaction kinetics

The hydrodesulphurization (HDS) activity of nickel molybdenum sulphided catalysts supported on activated carbon (NiMoS/AC), activated petroleum coke (NiMoS/APC), and conventional alumina (NiMo/γ‐Al2O3) have been compared using dibenzothiophene (DBT) as a model reactant. The reactions were carried out in a slurry‐phase batch microreactor at different reaction times (30–120 min) and temperatures (588–638 K) and a fixed H2 pressure (4.8 MPa). The NiMoS/APC catalyst had higher dispersion than the NiMoS/AC catalyst, resulting in a higher DBT conversion activity per gram of catalyst on the NiMoS/APC catalyst. However, similar activities were obtained on both catalysts when accounting for the NiMoS dispersion. The NiMoS/APC activity was marginally lower than the NiMoS/γ‐Al2O3 commercial catalyst, suggesting that activated petcoke is a promising support for NiMoS catalysts. The pseudo 1st order rate constants for both the direct desulphurization (DDS) and hydrogenation (HYD) reaction pathways were of similar magnitude on the NiMoS/APC catalyst, as were the apparent activation energies. Hence the selectivities for HYD versus DDS were favoured equally on the NiMoS/APC, unlike on NiMoS/Al2O3 where the DDS of DBT is favoured, or the NiMoS/AC where the DDS of DBT is favoured at higher temperatures (> 603 K). The results of this study demonstrate that raw petcoke derived from Canadian oilsands can be converted to a useful catalyst support for hydrotreating catalysts that have high NiMoS dispersion and HDS activity, comparable to that of a commercial NiMoS/Al2O3 catalyst.

Photodegradation of formylmethylflavin by side–chain and isoalloxazine ring cleavage in alkaline solution: A kinetic study

The photodegradation of fromylmethylflavin (FMF), a major intermediate product in the photolysis of riboflavin, in the pH range 8.0–12.0 has been studied. FMF undergoes photodegradation by side–chain cleavage to give lumichrome (LC) and lumiflavin (LF) in alkaline solution. It is also degraded by the hydrolysis of isoalloxazine ring to form 1,2–dihydro–1–methyl–2–keto–3–quinoxaline carboxylic acid (KA) and 1,2,3,4–tetrahydro–1–methyl–2,3–dioxoquinoxaline (DQ) and is oxidized to carboxymethylflavin (CMF) in alkaline solution. The photodegradation of FMF follows simultaneous first–order kinetics to form the side–chain, ring cleavage and oxidation products. The apparent first–order rate constants (kobs) for these reactions have been determined and are in the range of 0.15 (pH 8.0) to 4.98 × 102 min–1 (pH 12.0). The rate constants for the formation of the photoproducts (LC, LF, CMF, KA, DQ) have also been determined. The formation of the photoproducts is enhanced with pH due to the sensitivity of flavin triplet to alkaline hydrolysis. FMF and photodegradation products have been determined by a multicomponent spectrofluorimetric method in degraded solutions. It involves the separation of LC and LF by chloroform extraction at pH 2 followed by the choloroform extraction of undegraded FMF at pH 6.5 and their assay at 478 (LC) and 530 nm (LF and FMF), respectively. The aqueous phase is used for the assay of CMF, KA and DQ at 530, 443 and 420 nm, respectively. The mode of photodegradation of FMF has been discussed.

Developing a julolidine-fluorescein-based hybrid as a highly sensitive fluorescent probe for sensing and bioimaging cysteine in living cells

Cysteine (Cys) plays an important role in both maintaining intracellular redox homeostasis and regulating protein structure and function, developing fluorescence probes for monitoring Cys selectively and sensitively is thereby highly needed for understanding its pathophysiological significance. Herein we designed a new fluorescent probe (FRCA) composed of a julolidine-fluorescein-based hybrid as the fluorescence reporter and an acrylate moiety as the Cys response site. It manifested the following advantage: a turn-on fluorescence response at 567 nm when excited at 538 nm in phosphate buffer solution, rapid discrimination of Cys from other biothiols (glutathione and homocysteine) and cysteine-containing bovine serum albumin by virtue of its different second order rate constants with them, and a very low detection limit of 39.2 nM. Through a combination of mass spectrum analysis and density functional theory calculation we further identified its sensing mechanism to Cys as suppression of photo-induced electron transfer quenching. Additionally, this probe was successfully used to imagine Cys in HepG2 cells.

