Special Issue "Greener and Sustainable Chemistry"

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A special issue of Applied Sciences (ISSN 2076-3417). This special issue belongs to the section "Applied Chemistry".

Deadline for manuscript submissions: closed (15 May 2013)

Special Issue Editor

Guest Editor
Dr. Rajender S. Varma

Sustainable Technology Division, National Risk Management Research Laboratory, US Environmental Protection Agency, 26 West Martin Luther King Drive, MS 443, Cincinnati, OH 45268, USA
Website | E-Mail
Phone: 513-487-2701
Interests: Nano-catalysts; magnetic nano-catalysts; greener synthesis; sustainable chemistry; continuous flow chemistry

Special Issue Information

Dear Colleagues,

Chemistry in the new millennium is embracing the concept of “green chemistry” and “sustainability” to meet the scientific challenges of protecting the human health and environment while maintaining commercial success of newer processes. This emerging area of Green Chemistry is defined as “the utilization of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture, and application of chemical products” and envisages minimum hazard as the performance criteria while designing new chemical protocols. Among others, the desired approach may encompass alternative activation methodology, such as mechanochemical mixing, and microwave-, and ultrasonic irradiation. Essentially, the strategy has to follow “benign by design” principles and make an effort to utilize renewable resources wherever possible. The contributions in this issue try to address some of these issues for sustainability.

Dr. Rajender S. Varma
Guest Editor

Submission

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. Papers will be published continuously (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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Keywords

  • benign by design
  • solvent-free chemistry
  • chemistry in water
  • mechanochemical mixing
  • microwave irradiation
  • ultrasonic irradiation
  • nano-catalysis

Published Papers (8 papers)

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Editorial

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Open AccessEditorial Greener and Sustainable Chemistry
Appl. Sci. 2014, 4(4), 493-497; doi:10.3390/app4040493
Received: 25 August 2014 / Accepted: 18 September 2014 / Published: 29 September 2014
Cited by 2 | PDF Full-text (416 KB) | HTML Full-text | XML Full-text
Abstract
In the pursuit towards attaining sustainability, arrays of greener pathways are being carved to address the needs of the diverse chemical universe. The evolving area of green and sustainable chemistry envisions minimum hazard as the performance criterion while designing new chemical processes. Green
[...] Read more.
In the pursuit towards attaining sustainability, arrays of greener pathways are being carved to address the needs of the diverse chemical universe. The evolving area of green and sustainable chemistry envisions minimum hazard as the performance criterion while designing new chemical processes. Green Chemistry is defined as "the utilization of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture, and application of chemical products" [1]. Sustainable processes are being sought to explore alternatives to conventional chemical syntheses and transformations. Among several thrust areas for achieving this target includes: the utility of alternative feedstocks, preferably from renewable materials or waste from other industries; unconventional efficient reaction conditions and eco-friendly reaction media to accomplish the desired chemical transformations with minimized by-products or waste generation, and ideally avoiding the use of conventional volatile organic solvents, wherever possible. Other avenues for achieving this objective are to explore the generation of efficient catalytic processes, particularly magnetically retrievable nano-catalysts [1,2,3,4]. In addition to greener synthesis, the recyclability and reuse aspects for catalytic systems are extremely significant particularly when it boils down to the use of endangered elements and precious catalysts. Several friendlier applications in catalysis have been advanced via magnetically recoverable and recyclable nano-catalysts for oxidation, reduction, and multi-component condensation reactions [1,2,3,4] and this has made a terrific impact on the development of green chemical pathways [1]. The greener preparation of nanoparticles has been exemplified via the use of vitamins B1, B2, C, and tea [5] and wine polyphenols [6], beet juice [7] and other agricultural residues which function both as reducing and capping agents. This avoids the need to deploy toxic reducing agents, such as borohydrides or hydrazines and empowers simple and aqueous green synthetic methods to produce bulk quantities of nano-catalysts without the requirement for large amounts of insoluble templates [8].  [...] Full article
(This article belongs to the Special Issue Greener and Sustainable Chemistry)

