The kinetics and modeling of dual-wavelength controlled photopolymerization confinement (PC) are presented and measured data are analyzed by analytic formulas and numerical data. The UV-light initiated inhibition effect is strongly monomer-dependent and different monomers have different C=C bond rate constants and conversion efficacy. Without the UV-light, for a given blue-light intensity, higher initiator concentration (C₁₀) and rate constant (k’) lead to higher conversion, as also predicted by analytic formulas, in which the total conversion rate (R_T) is an increasing function of k’R, which is proportional to k[gB₁C₁]^0.5. However, the coupling factor b₁ plays a different role that higher b₁ leads to higher conversion only in the transient regime; whereas higher b₁ leads lower steady-state conversion. For a fixed initiator concentration C₁₀, higher inhibitor concentration (C₂₀) leads to lower conversion due to stronger inhibition effect. However, same conversion reduction was found for the same H-factor of H₀ = [b₁C₁₀ - b₂C₂₀]. Conversion of blue-only are much higher than that of UV-only and UV-blue combined, in which high C₂₀ results a strong reduction of blue-only-conversion, such that the UV-light serves as the turn-off (trigger) mechanism for the purpose of spatial confirmation within the overlap area of UV and blue light. For example, UV-light controlled methacrylate conversion of a glycidyl dimethacrylate resin formulated with a tertiary amine co-initiator, and butyl nitrite, subject to a continuous exposure of a blue light, but an on-off exposure of a UV-light. Finally, we developed a theoretical new finding for the criterion of a good material/candidate governed by a double ratio of light-intensity and concentration, [I₂₀C₂₀.]/[I₁₀C₁₀].

Tough and antimicrobial dual-crosslinked poly((trimethylamino)ethyl methacrylate chloride)-phytic acid hydrogel (pTMAEMA-PA) has been synthesized by adding chemical crosslinker and docking physical crosslinker of multivalent phytic acid into a cationic polyelectrolyte network. By increasing the loading concentration of PA, the tough hydrogel exhibits compressive stress of >1 MPa, along with high elasticity and fatigue-resistant properties. The enhanced mechanical properties of pTMAEMA-PA were stem from multivalent ion effect of PA via the formation of ion bridges within polyelectrolytes. In addition, a comparative study for a series of pTMAEMA-counterion complexes was conducted to elaborate the relationship between swelling ratio and mechanical strength. The study also revealed secondary factors, such as ion valency, ion specificity and hydrogen bond formation, holding crucial roles in tuning mechanical properties of the polyelectrolyte hydrogel. Furthermore, in bacteria attachment and disk diffusion tests, pTMAEMA-PA exhibits superior fouling resistance and antibacterial capability. The results reflect the fact that PA enables chelating strongly with divalent metal ions, hence, disrupting the outer membrane of bacteria, as well as dysfunction of organelles, DNA and protein. Overall, the work demonstrated a novel strategy for preparation of tough polyelectrolyte with antibacterial capability via docking PA to open up the potential use of PA in medical application.

Polyvinyl guanidineacetic (PVG) was prepared by the chemical grafting between poly(vinyl alcohol) (PVA) and guanidineacetic acid. The results showed that the guanidineacetic groups were successfully introduced into the polyvinyl alcohol by fourier transform infrared (FTIR) and thermogravimetry (TG). The effects of the amount of catalyst and reaction time on the PVG grafting rate were investigated. The PVG/NWF composite membrane as a heterogeneous catalyst for biodiesel production was successfully prepared by the solvent phase inversion. The effects of mass ratio of methanol/soybean oil and reaction temperature on the conversions using the composite membrane for transesterification were studied. And the reusability of the composite membrane and the kinetics of the reaction catalyzed by the composite membrane were also investigated. The conversions obtained from the model are in good agreement with the experimental data.

Asymmetric reduction of enoates, imines and ketones are among the most important reactions in biocatalysis. These reactions are routinely conducted using enzymes that use nicotinamide cofactors as reductants. The deazaflavin cofactor F₄₂₀ also has electrochemical properties that make it suitable as an alternative to nicotinamide cofactors for use in asymmetric reduction reactions. However, cofactor F₄₂₀-dependent enzymes remain under-explored as a resource for biocatalysis. In this review, we consider the cofactor F₄₂₀-dependent enzyme families with greatest potential for the discovery of new biocatalysts: the flavin/deazaflavin-dependent oxidoreductases (FDORs) and the luciferase-like hydride transferases (LLHTs). We discuss characterized F₄₂₀-dependent reductions that have potential for adaptation for biocatalysis, and we consider the enzymes best suited for use in the reduction of oxidized cofactor F₄₂₀ to allow cofactor recycling in situ. We also discuss recent advances in the production of cofactor F₄₂₀ and its functional analog F_O-5’- phosphate, which remains an impediment to the adoption of this family of enzymes for industrial biocatalytic processes. Finally, we discuss the prospects for the use of this cofactor and dependent enzymes as a resource for industrial biocatalysis.

The remediation of dredged marine sediments contaminated by heavy metals has drawn increasing attention worldly. The immobilization was regarded as a promising method to reduce adverse impacts on marine ecosystem. In this study, kaolinite and limestone were used as amendments to immobilize heavy metals (e.g. Zn, Pb and Cu) respectively in dredged marine sediments collected from the coastal zone adjacent to Tianjin Port in Bohai Bay. The sequential extraction procedure was applied to identify the mobility of heavy metals and further to evaluate the immobilization effect of amendments. The physical-chemical properties of sediments, such as pH, electrical conductivity (EC), salinity, and total organic carbon (TOC), were also measured to better understand their influence on heavy metals’ mobility. In addition, the compositions of clay minerals were also analyzed to identify the transformation process of minerals in the sediments. The results of sequential extraction procedure indicated that mobile fractions of heavy metals were converted into relatively stable fractions because of the two amendments. In addition, EC, salinity and TOC decreased moderately while no obvious variations of pH in the sediments were observed with the addition of the the kaolinite and the limestone. The percentage of montmorillonite decreased to minimum value while that of chlorite increased gradually during the experimental periods for 40 days probably due to complexation reaction. It was confirmed that both kaolinite and limestone can effectively reduce the mobility and bioavailability of heavy metals, particularly for Zn, generally, limestone has a better immobilization effect compared with kaolinite.

Sulfonated carbon was used as an efficient and reusable heterogeneous solid acid catalyst for the synthesis of biodiesel via esterification of oleic acid with methanol under high voltage conditions. Using an inexpensive and reusable catalyst, environmental benignity, excellent yields in short times, synthesis in atmospheric pressure and low temperature conditions are some of the important features of this protocol. In the final results were confirmed by GC.

The abundance, distribution and composition of marine debris (> 5 cm) and small microplastics (11 μm) from five rivers in South Eastern, Nigeria was investigated. This study provided the first assessment of the type and quantity of marine litter and microplastics in Nigeria. A total of 3487 macrodebris items/m2 were counted with the following distribution; plastics (59 %) > metal (10 %) > cloth (7 %), paper /cardboard (7 %), rubber (7 %) > glass/ceramics (5 %), medical and agro-based waste (3 %) > wood (2 %). The cleanliness of the river assessed with clean coast index (CCI) ranged from “very clean” at Okumpi and Obiaraedu river to “extremely dirty” at Nwangele river. Microplastics abundance ranged from 440 to 1556 particles/L, with high accumulation at downstream. Fragment shape was most abundant while fiber and film followed. The distribution of plastic types was; PET (29 %) > PE (22 %) > PVC (16 %) > PP (14 %) > other (6 %) respectively. Significant relationship was found between the total abundances of microplastics and different macrodebris groups suggesting that microplastics were abundant in areas where the macrodebris abundance was high. Our results provide baseline information for future assessments. Management actions should focus on input prevention including proper waste management, recycling of plastics, and strict penalties for illegal dumping of wastes.

Curcumin has restrained clinical applications due to poor bioavailability. This study aimed to synthesize cockle shell-derived calcium carbonate (aragonite) nanoparticles (CSCaCO3NP) for delivery of curcumin and to evaluate its kinetic release in vitro. CSCaCO3NP was synthesized and conjugated with curcumin (Cur-CSCaCO3NP) using a simple top down approach and characterized for its physicochemical properties as a potential curcumin carrier. In vitro release profile was assessed using dialysis bag membrane method. The release data were fitted to Korsmeyer-Peppas, Zero order and Higuchi models to evaluate the mechanism of release pattern. A spherical shaped CSCaCO3NP with a surface area of 14.48±0.1 m2/g, average mean diameter size of 21.38±2.7 nm and a zeta potential of -18.7 mV was synthesized which has a high loading content and encapsulation efficiency. The FT-IR and XRD revealed less observable changes on the peaks after conjugation. In vitro kinetic release profile demonstrated sustained release and best fitted to the Higuchi equation model. The results of this study showed the capacity of the synthesized CSCaCO3NP to encapsulate curcumin efficiently with a stable release in vitro. This could give an insight and supportive ideas on the potentials of CSCaCO3NP for curcumin delivery. Therefore, CSCaCO3NP holds future prospects in preclinical framework to enhance curcumin efficacy for oral therapeutic applications.

