Convenient synthesis of hydroxytyrosol and its lipophilic derivatives from tyrosol or homovanillyl alcohol

Hydroxytyrosol, a naturally occurred o-phenolic compound exhibiting antioxidant properties, was synthesized by a three-step high-yielding procedure from natural and low-cost compounds such as tyrosol or homovanillyl alcohol. First, the efficient chemoselective protection of the alcoholic group of these compounds was performed by using dimethyl carbonate (DMC) as reagent/solvent; second, the oxidation with 2-iodoxybenzoic acid (IBX) or Dess-Martin periodinane reagent (DMP) and in situ reduction with sodium dithionite (Na2S2O4) allowed the preparation of carboxymethylated hydroxytyrosol; finally, by a mild hydrolytic step, hydroxytyrosol was obtained in high yield and purity, as confirmed by NMR spectra and HPLC profile. By using a similar methodology, lipophilic hydroxytyrosol derivatives, utilized as additives in pharmaceutical, food, and cosmetic preparations, were prepared. In fact, at first the chemoselective protection of the alcoholic group of tyrosol and homovanillyl alcohol was performed by using acyl chlorides without any catalyst to obtain the corresponding lipophilic derivatives, and then these compounds were converted in good yield and high purity into the hydroxytyrosol derivatives by oxidative/reductive pathway with IBX or DMP and Na2S2O4.     

Production in large quantities of highly purified hydroxytyrosol from liquid-solid waste of two-phase olive oil processing or "Alperujo"

The effect of hydrothermal treatment of two-phase olive waste (alperujo) on the solubilization of hydroxytyrosol was studied. Different conditions of saturated steam were assayed. A high amount of hydroxytyrosol was solubilized and increased with increasing steaming temperature and time, reaching 1.4-1.7 g/100 g of dry alperujo. The effect of acidic (H(2)SO(4)) and basic (NaOH) catalysts was also evaluated. Acid-catalyzed treatment was more effective at milder conditions, whereas the alkali-catalyzed conditions were not very suitable. In the present study, the extracted hydroxytyrosol was purified by means of a new, simple, and inexpensive chromatographic system, under international patent application (PCT/ES02/00058). From 1000 kg of alperujo, with 70% humidity, can be obtained approximately 4.5-5 kg of hydroxytyrosol. After a purification process, at least 3 kg of hydroxytyrosol, at 90-95% purity, would be obtained. The purified compound was identified by HPLC/UV and (1)H and (13)C NMR analyses, and its antioxidant activity was tested on refined olive oil without antioxidants by Rancimat method. The oxidative stability of refined olive oil was increased by a factor of 1.71 in the presence of 100 ppm of hydroxytyrosol.     

Toward a high yield recovery of antioxidants and purified hydroxytyrosol from olive mill wastewaters

We investigated to develop effective procedures to recover the potentially high-added-value phenolic compounds contained in the discontinuous three-phase olive processing wastewaters (OMW). Particular emphasis was made to extract and purify hydroxytyrosol, one of the major compounds occurring in OMW. Batch optimization experiments showed that ethyl acetate is the most efficient solvent for the recovery of phenolic monomers from OMW. The latter was used with an optimal pH equal to 2. Furthermore, the percentage of each monomer, and particularly hydroxytyrosol, in the extract was maximum for a solvent ratio and a theoretical extraction stage number equal to 2 and 3, respectively. High yield (85.46%) recovery of hydroxytyrosol was achieved from OMW using a three-staged continuous counter-current liquid-liquid extraction unit. Hydroxytyrosol (1.225 g) were extracted per liter of OMW. One gram of hydroxytyrosol per liter of OMW was then purified by means of a chromatographic system which could be adapted to a large scale production process.     

Genotoxic potential of waste waters from a leather industry

The genotoxic potential of tannery waste water was evaluated by means of the induction of gene conversion and point mutation in Saccharomyces cerevisiae D7 strain. Neither a toxic nor a genotoxic response was obtained after a 2 hr incubation of raw water samples with the strain. A dose-related increase in the induced gene conversion and mitotic reversion was obtained when dilutions of the raw effluent were incubated for 24 hr. Samples of the waste water were also passed through an XAD2 resin column. The column was sequentially eluted with ethyl ether, chloroform and methanol. The ether and methanol fractions showed a positive genotoxic response.     

