Stefano Mantegna

A new pilot flow reactor for high-intensity ultrasound irradiation. Application to the synthesis of biodiesel.

In recent years, chemistry in flowing systems has become more prominent as a method of carrying out chemical transformations, ranging in scale from microchemistry up to kilogram-scale processes. Compared to classic batch ultrasound reactors, flow reactors stand out for their greater efficiency and flexibility as well as lower energy consumption. This paper presents a new ultrasonic flow reactor developed in our laboratory, a pilot system well suited for reaction scale up. This was applied to the transesterification of soybean oil with methanol for biodiesel production. This reaction is mass-transfer-limited initially because the two reactants are immiscible with each other, then because the glycerol phase separates together with most of the catalyst (Na or K methoxide). In our reactor a mixture of oil (1.6 L), methanol and sodium methoxide 30% in methanol (wt/wt ratio 80:19.5:0.5, respectively) was fully transesterified at about 45 degrees C in 1h (21.5 kHz, 600 W, flow rate 55 mL/min). The same result could be achieved together with a considerable reduction in energy consumption, by a two-step procedure: first a conventional heating under mechanical stirring (30 min at 45 degrees C), followed by ultrasound irradiation at the same temperature (35 min, 600 W, flow rate 55 mL/min). Our studies confirmed that high-throughput ultrasound applications definitively require flow reactors.

Regulation of HMGCoA Reductase Activity by Policosanol and Octacosadienol, a New Synthetic Analogue of Octacosanol

Octacosa-10,19-dien-1-ol is a newly synthesized long-chain alcohol, an unsaturated analogue of 1-octacosanol, the major component of policosanol, the purified natural mixture of different higher aliphatic alcohols obtained from sugarcane wax. Our efficient synthetic protocol (five steps with 50% overall yield) is well suited for gram scale preparations and a rapid generation of analogues with different degrees of unsaturation. Beneficial effects of policosanol in the prevention of atherosclerosis and thromboembolic disorders have been reported and related to the inhibition of sterol biosynthesis possibly by the regulation of the activity of HMGCoA reductase mediated by AMP-dependent kinase AMPK. We have compared the effect of octacosadienol and policosanol on the regulation of HMGCoA reductase in HUVEC and HepG2 human hepatoma cells. Octacosadienol was as effective as policosanol in inhibiting the upregulation of HMGCoA reductase, in inducing the phosphorylation of AMPK and in downregulating the HMGCoA reductase mRNA.

UAE, MAE, SFE-CO2 and classical methods for the extraction of Mitragyna speciosa leaves

Mitragyna speciosa, a tropical plant indigenous to Southeast Asia, is well known for its psychoactive properties. Its leaves are traditionally chewed by Thai and Malaysian farmers and manual labourers as it causes a numbing, stimulating effect. The present study aims to evaluate alkaloid yield and composition in the leaf extracts. For this purpose we have compared several non-conventional extraction techniques with classic procedures (room temperature or under heating). Dried M. speciosa leaves belonging to three batches of different origin (from Thailand, Malaysia and Indonesia) were extracted using ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE) and supercritical carbon dioxide extraction SFE-CO(2), using methanol, ethanol, water and binary mixtures. The extracts were compared using an HPLC/ESI-MS analysis of mitragynine and four other related alkaloids which were present in the alkaloid fraction. The extraction technique influences both the raw product yield and the relative alkaloid content of M. speciosa leaves. Of the several methods tested, MAE in a closed vessel at 110 °C (60 W, methanol/water 1:1) gave the highest alkaloid fraction amount, while UAE with an immersion horn at 25 °C (21.4 kHz, 50 W, methanol) showed the best yield for mitragynine. This work may prove to be a useful contribution to forensic, toxicological and pharmacognosy studies. Although the potential applications of M. speciosa alkaloids clearly need further investigation, these results may facilitate the scaling-up of their extraction.

The combination of oxalic acid with power ultrasound fully degrades chrysotile asbestos fibres.