ZnO catalyzed transesterification of Madhuca indica oil in supercritical methanol

An integrated pathway (heterogeneous catalyst with supercritical pathway) was studied to develop a most viable route for the synthesis of fatty acid methyl esters useful as biodiesel. Madhuca indica (Mahua) oil was transesterified using supercritical methanol and ZnO at 523 K, 10 MPa and molar ratio of 40:1 (alcohol:oil). ZnO was synthesized by solution combustion using various fuels (urea, glycine, lactose, oxalyl dihydrazide, ascorbic acid (AA)). Also, different morphologies of ZnO (nanorods (NR), nanoflowers, nanoparticles, nanospheres) were obtained via hydrothermal, precipitation, sonochemical and sol-gel synthesis. Pseudo first order rate constants ranging from (3.46 to 16.7) × 10−4 s−1 (>0.99 × 10−4 s−1 for uncatalyzed reaction) at 523 K, 10 MPa were obtained. ZnO-AA (solution combustion) and ZnO-NR (hydrothermal) were found to be the most active catalysts. Activation energies of 42 kJ/mol and 17 kJ/mol (<75 kJ/mol for uncatalyzed reaction) were obtained with ZnO-AA and ZnO-NR indicating the superiority of the integrated process.

Enhanced oxidation of aniline using Fe(III)-S(IV) system: Role of different oxysulfur radicals

In this paper, the efficiency of Fe(III)-S(IV) system used for advanced oxidation processes (AOPs) has been investigated using aniline as a pollutant model compound in water. The chemical kinetics, influencing factors, and mechanism of aniline oxidation are examined with an emphasis on the contribution of the different oxysulfur radicals (mainly SO4− and SO5−). Our results show a significant enhancement in the efficiency of aniline oxidation observed at pH 4.0 with 1.0 mM S(IV) and 0.1 mM Fe(III) concentrations. Moreover, the degradation efficiency drastically decreases to 10% in the absence of oxygen indicating the significant role of oxygen in this type of process. Through competition kinetic experiments and radical scavenger experiments, it is shown that SO5− is responsible for about 60% of the aniline oxidation in the Fe(III)-S(IV) system under the typical conditions investigated in this work. For the first time we have determined the second order rate constant between SO5− and aniline (5.8 ± 0.6 × 106 M−1 s−1 (at pH 3.0) and SO4− and aniline 7.7 ± 0.5 × 109 M−1 s−1 (at pH 3.0)). Sequential experiments with successive additions of sulfite drastically improve the oxidation efficiency. These findings may provide a precise understanding of the overall mechanism and may have promising implications in developing a new cost-effective technology for the treatment of organic compounds-containing water. Furthermore, the results of this work help to understand the relevance and mechanism of organic contaminants oxidation by SO5−, which has not been given much attention in conventional SR-AOPs using peroxymonosulfate.

Comparative Study of Kinetic and Mechanistic Study of Oxidation of L-Alanine and L-Proline by Sodium Periodate Catalyzed by Osmium(VIII) in Micromolar Concentrations

The kinetics of oxidation of two aliphatic α-amino acids (AA), namely, alanine and proline by NaIO4 has been investigated in alkaline medium in the presence of osmium(VIII) catalyst at a constant ionic strength of 1.0 mol dm–3 and at 25°C. The reactions were very slow to be measured in the absence of the catalyst. The reactions have a first order with respect both to [Os(VIII)] and [NaIO4], and fractional order with respect to both [L-alanine] (Ala) and [L-proline](Pro). The reaction show negligible effect of dielectric constant and ionic strength of medium. Increasing [OH–] concentration was found to decrease the oxidation rates while mercuric acetate acts as scavenger for both the reactions. A plausible oxidation mechanism has been proposed and the rate law expression has been derived. Both spectral and kinetic evidences revealed formation of intermediate complexes between AA and Os(VIII) before the rate-controlling step. Kinetic investigations have revealed that the order of reactivity is Pro > Ala. The complex thus formed reacts with the oxidant [NaIO4] by an inner-sphere mechanism with formation of the oxidation products of the amino acids which were identified as the corresponding carboxylic compounds, ammonium ion and carbon dioxide. The activation parameters of the first order rate constants were evaluated and discussed.