High-yielding preparation of a stable precursor of hydroxytyrosol by total synthesis and from the natural glycoside oleuropein

The unprecedented acetonide of the antioxidant hydroxytyrosol has been synthesized by a two-step high-yielding procedure and found to be both purifiable by chromatography and stable over a wide pH range. The protection stabilizes hydroxytyrosol against oxidation, thereby allowing long-term storage. The protection can quantitatively be removed, under nonaqueous conditions, to afford pure hydroxytyrosol suitable for use as an additive in food and cosmetic preparations. Extension of the same methodology to the natural and easily accessible glycoside oleuropein, followed by saponification of the resulting complex mixture of acetonides, allowed hydroxytyrosol acetonide to be recovered in high yield. This constitutes a new interesting methodology to obtain the antioxidant hydroxytyrosol.     

Chemical and cellular antioxidant activity of phytochemicals purified from olive mill waste waters

The isolation and identification of a phytocomplex from olive mill waste waters (OMWW) was achieved. The isolated phytocomplex is made up of the following three phenolic compounds: hydroxytyrosol (3,4-DHPEA), tyrosol (p-HPEA) and the dialdehydic form of decarboxymethyl elenolic acid, linked with (3,4-dihydroxyphenyl)ethanol (3,4-DHPEA-EDA). The purification of this phytocomplex was reached by partial dehydration of the OMWW, followed by liquid-liquid extraction with ethyl acetate and middle pressure liquid chromatography (MPLC) on a Sephadex LH-20 column. The phytocomplex accounted for 6% of the total phenolic content of the OMWW. The phytocomplex and individual compounds were tested for antioxidant capacity by the oxygen radical absorbance capacity (ORAC) method. The ORAC phytocomplex produced 10,000 ORAC units/g dry weight, whereas the cellular antioxidant activity, measured by the cellular antioxidant activity in red blood cell (CAA-RBC) method, demonstrated that the phytocomplex and all of the components are able to permeate the cell membrane thus exhibiting antioxidant activity inside the red blood cells. Our phytocomplex could be employed in the formulation of fortified foods and nutraceuticals, with the goal to obtain substantial health protective effects due to the suitable combination of the component molecules.     

Mild photochemical synthesis of the antioxidant hydroxytyrosol via conversion of tyrosol

Hydroxytyrosol, a naturally occurred orthodiphenolic antioxidant molecule found in olive oil and olive mill wastewaters, was obtained from the wet hydrogen peroxide photocatalytic oxidation of its monophenolic precursor tyrosol. The liquid-phase oxidation of tyrosol to hydroxytyrosol was performed by use of an iron-containing heterogeneous catalyst (Al-Fe)PILC with the assistance of UV irradiation at 254 nm and at room temperature. The spectroscopic and HPLC data of the synthesized compound proved to coincide fully with those of a pure sample obtained by continuous countercurrent extraction. This reaction was found to be light-induced. The hydroxytyrosol synthesis reaction reached its maximum yield of 64.36% under the optimized operating conditions of 3.6 mM tyrosol, 0.5 g L(-1) catalyst, and 10(-2) M H2O2 with the assistance of UV light. Increasing the initial hydrogen peroxide concentration more than 10(-2) M has a diminishing return on the reaction efficiency. Catalyst can be recuperated by means of filtration and then reused in a next run after regeneration since its activity did not significantly decrease (<10%). The reaction synthesis is operationally simple and could find application for industrial purposes.     

Economics of solid waste recovery

A brief review of the origins and quantities of combustible refuse generated in the United States is followed by estimates of quantities collectable into aggregates that permit reasonably economic conversion to energy or fuels. The principal processes for conversion are briefly described and their status (research, development, demonstration or commercial plants) noted. Capital and other requirements for a large scale introduction of energy converting refuse disposal operations are estimated. The impact of energy conversion methods of refuse disposal are noted.     