Coffee and caffeine have been used as solar absorbers and also to increase the thermal stability and efficiency of perovskite solar cells. In this work, we report the sensing of extremely alkaline pH by colloidal coffee solution aided by generation of an optical absorption band in the near-UV region. This generation of absorption band could be explained by the orientation induced dipole-dipole interactions arising from differing caffeine-solvent interactions with varying pH. Such a generation leads to the lowering of direct as well as indirect bandgaps from 4 eV-->2.8 eV& 3.4 eV-->2.5 eV, respectively. We also estimate the changes in optical energy storage efficiency, inferring it to be highest for pH 11 having the highest intensity of the generated absorption band (λ_abs≈360 nm). With these observations and further deductions, the work reported in this paper would be of immense interest to the researchers working in the field of development of chemical pH sensors and also in the development of novel UV absorbers.

A valorization process of spent coffee grounds (SCG) was studied. Thus, a two-stage process, a stage of extraction of the polyphenols and a stage of obtaining activated carbon (AC) by a carbonization process, was performed. The extraction was carried out with a hydro-alcoholic solution in a pressure reactor, modifying time and temperature. To optimize the extraction of polyphenols, a two-level factorial design with three replications at the central values was used. The best results were obtained by performing the extraction at 80 ºC during 30 min, using a mixture of EtOH:H₂O 1:1 (v/v) as extraction solution. Caffeine and chlorogenic acid were the most abundant compounds in the analysed extracts, ranging from 0.09 to 4.8 mg∙g^-1 and 0.06 to 9.7 mg∙g^-1, respectively. The precursor obtained in the extraction stage were transformed into AC. An experimental design was realized in order to analyze the influence of different variables in the AC obtained process (reaction time and amount of potassium hydroxide used). Actived carbons with BET specific surface (S_BET) comprised between 1600 m²∙g^-1 and 2330 m²∙g^-1 had a microporous surface. Under the optimum conditions, the obtained AC presented a maximum adsorption capacity of methylene blue (q_m) between 411 mg∙g^-1 and 813 mg∙g^-1.

This paper describes the physico-chemical study of the adsorption of dysprosium (Dy³⁺) in aqueous solution onto two types of activated carbons synthesized from spent coffee ground. KOH activated carbon is a microporous material with a specific BET surface area of 2330 m²·g^-1 and pores with a diameter of 3.2 nm. Carbon activated with water vapor and N₂ is a solid mesoporous, with pores of 5.7 nm in diameter and a specific surface of 982 m²·g^-1. A significant dependence of the adsorption capacity on the solution pH was found, while it does not depend significantly neither on the dysprosium concentration nor on the temperature. A maximum adsorption capacity of 31.26 mg·g^-1 and 33.52 mg·g^-1 for the chemically and physically activated carbons, respectively, were found. In both cases, the results obtained from adsorption isotherms and kinetic study were better fit to a Langmuir model and a pseudo-second-order kinetics. In addition, thermodynamic results indicate that dysprosium adsorption onto both activated carbons is an exothermic, spontaneous and favorable process.

Silybum marianum (L.) Gaertn. (aka milk thistle) constitute the almost exclusive source of silymarin, a mixture of different flavonolignans, and is thus considered as a unique model for their extraction. The present research deals with ultrasound-assisted extraction (UAE) of S. marianum flavonolignans and their quantification using LC system. The optimal conditions for UAE were: aqueous EtOH 54.5% (v/v) as solvent, applying an ultrasound frequency of 36.6 kHz during an extraction time of 60 min at 45°C with a liquid to solid ratio of 25:1 ml/g DW. Following optimization, the extraction method was validated according to international standards of the association of analytical communities (AOAC) in order to ensure its precision and accuracy for the quantitation of the individual silymarin components. The efficiency of UAE was compared with maceration protocol of the same duration. The optimized and validated conditions allowed highest extraction yields of flavonolignans in comparison to maceration. The antioxidant capacity of the extracts was confirmed by the CUPRAC assays and inhibition of advanced glycation end products. The skin anti-aging action was also confirmed toward the strong in vitro inhibition capacity of the obtained extract against collagenase and elastase enzymes. The procedure presented here allows a green efficient extraction and quantification of the main flavonolignans from the fruits of S. marianum with attractive antioxidant and anti-aging activities for future cosmetic applications.

Nanotechnology is a multidisciplinary science covering matters involving nanoscale level that is being developed for a great variety of applications. Nanomedicine is one of these attractive and challenging uses focused on the employment of nanomaterials in medical applications such as drug delivery. However, the uses of these nanometric systems requires specific parameters to establish the possible advantages and disadvantages in specific applications. This review presents the fundamental factors of nanoparticles and it´s microenvironment that must be considered to make an appropriate design for medical applications: (i) Interactions between nanoparticles and their biological environment, (ii) the interaction mechanisms, (iii) and the physicochemical properties of nanoparticles. On the other hand, the repercussions of the control, alteration and modification of these parameters in the final applications. Additionally, we here briefly report the implications of nanoparticles in nanomedicine and provide perspectives for some particular applications which still are challenged

Carbon-based nanomaterials, such as carbon nanomaterials, play an important role in many promising nanomaterials in the field of biomedicine. Among them, carbon nanomaterials are a new kind of porous carbon nanomaterials with great application potential. Therefore, based on carbon nanomaterials, the interaction between biomaterials and cells and surface modification were analyzed. Studies have shown that the interaction between the surface of biological materials and cells is mainly the mutual molecular recognition between the surface receptors of cell membranes and the ligands on the surface of biomaterials. Therefore, biomimetic modification of the surface of biomaterials is used to enhance cell affinity and specific recognition. The carbon nanomaterial has a large specific surface area and pore volume, can provide high drug-loading capacity, has an adjustable pore structure and pores, can control the release of the drug molecules, and has a good application prospect in the field of drug delivery systems.

Sensors became integrated through the control condition arrangement, either for visual, mechanical, biological, or chemical applications. New stuff is designed for detection, as Diluted Magnetic Semiconductors (DMS), and are considered attractive candidates that consist of a traditional 111- V, II-VI, or group IV semiconductor. Manganese Mn-doped GaN (Mn.Gac.N) epitaxial velum has a unique magnetic, visual and chemical properties in order to control system intelligent for detector design. The subject area of the magnetic properties of MnxGal-xN is on a large scale available, there are only a few studies on the visual properties and electrochemical properties of MnxGal-xN epitaxial velums. Where MnGaN velums were used in spintronic and opto-electronic applications according to their magnetic characterization and constructed MnGaN electrode are drop fabric potential for potentiometric sensor applications since they have good performance as ion-selective electrodes. The electrical and magnetic properties that allow the control of electron spin as well as complaint period, makes the materials ideal for spintronic applications. Designing such spintronic and optoelectronic devices based on MnxGal-xN requires a broader agreement of physical, visual, electrical and chemical properties epitaxial velums that are still seldom in the literature. This bailiwick displays the potential use of MnGaN semiconductor as an all solid-state potentiometric sensor for measuring anions in solutions in the control engineering field.

Food preservatives are compound that are used for the treatment of food to improve the shelf life. In the food industry, is necessary to monitor all processes, for both safety and quality of the product. An electronic nose (or e-nose) is a biomimetic olfactory system that could find numerous industrial applications, including food quality control. Commercial electronic noses are based on sensor arrays composed by a combination of different sensors, which include conductometric metal oxide devices. Metal oxide nanowires are considered among the most promising materials for the fabrication of novel sensing devices, which can enhance the overall performances of e-noses in food applications. In the present work, is reported the fabrication of a novel sensor array based on SnO2, CuO and WO₃ nanowires deposited on top of commercial μHPs, provided by ams Sensor Solutions Germany GmbH. The array was tested for the discrimination of four typical compounds added to food products or used for their treatment to increase the shelf life: ethanol, acetone, nitrogen dioxide and ozone. Results are very promising: the sensors array was able to operate for long time consuming less than 50mW for each single sensor, and PCA analysis confirms that the device was able to discriminate between different compounds.

Grape foods fermented with probiotics are sources of beneficial bacteria for the GI tract and also have a high antioxidant capacity. The addition of probiotics to ferment food has always been a traditional process; therefore, probiotic dairy and non-dairy products might contribute to a daily antioxidant diet to improve consumers’ life quality and health. This research was undertaken to determine the viability of 4 wild isolates of Lactobacillus for storage at 5 and 25ºC within 90 days in simulated synthetic grape media and a standard grape marmalade formulation. Changes in active culture numbers, pH level, glucose concentration, and antioxidant properties were evaluated. Most of the isolates demonstrated higher growth in the grape marmalade than the synthetic grape marmalade, which was greater than 7 Log cfu/g within 90 days of storage at 5ºC. In addition, most of the wild isolates grew beyond the critical count of 106 cfu/g in sampling between 60 and 90 days of storage. Moreover, fermented grape marmalade with probiotics showed a strong antioxidant capacity that failed to differ significantly with the synthetic medium. The study confirmed L. paraplantarum, L. plantarum, W. paramesenteroides, and E. feacalis were ideal probiotics for fermentation process of grape marmalade.

