Hybrid method for accurate starch estimation in adulterated turmeric using Vis-NIR spectroscopy.

Turmeric is widely used as a health supplement and foodstuff in South East Asian countries because of its medicinal benefits. Like several other plants and peppers, turmeric is prone to exploitation because of its economic value, rising consumer need, and essential food element that adds colour and flavour. Due to this, quick and comprehensive testing processes are needed to detect adulterants in turmeric. In this study, pure turmeric powders were mixed with starch in proportions ranging from 0 to 50% with a 1% variation to obtain different combinations. Reflectance spectra of pure turmeric and starch mixed samples were recorded using a JASCO-V770 spectrometer from 400 to 2050 nm. The recorded spectra were pre-processed using a Multiplicative Scatter Correction (MSC) and Standard Normal Variate (SNV). The Savitzky-Golay (SG) filter was initially applied to these original (X), MSC, and SNV-corrected spectra. Secondly, the Extra Tree Regressor (ETR) feature selection method was employed to select the best features. Finally, principal component analysis (PCA) was used to reduce the dimension of the selected features. The stacked generalization method was applied to improve the performance of this work. Both regressors and classifier stacking techniques have been tested with different classification and regression methods. The K-Nearest Neighbours (KNN), Decision Tree (DT), and Random Forest (RF) models were used as base learners, and Logistic Regression (LRC) was used as a meta-model for classification and Linear Regression (LR) for regression analysis. The proposed method achieved the best regression performance with r2 of 0.999, Root Mean Square Error (RMSE) of 0.206, Ratio of Performance to Deviation (RPD) of 73.73, and Range Error Ratio (RER) of 480.58, whereas 100% F1 score and Matthew's Correlation Coefficient (MCC) classification performance.

Advances in Electrochemical and Catalytic Performance of Nanostructured FeCo2 O4 and Its Composites.

It is well established that the excessive and uncontrolled use of fossil fuels and organic chemicals have put a risk to the earth's environment and the life that sustains within it. Carbon-free, sustainable, alternative energy technologies have therefore become the prime focus of current research. Smart inorganic materials have emerged as the potential solution to suffice energy needs and remediate the organic pollutants discharged to the environment. One such promising, versatile material is FeCo2 O4 which has gained immense research interest in the present decade due to its high efficiency and performance in energy and environmental applications. Innovative material design strategies involving the interplay of nanostructured morphology, chemical composition, redox surface states, and defect engineering have significantly enhanced both electrochemical and catalytic properties of FeCo2 O4 . Therefore, this review article aims to provide the first-ever comprehensive account of the latest research and developments in design-synthesis strategies, characterization techniques, and applications of nanostructured FeCo2 O4 and its composites in various electrochemical as well as catalytic applications. A detailed account of the nanostructured FeCo2 O4 and its composites in various energy storage and conversion devices such as supercapacitors (SCs), batteries, and fuel cells has been presented. Furthermore, a special section has been devoted to highlight the role of FeCo2 O4 in enhancing the sluggish reaction kinetics of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in water splitting application. This review also highlights the role of nanostructured FeCo2 O4 in photocatalytic waste water treatment, gas sensing, and dual-phase membrane technologies wherein FeCo2 O4 has demonstrated promising performance.

Naphthalene diimides: perspectives and promise.

In this review, we describe the developments in the field of naphthalene diimides (NDIs) from 2016 to the presentday. NDIs are shown to be an increasingly interesting class of molecules due to their electronic properties, large electron deficient aromatic cores and tendency to self-assemble into functional structures. Almost all NDIs possess high electron affinity, good charge carrier mobility, and excellent thermal and oxidative stability, making them promising candidates for applications in organic electronics, photovoltaic devices, and flexible displays. NDIs have also been extensively studied due to their potential real-world uses across a wide variety of applications including supramolecular chemistry, sensing, host-guest complexes for molecular switching devices, such as catenanes and rotaxanes, ion-channels, catalysis, and medicine and as non-fullerene accepters in solar cells. In recent years, NDI research with respect to supramolecular assemblies and mechanoluminescent properties has also gained considerable traction. Thus, this review will assist a wide range of readers and researchers including chemists, physicists, biologists, medicinal chemists and materials scientists in understanding the scope for development and applicability of NDI dyes in their respective fields through a discussion of the main properties of NDI derivatives and of the status of emerging applications.

Surface functionalized highly porous date seed derived activated carbon and MoS2 nanocomposites for hydrogenation of CO2 into formic acid.

