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Rapid, simple, and low-cost screening procedures are necessary for the detection of harmful compounds in the effluent that flows out of point sources such as industrial outfall. The present study investigated the effects on a novel sensor of harmful compounds such as KCN, phenol, and herbicides such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (atrazine), and 2-N-tert-butyl-4-N-ethyl-6-methylsulfanyl-1,3,5-triazine-2,4-diamine (terbutryn). The sensor employed an electrode system that incorporated the photocurrent of intra-cytoplasmic membranes (so-called chromatophores) prepared from photosynthetic bacteria and linked using carbon paste electrodes. The amperometric curve (photocurrent-time curve) of photo-induced electron transfer from chromatophores of the purple photosynthetic bacterium Rhodobacter sphaeroides to the electrode via an exogenous electron acceptor was composed of two characteristic phases: an abrupt increase in current immediately after illumination (I₀), and constant current over time (Ic). Compared with other redox compounds, 2,5-dichloro-1,4-benzoquinone (DCBQ) was the most useful exogenous electron acceptor in this system. Photo-reduction of DCBQ exhibited Michaelis-Menten-like kinetics, and reduction rates were dependent on the amount of DCBQ and the photon flux intensity. The Ic decreased in the presence of KCN at concentrations over 0.05 μM (=μmol·dm(-3)). The I₀ decreased following the addition of phenol at concentrations over 20 μM. The Ic was affected by terbutryn at concentrations over 10 μM. In contrast, DCMU and atrazine had no effect on either I₀ or Ic. The utility of this electrode system for the detection of harmful compounds is discussed.

Gold nanocrystals are promising as catalysts and for use in sensing/imaging systems, photonic/plasmonic devices, electronics, drug delivery systems, and for photothermal therapy due to their unique physical, chemical, and biocompatible properties. The use of various organic templates allows control of the size, shape, structure, surface modification and topology of gold nanocrystals; in particular, currently the synthesis of gold nanorods requires a cytotoxic surfactant to control morphology. To control the shape of gold nanocrystals, we previously demonstrated the de novo design and synthesis of a β-sheet-forming nonapeptide (RU006: Ac-AIAKAXKIA-NH2, X=L-2-naphthylalanine, Nal) and the fabrication of gold nanocrystals by mixing RU006 and HAuCl4 in water. The reaction afforded ultrathin gold nanoribbons 50-100 nm wide, several nanometers high, and microns long. To understand the mechanism underlying gold nanoribbon formation by the RU006 system, we here report (i) the effects of replacement of the Nal aromatic side chain in the RU006 sequence with other aromatic moieties, (ii) the electrochemical properties of aromatic side chains in the de novo designed template peptides to estimate the redox potential and number of electrons participating in the gold crystallization process, and (iii) the stoichiometry of the RU006 system for gold nanoribbon synthesis. Interestingly, RU006 bearing a naphthalene moiety (oxidation peak potential of 1.50 V vs Ag/Ag(+)) and an analog [Ant(6)]-RU006 bearing a bulky anthracene moiety (oxidation peak potential of 1.05 V vs Ag/Ag(+)) allowed the growth of anisotropic (ribbon-like) and isotropic (round) gold nanocrystals, respectively. This trend in morphology of gold nanocrystals was attributed to spatially-arranged hydrophobic cavities sufficiently large to accommodate the gold precursor and to allow directed crystal growth driven by cross-linking reactions among the naphthalene rings. Support for this mechanism was obtained by decreasing the mole fraction of [Ant(6)]-RU006 against the total concentration of [Ant(6)]-RU006 and [Phe(6)]-RU006: absorption spectra similar to that for RU006 were obtained. Differences in the redox properties of the anthracene and naphthalene moieties scarcely affected morphology. We propose that construction of an appropriate hydrophobic cavity is important for templating gold nanocrystal architectures by peptide self-assembly. This mechanism would be applicable for developing simple, low toxicity, mild synthetic methods for constructing metallic nanomaterials for therapeutic use., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Chitosan, a naturally occurring biopolymer derived from chitin, has emerged as a highly promising instrument for the production and application of metal nanoparticles. The present review delves into the several functions of chitosan in the development and operation of metal nanoparticles, emphasizing its aptitudes as a green reducing agent, shape-directing agent, size-controlling agent, and stabilizer. Chitosan's special qualities make it easier to manufacture metal nanoparticles and nanocomposites with desired characteristics. Furthermore, there is a lot of promise for chitosan-based nanocomposites in a number of fields, such as metal removal, water purification, and photoacoustic, photothermal, antibacterial, and photodynamic therapies. This thorough analysis highlights the potential application of chitosan in the advancement of nanotechnology and the development of medicinal and environmental solutions. [ABSTRACT FROM AUTHOR]

Heavy metals represent a class of chemical elements that includes metalloids, bases and transition metals, lanthanides, and actinides. They are distinguished for their toxicity in small concentrations and their negative effects on the environment and human health; consequently, their monitoring has to be improved to manage the risks. The determination of heavy metals is carried out mainly by analytical methods, using spectroscopy, spectrometry, and electroanalysis. However, the interest has shifted to new and faster methodologies and techniques for heavy metal analysis, with particular emphasis on voltammetry. Voltammetry is preferred for heavy metal detection owing to the advantages of low cost, simplicity, ease of operation, fast analysis, portability, the ability to monitor environmental samples in the field, and high sensitivity and selectivity. Therefore, this study summarizes the applications of voltammetry in heavy metal determination mainly in water, soil, and plant samples, and presents an evaluation of sensitivity, selectivity, and applicability. [ABSTRACT FROM AUTHOR]

