Selective Oxidation of 1,2-Propanediol to Carboxylic Acids Catalyzed by Copper Nanoparticles.

Copper nanoparticles with different particle sizes were prepared by a wet chemical reduction method in the presence of organic modifiers, such as citric acid (CA), hexadecyl trimethyl ammonium bromide, Tween-80 (Tween), and polyethylene glycol 6000. Selective oxidation of sustainable 1,2-propanediol with O2 to high-valued lactic, formic, and acetic acids catalyzed by the copper nanoparticles in an alkaline medium was investigated. The small-sized CuCA nanoparticles with the average particle size of 15.2 nm favored the formation of acetic and formic acids while the CuTween nanoparticles with the average particle size of 26.9 nm were beneficial to the formation of lactic acid. The size effect of copper nanoparticles on the catalytic oxidation of 1,2-propanediol to the carboxylic acids was obvious.

Conversion of Glycerol to Lactic Acid Catalyzed by Different-Sized Cu2O Nanoparticles in NaOH Aqueous Solution.

Different-sized Cu2O nanoparticles with the average particle sizes ranging from 115 to 423 nm were prepared starting from CuSO4 using ascorbic acid as the reductant at room temperature. When Cu2O nanoparticles were used as the catalysts for hydrothermal conversion of glycerol at 230 °C in a NaOH aqueous solution, Cu2O nanoparticles effectively catalyzed the hydrothermal conversion of glycerol to lactic acid as compared to the conventional hydrothermal conversion of glycerol in a "pure" NaOH aqueous solution. Small-sized Cu2O nanoparticles showed higher catalytic activity than the large-sized ones. In a wide glycerol concentration range of 1­2.5 mol/L and a low mole ratio of Cu2O nanoparticle to glycerol of 2.5:100, the glycerol conversion and lactic acid selectivity were more than 86.2% and 87.2%, respectively, after reacting at 230 °C for 2 h.

Catalytic Conversion of Glycerol to Lactic Acid Over Metallic Copper Nanoparticles and Reaction Kinetics.

Different-sized metallic Cu° nanoparticles were prepared by the wet chemical reduction method with organic modifiers. The small-sized Cu° nanoparticles (Cu(PEG)) prepared by using polyethylene glycol as the organic modifier exhibited high catalytic activity for the hydrothermal conversion of glycerol to lactic acid. When the reaction was carried out with the initial glycerol and NaOH concentrations of 1.0 and 1.1 mol L⁻¹ at 230 °C for 4 h, the lactic acid selectivity reached 91.9% at the glycerol conversion of 98.0%. Over CuPEG (36.9 nm) and Cublank (118.3 nm) catalysts, the reaction activation energies were 76.3 and 86.5 kJ mol⁻¹, respectively.

Oxidation of 1,2-Propanediol to Carboxylic Acid Over Hydroxyapatite Nanorod-Supported Metallic Cu0 Nanoparticles.

Hydroxyapatite nanorod-supported metallic Cu0 nanoparticle catalysts (Cux/HAP) were prepared by the wetness chemical reduction method. The metallic Cu0 nanoparticles were well dispersed on the surfaces of the HAP nanorods. The alkaline HAP nanorods inhibited the crystal growth of the metallic Cu0 nanoparticles. The HAP nanorods also retarded the oxidation of the metallic Cu0 nanoparticles. The Cux/HAP catalyst exhibited a higher catalytic activity for the oxidation of 1,2-propanediol with gaseous oxygen to lactic, acetic, and formic acids with the total selectivity of 70.3% even at a lower reaction temperature of 140 °C. The total selectivity of lactic, acetic, and formic acids reached 93.1% at a mild reaction temperature of 180 °C. However, the sole monometallic Cu0 nanoparticles or HAP nanorods had no catalytic activity for the oxidation of 1,2-propanediol. The metallic Cu0 nanoparticles and alkaline HAP nanorods in the Cux/HAP catalyst synergistically catalyzed the oxidation of 1,2-propanediol to carboxylic acid.

Functional characterization of bimetallic CuPdx nanoparticles in hydrothermal conversion of glycerol to lactic acid.

The crude glycerol from biomass represents an abundant and inexpensive resource which can be utilized in producing food additives such as lactic acid. The direct transformation of bioderived glycerol to lactic acid under the catalysis of bimetallic CuPdx nanoparticles as well as monometallic Cu and Pd was investigated in hydrothermal conditions. The properties of fresh and spent bimetallic CuPdx nanoparticles were characterized with various physicochemical techniques viz. XRD, TEM, HRTEM, XPS, and AAS measurements. Catalytic activity of the prepared CuPdx nanoparticles is superior to the monometallic ones due to the alloying trend and synergistic effects. At optimal experimental conditions (100 ml of glycerol and NaOH solution, catalyst/glycerol mass ratio 2:100, 220°C, and 2.0 hr), the desired lactic acid selectivity catalyzed by the bimetallic CuPd2 , CuPd3 , and CuPd4 catalysts reached 95.3%, 91.4%, and 90.9%, respectively. PRACTICAL APPLICATIONS: Lactic acid, a widely used food additive, was traditionally produced by fermentation. However, due to the limitation such as time-consuming and complex separation procedure, interest has been attracted in developing an alternative approach toward efficient production of lactic acid. An attempt was made in present study to use the biodiesel byproduct, glycerol, and chemical conversion to high-valued lactic acid. Compared with traditional biological fermentation route, it was evidenced that glycerol selective transformation to lactic acid involves a new chemical reaction path for commodity lactic acid with a large availability and economic efficiency. This finding is significant for sustainable development of biodiesel industry and elimination of environmental issues arising from the abandoned crude glycerol.