Effect of Temperature on Interesterification of Rapeseed Oil with Methyl Acetate in Presence of BuOK/BuOH

If the interesterification reaction of rapeseed oil with methyl acetate at reactant to oil molar ratio of 18:1 in presence of potassium tert-butoxide in tert-butanol of molar ratio to oil 0.08 is conducted at a temperature of about 35 °C, reaction time for full conversion of oil is shorter than one hour, while at a temperature of 55 °C it is approximately 15 minutes. Reaction time at the desired temperature has a wide "optimal" range and cannot be an effective variable for the process optimisation. Experimental results at the temperature of 25 °C confirm the pseudo-first order of the reaction, which lowered towards the end of the reaction. The pseudo-first order rate constant was 0.63 min-1. Fuel characteristics of the interesterification reaction mixtures without purification improved with the rising of reaction temperature from 35 °C to 55 °C, however, they fail to meet the requirements of standard EN14214 for biodiesel. Methyl acetate to oil molar ratio 18:1 is too low for obtaining products with kinematic viscosity below 5.0 mm2/s.

Model peptide for anti-sigma factor domain HHCC zinc fingers: high reactivity toward 1O2 leads to domain unfolding.

All organisms have to cope with the deleterious effects of reactive oxygen species. Some of them are able to mount a transcriptional response to various oxidative stresses, which involves sensor proteins capable of assessing the redox status of the cell or to detect reactive oxygen species. In this article, we describe the design, synthesis and characterization of Zn·LASD(HHCC), a model for the Zn(Cys)2(His)2 zinc finger site of ChrR, a sensor protein involved in the bacterial defence against singlet oxygen that belongs to the family of zinc-binding anti-sigma factors possessing a characteristic H/C-X24/25-H-X3-C-X2-C motif. The 46-amino acid model peptide LASD(HHCC) was synthetized by solid phase peptide synthesis and its Zn2+-binding properties were investigated using electronic absorption, circular dichroism and NMR. LASD(HHCC) forms a 1 : 1 complex with Zn2+, namely Zn·LASD(HHCC), that adopts a well-defined conformation with the Zn2+ ion capping a 3-helix core that reproduces almost perfectly the fold of the ChrR in the vicinity of its zinc site. H2O2 reacts with Zn·LASD(HHCC) to yield a disulfide with a second order rate constant of 0.030 ± 0.002 M-1 s-1. Zn·LASD(HHCC) reacts rapidly with singlet oxygen to yield sulfinates and sulfonates. A lower limit of the chemical reaction rate constant between Zn·LASD(HHCC) and 1O2 was determined to be 3.9 × 106 M-1 s-1. Therefore, the Zn(Cys)2(His)2 site of Zn·LASD(HHCC) appears to be at least 5 times more reactive toward these two oxidants than that of a classical ββα zinc finger. Consequences for the activation mechanism of ChrR are discussed.

Biological Reduction of Nitrate and Perchlorate in Soil Microcosms: An Electron Donor Comparison of Glycerol, Emulsified Oil, and Mulch Extract