In recent years, polyureas with dynamic hindered urea bonds (HUBs), as a class of promising biomedical polymers, have attracted attention as a benefit of their controlled hydrolytic property. The effect of the chemical structures on the properties of polyureas and their assemblies was rarely reported. In this study, four kinds of polyureas with different chemical groups have been synthesized, and the polyurea from cyclohexyl diisocyanate and tert-butyl diamine showed the fastest hydrolytic rate. The amphiphilic polyurea composed of hydrophobic cyclohexyl-tert-butyl polyurea and hydrophilic poly(ethylene glycol) was synthesized for controlled delivery of antitumor drug paclitaxel (PTX). The PTX-loaded PEGylated polyurea micelle more effectively entered into the murine breast cancer 4T1 cells and inhibited the corresponding tumor growth in vitro and in vivo. Therefore, the PEGylated polyurea with adjustable degradation might be a promising polymer matrix for drug delivery.

In the study, a new correction method was applied to reduce error during detection on mixed pesticide residue in apples by using Raman spectra. Combined with self-built pesticide residues detection system by Raman spectroscopy and the application of surface enhancement technology, rapid real-time qualitative and quantitative analysis of deltamethrin and acetamiprid residues in apples can be applied effectively. In quantitative analysis, compared with the intensity value of characteristic peaks of single pesticide with same concentration, the intensity value of characteristic peaks of the two pesticides decreased after mixing the pesticides, which interferes the results severely. By comparing the difference in the intensity of characteristic peaks of single and mixed pesticides, a correction method is proposed to eliminate the influence of pesticides mixture. Characteristic peak intensity values of gradient concentration pesticide from 10-1 g•kg-1 to 10-6 g•kg-1 and Lagrangian interpolation are applied in the correction method. And a smooth surface is applied to describe the correction ratio of characteristic peak intensity. Through detecting the characteristic peak intensity values of the mixed pesticide, correction ratio will be obtained. Then real values of the peak intensity of pesticides and the content of each component of the mixed pesticide will be acquired by the correction method. Correlation coefficient of model validation exceeds 0.88 generally and Root Mean Square Error also decreases obviously after correction, which proved the reliability of the method.

We report the development of an extrinsic self-healing coating system that shows no fluorescence from the intact coating, yellowish fluorescence in cracked regions, and greenish fluorescence in healed regions, thus allowing the separate monitoring of cracking and healing of coatings. This fluorescence monitoring self-healing system consisted of a top coating, an epoxy matrix resin containing mixed dye-loaded in single microcapsule. The dye-loaded microcapsules consisted of a poly(urea-formaldehyde) shell encapsulating a healing agent containing MAT-PDMS and styrene, a photo-initiator and a mixture of two dyes, one that fluoresces only in the solid state (DCM) and a second that fluoresces dramatically increased in the solid than solution state (4-TPAE). A mixture of the healing agent, photo-initiator and the two dyes was yellow due to fluorescence from DCM. On UV curing of this mixture, however, the color changed from yellow to green and the fluorescence intensity increased due to fluorescence from 4-TPAE in the solid state. When a self-healing coating embedded with microcapsules containing the DCM/4-TPAE dye mixture was scratched, the damaged region exhibited a yellowish color that changed to green after healing. Thus, the self-healing system reported here allows the separate monitoring of cracking and healing based on changes in fluorescence color.

A new di-mannitol adipate ester-based zinc metal alkoxide (DMAE-Zn) was synthesized as a bi-functional PVC thermal stabilizer for the first time. The materials were characterized with Fourier-transform Infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). Characterization results confirmed the formation of Zn-O bonds in DMAE-Zn; and that DMAE-Zn had a high decomposition temperature and a low melting point. The thermal stability of DMAE-Zn on PVC also was tested by conductivity test, thermal aging test, and UV-visible spectroscopy (UV-VIS) test. PVC stabilized by DMAE-Zn had a good initial color and excellent long-term stability. UV-VIS also showed that the conjugated structure in PVC stabilized by DMAE-Zn was almost all of the triene, suggesting that the addition of DMAE-Zn would suppress the formation of conjugated structures above tetraene. Dynamic processing performance of PVC samples tested by torque rheometer indicated that, having a good compatibility with PVC chains in the amorphous regions, DMAE-Zn contributed good plasticizing effect to PVC. DMAE-Zn thus effectively demonstrates bi-functional roles, e.g., thermal stabilizers and plasticizers to PVC. Furthermore, FT-IR, HCl absorption capacity test, and complex ZnCl₂ test were also used to verify the thermal stability mechanism of DMAE-Zn for PVC.

The effect of microstructure and chemistry of passive films on the kinetics of passive layer growth and passivity breakdown of some Ti-based alloys, namely Ti-6Al-4V, Ti-6Al-7Nb and TC21 alloys was studied. The rate of pitting corrosion was evaluated using cyclic polarization measurements. Chronoamperometry was applied to assess the passive layer growth kinetics and breakdown. Microstructure influence on the uniform corrosion rate of these alloys was also investigated employing Tafel extrapolation and dynamic electrochemical impedance spectroscopy. Corrosion studies were performed in 0.9% NaCl solution at 37 oC, and the obtained results were compared with ultrapure Ti (99.99%). The different phases of the microstructure were characterized by X-ray diffraction and scanning electron microscopy. Chemical composition and chemistry of the corroded surfaces were studied using X-ray photoelectron analysis. For all studied alloys, the microstructure consisted of α matrix, which was strengthened by β phase. The highest and the lowest values of the β phase’s volume fraction were recorded for TC21 and Ti-Al-Nb alloys, respectively. The uniform corrosion rate and pitting corrosion resistance (R_pit) of the studied alloys were enhanced following the sequence: Ti-6Al-7Nb < Ti-6Al-4V << TC21. The corrosion resistance of Ti-Al-Nb alloy approached that of pure Ti. The obvious changes in the microstructure of these alloys, together with XPS findings, were adopted to interpret the pronounced variation in their corrosion rates.

Suzuki cross-coupling reaction has developed one of the furthermost effectual approaches for the synthesis of biaryls or substituted aromatic moieties from aryl halides and arylboronic acids with a palladium-catalyst in the past two era’s. Herein, Pd-free layered double hydroxide containing nickel catalysts were prepared by co-precipitation method under ultrasonic irradiation and N2 atmosphere with different molar ratios of Ni: Mg: Al and coded as (1NiLDHs-Dr), (1.5NiLDHs-Dr) and (2NiLDHs-Dr). A series of reduced catalysts under 5%H2/N2 at different temperatures were coded as 1NiLDHs-R200, 1.5NiLDHs-R200 and 2NiLDHs-R200. As-synthesized 2NiLDHs-Dr was the superlative catalyst when coupling different aryl halides with different boronic acids derivatives. Deep investigation of all catalysts was done using different techniques such as inductively coupled plasma optical emission spectroscopy (ICP-OES), x-ray photoelectron spectroscopy (XPS), powder x-ray diffraction (XRD), thermogravimetric analyses (TGA), Fourier transfer infrared (FTIR), scanning electron microscope (SEM) connected with energy dispersive x-ray (EDX) and N2-physisorption at -196 ℃. The results attained verified that ɑ-Ni(OH)2 was fashioned for 2NiLDHs-Dr catalyst and the enclosure of nickel ions in the cationic sheet of layered structure were responsible for the fascinating catalytic efficacy rather than the basic nature of material. The Ni-containing LDHs catalysts encourage forthcoming studies in Pd-free catalyzed C-C coupling reactions.

As novel materials for carbon capture, phase change solvents can separate into two immiscible phases during the CO2 capturing procedure under a certain temperature. The solvent systems can significantly decrease the energy consumption since the solvents can be regenerated by only heating the rich-CO2 phase. In this work, amino acid ionic liquids (AAILs) were synthesized using quaternary ammonium salts and amino acids as raw materials, and the aqueous solutions were prepared as novel liquid-solid phase change solvents. The results showed that the solvents had excellent CO2 absorption capacity, and the AAILs functionalized by glycine and tryptophan exhibited significant phase change properties. The mechanism of phase-change of the solvent were mainly due to the lower solubility of the product after reaction between AAILs and CO2. The solvent with tryptophan as anion could be regenerated by only heating the CO2-riched solid phase, which might significantly decrease energy consumption of regeneration. And the absorbent could be reused with the regenerated absorption ratio up to 79%. The solvent system has great potential in industrial application due to the easy operation process and efficient recycling ability.

