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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Green Chemistry".

Deadline for manuscript submissions: closed (30 November 2010) | Viewed by 97162

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Special Issue Editors

Prof. Dr. Tomoko Matsuda

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Guest Editor

Tokyo Institute of Technology, Graduate School of Bioscience and Biotechnology, Department of Bioengineering, 4259 Nagatsuta, Midori-ku, Yokohama, 226-850, Japan
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Matthew Z. Yates

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Guest Editor

Department of Chemical Engineering, University of Rochester, Rochester, NY, USA
Interests: nanomaterials hydroxyapatite composite advanced materials; fine particles; crystallization ;thin films; membranes; coatings; colloidal assembly; microencapsulation; supercritical fluids

Special Issue Information

Dear Colleagues,

Supercritical carbon dioxide has been recognized as a green solvent with high functionality as it possesses both gas-like low viscosities, high diffusivities, and liquid-like solubilizing power together with a tunability of these properties. The advantages of nonflammability, low toxicity and high availability have also promoted the development in applications using supercritical carbon dioxide. Importantly, these successes are owing to achievements of basic researches. Therefore, this special issue will present novel, unique and innovative application research as well as basic research with high quality concerning supercritical carbon dioxide to create new fields in its application. I also hope that this issue will contribute to build a sustainable society.

Tomoko Matsuda
Guest Editor

Keywords

supercritical carbon dioxide
green chemistry
green solvent, reaction
catalyst, biocatalyst
extraction
chromatography

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Published Papers (7 papers)

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Research

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11 pages, 239 KiB

Open AccessArticle

Mutual Solubility Study in Supercritical Fluid Extraction of Tocopherols from Crude Palm Oil Using CO₂ Solvent

by Reza Davarnejad, Zainal Ahmad, Suhairi A. Sata, Mostafa Keshavarz Moraveji and Farzaneh Ahmadloo

Int. J. Mol. Sci. 2010, 11(10), 3649-3659; https://doi.org/10.3390/ijms11103649 - 28 Sep 2010

Cited by 8 | Viewed by 9435

Abstract

In this article, the mutual solubility of tocopherols from crude palm oil was studied using carbon dioxide as a solvent at the temperatures of 80, 100 and 120 ºC. Each sample from the phase equilibrium unit contained two parts. The liquid part was analyzed by gas chromatography (GC) in order to measure the tocopherol composition and, on the other hand, the vapor phase was conducted in an expansion vessel in order to measure the pressure increment during the expansion process. Two phase equilibrium data was calculated using the liquid phase composition and pressure increments during the expansion process. Results showed that the maximum solubility of tocopherols was around 2.27% at a temperature of 120 ºC and at pressure of 5.44 MPa. Full article

(This article belongs to the Special Issue Supercritical Carbon Dioxide)

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9 pages, 168 KiB

Open AccessArticle

β-Sitosterol: Supercritical Carbon Dioxide Extraction from Sea Buckthorn (Hippophae rhamnoides L.) Seeds

by Marie Sajfrtová, Ivana Ličková, Martina Wimmerová, Helena Sovová and Zdeněk Wimmer

Int. J. Mol. Sci. 2010, 11(4), 1842-1850; https://doi.org/10.3390/ijms11041842 - 22 Apr 2010

Cited by 73 | Viewed by 12855

Abstract

Supercritical fluid extraction represents an efficient and environmentally friendly technique for isolation of phytosterols from different plant sources. Sea buckthorn (Hippophae rhamnoides L.) seeds were extracted with supercritical carbon dioxide at pressures ranging from 15–60 MPa and temperatures of 40-80 °C. Oil and β-sitosterol yields were measured in the extraction course and compared with Soxhlet extraction with hexane. The average yield of β-sitosterol was 0.31 mg/g of seeds. The maximum concentration of β-sitosterol in the extract, 0.5% w/w, was achieved at 15 MPa, 40 °C, and a carbon dioxide consumption of 50 g/g of seeds. The extraction rate was maximal at 60 MPa and 40 °C. Both β-sitosterol yield and its concentration in the extract obtained with hexane were lower than with carbon dioxide. Full article

(This article belongs to the Special Issue Supercritical Carbon Dioxide)

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9 pages, 947 KiB

Open AccessCommunication

Development of a Novel Catalytic Membrane Reactor for Heterogeneous Catalysis in Supercritical CO₂

by Nazrul M. Islam, Maya Chatterjee, Yutaka Ikushima, Toshiro Yokoyama and Hajime Kawanami

Int. J. Mol. Sci. 2010, 11(1), 164-172; https://doi.org/10.3390/ijms11010164 - 13 Jan 2010

Cited by 12 | Viewed by 12385

Abstract

A novel type of high-pressure membrane reactor has been developed for hydrogenation in supercritical carbon dioxide (scCO₂). The main objectives of the design of the reactor are the separate feeding of hydrogen and substrate in scCO₂ for safe reactions in a continuous flow process, and to reduce the reaction time. By using this new reactor, hydrogenation of cinnamaldehyde into hydrocinnamaldehyde has been successfully carried out with 100% selectivity at 50 °C in 10 MPa (H₂: 1 MPa, CO₂: 9 MPa) with a flow rate of substrate ranging from 0.05 to 1.0 mL/min. Full article