AbstractDiverse technologies have been developed and tested for their efficacy in remediating perchlorate‐contaminated surface water, groundwater, and soil. Biological reduction, particularly when coupled with electron donor augmentation, has been shown to be one of the most cost‐effective alternatives. Numerous electron donors have been evaluated in the literature, but few studies have compared standard vs. slow‐release electron donors for sequential nitrate and perchlorate reduction. This study evaluated the efficacy and kinetics of biological reduction in soil microcosms augmented with emulsified oil (EO), glycerol, and mulch extract. Results indicated that EO and glycerol spiked at approximately 100 times stoichiometric excess (i.e., 100x) achieved similar overall reductions and degradation rates for nitrate and perchlorate, although nitrate appeared to exhibit zero order kinetics while perchlorate exhibited first order kinetics. The zero order rate constants for nitrate reduction were 3.32 mg/L d and 2.57 mg/L d for EO and glycerol, respectively. The first order rate constant for perchlorate reduction was 0.36 day−1 for both EO and glycerol. Stable chemical oxygen demand (COD) concentrations also highlighted the slow‐release properties of EO, which would reduce electron donor consumption in comparison to soluble substrates in soil remediation applications. The microcosms augmented with mulch extract failed to demonstrate any nitrate or perchlorate reduction due to the extract's lower COD concentration. Augmentation with compost or additional processing (i.e., concentration) would be necessary to make the extract a viable alternative.

Simulated solar driven photolytic ozonation for the oxidation of aqueous recalcitrant-to-ozone tritosulfuron. Transformation products and toxicity

This work reports the combination of ozone and solar radiation as an advanced oxidation process to remove the herbicide tritosufuron (TSF) in water. Firstly, the recalcitrance of TSF has been assessed, obtaining an ozonation second order rate constant of 5–154 M−1 min−1 in the range of pH from 5 to 8; while the rate constant with HO was found to be (1.8–3.1)·109 M−1 s−1. Secondly, the simultaneous application of simulated solar radiation in between 300 and 800 nm and ozone resulted positive in the oxidation rate of TSF. Mineralization extent was also higher. Less effective oxidation was achieved after limiting the radiation to the range 360–800 nm or 390–800 nm; also completely inappropriate for mineralization. Thirdly, the detected transformation products (TPs) demonstrated the vulnerability of TSF molecule to be attacked by HO in the sulfonylurea bridge. The combination of ozone and radiation of 300–800 nm led to the most effective removal of the TPs. Finally, after the photolytic ozonation treatment toxicity was also evaluated in terms of phytotoxicity towards the germination and root elongation of Lactuca Sativa seeds, and toxicity by immobilization tests of Daphnia Magna.

Engineering SpyCatcher Variants with Proteolytic Sites for Less‐Trace Ligation

Summary of main observation and conclusionThe SpyTag/SpyCatcher reaction is a powerful tool for bioconjugation, but it leaves a complex of considerable size after ligation. To facilitate removal of the catalytic fragment, proteolytic recognition sites (such as DDDDK, AVLQ, and WELQ) were directly engineered into the first or second loop of SpyCatcher at locations after the reactive lysine to give a set of cleavable SpyCatcher variants. Among them, SpyCatcherDDDDK exhibits excellent reactivity with SpyTag and could still be cleaved proteolytically by enterokinase after ligation. Notably, SpyCatcherDDDDK is disordered in solution and forms an ordered complex upon reaction with SpyTag with a second order rate constant of 99.2 ± 0.1 M–1·s–1, which is comparable to, if not faster than, most click reactions. The results demonstrate the high sequence plasticity of SpyCatcher and suggest that covalent bond formation may confer robustness on the folded structure against extensive mutation. These variants add to the expanding toolbox of genetically‐encoded peptide‐protein chemistry with diverse features.

Photocatalytic activity of biosynthesized CeO2 nano particles

This paper focuses on a cost effective and environment friendly technique for green synthesis of cerium oxide (CeO2) nano particles from cerium (III) nitrate hexahydrate solution by co-precipitation method using the leaf extract of different species of Artemisia pallens which acts as reducing and capping agent. The prepared CeO2 nano particles were characterized by XRD, TEM, FTIR, UV–Vis spectroscopy. The Photocatalytic activity of the prepared ceria powders was determined by their ability to degrade Methylene blue solution under UV-light radiation. The photo degradation result observed with 10 mg/L ceria at pH = 11 for 180 min have highest output and pseudo 1st order rate constant was 0.983.