Chitosan decorated copper nanoparticles (CS/CuNPs) catalysts were synthesized via reduction methods utilizing green protocol. The CS/CuNPs hybrid catalysts were tested for the synthesis of quinoline derivatives utilizing one-pot multicomponent reaction (MCR) under ultrasonic irradiation. The best catalyst (CS/CuNPs) that provided good conversion reaction yield and high turnover frequency (TOF) was characterized using Fourier transform infrared (FTIR), Thermogravimetric analyses (TGA), X-ray diffraction (XRD), , scanning electron microscopy (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. Generalization of the scope of the proposed catalytic process was studied using different aldehydes. Excellent products yield and high TOF in even shorter reaction time (~5 min) was attained. Recyclability performance of the catalyst over five times re-use without detectable loss in product yield was recorded. The current method is green process utilizing environmentally benign catalyst and considered to be promising sustainable protocol for the synthesis of fine chemicals.

Chitosan decorated copper nanoparticles catalysts (CSCuNPs) were synthesized via reduction methods utilizing green protocol. The CSCuNPs catalysts were tested for the synthesis of quinoline derivatives utilizing one-pot multicomponent reaction (MCR) under ultrasonic irradiation. The best catalyst (Cu-CS-NPs) that provided good conversion reaction yield and high turnover frequency (TOF) was characterized using FTIR, TGA, XRD, TEM and XPS techniques. Generalization of the scope of the proposed catalytic process was studied using different aldehydes. Excellent products yield and high TOF in even shorter reaction time (~5 min) was attained. Recyclability performance of the catalyst over five times re-use without detectable loss in product yield was recorded. The current method is green process utilizing environmentally benign catalyst and considered to be promising sustainable protocol for the synthesis of fine chemicals.

The corrosion inhibition performance of pyridine derivatives (4-methylpyridine and its quaternary ammonium salts) and sulfur-containing compounds (thiourea and mercaptoethanol) with different molar ratios on carbon steel in CO2-saturated 3.5 wt.% NaCl solution was investigated by weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy and scanning electron microscopy. The synergistic corrosion inhibition mechanism of mixed inhibitors was elucidated by the theoretical calculation and simulation. The molecule of pyridine derivatives compound with larger volume has the priority to adsorb on the metal surface, while the molecules of sulfur-containing compounds with smaller volume fill in vacancies. A dense adsorption film would be formed when 4-PQ and sulfur-containing compounds are added at a proper mole ratio.

Pharmaceuticals contain biologically active components that can pollute water courses as a result of the excretions from individuals and/or uncontrolled release of residues from chemical plants, and they can pose a hazard to health. Pharmaceutical residues can persist at low concentrations in the environment, and thus may be potentially harmful to aquatic animals and to humans.  Controlling and monitoring such residues are therefore a prime interest, for example, a solid-phase extraction uses solid sorbents to purify and preconcentrate the residues prior to their chemical analysis. In the present study, poly (acrylonitrile-co-divinylbenzene-80) sorbents are synthesised by varying the comonomer feed ratios under precipitation polymerisation conditions to deliver a family of porous polymer microspheres. Acrylonitrile confers polar characters onto the sorbents, and the acrylonitrile-derived nitrile groups can be chemically transformed via polymer-analogous reactions into thioamide and sulfonated residues which make the sorbents even more suitable for the capture of polar analytes, including selected pharmaceuticals. The utility of the porous thioamide-sulfonated containing sorbents is demonstrated via the dispersion-solid phase extraction of mefenamic acid from aqueous media; mefenamic acid is an anthranilic acid derivative which is a potent, non-steroidal anti-inflammatory drug which is found in environmental waters at low concentrations.

Aflatoxins in feeds cause great health hazards to animals and in advance, to human. Potential of crude clays designated AC, KC, CC and MC and ashes VA and RA were evaluated for their capacity to adsorb aflatoxins B₁ (AFB₁), B₂ (AFB₂), G₁ (AFG₁) and G₂ (AFG₂) relative to a commercial binder Mycobinder^R (Evonik Industries AG) using in-vitro technique. On average, CC, VA, KC, MC, AC, RA and Mycobind^R adsorbed 39.9%, 51.3%, 61.5%, 62.0%, 72.6%, 84.7% and 98.1% of the total aflatoxins in buffered solution, respectively. The capacity of AC and RA was statistically (p<0.05) better in binding aflatoxins next to Mycobind^R. Capacity of the TBM and Mycobind^R to bind aflatoxins, seemed to follow the trend of their cation exchange capacity (CEC). The CEC (meq/100g) of CC, MC, KC, VA, AC, RA and Mycobind^R were 7.0, 15.4, 18.8, 25.4, 27.2, 27.2 and 38.9, respectively. On average 96.3%, 42.7%, 80.8% and 32.1% of AFB1, AFB2, AFG1 and AFG2 were adsorbed, respectively.  Binding capacity of the clays and ashes relative to Mycobind^R was about 100% for AC and RA, 50% for KC, MC and VA and 33.3% for CC.  The AC and RA seem to be promising resources in binding aflatoxins in solution.

This work is aiming to motivation on the prospect of evolving new thiazole dyes with respectable application properties, expected pharmacological activities. Curcumin Coupling with diverse diazonium salts of 2-amino thiazole derivatives as 2-aminobenzothiazole, 2- amino-5-phenylthiazole, 2 amino-5-methylthiazole and 2 amino-5-nitrothiazole to produce novel azo dyes. All synthesised dyes were completely confirmed their structures via elemental and spectroscopic techniques. The synthesised thiazole derivatives were examined for their “antimicrobial, anticancer and antioxidant” activities. All of the synthesized dyes were applied on synthetic fabrics as polyester and successively their dyeing properties, “light, washing, perspiration, rubbing and sublimation” fastness were evaluated. Prepared dyestuffs are suitable for dyeing polyester fabrics. It was initiate that all of prepared dyes own extraordinary colour hue, along with respectable fastness properties. Also the synthesised thiazole derivatives display moral pharmacology activity.

Chitosan decorated copper nanoparticles catalysts (CSCuNPs) were synthesized via reduction methods utilizing green protocol. The CSCuNPs catalysts were tested for the synthesis of quinoline derivatives utilizing one-pot multicomponent reaction (MCR) under ultrasonic irradiation. The best catalyst (Cu-CS-NPs) that provided good conversion reaction yield and high turnover frequency (TOF) was characterized using FTIR, TGA, XRD, TEM and XPS techniques. Generalization of the scope of the proposed catalytic process was studied using different aldehydes. Excellent products yield and high TOF in even shorter reaction time (~5 min) was attained. Recyclability performance of the catalyst over five times re-use without detectable loss in product yield was recorded. The current method is green process utilizing environmentally benign catalyst and considered to be promising sustainable protocol for the synthesis of fine chemicals.

Highly macroporous thin films of WO₃ were fabricated on transparent conductive substrates by application of a polymeric organic paste loaded with an amine/tungstate complex.  After spin-coating and annealing at 550^oC, the resulting yellow films are found to be comprised of channeled array of clustered nanoparticles.  These channels are confirmed by scanning electron microscopy to extend through the entire length of the coating.  The high porosity of the material enables the insertion of a co-catalyst into the internal structure of the film.  These internally functionalized composites demonstrate good photosensitivity and stability in neutral electrolyte.

The seeds of cultivated peanut, Arachis hypogaea, are an agronomically important crop produced for human nutrition, oilseed and feed stock. Peanut seed is the single most expensive variable input cost and thus producers require seed with excellence performance in terms of germination efficiency. During the maturation process, triglycerides are stored in oil bodies as an energy resource during germination and seedling development. The stability of oil body membranes is essential for nutrient mobilization during germination. This study focused on evaluating the phytosterol composition in seed components including the kernel, embryo (heart), and seed coat or skin. Samples of different maturity classes were analyzed for macronutrient and phytosterol content. The three most abundant phytosterols, β-sitosterol, campesterol, and stigmasterol, comprised 82.29%, 86.39%, and 94.25% of seed hearts, kernels, and seed coats, respectively. Stigmasterol concentration was highest in the seed kernel providing an excellent source of this sterol known to have beneficial effects on human health. Peanut hearts contained the highest concentration of sterols by mass potentially providing protection and resources for the developing seedling. The amount of α-tocopherol increases in peanut hearts during the maturation process providing protection from temperature stress and stability required for seedling vigor. These results suggest that phytosterols may play a significant role in the performance of seeds and provides a possible explanation for the poor germination efficiency of immature seeds.

Traditional edible barbecue products use with lemon juice not only make the barbecue more delicious but also reduce the risk of PAHs in the barbecue products. One of the major economics crops in Taiwan, the waste from citrus fruits was very tremendous mass. However, the peelings of citrus fruits are rich in essential oil, especially, the limonene is the major. Whether the anti-carcinogenesis activities of terpene, such as limonene, in citrus fruits essential oil extraction. This study to demonstrate the PAHs content in fish skin increased markedly after being roasted at 210℃ for 20 minutes and greater mutagenicity risk of roasted fish skin was observed by Ame's test. The reduction of mutagenicity risk of roasted fish skin, which the antimutagenic abilities of substances in descending order were limonene > cold pressure oil > lemon >grapefruit. The antimutagenicity rate and ability of the three extracts were limonene: 18–23%; cold-pressed lemon oil: 18–22%; and steam distilled lemon essential oil: 8–16%. The obvious anti- mutagenicity effects against the PAHs mutagenicity of roasted fish skins can be found in citrus fruits essential oil extraction.