Surface entrapment of toxic metals from electroplating waste and their possible recovery

Heavy metal ions such as Cr, Ni, Cu, Cd and Zn have been removed from the electroplating waste using Fe(III) hydroxide as adsorbent. The maximum removal of these metal ions (>90%) occurred at pH 8 to 9. Removal of SO ₄ ^2? (98%) occurred at pH 4. Anions were found to play a negative role in the adsorption phenomenon. Metal ion Sorption has been found to decrease with increasing anionic concentrations. The methodology proposed might provide an inexpensive and economical procedure for removal and recovery of toxic metals from electroplating wastes.     

城肥开发与农业应用

论述了兰州市城肥的数量、利用现状及存在的问题，城肥利用长期得不到合理开发，污染环境和水源。提出了解决城肥利用的基本途径和发展前景。     

A practical and convenient synthesis of hotrienol,an excellent fruity smelling compound

The practical and convenient synthesis of hotrienol, which is an excellent fruity smelling compound, has been performed by the ene-type chlorination of linalyl acetate and then dehydrochlorinated by lithium bromide and lithium carbonate in DMF, followed by hydrolysis in three steps with an overall yield of 55%.     

Production of triacetylhydroxytyrosol from olive mill waste waters for use as stabilized bioantioxidant

A hydroxytyrosol triacetyl derivative was very efficiently produced as a highly pure stabilized antioxidant compound by a short treatment of olive mill waste water (OMWW) organic extracts, rich in hydroxytyrosol, with an acetylating mixture composed of HClO4-SiO2 and Ac2O (Chakborti and Gulhane reaction), in mild and safe conditions. A successive single step of middle pressure liquid chromatography (MPLC) purification of the reaction product was performed, with an overall yield of 35.6%. (This process, including both the Chakborti and Gulhane reaction and the MPLC purification, is protected by an international patent under PCT/IT2005/000781.) The o-diphenol triacetyl derivative was also produced by direct reaction of hydroxytyrosol, previously purified by MPLC, with HClO4-SiO2 and Ac2O, with an overall yield of 29.5%. A further procedure for the production of the hydroxytyrosol triacetyl derivative was consistent with the direct treatment of raw OMWW with the acetylating agent and a single step of MPLC purification, with an overall yield of 27.6%. The purified natural triacetylhydroxytyrosol confirmed the same strong protective effects against the oxidative stress in human cells as the corresponding synthetic compound, likely because of the biochemical activation of the acetyl derivative into the active parent hydroxytyrosol by esterases. We therefore propose the utilization of OMWW for recovering hydroxytyrosol as a natural antioxidant in a chemically stabilized form, with a good yield, which can be potentially used as a nontoxic functional component in nutritional, pharmaceutical, and cosmetic preparations.     

Lipid-lowering and antioxidant effects of hydroxytyrosol and its triacetylated derivative recovered from olive tree leaves in cholesterol-fed rats

This study was designed to test the lipid-lowering and antioxidative activities of triacetylated hydroxytyrosol compared with its native compound, hydroxytyrosol, purified from olive tree leaves. Wistar rats fed a standard laboratory diet or a cholesterol-rich diet for 16 weeks were used. The serum lipid levels, the thiobarbituric acid-reactive substances (TBARS) level, as an indicator of lipid peroxidation, and the activity of superoxide dismutase (SOD) as well as that of catalase (CAT) were examined. The cholesterol-rich diet induced hypercholesterolemia that was manifested in the elevation of total cholesterol (TC), triglycerides (TG), and low-density lipoprotein cholesterol (LDL-C). Administration of hydroxytyrosol and triacetylated hydroxytyrosol (3 mg/kg of body weight) decreased the serum levels of TC, TG, and LDL-C significantly and increased the serum level of high-density lipoprotein cholesterol (HDL-C). Furthermore, the content of TBARS in liver, heart, kidney, and aorta decreased significantly when hydroxytyrosol and its triacetylated derivatives were orally administered to rats compared with those fed a cholesterol-rich diet. In addition, triacetylated hydroxytyrosol and hydroxytyrosol increased CAT and SOD activities in the liver. These results suggested that the hypolipidemic effect of triacetylated hydroxytyrosol and hydroxytyrosol might be due to their abilities to lower serum TC, TG, and LDL-C levels as well as to their antioxidant activities preventing the lipid peroxidation process.     