(This article belongs to the Special Issue Supercritical Carbon Dioxide)

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17 pages, 258 KiB

Open AccessArticle

A Study of the Crystallization, Melting, and Foaming Behaviors of Polylactic Acid in Compressed CO₂

by Wentao Zhai, Yoorim Ko, Wenli Zhu, Anson Wong and Chul B. Park

Int. J. Mol. Sci. 2009, 10(12), 5381-5397; https://doi.org/10.3390/ijms10125381 - 16 Dec 2009

Cited by 205 | Viewed by 15605

Abstract

The crystallization and melting behaviors of linear polylactic acid (PLA) treated by compressed CO₂ was investigated. The isothermal crystallization test indicated that while PLA exhibited very low crystallization kinetics under atmospheric pressure, CO₂ exposure significantly increased PLA’s crystallization rate; a high crystallinity of 16.5% was achieved after CO₂ treatment for only 1 min at 100 °C and 6.89 MPa. One melting peak could be found in the DSC curve, and this exhibited a slight dependency on treatment times, temperatures, and pressures. PLA samples tended to foam during the gas release process, and a foaming window as a function of time and temperature was established. Based on the foaming window, crystallinity, and cell morphology, it was found that foaming clearly reduced the needed time for PLA’s crystallization equilibrium. Full article

(This article belongs to the Special Issue Supercritical Carbon Dioxide)

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11 pages, 290 KiB

Open AccessArticle

Microwave Effect for Glycosylation Promoted by Solid Super Acid in Supercritical Carbon Dioxide

by Hiroshi Hinou, Naohiro Saito, Masato Ogawa, Takahiko Maeda and Shin-Ichiro Nishimura

Int. J. Mol. Sci. 2009, 10(12), 5285-5295; https://doi.org/10.3390/ijms10125285 - 8 Dec 2009

Cited by 13 | Viewed by 14123

Abstract

The effects of microwave irradiation (2.45 GHz, 200 W) on glycosylation promoted by a solid super acid in supercritical carbon dioxide was investigated with particular attention paid to the structure of the acceptor substrate. Because of the symmetrical structure and high diffusive property of supercritical carbon dioxide, microwave irradiation did not alter the temperature of the reaction solution, but enhanced reaction yield when aliphatic acceptors are employed. Interestingly, the use of a phenolic acceptor under the same reaction conditions did not show these promoting effects due to microwave irradiation. In the case of aliphatic diol acceptors, the yield seemed to be dependent on the symmetrical properties of the acceptors. The results suggest that microwave irradiation do not affect the reactivity of the donor nor promoter independently. We conclude that the effect of acceptor structure on glycosylation yield is due to electric delocalization of hydroxyl group and dielectrically symmetric structure of whole molecule. Full article

(This article belongs to the Special Issue Supercritical Carbon Dioxide)

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7 pages, 182 KiB

Open AccessArticle

Enzymatic Reactions in Near Critical CO₂: The Effect of Pressure on Phenol Removal by Tyrosinase

by Priscilla Amaral, Daniela Garcia, Miguel Cardoso, Marisa Mendes, Maria Alice Coelho and Fernando Pessoa

Int. J. Mol. Sci. 2009, 10(12), 5217-5223; https://doi.org/10.3390/ijms10125217 - 1 Dec 2009

Cited by 11 | Viewed by 13340

Abstract

The use of enzymes in supercritical CO₂ (SCCO₂) has received extensive attention in recent years. Biocatalysts have the advantage of substrate specificity and SCCO₂ offers several advantages over liquid solvents. This work deals with the utilization of SCCO₂ as a medium for the enzymatic removal of phenol from aqueous solutions using tyrosinase. Since the presence of oxygen is crucial for the enzyme-catalyzed oxidation, the substantial solvating power of SCCO₂ makes it a promising medium for such reactions. The conversion of phenol was higher at 10 MPa. Under near critical conditions (7 MPa, 35 ºC), the addition of air at 5 × 10⁵ Pa of pressure improved phenol removal. Full article

(This article belongs to the Special Issue Supercritical Carbon Dioxide)

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Review

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21 pages, 198 KiB

Open AccessReview

A Review on the Effects of Supercritical Carbon Dioxide on Enzyme Activity

by Zdenĕk Wimmer and Marie Zarevúcka

Int. J. Mol. Sci. 2010, 11(1), 233-253; https://doi.org/10.3390/ijms11010233 - 19 Jan 2010

Cited by 143 | Viewed by 18467

Abstract

Different types of enzymes such as lipases, several phosphatases, dehydrogenases, oxidases, amylases and others are well suited for the reactions in SC-CO₂. The stability and the activity of enzymes exposed to carbon dioxide under high pressure depend on enzyme species, water content in the solution and on the pressure and temperature of the reaction system. The three-dimensional structure of enzymes may be significantly altered under extreme conditions, causing their denaturation and consequent loss of activity. If the conditions are less adverse, the protein structure may be largely retained. Minor structural changes may induce an alternative active protein state with altered enzyme activity, specificity and stability. Full article

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