In this study we investigated the potential of two non-edible oil extracts from seeds of Colliguaya Integerrima (CIO) and Colliguaja Salicifolia (CSO) to use as a renewable source for polyols and eventually polyurethane foams or biodiesel. For this purpose, two novel polyols from the aforementioned oils were obtained in a one-single step reaction using a mixture of hydrogen peroxide and acetic acid. The polyol derivatives obtained from the two studied oils were characterized by spectral (FT-IR, ¹H NMR and ¹³C NMR), physico-chemical (e.g. chromatographic analysis, acid value, oxidizability values, iodine value, peroxide value, saponification number, kinematic viscosity, theorical molecular weights, density, hydroxyl number and hydroxyl functionality) and thermal (TGA) analyses according to standard methods. Physico-chemical results revealed that all parameters, with the exception of the iodine value, were higher for bio-polyols (CSP and CIP polyols) compared to the starting oils. The NMR, TGA and FT-IR analyses demonstrated the formation of polyols. Finally, the OH functionality values for CIP and CSP polyols were 4.50 and 5.00, respectively. This result indicated the possible used of CIP and CSP polyols as a raw material for the preparation of polyurethane rigid foams.

Suzuki cross-coupling reaction has developed one of the furthermost effectual approaches for the synthesis of biaryls or substituted aromatic moieties from aryl halides and arylboronic acids with a palladium-catalyst in the past two era’s. Herein, Pd-free layered double hydroxide containing nickel catalysts were prepared by co-precipitation method under ultrasonic irradiation and N2 atmosphere with different molar ratios of Ni: Mg: Al and coded as (1NiLDHs-Dr), (1.5NiLDHs-Dr) and (2NiLDHs-Dr). A series of reduced catalysts under 5%H2/N2 at different temperatures were coded as 1NiLDHs-R200, 1.5NiLDHs-R200 and 2NiLDHs-R200. As-synthesized 2NiLDHs-Dr was the superlative catalyst when coupling different aryl halides with different boronic acids derivatives. Deep investigation of all catalysts was done using different techniques such as inductively coupled plasma optical emission spectroscopy (ICP-OES), x-ray photoelectron spectroscopy (XPS), powder x-ray diffraction (XRD), thermogravimetric analyses (TGA), Fourier transfer infrared (FTIR), scanning electron microscope (SEM) connected with energy dispersive x-ray (EDX) and N2-physisorption at -196 ℃. The results attained verified that ɑ-Ni(OH)2 was fashioned for 2NiLDHs-Dr catalyst and the enclosure of nickel ions in the cationic sheet of layered structure were responsible for the fascinating catalytic efficacy rather than the basic nature of material. The Ni-containing LDHs catalysts encourage forthcoming studies in Pd-free catalyzed C-C coupling reactions.

In this work, the solar light-induced redox photoactivity of the ZnO semiconductor material was used to prepare at room temperature CuxO-ZnO composite catalysts with a control of the chemical state of the copper oxide phase. The preparation of Cu2(I)O-ZnO and Cu(II)O-ZnO composite catalysts was achieved by using Cu(acac)2 in THF-water and Cu(NO3)2 in water as metallic precursor, respectively. Prior to the implementation of the photo-assisted synthesis method, the most efficient photoactive ZnO material was selected among different ZnO materials prepared by the low temperature polyol method and through the precipitation method with carbonates and carbamates as precipitation agent, by taking the photocatalytic degradation of the 4-chlorophenol compound in water under simulated solar light as model reaction. The ZnO support materials were characterized by XRD, BET, TGA, SEM and TEM, and the synthesis method was strongly influencing their photoactivity in terms of 4-chlorophenol degradation and of total organic carbon removal. The most photoactive ZnO material was prepared by precipitation with carbonates and calcined at 300°C, and was taking advantage of a high specific surface area and a small mean crystallite size for achieving a complete 4-chlorophenol mineralization within 70 min of reaction, with a minimum Zn2+ released to the solution due to surface photocorrosion. Beside thermal catalysis applications, this work opened a new route for the facile synthesis of Cu2O-ZnO heterojunction photocatalysts, that could take advantage under solar light of the heterojunction built between the p-type semi-conductor Cu2O with direct visible light band gap and the ZnO semiconductor phase.

Inorganic nanoparticles based on magnetite improve the mechanical, thermal, and magnetic properties of microporous cryogel polymer composites. Here we report the synthesis of microporous cryogel based on the crosslinked sodium vinyl sulfonate (Na-VS) and 2-acrylamido-2-methylpropane sulfonic acid sodium salt (Na-AMPS). The magnetite nanoparticles were inserted into Na-VS/Na-AMPS cryogel either during its crosslinking polymerization or by in-situ technique after its crosslinking.  The morphology, particle sizes, thermal stability and magnetite contents of Na-VS/Na-AMPS cryogel and its magnetite composites were investigated. The prepared Na-VS/Na-AMPS cryogel and its magnetite composites were used as adsorbents for methylene blue (MB) cationic dye using optimum conditions. The magnetite Na-VS/Na-AMPS cryogel composite prepared by in-situ technique achieved the best adsorption MB removal capacity for 7 cycles among the other adsorbents via chemical adsorption mechanism at room temperature.

Antioxidant activity is an essential feature required for oxygen-sensitive merchandise and goods, such as food and corresponding packaging as well as materials used in cosmetics and biomedicine. For example, vanillin, one of the most prominent antioxidants, is fabricated from lignin, the second most abundant natural polymer in the world. Antioxidant potential is primarily related to the termination of oxidation propagation reactions through hydrogen transfer. The application of technical lignin as a natural antioxidant has not yet been implemented in the industrial sector, mainly due to the complex heterogeneous structure and polydispersity of lignin. Thus, current research focuses on various isolation and purification strategies to improve the compatibility of lignin material with substrates and enhancing its stabilizing effect. This contribution presents antioxidant capacity studies of various lignins depending on purification degree of the raw material. In detail, the antioxidant potential of lignin-based compounds is studied using the DPPH (2,2-diphenyl-1-picrylhydrazyl) assay. The purification procedure was monitored by thin layer chromatography (TLC) and showed that double-fold selective extraction is the most efficient purification procedure (confirmed by UV-Vis, FTIR, HSQC and 31P NMR spectroscopy, SEC and XRD analysis). Results are discussed regarding the dependency of antioxidant activity on lignin structure and biomass source. Thus, lignins obtained from industrial black liquor are compared with beech wood samples. In addition, the influence of lignin isolation (kraft versus organosolv) is discussed. Values of the antioxidant activity (DPPH inhibition) of kraft lignin fractions were 62-68% while beech and spruce/pine-mixed lignins showed values between 26, 64 and 42%, respectively. TPC values of the different isolated kraft lignin fractions varied between 26-35%, while beech, spruce/pine lignins were 34, 30 and 34%, respectively. Storage decreased the TPC values and increased the DPPH inhibition.

Considerable attention has been given to the research field of bioorganometallic chemistry, which is a hybrid chemistry field between biology and organometallic chemistry. The introduction of biomolecules, which have hydrogen bonding sites and chiral centers, into organometallic compounds is considered to be a promising strategy to construct chirality-organized bioorganometallic conjugates. This feature paper sketches an outline of induction of helical chirality into bioorganometallic conjugates. Topics covered include control of the helical chirality of 1,n’-disubstituted ferrocene moieties in ferrocene-dipeptide conjugates and the chirality induction of the Au(I)–Au(I) axis in the dinuclear organogold(I)-uracil conjugates.