Flow systems for precise and accurate coulometric determinations of ions that were developed on the basis of electrolytic ion transfer at the aqueous|organic solution (W|O) interface are reviewed. The electrolysis cell in the system is composed of a porous poly(tetrafluoroethylene) tube (1.0 mm inner diameter), a metal wire (0.8 mm diameter) inserted into the tube, O into which the tube is immersed, a reference electrode in O and a platinum wire counter electrode in O. The electrolysis is carried out by forcing W containing a species of interest to flow through the narrow gap between the tube and the metal wire. The coulometric determination can be performed with an efficiency of more than 99% and a precision of better than 0.2% based on the ion transfer under an optimum condition, even if the ion is redox inert such as Na(+), K(+), Mg(2+), Ca(2+), ClO(4)(-), picrate or alkylsulfonates. The system can be applied to selective electrolytic solvent extraction of ions.

A simple column electrode, S-CE, with a glassy carbon fibers working electrode stuffed into a Teflon tube was developed. The current-potential curves for the reductions of [Fe(CN)(6)](3-) and Fe(3+) observed at the S-CE were analyzed based on a theory for those at an ordinary column electrode. A quantitative electrolysis was performed at the S-CE rapidly within 20 s. An accurate and precise coulometric determination could be attained at the S-CE even with a fairly dilute solution. For example, coulometric reductions of 5 x 10(-5) and 5 x 10(-6) M Fe(3+) were attained with efficiencies (n = 5) of 99.7 +/- 0.2 and 101.9 +/- 1.1%, respectively.

It is well known that calcium oxide (CaO) has better catalytic efficiency than most heterogeneous catalysts in many transesterification reactions. However, the gradual deactivation problem prevents its large-scale application in industry. In this paper, the deactivation mechanism of CaO in a fixed-bed reactor is investigated based on the transesterification reaction of propylene carbonate and methanol. The leaching amount of CaO during the reaction was estimated by the concentration of Ca in the products. The pretreated and recovered catalysts were characterized by FT-IR, XRD, TG-MS and SEM-EDS. It is evident from experiments and characterization that the deactivation process of CaO is accompanied by the leaching of calcium species and the generation of CaCO3, which are also verified by DFT calculations. At high temperature and high weight hourly space velocity, the deactivation was attributed to the formation of dense CaCO3 shell, which prevents the contact between the feedstock and the active species inside. [ABSTRACT FROM AUTHOR]

A series of KF/Mg-Fe oxides were fabricated via the solid-state reaction between KF and Mg-Fe oxides. Especially, when 20 wt % KF was supported on the Mg-Fe bi-metal oxides and calcined at 400-600 °C, the solid material with more basic sites than the support itself was obtained. When applied as catalyst to dimethyl carbonate (DMC) synthesis through transesterification of ethylene carbonate (EC) and methanol, this material can afforded up to 88 % yield and 97 % selectivity toward DMC in 2 h under reflux conditions with the molar ratio of methanol to ethylene carbonate set at 8. It is worth noting that the catalyst was easily separated and reused, retaining at least 89 % catalytic activity during the first four recycles. Although an attenuated activity was still observed due to the inevitable filtration loss and dissolution, this solid base can still provide clues to the development recyclable catalyst in green synthesis of DMC., (© 2024 Wiley-VCH GmbH.)

Currently, biodiesel is pointed out worldwide as the main alternative in the complementation and substitution of petrochemical diesel. However, the current industrial route of synthesis of this biofuel depends on the cost of raw materials (which are also destined for food purposes) and the expense of the production process. Aiming to remedy this obstacle, the use of solid, sustainable, low‐cost, efficient, and reusable catalysts in residual raw materials, such as waste cooking oils, has been highlighted as a promising alternative. This work focused on studying the influence of the glycerin content used in the preparation by wet impregnation of catalyst calcium diglyceroxide in the efficiency of transesterification of waste cooking oil. The catalyst was synthesized from CaO from chicken eggshell, raw glycerin co‐product from biodiesel, and methanol. The transesterification reactions were performed using 120 g of frying residual oil, methanol: oil molar rate of 6:1, constant shaking, and reaction temperature of 63 ± 1°C for 180 min. The catalyst material synthesized with residual glycerin was active for four reactions (without reactivation of its sites) with high percentages of efficiency of 96.13, 96.85, 95.93, and 91.65, respectively. It was noted that the glycerol purity correlated with changes in the structural morphology of the final compound, as well as changes in the leaching rate, acidity index, water content, and ester content of the blends. It was found that adding 15% water to the lipid material correlated with an increase in ester content (99%) in the synthesized biodiesel. [ABSTRACT FROM AUTHOR]