Quantitative structure-activity relationship models for predicting reaction rate constants of organic contaminants with hydrated electrons and their mechanistic pathways

The hydrated electron (eaq−)-based reduction processes are promising for removing organic pollutants in water engineering systems. The reductive kinetics, especially the second order rate constants (keaq−) of eaq− with organic compounds, is important for evaluating and modeling the advanced reduction processes. In this study, the keaq−values for aliphatic compounds and phenyl-based compounds are, for the first time, modeled by the quantitative structure-activity relationship (QSAR) method. The structural features governing the reactivity of two classes of organic compounds toward eaq− were revealed, and the energy of the lowest unoccupied molecular orbital (ELUMO), one-electron reduction potential (ERED) and polarizability (α) were found to be the important molecular parameters in both two models. The built QSAR models provide robust predictive tools for estimating the removal of emerging pollutants using eaq− during wastewater treatment processes. Additionally, quantum chemical calculations were employed to probe into the mechanism and feasibility of the single electron transfer (SET) pathway in the eaq−-based reduction process. The thermodynamic investigation suggests that the compounds with electron-withdrawing groups tend to possess higher keaq− and lower Gibbs free energy (ΔGSET) and Gibbs free energies of activation (∆‡GSET∘) than the ones with electron-donating groups, indicating the SET process occurs more readily. It is also found that the refractory halogenated compounds can achieve dehalogenation via the SET pathway.

A systematic investigation on the bactericidal transient species generated by photo-sensitization of natural organic matter (NOM) during solar and photo-Fenton disinfection of surface waters

In this work, the role of dissolved oxygen in the solar and the photo-Fenton-mediated E. coli inactivation process was put under scrutiny. The effect of transient species that were produced in the presence of various natural organic matter isolates (NOM), namely Suwannee River (SR) NOM, Nordic Reservoir (NR) NOM, SR Humic acid (SRHA), and SR Fulvic acid (SRFA) was studied in detail. The role of 1O2 in this reaction was systematically evaluated by modifying the O2 concentration (N2/O2 purging) and the matrix composition (10, 50, and 100% deuterium oxide (D2O) v/v). In the presence of NOM, 1O2 was generated and the enhancement of E. coli inactivation rate due to charge transfer from triplet state to molecular oxygen. The comparison between SR and NR NOM showed that for these compounds, triplet state of NOM (3NOM*), and 1O2 were the more favorable active species in E. coli inactivation, respectively. Also, the second order rate constants (kE. coli2nd) of E. coli with 3NOM*, and 1O2 were calculated by using the steady state approximation. The obtained results showed that the rate values of 1O2 related to NR NOM was ∼ 5.6 times higher than SR NOM, while the rate values of 3NOM* for SR NOM was ∼ 8.7 times higher than NR NOM. We also determined the effect of these organic matter isolates in the photo-Fenton process and its constituents (solar/Fe2+, solar/H2O2, and solar/Fe2+/H2O2). In presence of NOM, the photo-Fenton process inactivation rates increased which confirmed that the combined processes has additional pathways generated with disinfecting effect during solar exposure of bacteria.

Hexavalent chromium reduction through redox electrolytic cell with urea and cow urine as anolyte