农林废弃物对厨余垃圾堆肥腐殖化的影响与微生物驱动机制

高碳源农林辅料复配是实现厨余垃圾好氧堆肥促腐提质的关键技术,但不同辅料对厨余垃圾堆肥过程腐殖化的影响及其相应的微生物驱动机制仍不清楚,从而限制了对辅料的有效筛选与利用。为此,该研究选用园林废弃物、玉米秸秆和西瓜秧3种典型高碳源农林废弃物为辅料,探究其对厨余垃圾堆肥过程有机质腐殖化的调控效果与机制。研究结果表明：相较于园林废弃物和西瓜秧,添加15%玉米秸秆（湿质量）作为辅料,能够有效调节堆体物料结构,富集功能微生物,促进厨余垃圾堆肥产物腐熟度提升,种子发芽指数可达139%。具体而言,西瓜秧蛋白质含量较高,作为辅料能够在堆肥初期促进堆体快速升温,但不利于高温期延续,且产物腐殖化程度较低。相比之下,园林废弃物和玉米秸秆添加可以在高温期和降温腐熟期富集更多Ureibacillus、Bacillus Oceanobacillus和Flavobacterium等具有木聚糖降解和纤维素降解功能的细菌,促进有机质转化为多酚、氨基酸等腐殖质前驱物,进而推动稳定的腐殖酸生成。特别是玉米秸秆作为辅料时有效增加了具有木质纤维素降解功能的细菌,从而能够加速有机质的降解,促进腐殖化提升75%,研究结果为选取适宜的辅料强化厨余垃圾堆肥产品品质提供参考。     

Characterization and agricultural utilization of swine waste lagoon effluents

This investigation was conducted to determine the elemental composition of effluents from three anaerobic swine waste lagoons and one aerobic swine waste lagoon and to evaluate effects of effluent application on growth of corn (Zea mays L.) Wide variation occurred in the elemental composition of effluents among the four lagoons and among four sampling dates from each lagoon. Use of these effluents as irrigation water would lead to application of a wide range in amounts of nutrients to soil. Effluent application increased corn grain yield on a Woodstown loamy fine sand. This yield increase was attributed to alleviation of moisture stress and to correction of N deficiency.     

Distribution of hydroxytyrosol and hydroxytyrosol acetate in olive oil emulsions and their antioxidant efficiency

We employed a kinetic method to determine the distributions of the antioxidants hydroxytyrosol (HT) and hydroxytyrosol acetate (HTA) between the oil, aqueous, and interfacial regions of a model food emulsion composed of stripped olive oil, acidic water, and a blend of Tween 80 and Span 80 [hydrophilic–lipophilic balance (HLB) = 8.05] as an emulsifier. HT is oil-insoluble, but HTA is both oil- and water-soluble (partition constant P(O)(W) = 0.61). Results indicate that, at a given emulsifier volume fraction Φ(I), the fraction of HTA in the interfacial region is higher than that of HT. The percentage of both antioxidants increases with an increasing Φ(I), so that % HT > 40% at Φ(I) = 0.005 and % HT > 80% at Φ(I) = 0.04. HTA appears to be a better antioxidant than HT, as shown by an accelerated oxidative test (Schaal oven method). A correlation between their distribution in the emulsion and their efficiency was established.     

我国有机废弃物农业利用生态工程

论述了我国有机废弃物农业利用的现状与水平,分析了作物秸秆、畜禽粪便、沼气发酵残留物和有机垃圾农业利用的主要生态工程技术及效益,探讨了当前有机废弃物农业利用存在的主要问题及发展趋势。     

Antioxidant and other biological activities of olive mill waste waters.

During olive oil production, large volumes of water are generated and subsequently discarded. Olives contain a variety of bioactive components, and some of them, according to their partition coefficients, end up in the water phase. The current investigation aimed at comparing different methods for the extraction of biologically active components of the olive mill waste waters (OMWW) and evaluating the in vitro antioxidant and anti-inflammatory activities of the resulting extracts. The results indicate that OMWW extracts are able to inhibit human LDL oxidation (a process involved in the pathogenesis of atherosclerosis) and to scavenge superoxide anions and hypochlorous acid at concentrations as low as 20 ppm. Finally, two of the three extracts also inhibited the production of leukotrienes by human neutrophils. The potency of the extracts depended on their degree of refinement: extracts containing only low molecular weight phenols were the most effective.