This study aims to investigate the potential of zeolitic based catalysts for biodiesel production from waste sunflower vegetable oil. The zeolite-based catalyst was prepared by two impregnation steps. The obtained catalyst was examined for the transesterification reaction. The effect of operating variables and the synergetic effects between those variables were investigated. Other parameters such as catalyst impregnation time, stirring speed and catalyst particle size were also studied. Furthermore, the physical and chemical properties of the oil and the produced biodiesel were measured. Nearly complete 100% conversion and 96.7% yield were achieved using 11.5 MeOH/oil molar ratio, 6.4% catalyst dosage, at 50°C reaction temperature and reaction time of 2 hours. The properties of the obtained biodiesel are in agreement with the values specified by US and EU standards. [ABSTRACT FROM AUTHOR]

Meti shell contains calcium carbonate which can be calcined into CaO and used as a heterogeneous catalyst in biodiesel synthesis. This study evaluated the ability of CaO catalyst from Meti shell with concentrations of 1, 2, 3, 4, and 5% for the synthesis of biodiesel from Moringa seed oil at various transesterification times (1, 2, 3, and 4 hours). The presence of CaO in the Meti shell was indicated by diffraction at 2θ angles of 32.47°, 37.74°, 54.22°, 64.65°, and 67.67°C. Utilizing Ca° 3% and a transesterification reaction time of 3 hours resulted in an Rf value corresponding to the standard biodiesel Rf ranges, i.e. 0.69 and 0.66, respectively. The synthesized biodiesel has the highest methyl oleate content of 59.16% with characteristics that have met Indonesian National Standard (SNI 04-7182-2006), including water content of 0.004%, an acid number of 0.06 mg KOH/g, saponification number 273.6 mgKOH/g, iodine number 78.678 g iodine/100 g, the cloud point is 10°C, the pour point is 21°C, however, the cetane number is still below the minimum number of 51. [ABSTRACT FROM AUTHOR]

Vitamin E, a collection of lipophilic phenolic compounds based on chroman-6-ol, has a rich and fascinating oxidative chemistry involving a range of intermediate forms, some of which are proposed to be important in its biological functions. In this review, the available electrochemical and spectroscopic data on these oxidized intermediates are summarized, along with a discussion on how their lifetimes and chemical stability are either typical of similar phenolic and chroman-6-ol derived compounds, or atypical and unique to the specific oxidized isomeric form of vitamin E. The overall electrochemical oxidation mechanism for vitamin E can be summarized as involving the loss of two-electrons and one-proton, although the electron transfer and chemical steps can be controlled to progress along different pathways to prolong the lifetimes of discreet intermediates by modifying the experimental conditions (applied electrochemical potential, aqueous or non-aqueous solvent, and pH). Depending on the environment, the electrochemical reactions can involve single electron transfer (SET), proton-coupled electron transfer (PCET), as well as homogeneous disproportionation and comproportionation steps. The intermediate species produced via chemical or electrochemical oxidation include phenolates, phenol cation radicals, phenoxyl neutral radicals, dications, diamagnetic cations (phenoxeniums) and para–quinone methides. The cation radicals of all the tocopherols are atypically long-lived compared to the cation radicals of other phenols, due to their relatively weak acidity. The diamagnetic cation derived from α–tocopherol is exceptionally long-lived compared to the diamagnetic cations from the other β–, γ– and δ–isomers of vitamin E and compared with other phenoxenium cations derived from phenolic compounds. In contrast, the lifetime of the phenoxyl radical derived from α–tocopherol, which is considered to be critical in biological reactions, is typical for what is expected for a compound with its structural features. Over longer times via hydrolysis reactions, hydroxy para–quinone hemiketals and quinones can be formed from the oxidized intermediates, which can themselves undergo reduction processes to form intermediate anion radicals and dianions. Methods for generating the oxidized intermediates by chemical, photochemical and electrochemical methods are discussed, along with a summary of how the final products vary depending on the method used for oxidation. Since the intermediates mainly only survive in solution, they are most often monitored using UV-vis spectroscopy, FTIR or Raman spectroscopies, and EPR spectroscopy, with the spectroscopic techniques sometimes combined with fast photoinitiated excitation and time-resolved spectroscopy for detection of short-lived species. [ABSTRACT FROM AUTHOR]

Co-contamination by organic solvents (e.g., toluene and tetrahydrofuran) and metal ions (e.g., Cu2+) is common in industrial wastewater and in industrial sites. This manuscript describes the separation of THF from water in the absence of copper ions, as well as the treatment of water co-polluted with either THF and copper, or toluene and copper. Tetrahydrofuran (THF) and water are freely miscible in the absence of lauric acid. Lauric acid separates the two solvents, as demonstrated by proton nuclear magnetic resonance (1H NMR) and Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR). The purity of the water phase separated from 3:7 (v/v) THF:water mixtures using 1 M lauric acid is ≈87%v/v. Synchrotron small angle X-Ray scattering (SAXS) indicates that lauric acid forms reverse micelles in THF, which swell in the presence of water (to host water in their interior) and ultimately lead to two free phases: 1) THF-rich and 2) water-rich. Deprotonated lauric acid (laurate ions) also induces the migration of Cu2+ ions in either THF (following separation from water) or in toluene (immiscible in water), enabling their removal from water. Laurate ions and copper ions likely interact through physical interactions (e.g., electrostatic interactions) rather than chemical bonds, as shown by ATR-FTIR. Inductively coupled plasma—optical emission spectrometry (ICP-OES) demonstrates up to 60% removal of Cu2+ ions from water co-polluted by CuSO4 or CuCl2 and toluene. While lauric acid emulsifies water and toluene in the absence of copper ions, copper salts destabilize emulsions. This is beneficial, to avoid that copper ions are re-entrained in the water phase alongside with toluene, following their migration in the toluene phase. The effect of copper ions on emulsion stability is explained based on the decreased interfacial activity and compressional rigidity of interfacial films, probed using a Langmuir trough. In wastewater treatment, lauric acid (a powder) can be mixed directly in the polluted water. In the context of groundwater remediation, lauric acid can be solubilized in canola oil to enable its injection to treat aquifers co-polluted by organic solvents and Cu2+. In this application, injectable filters obtained by injecting cationic hydroxyethylcellulose (HEC +) would impede the flow of toluene and copper ions partitioned in it, protecting downstream receptors. Co-contaminants can be subsequently extracted upstream of the filters (using pumping wells), to enable their simultaneous removal from aquifers. [ABSTRACT FROM AUTHOR]