Optimization of betacyanins from agricultural by-products using pressurized hot water extraction for antioxidant and in vitro oleic acid-induced steatohepatitis inhibitory activity.

Pressurized hot water extraction (PHWE) is proposed to recover betacyanins from agricultural by-products (pitaya fruits peels (PFP), red beet stalks (RBS), and cactus pear peels (CPP)). The extraction yield of betacyanins was optimized by response surface methodology. The optimal PHWE conditions were attained and the actual yields of betacyanins under optimal conditions were well matched with the predicted yields. In addition, betacyanin pigment compositions as well as superoxide anion scavenging activity of individual betacyanins extract (BE) produced in optimal PHWE conditions were characterized by HPLC-ESI/MSn and cyclic voltammetry. Furthermore, the inhibitory activity of three BEs on oleic acid-induced steatohepatitis in cellular model was comparatively investigated. The results showed that unlike PFP, RBS, and CPP presented excellent efficacy in decreasing intracellular triglyceride and reactive oxygen species, inhibiting the release of alanine aminotransferase and aspartate aminotransferase as well as regulating fatty acid synthase and carnitine palmitoyltransferase 1 mRNAs expression. Practical applications In this study, PHWE, is firstly proposed for the enhancement of the extraction of betacyanins from three agricultural by-products. Betacyanin-rich extracts by PHWE method exhibit excellent activities in inhibition of ROS and regulation of lipid metabolism in hepatic cells. It suggests that PHWE has a strong potentiality in keeping bioactivity of BEs, which is significant for the production of betacyanins functional foods.

Voltammetric, spectroscopic, and cellular characterization of redox functionality of eckol and phlorofucofuroeckol-A: A comparative study.

Interest in phlorotannins has increased in recent years largely due to antioxidant capacity, however, the redox mechanism of phlorotannins is still obscure. In the present study, the electrochemical oxidation mechanisms of eckol (EL) and phlorofucofuroeckol-A (PFF-A), two representative phlorotannin compounds, were comparatively analyzed in a wide pH range using cyclic and differential pulse voltammetry as well as spectroscopic assay. The voltammetric study revealed that EL and PFF-A were successively oxidized in three pH-dependent steps. Moreover, it was found that the PFF-A presented a stronger proton and electron transferring activity as compared to EL since PFF-A exhibited lower acid-base dissociation constant (pKa ) value and higher heterogeneous rate constant (kbh ) value in the first oxidation step. These property were further evidenced by comparison of direct antioxidant activity (i.e., superoxide anion and peroxide radicals) as well as indirect antioxidant activity (i.e., mRNA expression of two phase II enzymes) between EL and PFF-A. PRACTICAL APPLICATIONS: Phlorotannins from edible algae have been regarded as novel antioxidants those presented high application potential in food industry. Even though antioxidant activity of phlorotannin compounds have been widely investigated in both in vitro and in vivo studies, very few reports focused on electron transferring functionality which is chemical basis for antioxidant process. Herein, the oxidative mechanisms of two representative phlorotannins were comparatively analyzed using multiple electrochemical methods. This is hopefully to give information on the chemical meaning behind the antioxidant activity of dietary phlorotannins.

Comparative analysis of oxidative mechanisms of phloroglucinol and dieckol by electrochemical, spectroscopic, cellular and computational methods.

Numerous studies have been carried out on the redox activities of phenolic compounds from terrestrial plants, however, the redox pathway of phlorotannins, a type of marine algae-derived polyphenol, is far from clear. In the present study, the redox mechanisms of two phlorotannins, phloroglucinol (PL) and dieckol (DL), were comparatively scrutinized. Differential pulse voltammetry was conducted in the pH range 2.0-12.0 to determine the acid-base dissociation constant (pK a) and the number of electrons and protons involved in the redox reactions of two phlorotannins. Cyclic voltammetry was applied to obtain the heterogeneous electron transfer rate constant (k 0). By means of computational calculation, UV-vis spectroscopy, and electrochemical analysis, it is proposed that PL oxidation in the whole pH range undergoes two steps which are dominated by proton-coupled electron transfer (PCET) (pH ≤ 9) and sequential proton-loss electron transfer (SPLET) mechanisms (pH > 9), respectively. In contrast, the multiple steps taking place in the DL oxidation process rely on PCET (pH ≤ 5), mixed SPLET/PCET (5 < pH ≤ 10), and electron transfer (pH > 10) mechanisms, respectively. Also, the lower proton affinity and ionization potential values of DL, which are attributed to its conjugated Cπ-O-Cπ moieties, lead to relatively higher redox activity as compared to PL in various chemical and cellular models. These findings may provide useful insights into the oxidative conversion of phlorotannins in their biological and chemical processes.

Selective Chlorination of Toluene to p-Chlorotoluene Catalyzed by Nanosized Zeolite K-L Catalysts.

Nanosized zeolite K-L catalysts were synthesized by the hydrothermal method starting from silica sol and potassium aluminate. The crystallinities of the zeolite K-L catalysts increased with increasing the SiO2/Al2O3 mole ratio of reaction solution and prolonging the autoclaving time. Nanosized and well-dispersed zeolite K-L catalysts were synthesized when the SiO2/Al2O3 mole ratio was more than 26:1. Well-crystallized and nanosized zeolite K-L catalysts showed high catalytic activity for the chlorination of toluene to p-chlorotoluene. When the nanosized zeolite K-L catalyst was synthesized with the SiO2/Al2O3 mole ratio of 31:1 at the autoclaving temperature of 150 °C for 96 h, the selectivities of p-chlorotoluene and o-chlorotoluene were 76.2% and 20.0%, respectively, at the complete conversion of toluene.