The simultaneous action of power ultrasound and oxalic acid, as a chelating agent, rapidly converts chrysotile asbestos into water soluble material and a non-asbestos debris, not classifiable as hazardous under worldwide safety regulations.

Extraction of kiwi seed oil: Soxhlet versus four different non-conventional techniques

Kiwi seed oil has a nutritionally interesting fatty acid profile, but a rather low oxidative stability, which requires careful extraction procedures and adequate packaging and storage. For these reasons and with the aim to achieve process intensification with shorter extraction time, lower energy consumption and higher yields, four different non-conventional techniques were experimented. Kiwi seeds were extracted in hexane using classic Soxhlet as well as under power ultrasound (US), microwaves (MWs; closed vessel) and MW-integrated Soxhlet. Supercritical CO2 was also employed and compared to the other techniques in term of yield, extraction time, fatty acid profiles and organoleptic properties. All these non-conventional techniques are fast, effective and safe. A sensory evaluation test showed the presence of off-flavours in oil samples extracted by Soxhlet and US, an indicator of partial degradation.

Surface Reactivity and Cell Responses to Chrysotile Asbestos Nanofibers

High aspect-ratio nanomaterials (HARNs) have recently attracted great attention from nanotoxicologists because of their similarity to asbestos. However, the actual risk associated with the exposure to nanosized asbestos, which escapes most regulations worldwide, is still unknown. Nanometric fibers of chrysotile asbestos have been prepared from two natural sources to investigate whether nanosize may modulate asbestos toxicity and gain insight on the hazard posed by naturally occurring asbestos, which may be defined as HARNs because of their dimensions. Power ultrasound was used to obtain nanofibers from two different chrysotile specimens, one from the dismissed asbestos mine in Balangero (Italian Western Alps) and the other from a serpentine outcrop in the Italian Central Alps. Electron microscopy, X-ray diffraction, and fluorescence spectroscopy revealed that the procedure does not affect mineralogical and chemical composition. Surface reactions related to oxidative stress, free radical generation, bioavailability of iron, and antioxidant depletion, revealed a consistent reduction in reactivity upon reduction in size. When tested on A549 human epithelial cells, the pristine but not the nanosized fibers proved cytotoxic (LDH release), induced NO production, and caused lipid peroxidation. However, nanofibers still induced some toxicity relevant oxidative stress activity (ROS production) in a dose-dependent fashion. The reduction in length and a lack of poorly coordinated bioavailable iron in nanochrysotile may explain this behavior. The present study provides a one-step procedure for the preparation of a homogeneous batch of natural asbestos nanofibers and shows how a well-known toxic material might not necessarily become more toxic than its micrometric counterpart when reduced to the nanoscale.

Biodiesel production process intensification using a rotor-stator type generator of hydrodynamic cavitation

Triglyceride transesterification for biodiesel production is a model reaction which is used to compare the conversion efficiency, yield, reaction time, energy consumption, scalability and cost estimation of different reactor technology and energy source. This work describes an efficient, fast and cost-effective procedure for biodiesel preparation using a rotating generator of hydrodynamic cavitation (HC). The base-catalyzed transesterification (methanol/sodium hydroxide) has been carried out using refined and bleached palm oil and waste vegetable cooking oil. The novel HC unit is a continuous rotor-stator type reactor in which reagents are directly fed into the controlled cavitation chamber. The high-speed rotation of the reactor creates micron-sized droplets of the immiscible reacting mixture leading to outstanding mass and heat transfer and enhancing the kinetics of the transesterification reaction which completes much more quickly than traditional methods. All the biodiesel samples obtained respect the ASTM standard and present fatty acid methyl ester contents of >99% m/m in both feedstocks. The electrical energy consumption of the HC reactor is 0.030kWh per L of produced crude biodiesel, making this innovative technology really quite competitive. The reactor can be easily scaled-up, from producing a few hundred to thousands of liters of biodiesel per hour while avoiding the risk of orifices clogging with oil impurities, which may occur in conventional HC reactors. Furthermore it requires minimal installation space due to its compact design, which enhances overall security.