Chlor-alkali process industries produce a million tonnes of brine sludge which are dumped in landfills. Brine sludge waste can be thermally modified and applied as a heterogeneous basic catalyst to synthesise biodiesel from waste cooking oil (WCO). In this work, an experimental design obtained by response surface methodology was used to study the effects of process parameters and hence, optimise the transesterification process. A quadratic model was generated to estimate the yield of biodiesel to its process variables. A biodiesel yield of value 97.8 wt % was optimally achieved using numerical optimisation method at a reaction period; methanol to oil weight ratio, a catalyst to oil weight ratio, and temperature of 1.53 hr, 29.8 wt %, 2.47 wt %, and 60.31°C, respectively. The brine sludge waste catalyst was reutilised up to four times without being deactivated. Morphological modifications of the brine sludge after calcination and transesterification were characterised using a scanning electron microscope (SEM) and X-ray diffraction (XRD). From the basic fuel properties specifications stipulated in the ASTM standard, it was found WCO biodiesel properties were within the acceptable range. [ABSTRACT FROM AUTHOR]

The utilization of waste cooking oil (WCO) and bleached palm oil (BPO) for the production of biodiesel in the presence of hydrothermally treated calcium oxide (CaO) derived from waste chicken eggshells was investigated. Waste chicken eggshells were calcined at 850 °C and then hydrothermally treated at 120 and 140 °C to produce two sets of CaO catalysts. Hydrothermal treatment of the catalysts resulted in a decrease of the crystallite size from 47 to 30 and 28 nm at temperatures of 120 and 140 °C. The catalytic performance of the CaO catalysts was evaluated with WCO and BPO, respectively. WCO gave biodiesel yields of 82.7 and 83.1 % for CaO catalysts aged at 120 and 140 °C respectively. BPO gave 79.4 and 79.6 % yields, respectively, for the same set of catalysts. [ABSTRACT FROM AUTHOR]

Heterogeneous basic catalysts, namely calcium oxide, are referred to as promising catalysts for biodiesel (FAME, fatty acid methyl esters) production since they can be easily separated from the reaction medium allowing them to operate in a continuous mode. Despite the relatively high catalytic activity of calcium catalysts, they present slower alcoholysis rates than homogeneous conventional catalysts (sodium or potassium methanoate). In order to improve the catalytic activity, CaO-based catalysts, modified with alkali elements (Li, Cs, Sr, and Mg) were prepared. Dopant element contents of 10% and 30%, as weight basis (5–50% molar), were introduced by wet impregnation using aqueous solutions of nitrate salts. The effect of calcination temperature (575°C and 800°C) on both activity and stability was studied. All the prepared catalysts, raw and alkali modified, showed pKa<15.0 when characterized by Hammett indicators in methanolic solution. Such basicity is characteristic of Ca hydroxide, thus indicating that the catalysts surfaces were covered with Ca-OH species. FAME yield, in soybean oil methanolysis, higher than 96% was obtained for the first batch reaction for all the tested catalysts showing that alkali dopants have an almost nihil effect on the catalysts performances. The deactivation tests performed with catalysts without intermediate reactivation showed that calcination temperature plays a major role in stability as it enhances the formation of calcium diglyceroxide. The presence of Ca hydroxide in fresh catalysts appears to be responsible for fast deactivation. The dopant elements prompt the catalysts deactivation. Catalysts calcined at higher temperatures showed slower deactivation, which can be due to the formation of larger particles, thus reducing the contact with the formed glycerin. Alkali dopants enhanced the CaO sintering for the highest calcination temperature. Calcium diglyceroxide formed during the reaction is responsible for deactivating the catalyst, due to leaching, and such effect is prompted by alkali dopants. [ABSTRACT FROM AUTHOR]

Photobioelectrocatalysis has recently attracted particular research interest owing to the possibility to achieve sunlight-driven biosynthesis, biosensing, power generation, and other niche applications. However, physiological incompatibilities between biohybrid components lead to poor electrical contact at the biotic-biotic and biotic-abiotic interfaces. Establishing an electrochemical communication between these different interfaces, particularly the biocatalyst-electrode interface, is critical for the performance of the photobioelectrocatalytic system. While different artificial redox mediating approaches spanning across interdisciplinary research fields have been developed in order to electrically wire biohybrid components during bioelectrocatalysis, a systematic understanding on physicochemical modulation of artificial redox mediators is further required. Herein, we review and discuss the use of diffusible redox mediators and redox polymer-based approaches in artificial redox-mediating systems, with a focus on photobioelectrocatalysis. The future possibilities of artificial redox mediator system designs are also discussed within the purview of present needs and existing research breadth. [ABSTRACT FROM AUTHOR]