In recent years, substantial progress has been made towards developing effective catalysts for the hydrogenation of CO2 into fuels. However, the quest for a robust catalyst with high activity and stability still remains challenging. In this study, we present a cost-effective catalyst composed of MoS2 nanosheets and functionalized porous date seed-derived activated carbon (f-DSAC) for hydrogenation of CO2 into formic acid (FA). As-fabricated MoS2/f-DSAC catalysts were characterized by FE-SEM, XRD, Raman, FT-IR, BET, and CO2-TPD analyses. At first, bicarbonate (HCO3-) was successfully converted into FA with a high yield of 88% at 200 °C for 180 min under 10 bar H2 atmosphere. A possible reaction pathway for the conversion of HCO3- into FA is postulated. The catalyst has demonstrated high activity and long-term stability over five consecutive cycles. Additionally, MoS2/f-DSAC catalyst was effectively used for the conversion of gaseous CO2 into FA at 200 °C under 20 bar (CO2/H2 = 1:1) over 15 h. The catalyst exhibited a remarkable TOF of 510 h-1 with very low activation energy of 12 kJ mol-1, thus enhancing the catalytic conversion rate of CO2 into FA. Thus, this work demonstrates the MoS2/f-DSAC nanohybrid system as an efficient non-noble catalyst for converting CO2 into fuels.

Designing a Rare DNA-Like Double Helical Microfiber Superstructure via Self-Assembly of In Situ Carbon Fiber-Encapsulated WO3-x Nanorods as an Advanced Supercapacitor Material.

Double helical DNA structure is one of the most beautiful and fascinating nanoarchitecture nature has produced. Mimicking nature's design by the tailored synthesis of semiconductor nanomaterials such as WO3 into a DNA-like double helical superstructure could impart special properties, such as enhanced stability, electrical conductivity, information storage, signal processing, and catalysis, owing to the synergistic interaction across helices. However, double helical WO3 synthesis is extremely challenging and has never been reported earlier. This investigation presents the first-ever report on a facile synthesis route for designing a DNA-like double helical WO3-x/C microfiber superstructure via self-assembly of in situ carbon fiber-encapsulated WO3-x nanorods. This innovative design strategy is completely template-free and does not require predesigned helical templates or hydro/solvothermal treatment. Detailed spectroscopic material characterization and electrochemical studies confirmed that the double helical structure with carbon fiber-WO3-x heterostructures enabled effective induction and distribution of oxygen vacancies along with W5+/W6+ redox surface states. Furthermore, faster electrode-electrolyte interfacial kinetics, improved electrical conductivity, and cycling stability has been observed in the carbon fiber-WO3-x heterostructures which resulted in a high area specific capacitance of 401 mF cm-2 at 2 mA cm-2 with excellent capacitance retention of >94% for more than 5000 cycles. Additionally, the carbon fiber-WO3-x heterostructures demonstrated promising performance when fabricated in a solid-state asymmetric supercapacitor device with the power density of 498 W kg-1 at an energy density of 15.4 W h kg-1. Therefore, the rare DNA-like double helical WO3-x/C superstructure synthesized in this study could open new doorways toward in situ, facile fabrication of double helical superstructures for energy and environmental applications.

GO crosslinked hydrogel nanocomposites of chitosan/carboxymethyl cellulose - A versatile adsorbent for the treatment of dyes contaminated wastewater.

Graphene oxide (GO) crosslinked nanocomposites hydrogels (NCH) of chitosan (CS) and carboxymethyl cellulose (CMC) were synthesized and the feasibility of its application as a versatile adsorbent for the remediation of cationic (methylene blue, MB) as well as anionic (methyl orange, MO) dyes contaminated wastewater was explored. Initially, GO was functionalized with vinyltriethoxysilane which was subsequently used as a chemical crosslinker to synthesize the NCH of CS and CMC (CS/CMC-NCH) with the polymeric mixture of diallyldimethylammonium chloride and 2-acrylamido-2-methyl-1-propanesulfonic acid. About 99% dye was adsorbed from 50 mg/L dye solution of MB dye with 0.4 g/L of CS/CMC-NCH at pH 7, whereas, for MO about 82% dye was adsorbed with 0.6 g/L of CS/CMC-NCH at pH 3. The Adsorption of both dyes is well explained using pseudo-second-order and Langmuir models with the maximum adsorption capacities of 655.98 mgdye/gads for MB and 404.52 mgdye/gads for MO. Thermodynamics studies suggested spontaneous and exothermic nature of the adsorption process with values of ΔS < 0 and ΔH > 0. Furthermore, CS/CMC-NCH showed excellent regeneration capacity for continuous twenty cycles of adsorption-desorption. Therefore, the synthesized CS/CMC-NCH is a versatile adsorbent that can treat both anionic and cationic dyes contaminated wastewater.