New Detoxification Processes for Asbestos Fibers in the Environment

Airborne asbestos fibers are associated with many serious detrimental effects on human health, while the hazard posed by waterborne fibers remains an object of debate. In adopting a precautionary principle, asbestos content in water needs to be kept as low as possible and polluting waters with asbestos should be avoided. Turci et al. (2008) recently reported a method for the decontamination of asbestos-polluted waters or landfill leachates from chrysotile that combines power ultrasound (US) with oxalic acid (Ox), an acidic chelating molecule. In the previous study, the occurrence of antigorite, a polymorph of serpentine, the mineral group encompassing chrysotile asbestos, acted as a confounding factor for complete removal of chrysotile from water. The effects of US + Ox on pure chrysotile asbestos from Val Malenco, Italian Central Alps, were examined in this investigation. In the absence of mineral contaminants, a more rapid removal of pure chrysotile from water was undertaken with respect to the previous specimen. After only 12 h of combined US + Ox acid treatment, imaging (SEM) of mineral debris indicated complete loss of fibrous habit. In addition, crystallography and vibrational features of chrysotile were not detectable (x-ray powder diffraction [XRPD] and micro-Raman spectroscopy) and elemental analysis showed a low Mg/Si ratio, i.e., the loss of the brucitic layer in chrysotile (x-ray fluorescence, XRF). Some nanometric rod-shaped debris, observed in the previous study and tentatively recognized as serpentine antigorite, was now found to be made of amorphous silica, which is relatively safe and noncarcinogenic to humans, providing further assurance regarding the safety of treated product. Thus, data indicated the proposed method was effective in detoxifying waterborne chrysotile asbestos fibers.

Effects of ultrasonic and hydrodynamic cavitation on the treatment of cork wastewater by flocculation and Fenton processes.

This paper reports that ultrasonic (US) and hydrodynamic cavitation (HC) are efficient strategies for the environmental remediation of cork wastewater (CW). It is necessary to remove toxic, inhibitory or refractory organic matter from CW using physical and chemical techniques (pre-treatment) prior to performing conventional biological treatment. After this biological treatment, it is also critical to further decontaminate (post-treatment) in order to meet the discharge limitation. The pre-treatment of diluted CW using Fenton oxidation (FE) alone led to COD and polyphenol (PP) removal values of 30% and 61%, respectively, while HC and US resulted in 83-90% increases in COD reduction and 26-33% increases in PP reduction. Whereas 55% and 91% COD and PP removal were achieved using flocculation (Floc) alone, COD elimination was increased by a further 7-18% under HC and US. No noticeable improvement in PP elimination was observed. US did not enhance the Floc decontamination of the original concentrated CW, however, considerable quantities of white biofilm were surprisingly generated on the CW surface after the pre-treatment, thus indicating the improvement of biodegradability of the resulting liquid. In fact, the post-treatment stage, using FE alone after having filtered the biofilms, led to reductions of 53% in COD and 90% in PP. The HC and US protocols resulted in 26-34% increases in COD elimination. HC further enhanced PP elimination caused by FE, while US resulted in lower levels of PP elimination.

Optimization of biodiesel synthesis under simultaneous ultrasound-microwave irradiation using response surface methodology (RSM)

Abstract This work investigates the effect of simultaneous ultrasound-microwave irradiation on palm oil transesterification and uncovers optimal operating conditions. Response surface methodology (RSM) has been used to analyze the influence of reaction conditions, including methanol/palm oil molar ratio, catalyst concentration, reaction temperature and irradiation time on biodiesel yield. RSM analyses indicate 136 s and 129 s as the optimal sonication and microwave irradiation times, respectively. Optimized parameters for full conversion (97.53%) are 1.09% catalyst concentration and a 7:3.1 methanol/oil molar ratio at 58.4°C. Simultaneous ultrasound-microwave irradiation dramatically accelerates the palm oil transesterification reaction. Pure biodiesel was obtained after only 2.2 min while the conventional method requires about 1 h.