Reuse of waste such as eggshells and animal bones as a catalyst to convert waste cooking oil into biodiesel fuel was investigated. A mixture of bone and eggshell waste (50:50) was used as a catalyst for biodiesel production from waste cooking oil. Different calcination temperatures have been investigated for the catalyst and the highest production of biodiesel was found at 900°C. The experimental results showed that a methanol/oil ratio of 15:1, a mixture of bone and eggshell catalyst (900°C, 2 h) of 12 wt.%, a reaction temperature of 60°C gave a biodiesel yield of 94% at 4 h. The effects of calcination temperature and catalyst leaching were examined. The catalysts were characterized by x-ray diffraction, N2 adsorption-desorption, x-ray photoelectron spectroscopy, and Fourier-transform infrared spectrometry. [ABSTRACT FROM AUTHOR]

The Merbau wood waste ash-based catalyst was prepared via various calcination temperatures and was applied for biodiesel production from low-grade palm oil. The thermal investigations of calcination of Merbau wood were carried out at temperatures of 500, 600, 700, 800, and 900 ᴼC for 3 h. It was led to M700 as a catalyst based on the highest basicity as confirmed by the basicity test and x-ray diffraction analysis. The M700 mass toward methanol volume ratio was performed at 5%, 10%, 15%, 20% (w/v) on the application of conversion of LGPO into biodiesel. The products of biodiesel were prepared via reflux at temperature 80 ᴼC for 2 h and were characterized by GC-MS. The biodiesel product is predominantly methyl palmitate. The ash-methanol ratio of 15% gives the optimum biodiesel fraction conversion (78.7 % w/w). The optimum selectivity of the yield total of biodiesel given by 10%, namely 48.9% w/w, resulted in methyl ester (biodiesel) with C15-C19 consisting of methyl myristate, methyl palmitate, methyl linoleate, methyl oleic, methyl stearate. Moreover, a 10% weight catalyst to methanol showed the optimum decrease of FFA (89.0 ± 0.6 %). [ABSTRACT FROM AUTHOR]

Chromatophores of purple non-sulfur bacteria (PNSB) are invaginations of the cytoplasmic membrane that contain a relatively simple system of light-harvesting protein–pigment complexes, a photosynthetic reaction center (RC), a cytochrome complex, and ATP synthase, which transform light energy into the energy of synthesized ATP. The high content of negatively charged phosphatidylglycerol (PG) and cardiolipin (CL) in PNSB chromatophore membranes makes these structures potential targets that bind cationic antiseptics. We used the methods of stationary and kinetic fluorescence spectroscopy to study the effect of some cationic antiseptics (chlorhexidine, picloxydine, miramistin, and octenidine at concentrations up to 100 μM) on the spectral and kinetic characteristics of the components of the photosynthetic apparatus of Rhodobacter sphaeroides chromatophores. Here we present the experimental data on the reduced efficiency of light energy conversion in the chromatophore membranes isolated from the photosynthetic bacterium Rb. sphaeroides in the presence of cationic antiseptics. The addition of antiseptics did not affect the energy transfer between the light-harvesting LH1 complex and reaction center (RC). However, it significantly reduced the efficiency of the interaction between the LH2 and LH1 complexes. The effect was maximal with 100 μM octenidine. It has been proved that molecules of cationic antiseptics, which apparently bind to the heads of negatively charged cardiolipin molecules located in the rings of light-harvesting pigments on the cytoplasmic surface of the chromatophores, can disturb the optimal conditions for efficient energy migration in chromatophore membranes. [ABSTRACT FROM AUTHOR]

The photochromic and magnetic properties of two dithienylethene (DTE)-based complexes, [Dy(NO3)3(Lo)2(MeOH)] (1-o) and [Dy(NO3)3(Lo)3] (2-o) (Lo = 4,5-bis(2,5-dimethylthiophen-3-yl)-1,3-dimethyl-1,3-dihydro-2H-imidazol-2-one), were experimentally studied in detail with the help of theoretical calculations. Both complexes exhibit an instantaneous and strong reversible photochromic response to UV/Vis irradiation, as evidenced from spectroscopic tests, and complex 1-o behaves as a typical field-induced single-molecule magnet (SMM). By controlling the reaction ratio of Lo and Dy(NO)3, Lo replacing a coordinated methanol molecule in 1-o results in the production of complex 2-o, whose single-molecule behavior is off. Upon irradiation with 254 nm light, the SMM properties of 1-o deteriorate with the energy barrier decreasing from 68.1 to 44.3 K while the magnetic dynamics of complex 2-o shows no response to irradiation. Ab initio calculations reveal that the quantum tunnelling of magnetization between the ground Kramers doublets in 2-o is quite strong, leading to the disappearance of SMM behavior. For complex 1-o, the strong magnetic anisotropy and moderate quantum tunnelling of magnetization relative to 2-o give rise to an appropriate energy barrier for SMM. On the other hand, the decrease in energy barriers for 1-o after irradiation results from the weakening of magnetic anisotropy, which is caused by the stronger charge delocalization of the coordinated carbonyl oxygen atom of the ring-closed DTE ligand. By regulating the reactant ratio, two photochromic DTE-based Dy(III) complexes are obtained and the SMM properties of complex 1-o can be tuned by the light-induced isomerization of the dithienylethene ligand. [ABSTRACT FROM AUTHOR]