Super porous TiO2 photocatalyst: Tailoring the agglomerate porosity into robust structural mesoporosity with enhanced surface area for efficient remediation of azo dye polluted waste water.

The low surface area of TiO2 (50 m2g-1 - Degussa P25) due to randomly oriented, agglomerated nanostructures and charge carrier recombination tendency, has till date been its major limitation for photocatalytic remediation of polluted wastewater. This study presents an innovative process to design super porous TiO2 nanostructures with high effective surface area (238 m2g-1), robust, structurally ordered mesoporosity via a simple sol-gel assisted reflux method. Detailed material characterization studies suggest that the higher degree of intermolecular ligation in novel templates such as butanetetracarboxylic or tricarballylic acid modified titanium hydroxide gels resulted in retainment of the porous structure during the urea assisted combustion synthesis. The induction of robust structural porosity is accompanied by a reduction in pore size distribution, an increase in pore volume leading to significantly higher total surface area of the synthesized TiO2. Detailed investigation of dye adsorption kinetics and photocatalytic degradation kinetics, complemented by kinetic modeling analysis confirmed that the super porous TiO2 with robust mesoporous structure outperforms the rest of synthesized TiO2 catalyst (having only agglomerate porosity) in terms of its superior adsorption capacity, faster diffusion kinetics and photocatalytic activity for degradation of Amaranth dye. Thus, the super porous TiO2 shows promising potential for application in sustainable photocatalytic technology for remediation of wastewater contaminated with azo dyes.

Arginine-Induced Self-Assembly of Protoporphyrin to Obtain Effective Photocatalysts in Aqueous Media Under Visible Light.

The fabrication of controlled supramolecular nanostructures via self-assembly of protoporphyrin IX (PPIX) was studied with enantiomerically pure l-arginine and d-arginine, and we have shown that stoichiometry controlled the morphology formed. The nanostructure morphology was mainly influenced by the delicate balance of π-π stacking interactions between PPIX cores, as well as H-bonding between the deprotonated acidic head group of PPIX with the guanidine head group of arginine. PPIX self-assembled with l-/d-arginine to create rose-like nanoflower structures for four equivalents of arginine that were 5-10 µm in length and 1-4 µm diameter. We employed UV-vis, fluorescence spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), dynamic light scattering (DLS) and Fourier transform infrared spectroscopy (FT-IR) techniques to characterize the resulting self-assembled nanostructures. Furthermore, we investigated the catalytic activity of PPIX and arginine co-assembled materials. The fabricated PPIX-arginine nanostructure showed high enhancement of photocatalytic activity through degradation of rhodamine B (RhB) with a decrease in dye concentration of around 78-80% under simulated visible radiation.

Enhanced photocatalytic degradation of Amaranth dye on mesoporous anatase TiO2: evidence of C-N, N[double bond, length as m-dash]N bond cleavage and identification of new intermediates.

The photocatalytic degradation mechanism of Amaranth, a recalcitrant carcinogenic azo dye, was investigated using mesoporous anatase TiO2 under sunlight. Mesoporous anatase TiO2 of a high photocatalytic activity has been synthesized using a sol-gel method and its photocatalytic activity for the degradation of Amaranth dye has been evaluated with respect to Degussa P25. The effect of bi-dentate complexing agents like oxalic acid, ethylene glycol and urea on the surface properties of TiO2 catalyst has been investigated using TG-DTA, FTIR, HR-TEM, SAED, PXRD, EDS, UV-DRS, PL, BET N2 adsorption-desorption isotherm studies and BJH analysis. The influence of catalyst properties such as the mesoporous network, pore volume and surface area on the kinetics of degradation of Amaranth as a function of irradiation time under natural sunlight has been monitored using UV-Vis spectroscopy. The highest rate constant value of 0.069 min-1 was obtained for the photocatalytic degradation of Amaranth using TiO2 synthesized via a urea assisted sol-gel synthesis method. The effect of the reaction conditions such as pH, TiO2 concentration and Amaranth concentration on the photodegradation rate has been investigated. The enhanced photocatalytic activity of synthesized TiO2 in comparison with P25 is attributed to the mesoporous nature of the catalyst leading to increased pore diameter, pore volume, surface area and enhanced charge carrier separation efficiency. New intermediates of photocatalytic degradation of Amaranth, namely, sodium-3-hydroxynaphthalene-2,7-disulphonate, 3-hydroxynaphthalene, sodium-4-aminonaphthalenesulphonate and sodium-4-aminobenzenesulphonate have been identified using LC-ESI-MS for the very first time, providing direct evidence for simultaneous bond cleavage pathways (-C-N-) and (-N[double bond, length as m-dash]N-). A new plausible mechanism of TiO2 catalysed photodegradation of Amaranth along with the comparison of its toxicity to that of its degradation intermediates and products is proposed.