Groundwater contamination by nitrate and organic chemicals (e.g. 1,4-dioxane) is a growing worldwide concern. This work presents a new approach for simultaneously treating nitrate and 1,4-dioxane, which is based on UV sensitization of nitrate and sulfite, and the production of reactive species. Specifically, water contaminated with nitrate and 1,4-dioxane is irradiated by a UV source (< 250 nm) at relatively high doses, to sensitize in-situ nitrate and generate HO•. This leads to the oxidation of 1,4-dioxane (and other organics), and the (undesired) production of nitrite as an intermediate. Subsequently, sulfite is added at an optimized time-point, and its UV sensitization produces hydrated electrons which reacts and reduces nitrite. Our results confirmed the effectivity of the proposed treatment: UV irradiation of nitrate (at > 5 mg N/L) efficiently degraded 1,4-dioxane, while producing nitrite at levels higher than 1 mg N/L (its MCL in drinking water). Adding sulfite to the process after 10 minutes of irradiation reduced the concentration of nitrite, without affecting the degradation rate of 1,4-dioxane. The treated water contained elevated levels of sulfate; albeit at much lower concentration than its MCL. Treating water contaminated with nitrate and organic chemicals (often detected concomitantly) typically requires several (expensive) treatment processes. The proposed approach may present a cost-effective alternative, employing a single system for the treatment of nitrate and organic contaminants

Antibiotic residues in aquatic environment have the possibility to induce resistance in environmental bacteria, which ultimately might get transferred to pathogens making treatment of diseases difficultand poses a serious threat to public health. If antibiotic residues in the environment can be eliminated or reduced, it has the possibility to contribute antibiotic resistance. Towards this objective, water containing ciprofloxacin was treated with sunlight assisted photocatalysis using Fe doped ZnOnanoparticles for assessing the degradation potential of this system.Parameters like pH, temperature, catalytic dosage were assessed for the optimum performance of the system. To evaluate degradation of ciprofloxacin,both spectrophotometricas well as microbiological (loss of antibiotic activity)methods were employed. 100 mg/L Fe doped ZnO nanoparticle catalyst and sunlight intensity of 120,000–135,000 lux system gave optimum performance at pH 9 at 30 °C and 40 °C. At these conditions spectrophotometric analysis showed complete degradation of ciprofloxacin (10mg/L) by 210 min. Microbiological studies showed loss of antibacterial activity of the photocatalytically treated ciprofloxacin containingwater against Staphylococcus aureus (10⁸ CFU) in 60 min and for Escherichia coli (10⁸ CFU) in 75 min. Thedeveloped system, thus possess a potential for treatment of antibiotic contaminated waters for eliminating/reducing antibiotic residues from environment.

The continued application of organochlorine pesticides (OCPs) in indoor residual spraying has posed significant threat to human health in Northern part of South Africa, despite its ban. In this study, we investigated the occurrence and spatial distribution of DDTs and its metabolites in surface soil (30 samples) collected in and around the spray homesteads; demarcated into three concentric zones A, B, C in Tshilamusi Vhembe district, South Africa. DDTs were the most abundant of all the OCPs chemicals found in soil samples. The concentrations of DDT range from 12.19 to 65.69 µg/kg, with the highest occurring at zone A which is the zone of application. DDTs and all its metabolites considered in this study were found in appreciable concentrations in soil of Zones B and C, far from spray sites. The results showed a strong correlation between distance and concentration levels of DDTs and its metabolites. However, there is a need for proper monitoring of OCPs chemicals in other environmental matrices as well as relevant agencies enforcing strict adherence to regulations on consumption of OCPs.

Selective hydrogenation of nitrobenzene was carried out under solvent-free conditions using supported AuPd nanoparticles catalyst, prepared by modified impregnation method (MIm), as efficient catalyst. >99% yield of aniline (AN) was obtained after 15 hours at 90 °C, 3 bar H2 that can be used without any further purification or separation, therefore reducing cost and energy input. Supported AuPd nanoparticles catalyst, prepared by MIm, was found to be active and stable even after 4 recycle experiments whereas the same catalyst prepared by SIm deactivated during the recycle experiments. The most effective catalyst was tested for the chemoselective hydrogenation of 4-chloronitrobenzene (CNB) to 4-chloroaniline (CAN). The activation energy of CNB to CAN was found to be 25 kJ mol-1, while that of CNB to AN was found to be 31 kJ mol-1. Based on this, the yield of CAN was maximized (92%) by lowering the reaction temperature to 25 °C.

Herein, we report about the monometallic Ni and bimetallic Pd-Ni catalysts supported on CeO2-Al2O3 binary oxide, which were investigated in oxy-steam reforming of methanol (OSRM). Monometallic and bimetallic supported catalysts were prepared by wet aqueous impregnation and subsequent impregnation method, respectively. The physicochemical properties of the catalytic systems were investigated using various methods such as: BET, XRD, TPR-H2, TPD-NH3, XPS and SEM-EDS techniques. It has been proven that the addition of palladium to the nickel catalyst facilitates its reduction. The activity tests performed for all catalysts confirmed the promotion effect of palladium on catalytic activity of nickel catalyst and selectivity towards hydrogen production. Both nickel and bimetallic palladium-nickel supported catalysts showed excellent stability during the reaction. Such catalytic systems are valuable for the advance of the field of fuel cell technology.

A study has been carried out on Ta and Nb recovery by liquid-liquid extraction process using 4-methylacetophenone (4-MAcPh) as organic phase. The 4-MAcPh was compared to methylisobutylketone (MIBK) with respect to extraction efficiencies (kD values) at different concentrations of H2SO4 in the aqueous phase. The results showed a similar extraction of Nb for both solvents. However, for Ta extraction efficiency is increased by a factor of 1.3 for 4-MAcPh. In addition, the MIBK solubilized completely after 6 mol L-1 of H2SO4 against only a loss of 0.14 to 4% for 4-MAcPh between 6 and 9 mol L-1 of H2SO4. The potential of 4-MAcPh has also been studied to selectively recover Ta from a model capacitor waste solution. The results showed a selectivity for Ta in the presence of impurities such as Fe, Ni, Mn. The 4-MAcPh also presents the advantage of having physicochemical properties adapted to its use in liquid-liquid extraction technologies such as mixer-settlers.

Ferulic acid esters have been suggested as a group of natural chemicals with sunscreen function. The study aimed to utilize an environment-friendly enzymatic method to produce octyl ferulate by esterification of ferulic acid with octanol. The Box-Behnken design with response surface methodology (RSM) was adopted to evaluate the effects of synthesis variables, including reaction temperature (70–90 °C), enzyme amount (1000–2000 PLU) and stir speed (50–150 rpm), on the molar conversion of octyl ferulate. According to the joint test, both the reaction temperature and enzyme amount had great impacts on the molar conversion. RSM-developed second-order polynomial equation further showed great ability on data-fitting. Based on ridge max analysis, the optimum parameters for the biocatalyzed reaction were: 72 h reaction time, 92.2 °C reaction temperature, 1831 PLU enzyme amount and 92.4 rpm stir speed, respectively. Finally, the molar conversion of octyl ferulate under optimum condition was verified to be 93.2 ± 1.5%. In conclusion, high yield of octyl ferulate synthesized by commercial immobilized lipase under elevated temperature conditions has been suggested, which our findings could broaden the utilization of the lipase and provide a biocatalytic approach, instead of the chemical method, for ferulic acid ester synthesis.

A novel sunscreen containing Acacia catechu, remarkable local herb, was investigated for efficacy and standardized in this research.  The developed sunscreens were evaluated Sun Protection Factor (SPF), stability, skin allergy or irritation and the satisfaction. The highest SPF of A. catechu sunscreen with synthetic sunscreen agents was 30.344. While, the highest SPF of the A. catechu sunscreen without synthetic sunscreen agents was 24.381. The stability testing with the different conditions was found that the sunscreen products in the usual storage, had been stabilized even without preservative.  For irritation testing, there was no skin allergy and irritation from 20 volunteers.  Besides, results of the satisfaction evaluation for texture, consistency, sensory and odor after using the sunscreens, were high for all of the evaluation aspects.  Obviously, the results in this research revealed that A. catechu was applicable for being a great candidate in a sunscreen product.  Additionally, A. catechu sunscreen could prevent the adverse effects of UV radiation and artificial preservatives due to the UV absorption properties and antimicrobial properties of A. catechu.

To remove sulfur-containing compounds (SCC) from the diesel fraction 200-360 °C extraction systems have been created based on coordinating organic solvents - dimethylformamide and dimethylsulfoxide and chlorides (CoCl2, CuCl2, CdCl2, MnCl2 and CrCl3) and metal trifluoroacetates (Co (TFA)2, Cu(TFA)2 and Mn(TFA)2). Using PMR spectroscopy the coordination of chloride and metal trifluoroacetate on the oxygen atom in the carbonyl group of DMFA was shown to redistribute electron density in the solvent molecule and to enhance properties of the acceptor center localized on the nitrogen atom. The removal of sulfur-containing compounds from the diesel fraction proceeded under mild conditions - at the temperature of 25 °C and atmospheric pressure. The degree of SCC removal from the diesel fraction in 30 minutes extraction was more than 90%. The interaction of organic solvents with metal salts and sulfur-containing compounds of the diesel fraction was considered within the framework of the concept of "hard and soft acids and bases" (HSAB). The most complete SCC extraction was carried out by "DMFA - Mn(TFA)2, MnCl2 and CrCl3 systems, that was probably connected with the implementation of the" hard base - hard acid "system.

Activated carbons can be produced from biomass in a thermal process either in a direct carbonization-activation process or by first carbonizing the biomass and later on activating the biochars into activated carbons. The properties of the ACs are dependent on the type of process used for production. In this study, the properties of activated carbons produced in a one-stage and a two-stage process are considered. Activated carbons were produced by physical activation of two types of starting materials, bio chars produced from spruce and birch chips in a commercial carbonization plant and from the corresponding raw chips. The activated carbons produced were characterized regarding specific surfaces, pore volumes and pore size distributions. The un-activated bio chars had some degree of surface area 190 and 140 m²g^-1 for spruce and birch and pore volumes of 0.067 and 0.092 cm³g^-1. According to the results obtained, two slightly different types of activated carbons are produced depending if a one-stage or a two-stage carbonization and activation process is used. The ACs produced in the one-stage process had higher specific surface areas compared to the ones produced in a two-stage process (761-940 m²g^-1 vs. 540-650 m²g^-1) . In addition, total pore volumes were higher in one-stage process but development of micropores is greater compared to two-stage process. There was no significant difference in total carbon content between one-stage and two-stage process.