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Proton‐responsive photochromic molecules are attractive for their ability to react on non‐invasive rapid optical stimuli and the importance of protonation/deprotonation processes in various fields. Conventionally, their acidic/basic sites are on hetero‐atoms, which are orthogonal to the photo‐active π‐center. Here, we incorporate azulene, an acid‐sensitive pure hydrocarbon, into the skeleton of a diarylethene‐type photoswitch. The latter exhibits a novel proton‐gated negative photochromic ring‐closure and its optical response upon protonation in both open and closed forms is much more pronounced than those of diarylethene photoswitches with hetero‐atom based acidic/basic moieties. The unique behavior of the new photoswitch can be attributed to direct protonation on its π‐system, supported by 1H NMR and theoretical calculations. Our results demonstrate the great potential of integrating non‐alternant hydrocarbons into photochromic systems for the development of multi‐responsive molecular switches. [ABSTRACT FROM AUTHOR]

In this work, CaO@LiFe5O8 and (CaO‐Y2O3)@LiFe5O8 solid base catalysts were synthesized using LiFe5O8 as the magnetic core to support the active centers. The as‐prepared catalysts and commercial CaO were characterized using X‐ray diffraction, scanning electronic microscope, and CO2‐temperature‐programmed desorption techniques. The results indicated that CaO@LiFe5O8 and (CaO‐Y2O3)@LiFe5O8 solid base catalysts, which could be recycled under the external magnetic field because of their strong magnetism, exhibited better dispersibility and higher total number of basic sites compared with commercial CaO. Additional water and oleic acid were added to the reaction system of palm oil with methanol, and the catalyst was exposed to air to detect its stability in the reaction process. The experiments showed that the (CaO‐Y2O3)@LiFe5O8 solid base catalyst performed better and possessed not only good water resistance ability but also preferable tolerance to air exposure. In addition, response surface methodology based on the Box–Behnken design was used to optimize the process parameters for the synthesis of biodiesel from palm oil and methanol in the presence of (CaO‐Y2O3)@LiFe5O8. The optimum process conditions were determined as follows: reaction temperature was 64.96°C, reaction time 4.36 hr, methanol: oil 13, catalyst amount 3.73%, and the highest biodiesel yield reached 96.21%. [ABSTRACT FROM AUTHOR]

Purple non-sulfur bacteria are anoxygenic photosynthetic microorganisms characterized by an extremely versatile metabolism, allowing them to grow in a broad variety of conditions as well as in the presence of different contaminants. This characteristic motivates the interest in their employment in photo-bioelectrochemical systems applicable in environments with dynamic physico-chemical properties. While the photochemistry of purple bacteria has been intensively studied, their photo-bioelectrochemistry and extracellular electron transfer process with an electrode surface remain largely unexplored. Herein, the process of harvesting electrons from intact purple bacteria is reviewed, and the perspective of enthralling future research possibilities is presented, placing emphasis on the major challenges in the photo-bioelectrochemistry of purple bacteria. [ABSTRACT FROM AUTHOR]

The potential of hierarchically porous calcium oxide (Hr−CaO) as a destructive adsorbent for organophosphate pesticides has been explored in this work. Hr−CaO has been synthesized via an environment friendly precipitation method using water/ glycerol as the solvent system and gelatin as a template. As‐prepared CaO exhibits a hierarchically porous structure with a high surface area of 74.8 m2 g−1. The adsorption of phosmet on Hr−CaO obeys pseudo‐second order kinetics and is described well by the Langmuir adsorption isotherm model. Thermodynamic studies further explain the adsorption process to be exothermic and spontaneous. Fourier transform infrared (FTIR), Scanning electron microscopy (SEM) and Xray diffraction (XRD) analysis of Hr−CaO after phosmet adsorption and the fragmentation pattern of phosmet obtained through mass spectrometric studies suggest chemical interaction of phosmet with Hr−CaO. Density functional theory (DFT) studies further confirm highly exothermic destructive phosmet adsorption and degradation products matching the peaks obtained in the mass spectrum. [ABSTRACT FROM AUTHOR]

The present work investigates the production of biodiesel from Euglena sanguinea microalgal bio-oil using calcium methoxide as a heterogeneous catalyst. The catalyst was synthesized and characterized by Fourier Transform Infra-red (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Brunauer-Emmett-Teller (BET), basicity, and basic site strength analysis. Initially, bio-oil was extracted from mass-cultivated biomass obtained from Euglena sanguinea algae. It was further pretreated and transesterified using calcium methoxide catalyst at various experimental conditions by which an optimum yield of 94.83% was achieved. The catalyst yielded above 90% up to 5 cycles of recovery and recycling. The kinetic studies were investigated at various reaction temperatures to find the rate of reaction. The activation energy and pre-exponential factor for the transesterification reaction were found to be 99.33 kJ mol−1 and 1.07 × 1014 min−1 respectively. The properties of the produced biodiesel were within the limits of ASTM D6751 standard. [ABSTRACT FROM AUTHOR]