Low-Pressure Photolysis of 2,3-Pentanedione in Air: Quantum Yields and Reaction Mechanism.

Dicarbonyls in the atmosphere mainly arise from secondary sources as reaction products in the degradation of a large number of volatile organic compounds (VOC). Because of their sensitivity to solar radiation, photodissociation of dicarbonyls can dominate the fate of these VOC and impact the atmospheric radical budget. The photolysis of 2,3-pentanedione (PTD) has been investigated for the first time as a function of pressure in a static reactor equipped with continuous wave cavity ring-down spectroscopy to measure the HO2 radical photostationary concentrations along with stable species. We showed that (i) Stern-Volmer plots are consistent with low OH-radical formation yields in RCO + O2 reactions, (ii) the decrease of the photodissociation rate due to pressure increase from 26 to 1000 mbar is of about 30%, (iii) similarly to other dicarbonyls, the Stern-Volmer analysis shows a curvature at the lower pressure investigated, which may be assigned to the existence of excited singlet and triplet PTD states, (iv) PTD photolysis at 66 mbar leads to CO2, CH2O and CO with yields of (1.16 ± 0.04), (0.33 ± 0.02) and (0.070 ± 0.005), respectively, with CH2O yield independent of pressure up to 132 mbar and CO yield in agreement with that obtained at atmospheric pressure by Bouzidi et al. (2014), and (v) the PTD photolysis mechanism remains unchanged between atmospheric pressure and 66 mbar. As a part of this work, the O2 broadening coefficient for the absorption line of HO2 radicals at 6638.21 cm(-1) has been determined (γO2 = 0.0289 cm(-1) atm(-1)).

Photolysis of CH3CHO at 248 nm: evidence of triple fragmentation from primary quantum yield of CH3 and HCO radicals and H atoms.

Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH3CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO2 radicals by reaction with O2. The CH3 radical yield has been determined using the same technique following their conversion into CH3O2. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO2 profiles, obtained under various O2 concentrations, to a complex model, while the CH3 yield has been determined relative to the CH3 yield from 248 nm photolysis of CH3I. Time resolved HO2 profiles under very low O2 concentrations suggest that another unknown HO2 forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O2. HO2 profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH3CHO + hν(248nm) → CH3CHO*, CH3CHO* → CH3 + HCO ϕ(1a) = 0.125 ± 0.03, CH3CHO* → CH3 + H + CO ϕ(1e) = 0.205 ± 0.04, CH3CHO*[Formula: see text]CH3CO + HO2 ϕ(1f) = 0.07 ± 0.01. The CH3O2 quantum yield has been determined in separate experiments as ϕ(CH3) = 0.33 ± 0.03 and is in excellent agreement with the CH3 yields derived from the HO2 measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH3CHO. From arithmetic considerations taking into account the HO2 and CH3 measurements we deduce a remaining quantum yield for the molecular pathway: CH3CHO* → CH4 + CO ϕ(1b) = 0.6. All experiments can be consistently explained with absence of the formerly considered pathway: CH3CHO* → CH3CO + H ϕ(1c) = 0.

Experimental and modeling study of the oxidation of n-butane in a jet stirred reactor using cw-CRDS measurements.