A custom-designed series of unsymmetrical spiroalkanedithiols having tailgroups comprised of a terminally fluorinated chain and a hydrocarbon chain of varying lengths were synthesized and used to prepare self-assembled monolayers (SAMs) on gold substrates. The specific structure of the adsorbates was of the form [CH₃(CH₂)_n][CF₃(CF₂)₇(CH₂)₈]C[CH₂SH]₂, where n = 7, 9, and 12 (designated as F8H10-C10, F8H10-C12, and F8H10-C18, respectively). The influence of the length of the hydrocarbon chain in the bidentate dithiol on the structure and interfacial properties of the monolayer was explored. A structurally analogous partially fluorinated monodentate alkanethiol and the corresponding normal alkanethiols were used to generate appropriate SAMs as reference systems. Ellipsometric thickness measurements showed an unexpectedly low film thickness for the SAMs derived from the bidentate adsorbates, possibly due to disruptions in interchain packing caused by the fluorocarbon chains (i.e., phase-incompatible fluorocarbon-hydrocarbon interactions), ultimately giving rise to loosely packed and disordered films. Analysis by X-ray photoelectron spectroscopy (XPS) were also consistent with a model in which the films were loosely packed; additionally, the XPS spectra confirmed the attachment of the sulfur headgroups of the bidentate adsorbates onto the gold substrates. Studies of the SAMs by polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) suggested that as the length of the hydrocarbon chain in the adsorbates was extended, a more ordered surface was achieved by reducing the tilt of the fluorocarbon segment. The wettability data indicated that the adsorbates with longer alkyl chains were less wettable than those with shorter alkyl chains, likely due to an increase in interchain van der Waals forces in the former.

Adhesion of polymers to surfaces is of upmost importance in timely applications such as protective coatings, biomaterials, sensors, new power sources and soft electronics. In this context, this work examines the role of molecular interactions in the adhesion of polypyrrole thin films to flexible Indium Tin Oxide (ITO) electrodes grafted with aryl layers from various diazonium salts, namely 4-carboxybenzenediazonium (ITO-CO₂H), 4-sulfonicbenzenediazonium (ITO-SO₃H), 4-N,N dimethylbenzenediazonium (ITO-N(CH₃)₂), 4-aminobenzenediazonium (ITO-NH₂), 4-cyanobenzenediazonium (ITO-CN) and 4-N-phenylbenzenediazonium (ITO-NHPh). It was demonstrated that PPy thin layers were adherent to these surfaces, whereas adhesion failure was noted on bare ITO, following simple solvent washing or sonication. Adhesion of the polypyrrole was investigated in terms of the hydrophilic/hydrophobic character of the underlying aryl layer as probed by contact angle measurements. It was found that sulfonic acid doped polypyrrole (PPy-BSA) thin films were preferably deposited on the most hydrophobic surfaces. More importantly, the redox properties and electrochemical impedance of PPy were closely related to the hydrophobic character of the aryl layers. This work demonstrates that diazonium compounds are unique molecular glues for conductive polymers, and permit to tune their interfacial properties. With diazonium-based robust, architectured interfaces, one can design high performance materials for e.g.sensors, printed soft electronics and flexible thermoelectrics.

A highly crystallized monoclinic-scheelite type BiVO4 powders were successfully synthesized by solvothermal method. The as-synthesized BiVO4 powders were characterized by XRD, FE-SEM, Raman spectroscopy, UV-vis DRS spectroscopy and TA-PL. From the XRD data and Raman spectra, the monoclinic-scheelite phase BiVO4 sample can be obtained at higher solvothermal synthesis temperature more than 140 oC. The preparation conditions such as, the Bi/V molar ratio and synthesis temperature, have significantly effects on the morphologies of the BiVO4 samples. BVO2 sample shows the highest PL peak, which has the highest formation rate of OH radicals and the highest photocatalytic activity. This result suggests that the formation rate of OH radicals shows a good correlation with the photocatalytic activity.

Catalytic upgrading of bio-based platform molecules is one of promising approaches for biomass valorization. However, most solid catalysts are thermally and/or chemically unstable and difficult to prepare. In this study, a stable organic phosphonate-hafnium solid catalyst (PPOA-Hf) was synthesized, and acid-base bifunctional sites were found to play a cooperative role in the cascade transfer hydrogenation and cyclization of ethyl levulinate (EL) to γ-valerolactone (GVL). Under relatively mild reaction conditions of 160 ºC for 6 h, EL was completely converted to GVL in a good yield of 85%. The apparent activation energy was calculated to be 53 kJ/mol, which was lower than other solid catalysts for the same reaction. In addition, the PPOA-Hf solid catalyst did not significantly decrease its activity after five recycles, and no evident leaching of Hf was observed, indicating its high stability and potential practical application.

This study was conducted to search for green technology that can extract metabolites from neem leaves for use in the development of botanical pesticide against Bactrocera dorsalis (Hendel) (Diptera:Tephritidae). Rice wine, rice wash, vinegar and distilled water were used as solvents and hot infusion, maceration, hot continuous reflux (Soxhlet), and fermentation were the methods employed. The different leaf extracts prepared by green technology were evaluated for their potentials as pesticide against B. dorsalis. Vinegar extract via Soxhlet extraction (V-S) for eight (8) h registered to have the highest mortality but not significantly different from vinegar - fermentation (V-F), rice wash - Soxhlet (RWa-S), vinegar - maceration (V-M), distilled water - fermentation (DW-F), and rice wash - fermentation (RWa-F) extracts. Phythochemicals present in the extracts are affected by the solvent-extraction interaction. Among the sixteen solvent-extraction interactions, the use of rice wash and fermentation is the most economical method in extracting the extracting the active components of neem leaves against B. dorsalis. Rice wash is a waste that can be utilized in the development of a biopesticide from neem leaves for pest management of B. dorsalis. This is the first report that rice wash is used as extracting solvent in green synthesis.

A series of (benzoimidazol-2-ylmethyl)amine palladium(II) complexes have been employed as catalysts in the homogenous hydrogenation of alkenes and alkynes under mild conditions. A correlation between the catalytic activity and the nature of the ligand was established. Kinetic studies of the hydrogenation reactions of styrene established pseudo-first-order dependence on styrene substrate. On the other hand, partial orders with respect to H2 and catalyst concentrations were obtained consistent with the formation of palladium(II) monohydride species as the active species. The nature of the solvent used influenced the hydrogenation reactions, where coordinating solvents resulted in lower catalytic activities. Density functional theory investigations provided valuable insights into the reactivity trends and influence of complex structure on the hydrogenation reactions.

Oilfield produced water (OPW) is used to boost freshwater sources for crop irrigation in California's agriculturally important Central Valley. OPW is known to contain salts, metals, hydrocarbons, alkylphenols, naturally radioactive materials, biocides, and other compounds from drilling and production processes. Less is known about the potential uptake and accumulation of these compounds in crops and soil irrigated with OPW. In this study 23 potted mandarin orange plants were irrigated 2-3 times weekly (depending on season) with water containing three different concentrations of the known OPW heavy metals barium, chromium, lead, and silver. Seven sets of samples of soil and leaves and all fruits were collected and processed using microwave-assisted digestion (EPA Method 3051A). Processed samples were analyzed using ICP-OES. ANOVA, ANCOVA, and Tukey’s honest significant difference test were used to examine the effects of metal concentrations in the irrigation water, sample number, and number of watering days on the metal concentrations in the soil, leaf, and fruit samples. Accumulation of barium in soil and leaves was strongly positively associated with sample and number of watering days, increasing nearly 2,000-fold. Lead also showed an upward trend, increasing up to 560-fold over baseline level. Chromium showed an increase in the soil that tapered off, but less consistent results in the leaves and fruit. The silver results were more volatile, but also indicated at least some level of accumulation in the tested media. The smallest absolute accumulation was observed for chromium. Concentrations in the fruit were highest in the peel, followed by pith and juice. Accumulation of all heavy metals was generally highest in the soil and plants that received the highest irrigation water concentration. Considering the potential for adverse human health effects associated with ingesting soluble barium contained in food and drinking water, and to a lesser extent chromium and lead, the study signals that it is important to conduct further research into whether OPW contaminants can enter the food chain and pose risks to consumers.