The present study demonstrates the potential utilization of urea/cow urine as anolyte for Cr(VI) reduction via a simple three-chambered electrolytic cell. The inherent chemical energy in the dual-waste stream (Cr(VI)-urea/urine) is employed for its self-oxidation-reduction without the need for any external energy supply. Ni foam as electroactive anode and catalyst-free carbon felt as cathode, along with the appropriate positioning of ion-selective separators, indirectly improved the cell performance by impeding electrolyte crossover. A fundamental study involving five different membrane configurations was conducted herein to improve Cr(VI) reduction efficiency. The Cr(VI) reduction efficiencies were 11.84 ± 0.27%, 10.55 ± 0.17%, 77.24 ± 0.38% at 24 h, 13.57 ± 0.25% at 72 h with glass frit, cation exchange membrane (CEM), sandwiched membrane, and anion exchange membrane (AEM) as separators in a dual-chambered H-cell, respectively, with an initial Cr(VI) concentration of 100 mg/L. The fifth configuration, consisting of a middle chamber between the anode and cathode with the CEM close to the anode and the AEM close to the cathode resulted in a reduction efficiency of 79.98 ± 2.24% within 45 min for an initial Cr(VI) concentration of 400 mg/L. The first order rate constants were determined to be 0.024, 0.018, and 0.013 min−1 for Cr(VI) concentrations of 100, 200, and 400 mg/L, respectively. Moreover, when urea was replaced with cow urine as anolyte, a reduction efficiency of 98.94 ± 1.28% was achieved at pH 2 in 45 min with 400 mg/L as initial Cr(VI) concentration. Furthermore, the XPS spectra of reduced Cr corresponding to binding energies of 579.4 eV and 589.3 eV, respectively, confirmed the presence of low-toxic Cr(III). The effect of applied load, initial Cr(VI) and urea concentration, Cr(VI) reduction under different initial H2SO4 concentrations were succinctly investigated to evaluate the performance of the electrolytic cell. The redox electrolytic cell can thus be an alternative to the conventional chemical or energy intensive processes for the reduction of hexavalent chromium.

Extract of Ginkgo biloba leaves mediated biosynthesis of catalytically active and recyclable silver nanoparticles

In the present study, catalytically active Ag nanoparticles were biosynthesized by the extract of Ginkgo biloba leaves through a facile and green manner. Well-dispersed Ag nanoparticles in spherical shape with size of 20–40 nm were obtained. Catalyzing the reduction of four typical pollutants, 4-nitrophenol, congo red, methyl orange, and rhodamine B, were achieved using the synthesized Ag nanoparticles, with the full conversion in 15–100 min. The pseudo-first order rate constant was calculated to be 0.0452 min−1, 0.0568 min−1, 0.0805 min−1, and 0.285 min−1 for 4-nitrophenol, congo red, methyl orange, and rhodamine B, respectively. Furthermore, the catalytic activity can be preserved for 5 successive cycles. Wide applications in selective reduction reactions for pollutants treatment and fine chemical synthesis can be expected using the obtained catalytically active and recyclable Ag nanoparticles.

Impacts of photochemical ageing on the half-lives and diagnostic ratio of polycyclic aromatic hydrocarbons intrinsic to PM2.5 collected from 'real-world' like combustion events of wood and rice straw burning.

The present experimental study describes the characteristics of polycyclic aromatic hydrocarbons (PAHs) emitted with PM2.5 particles during wood and rice straw burning as well as impacts of photochemical ageing on the half lives of particulate PAHs and their diagnostic ratio values. The photochemical degradation kinetics experiments were carried out by exposing the PM2.5 to light and synthetic air flow. Pseudo first order rate constants were calculated based on PAH loss as a function of exposure time. Relatively quick degradation of lighter PAHs (3-rings) [(0.2-0.5)h-1] than heavier PAHs (4-6 rings) [(0.0005-0.03)h-1] indicates substantial impact of PAH-substrate interaction through π-π stacking with the carbonaceous substrates. Moreover, our results showed distinct PAH diagnostic ratios (DR) for wood and rice straw burnings which, however, change with time due to photochemical degradation. The later may add uncertainties in the applications of DR values for source apportionment. Furthermore, considerably large half lives (100-3000 h) of the carcinogenic PAHs as estimated under ambient solar radiation may cause poor and adverse air quality in long range and therefore demands immediate regulations against uncontrolled biomass burning.

Kinetic analysis of liquid phase photocatalysis and photolysis: A frequent disguise!

Abstract Studies of phenol photocatalyzed oxidation and of organic dye photolyzed or photocatalyzed destruction which explored variable initial concentrations, Co, often assumed pseudo first order behavior, and fitted data to a semilog plot of concentration, C(t) vs time, and found that the apparent first order rate constant decreases with increasing Co. We show from multiple literature examples that this behavior often disguises a true zero order initial rate of reaction. We recommend a re-analysis of existing literature reporting first order rate constants which vary with initial reactant concentration, Co.