The utilization of nonedible feedstocks for biodiesel production is getting top priority in the recent years, as they do not interfere with the global food economy. In the present study, calcium methoxide (Ca(OCH3)2) catalyst was synthesized for the production of biodiesel from Prunus armeniaca oil via transesterification reaction. Under optimized reaction conditions, the biodiesel yield of 89.93% was achieved and catalyst could be reused for four times with slight loss in activity. The fatty acid methyl esters in the produced biodiesel were detected by gas chromatography/mass spectrometry (GC/MS), and six fragments were identified based on mass-to-charge ratio (m/z) at different retention time. The fuel properties of the biodiesel obtained were in conformity with the ASTM standards. [ABSTRACT FROM AUTHOR]

Abstract: Reversible multicolor displays on solid media created from single‐molecule pigments are a long‐awaited goal. Herein, a new and simple molecular dyad, which can undergo switchable cyan (C), magenta (M), and yellow (Y) color changes in both solution and the solid state upon exposure to light, water/acid, and nucleophiles, has been designed and synthesized. The stimuli used herein can be applied independent of each other, which is beneficial for color changes without mutual interference. For comparison, mixtures of the two molecular switching motifs that form the basis of the dyad were also studied. The dyad greatly outperforms the corresponding mixed system with respect to reversible color switching on the paper substrate. Its potential for full‐color rewritable paper with excellent reversibility has been demonstrated. Legible multicolor prints, that is, high color contrast and resolution, good dispersion, and excellent reversibility, were achieved by using common water‐jet and light‐based printers. This work provides a very promising approach for the further development of full‐color switchable molecules, materials, and displays. [ABSTRACT FROM AUTHOR]

A series of micro-sized MgO catalysts with various morphologies have been prepared by varying the reaction temperature and stirring time during precipitation, and were investigated for the production of glycerol carbonate from the transesterification of glycerol with dimethyl carbonate. In contrast to other morphologies of MgO (e.g., rod-like, spherical, flower-like and nest-like), trapezoidal MgO demonstrated a superior performance with a yield of glycerol carbonate of more than 99%. Various techniques including N2 physical adsorption, XRD, CO2 chemical adsorption and EDS revealed that the unique catalytic activity of trapezoidal MgO was related to its lower specific surface area, bigger crystallite size, weaker surface basicity and fewer Mg atom vacancies compared to the other morphologies of MgO. The experimental conditions (e.g., the catalyst amount, solvent, reaction temperature and molar ratio between glycerol and dimethyl carbonate) were also found to play crucial roles in determining the yield of glycerol carbonate. Furthermore, CO2-TPD profiles and FT-IR spectra indicated that the weak surface basic sites occurring at 150 °C and the CO32− stretching vibration around 1448 cm−1 were responsible for the catalytic activity of the developed trapezoidal MgO in regeneration. [ABSTRACT FROM AUTHOR]

The removal of glyphosate and aminomethylphosphonic acid (AMPA) with synthetic water was carried out on a lab-scale nanofiltration unit using two membranes, NFX and NFW. The presence of humic acid and some inorganic matters (CaCl2 and NaCl) was tested in the experiment. The results demonstrate that NFX exhibits better separation performance than NFW. The herbicide filtration is found to have little effect on the permeate flux as compared to transmembrane pressure. Intermediate concentrations of NaCl act positively on foulant separation, and an increment of 3.3-5.4 percentage points in foulant rejection is obtained with the addition of 100 mg/L of NaCl. In Contrast, CaCl2 has negative effect on foulant separation during nanofiltration. Humic acid alone shows little influence on the rejection performance, whereas it is slightly improved in the coexistence of humic acid and CaCl2. The nanofiltration technology proves to be a good approach to treat the problem of pesticide micropollution in a one-step process. This work clearly shows that the composition of the water matrices may influence the efficiency of the nanofiltration process in terms of the separation of the micropollutants. [ABSTRACT FROM AUTHOR]

A low cost alkaline catalyst of dolomite (CaMg(CO3)2) was used to stabilize acacia sawdust bio-oil mixed with methanol. The upgrading efficiency was evaluated in terms of the total acid number (TAN) and viscosity. A change in the dolomite calcination temperature from 700 to 900 °C led to a significant change in the TAN and viscosity of the methanol-added bio-oil. Dolomite activated at higher temperatures had larger amounts of active CaO and MgO species due to the enhanced decarboxylation of calcium and magnesium carbonates. An increase in the dolomite content (1-5 wt%) decreased the TAN value of bio-oil remarkably. A thermal aging test of the methanol-added bio-oil upgraded using dolomite (calcined at 900 °C) at 50 °C for 24 h was carried out by storing the bio-oil at 80 °C for one week. Although the TAN value increased after the aging process, it was still lower than the TAN of raw bio-oil. In addition, increasing the methanol content (10-30 wt%) decreased the TAN and viscosity of the bio-oil significantly. [ABSTRACT FROM AUTHOR]