A series of MgAl-layered double hydroxide (MgAl-HT), the calcined form at 500^oC (MgAlO_x) and the re-hydrated one at 25^oC (MgAl-HT-RH) were synthesized. Physicochemical properties of the catalysts were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM). Surface area of the as-synthesized, calcined and re-hydrated catalysts was determined by N₂ physisorption at -196^oC. CO₂-teperature programmed desorption (CO₂-TPD) was applied to determine the basic sites of catalysts. The catalytic test reaction was carried out using benzaldehyde and their derivatives with nitromethane and their derivatives. The Henry products (1-15) were obtained in a very good yield using MgAl-HT-RH catalyst either by conventional method at 90^oC in liquid phase, or under microwave irradiation method. The mesoporous structure and basic nature of re-hydrated solid catalyst were responsible for their superior catalytic efficiency. The robust nature was determined by using the same catalyst for five times, where the product % yield was almost unchanged significantly.

Nickel molybdate, NiMoO₄, nanoparticles were synthesized via calcination of an oxalate complex in static air at 500 °C. The oxalate complex was analyzed by thermal gravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). The as-synthesized nickel molybdate was characterized by Brunauer–Emmett–Teller technique (BET), X-ray diffraction (XRD), and transmission electron microscopy (TEM) and its catalytic efficiency was tested in the reduction reaction of the three-nitrophenol isomers. The nickel molybdate displays a very high activity in the catalytic reduction of the nitro functional group to an amino. The reduction progress was controlled using UV-Vis absorption.

Nowadays, the study of preparing silica/rubber composites, which can be used in “green tire”, in energy saving method is fast-growing. In our work, silica modified by using alcohol polyoxyethylene ether (AEO) and 3-Mercaptopropyltriethoxysilane (K-MEPTS) together were investigated. Thermal gravimetric analyzer (TGA) result indicated that both AEO and K-MEPTS could be grafted on the silica surface. Raman spectroscopy confirmed that the AEO could generate a certain steric hindrance for the mercaptopropyl group on K-MEPTS. Silica modified by using AEO and K-MEPTS together can be completely co-coagulated with the rubber in preparing silica/natural rubber (NR) composites by latex compounding method. AEO can form a physical interface between silica and rubber; meanwhile, K-MEPTS can form a chemical interface between silica and rubber. The effects of chemical and physical interface between silica and rubber on dynamic and mechanical performances of silica/NR composites were also given in this research. A proper combination of physical and chemical interface between silica and NR can improve performances of silica/NR composites.

The activity and cyclability of Cu-MOF-74 as catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration and basic agent (type and concentration) were evaluated. High conversions were achieved at 120°C, 5 mol% of catalyst, NB/Ph ratio of 1:2, DMF as solvent and 1 equivalent of K2CO3 base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst.

A new approach for the preparation of polymer brush was developed via the union of controlled/“living” radical polymerization and click chemistry. The application of the approach realized the more quickly and accurate design and synthesis of the polymer brushes. A novel functional polymer brush of poly(acrylonitrile-g-glycidyl methacrylate) with tremendous application potential in the field of biology has been successfully synthesized via the new approach. The reaction conditions of click chemistry were optimized with the reaction time and the reactant ratio and judged from UV-vis spectra. Under the optimum of click chemistry, the novel functional polymer brushes were prepared. The GPC, FTIR analyses, 1H NMR spectrum and TGA were employed to ensure the successful synthesis of poly(acrylonitrile-g-glycidyl methacrylate) polymer brushes.

Enzymatic degradation of organic pollutants is a new and promising remediation approach. Peroxidases are one of the most commonly used classes of enzymes to degrade organic pollutants. However, it is generally assumed that all peroxidases behave similarly and produce similar degradation products. In this study, we conducted detailed studies of the degradation of a model aromatic pollutant, Sulforhodamine B dye (SRB dye), using two peroxidases—soybean peroxidase (SBP) and chloroperoxidase (CPO). Our results show that these two related enzymes had different optimum conditions (pH, temperature, H₂O₂ concentration...etc.) for efficiently degrading SRB dye. High-performance liquid chromatography and LC-mass spectrometry analyses confirmed that both SBP and CPO transformed the SRB dye into low molecular weight intermediates. While most of the intermediates produced by the two enzymes were the same, the CPO treatment produced at least one different intermediate. Furthermore, toxicological evaluation using lettuce (Lactuca sativa) seeds demonstrated that the SBP-based treatment was able to eliminate the phytotoxicity of SRB dye, but the CPO-based treatment did not. Our results show, for the first time, that while both of these related enzymes can be used to efficiently degrade organic pollutants, they have different optimum reaction conditions and may not be equally efficient in detoxification of organic pollutants.

A sustainable green one pot procedure for the synthesis of dihydropyrimidinones (DHPMs) derivatives by a three-component reaction of β-ketoester derivatives, aldehyde and urea or thiourea over the alkali-treated H-ZSM-5 zeolite under ball-milling has been developed. The product was isolated by simple washing of the crude reaction residue with ethyl acetate followed by evaporation of solvent. The hierachical zeolite catalyst (MFI27_6) showed high yield (86–96%) of dihydropyrimidinones (DHPMs), in very short time (10-30 min). The catalyst is recycled for subsequent reactions in four runs without appreciable loss of activity and high yields of products provide efficient protocol for Biginelli reactions.

Surface initiated atom transfer radical polymerization (SI-ATRP) is one of the most versatile technique to modify the surface properties of material. Recent developed metal free SI-ATRP makes such technique more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N- dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. SBA-15 based polymeric composite with adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous. This procedure provides a low cost, ready availability, and facile modification way to synthesize the polymeric composites without the contamination of metal.

Reactive NO_x is one of the major air pollutants, which also plays a key role as greenhouse gas. Many research efforts have been devoted to not only detection of NO_x in air but also abatement of NO_x emission. The aim of this mini review is to provide a panoramic snapshot of the electrochemical analysis methods for the emission and detection of NO_x in atmosphere, with special emphasis on NO_x sensor. The electrochemical detecting mechanism and materials for fabricating electrochemical gas sensors are discussed and the prospects and challenges in this area are also evaluated. This work will serve as a useful source to inform the interested audience of the latest developments and applications in the field of NO_x emission and electrochemical detection.

The structure of arylpiperazine moieties as an important pharmacophore could generate wide pharmacological activities．Arylpiperazine derivatives referred in this paper possessed antitumor activity. The title compounds were crystallized by slow evaporation. 2-(4-(2-(4-Phenylpiperazin-1-yl)ethyl)benzyl)isoindoline-1,3-dione(1), 2-(4-(2-(4-(4-Bromophenyl)piperazin-1-yl)ethyl)benzyl)isoindoline-1,3-dione (2) and 2-(4-(2-(4-(4-Chlorophenyl)piperazin-1-yl)ethyl)benzyl)isoindoline-1,3-dione (3) crystallizes in the triclinic space group P-1 with two molecules in the unit cell. The unit cell parameters for 1 are a = 6.9159(14) Å, b = 9.999(2) Å, c = 16.925(3) Å, α = 88.25(3)°, β = 85.14(3) °, γ = 79.22(3) °. The unit cell parameters for 2 are a = 6.9995(14) Å, b = 9.919(2) Å, c = 17.671(4) Å, α= 97.55(3)°, β = 92.19(3) °, γ = 102.23(3) °. The unit cell parameters for 1 are a = 6.9872(14) Å, b = 9.863(2) Å, c = 17.557(4) Å, α=96.81(3)°, β = 91.89(3) °, γ = 101.74(3) °. Pi-pi interactions were observed between molecules, and compound 2 and 3 showed halogen interactions between molecules nearby, which was different from compound 1.

The mesoporous heteroatom molecular sieve MCM-41 bulk crystals with the crystalline phase were synthesized via a one-step hydrothermal method using an ionic complex as template. The ionic complex template was formed by interaction between cetyltrimethylammonium ions and metal complex ion [M (EDTA)]2- (M=Co or Ni ). The materials were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, N2 adsorption–desorption isotherms, and X-ray absorption fine structure spectroscopy. The results showed that the materials possess a highly ordered mesoporous structure with the crystalline phase and possess high uniform ordered arrangement channels. The structure is in the vertical cross directions with a crystalline size of about 12 µm and high specific surface areas. The metal atoms were incorporated into the zeolite frameworks in the form of octahedral coordinate and have a uniform distribution in the materials. The amount of metal complexes formed by metal ion and EDTA is an essential factor for the formation of the vertical cross structure. Comparing to Si-MCM-41, the samples exhibited better conversion, higher selectivity for cumene cracking.

Diesel, gas oil, whole crudes, and bitumen samples were subjected to sulfoxidation, and then subjected to hydroxide attack in the presence of ethylene or propylene glycol. The resultant oils were analyzed by XRF for total sulfur and XANES spectroscopy for sulfur speciation at each stage. The combination of these analyses gave the total amount of sulfur as organic sulfide, sulfoxide, and sulfone at each stage of treatment so as to determine the effectiveness of the desulfonylation for sulfur compounds of different oxidation states.

Particulate matter (PM) is one of the problems faced in environmental science. It has health effects on man and animals in both developed and developing countries. Research and efforts have been on it several years back. Policy statements and efforts have been published. This review paper is an added information on air pollution. In it, efforts were made in discussing these: classification, effects, methodology, case studies and source apportionment. It is hoped that this paper would contribute to existing knowledge on PM.