The gas-phase oxidation of n-butane has been studied in an atmospheric jet-stirred reactor (JSR) at temperatures up to 950 K. For the first time, continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near-infrared has been used, together with gas chromatography (GC), to analyze the products formed during its oxidation. In addition to the quantification of formaldehyde and water, which is always difficult by GC, cw-CRDS allowed as well the quantification of hydrogen peroxide (H2O2). A comparison of the obtained mole fraction temperature profiles with simulations using a detailed gas-phase mechanism shows a good agreement at temperatures below 750 K, but an overestimation of the overall reactivity above this temperature. Also, a strong overestimation was found for the H2O2 mole fraction at higher temperatures. In order to improve the agreement between model and experimental results, two modifications have been implemented to the model: (a) the rate constant for the decomposition of H2O2 (+M) ↔ 2OH (+M) has been updated to the value recently proposed by Troe (Combust. Flame, 2011, 158, 594-601) and (b) a temperature dependent heterogeneous destruction of H2O2 on the hot reactor walls with assumed rate parameters has been added. The improvement (a) slows down the overall reactivity at higher temperatures, but has a negligible impact on the maximal H2O2 mole fraction. Improvement (b) has also a small impact on the overall reactivity at higher temperatures, but a large effect on the maximal H2O2 mole fraction. Both modifications lead to an improved agreement between model and experiment for the oxidation of n-butane in a JSR at temperatures above 750 K.

Gas-phase reaction of hydroxyl radical with hexamethylbenzene.

Aromatic hydrocarbons are important components of polluted ambient air. The reaction of OH radicals with hexamethylbenzene (HMB) is a prototype system to study ipso addition leading eventually to dealkylation. We have investigated the OH + HMB and OD + HMB reactions between 323 and 433 K using a discharge fast-flow reactor coupled to a time-of-flight mass spectrometer with single-photon VUV photoionization (10.54 eV). The H atom abstraction channel has been found to be equal to (13.7 ± 4.4) % at 330 K leading to (11.1 ± 3.6) % at 298 K, higher than predicted by commonly used structure-reactivity relationships. The back dissociation rate constant has also been measured and has been found to be smaller than the rate of other aromatic hydrocarbons, in good agreement with density functional theoretical calculations. The dealkylation channel, leading to pentamethylphenol (PMP) + CH(3), is always found to be the minor channel, estimated inferior to 2% at 298 K.

Formation of HO2 radicals from the 248 nm two-photon excitation of different aromatic hydrocarbons in the presence of O2.

The excitation energy dependence of HO(2) radical formation from the 248 nm irradiation of four different aromatic hydrocarbons (benzene, toluene, o-xylene, and mesitylene) in the presence of O(2) has been studied. HO(2) has been monitored at 6638.20 cm(-1) by cw-CRDS, and the formation of a short-lived, unidentified species, showing broad-band absorption around the HO(2) absorption line, has been observed. For all four hydrocarbons, the same HO(2) formation pattern has been observed: HO(2) is formed immediately on our time scale after the excitation pulse, followed by a formation of more HO(2) on a much longer time scale. Taking into account the absorption of the short-lived species, the yields of both types of HO(2) radicals are in agreement with a formation following 2-photon absorption by the aromatic hydrocarbons. The yields do not much depend on the nature of the aromatic hydrocarbon. For practical use in past and future experiments on aromatic hydrocarbons, an empirical value is given, allowing the estimation of the total concentration of HO(2) radicals formed at 40 Torr He in the presence of around [O(2)] = 1 × 10(17)cm(-3) as a function of the 248 nm excitation energy: [HO(2)]/[aromatic hydrocarbon] ≈ 2 × 10(-6) × E(2) (with E in mJ cm(-2)).

Measurement of absolute absorption cross sections for nitrous acid (HONO) in the near-infrared region by the continuous wave cavity ring-down spectroscopy (cw-CRDS) technique coupled to laser photolysis.

Absolute absorption cross sections for selected lines of the OH stretch overtone 2ν(1) of the cis-isomer of nitrous acid HONO have been measured in the range 6623.6-6645.6 cm(-1) using the continuous wave cavity ring-down spectroscopy (cw-CRDS) technique. HONO has been generated by two different, complementary methods: in the first method, HONO has been produced by pulsed photolysis of H(2)O(2)/NO mixture at 248 nm, and in the second method HONO has been produced in a continuous manner by flowing humidified N(2) over 5.2 M HCl and 0.5 M NaNO(2) solutions. Laser photolysis synchronized with the cw-CRDS technique has been used to measure the absorption spectrum of HONO produced in the first method, and a simple cw-CRDS technique has been used in the second method. The first method, very time-consuming, allows for an absolute calibration of the absorption spectrum by comparison with the well-known HO(2) absorption cross section, while the second method is much faster and leads to a better signal-to-noise ratio. The strongest line in this wavelength range has been found at 6642.51 cm(-1) with σ = (5.8 ± 2.2) × 10(-21) cm(2).