In this work, a new Fe3O4/AlFe/Te nanocomposite was synthesized by a one‐step sol–gel method. The Fe3O4 magnetic nanoparticles (MNPs) were prepared and then mixed with aluminum telluride (Al2Te3) in an alkali medium to produce the desired catalyst. After characterization of the Fe3O4/AlFe/Te nanocomposite by SEM, TEM, EDS, XRD, and ICP analyses, it was used in the esterification reaction. This heterogeneous catalyst showed high catalytic activity in the esterification of commercially available carboxylic acids with various alcohols to produce the desired esters at high conversions under neat conditions. The Fe3O4/AlFe/Te nanocomposites were separated from the reaction mixture via an external magnet and re‐used 8 times without significant loss of catalytic activity. [ABSTRACT FROM AUTHOR]

Abstract: Biodiesel was prepared from waste cooking oil combined with methanol. The process was performed via transesterification in a microreactor using kettle limescale as a heterogeneous catalyst and various cosolvents under different conditions. n‐Hexane and tetrahydrofuran were selected as cosolvents to investigate fatty acid methyl esters (FAMEs). To optimize the reaction conditions, the main parameters affecting FAME% including reaction temperature, catalyst concentration, oil‐to‐methanol volumetric ratio, and cosolvent‐to‐methanol volumetric ratio were studied via response surface methodology. Under optimal reaction conditions and in the presence of the cosolvents n‐hexane and tetrahydrofuran, high FAME purities were achieved. Considering the experimental results, the limescale catalyst is a unique material, and the cosolvent method can reduce significantly the reaction time and biodiesel production cost. [ABSTRACT FROM AUTHOR]

Transesterification of a mixture of vegetable oils with methanol using metal oxide catalysts derived from snail shell (SS) for biodiesel production was investigated. The metal oxides obtained from calcined snail shells in the temperature range of 650°–950 °C and modified by loading different potassium salts were used as a catalyst in the process. The catalysts were characterized by FT-IR, XRD, SEM-EDS, XPS and TGA. Catalytic activities of developed catalysts were also tested by Hammet indicator method and ion exchange method. The best calcination conditions were observed at 850°C for 4 hours based on biodiesel yield. The KF loaded snail shell gave highest biodiesel yield of 98 ± 1% in a batch reactor with highest basicity (15.9 mmoles/g) and basic strength measured by Hammet method. The optimized reaction conditions were: reaction temperature 65°C, reaction time 3 hours, methanol to oil molar ratio 9:1 and catalyst concentration 3wt%. Leaching and reusability tests confirm the stability of the catalyst as it encounters only 3% of leaching and small changes in catalytic activity up to five runs in terms of biodiesel yield. [ABSTRACT FROM AUTHOR]

Lithium silicate is one of the suitable heterogeneous catalysts for biodiesel production. The possibilities of large number of combinations of different reaction parameters make the optimization of biodiesel production process over various heterogeneous catalysts highly tedious, necessitating the development of alternate strategies for parameter optimization. Here, Box-Behnken design (BBD) coupled with response surface methodology (RSM) is employed to optimize the process parameters required for the production of biodiesel from waste cooking oil using lithium silicate as catalyst. Simple method of impregnation was performed for the material preparation and the catalyst was analyzed using different techniques. It was found that the activity is directly proportional to the basicity data obtained from temperature programmed desorption (TPD) of CO over various catalyst systems. The material exhibits macroporous morphology and the major crystalline phase of the most active catalyst was found to be LiSiO. The effects of different reaction parameters were studied and a biodiesel yield of 100% was obtained under the predicted optimum reaction conditions of methanol : oil molar ratio 15 : 1, catalyst amount 7 wt%, reaction temperature 55 °C and reaction time 2.5 h. The validation experiments showed a correlation coefficient of 0.95 between the predicted and experimental yield of biodiesel, which indicates the high significance of the model. The fuel properties of biodiesel obtained under the optimum conditions met the specifications as mentioned in ASTM D6751 and EN 14214 standards. Catalyst heterogeneity and low reaction temperature are the major attractions of the present biodiesel preparation strategy. [ABSTRACT FROM AUTHOR]

To test the feasibility of biodiesel production using rendered fat from avian influenza (AI) infected poultry in a burial site, we conducted a laboratory-scale transesterification. Each content of fatty acid methyl esters (FAME) was identified to estimate the characteristics of produced biodiesel. Analytical results of the whole FAME profile show that the rendered fat from AI carcass can be a useful source of biodiesel production. The results show 47% of total fat mass can be recovered as biodiesel. Although natural biodegradation in the burial site and soil impurities lowered the yield, the compositional properties of FAMEs confirm that the produced biodiesel presents adequate fuel characteristics, satisfying common biodiesel specifications. These findings provide evidence that our approach can be a viable option to recycle buried carcass sustainably while terminating burial sites. [ABSTRACT FROM AUTHOR]

We prepared nanoscale, modularizable, self-assembled peptide nanoarchitectures with diameters less of than 20 nm by combining β-sheet-forming peptides tethering a cell-penetrating peptide or a nuclear localization signal sequence. We also found that doxorubicin (Dox), an anti-cancer drug, was non-covalently accommodated by the assemblies at a ratio of one Dox molecule per ten peptides. The Dox-loaded peptide assemblies facilitated cellular uptake and subsequent nuclear localization in HeLa cells, and induced cell death even at low Dox concentrations. This peptide nanocarrier motif is a promising platform for a biocompatible drug delivery system by altering the targeting head groups of the carrier peptides. [ABSTRACT FROM AUTHOR]