Research

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Open AccessArticle A Solvent-Free, One-Step, One-Pot Gewald Reaction for Alkyl-aryl Ketones via Mechanochemistry
Appl. Sci. 2014, 4(2), 171-179; doi:10.3390/app4020171
Received: 16 November 2013 / Revised: 25 February 2014 / Accepted: 18 March 2014 / Published: 8 April 2014
Cited by 6 | PDF Full-text (245 KB) | HTML Full-text | XML Full-text
Abstract
Herein, we report on the solvent-free synthesis of 2-aminothiophenes via the Gewald reaction. Utilizing high speed ball milling conditions, we discovered the Gewald reaction can be catalytic in base, and conducted under aerobic conditions. Using thermal heat in tandem with the mixer/mill significantly
[...] Read more.
Herein, we report on the solvent-free synthesis of 2-aminothiophenes via the Gewald reaction. Utilizing high speed ball milling conditions, we discovered the Gewald reaction can be catalytic in base, and conducted under aerobic conditions. Using thermal heat in tandem with the mixer/mill significantly increases the rate of reaction. Full article
(This article belongs to the Special Issue Greener and Sustainable Chemistry)
Open AccessCommunication Properties of Thermosets Derived from Chemically Modified Triglycerides and Bio-Based Comonomers
Appl. Sci. 2013, 3(4), 684-693; doi:10.3390/app3040684
Received: 30 September 2013 / Revised: 11 November 2013 / Accepted: 20 November 2013 / Published: 4 December 2013
Cited by 6 | PDF Full-text (325 KB) | HTML Full-text | XML Full-text
Abstract
A series of materials was prepared by curing acrylated epoxidized soybean oil (AESO) and dibutyl itaconate (DBI) or ethyl cinnamate (EC) comonomers to provide examples of thermosets with a high proportion of bio-based carbon, in accordance with the principles of green chemistry. The
[...] Read more.
A series of materials was prepared by curing acrylated epoxidized soybean oil (AESO) and dibutyl itaconate (DBI) or ethyl cinnamate (EC) comonomers to provide examples of thermosets with a high proportion of bio-based carbon, in accordance with the principles of green chemistry. The comonomers, representative of cellulose-derived (DBI) or potentially lignin-derived (EC) raw materials, were tested at levels of 25%, 33%, and 50% by mass and the resulting products were characterized by infrared spectroscopy, thermogravimetric analysis, and dynamic mechanical analysis. Both DBI and EC were incorporated into the thermosets to a high extent (>90%) at all concentrations tested. The AESO-DBI and AESO-EC blends showed substantial degradation at 390–400 °C, similar to pure AESO. Glass transition temperatures decreased as comonomer content increased; the highest Tg of 41.4 °C was observed for AESO-EC (3:1) and the lowest Tg of 1.4 °C was observed for AESO-DBI (1:1). Accordingly, at 30 °C the storage modulus values were highest for AESO-EC (3:1, 37.0 MPa) and lowest for AESO-DBI (1:1, 1.5 MPa). Full article
(This article belongs to the Special Issue Greener and Sustainable Chemistry)
Open AccessCommunication Aqueous Microwave-Assisted Solid-Phase Synthesis Using Boc-Amino Acid Nanoparticles
Appl. Sci. 2013, 3(3), 614-623; doi:10.3390/app3030614
Received: 13 May 2013 / Revised: 26 June 2013 / Accepted: 5 July 2013 / Published: 24 July 2013
Cited by 3 | PDF Full-text (1258 KB) | HTML Full-text | XML Full-text
Abstract
We have previously developed water-based microwave (MW)-assisted peptide synthesis using Fmoc-amino acid nanopaticles. It is an organic solvent-free, environmentally friendly method for peptide synthesis. Here we describe water-based MW-assisted solid-phase synthesis using Boc-amino acid nanoparticles. The microwave irradiation allowed rapid solid-phase reaction of
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We have previously developed water-based microwave (MW)-assisted peptide synthesis using Fmoc-amino acid nanopaticles. It is an organic solvent-free, environmentally friendly method for peptide synthesis. Here we describe water-based MW-assisted solid-phase synthesis using Boc-amino acid nanoparticles. The microwave irradiation allowed rapid solid-phase reaction of nanoparticle reactants on the resin in water. We also demonstrated the syntheses of Leu-enkephalin, Tyr-Gly-Gly-Phe-Leu-OH, and difficult sequence model peptide, Val-Ala-Val-Ala-Gly-OH, using our water-based MW-assisted protocol with Boc-amino acid nanoparticles. Full article
(This article belongs to the Special Issue Greener and Sustainable Chemistry)
Open AccessArticle Photopolymerization Reactions: On the Way to a Green and Sustainable Chemistry
Appl. Sci. 2013, 3(2), 490-514; doi:10.3390/app3020490
Received: 15 March 2013 / Revised: 28 March 2013 / Accepted: 1 April 2013 / Published: 24 April 2013
Cited by 15 | PDF Full-text (705 KB) | HTML Full-text | XML Full-text
Abstract
The present paper reviews some aspects concerned with the development of green technologies in the photopolymerization area: use of visible light sources (Xe and Hg-Xe lamps, diode lasers), soft irradiation conditions (household lamps: halogen lamp, fluorescence bulbs, LED bulbs), sunlight exposure, development of
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The present paper reviews some aspects concerned with the development of green technologies in the photopolymerization area: use of visible light sources (Xe and Hg-Xe lamps, diode lasers), soft irradiation conditions (household lamps: halogen lamp, fluorescence bulbs, LED bulbs), sunlight exposure, development of very efficient photoinitiating systems and use of renewable monomers. The drawbacks/breakthroughs encountered when going on the way of a greener approach are discussed. Examples of recent achievements are presented. Full article
(This article belongs to the Special Issue Greener and Sustainable Chemistry)
Open AccessArticle Ultrasonics Promoted Synthesis of 5-(Pyrazol-4-yl)-4,5-Dihydropyrazoles Derivatives
Appl. Sci. 2013, 3(2), 457-468; doi:10.3390/app3020457
Received: 31 January 2013 / Revised: 26 February 2013 / Accepted: 27 March 2013 / Published: 16 April 2013
Cited by 3 | PDF Full-text (215 KB) | HTML Full-text | XML Full-text
Abstract
A series of new 1,3-diaryl-5-(1-phenyl-3-methyl-5-chloropyrazol-4-yl)-4,5-dihydropyrazole derivatives have been synthesized under sonication conditions in ethanol or methanol/glacial acetic acid mixture (5/1 ratio) with two equivalents of hydrazines and seven kinds of chalcone-like heteroanalogues obtained from 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde. The structures were established on the
[...] Read more.
A series of new 1,3-diaryl-5-(1-phenyl-3-methyl-5-chloropyrazol-4-yl)-4,5-dihydropyrazole derivatives have been synthesized under sonication conditions in ethanol or methanol/glacial acetic acid mixture (5/1 ratio) with two equivalents of hydrazines and seven kinds of chalcone-like heteroanalogues obtained from 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde. The structures were established on the basis of NMR, IR, MS and element analysis. This method provides several advantages over current reaction methodologies, including a simple work-up procedure, shorter reaction times (2–20 min) and good yields (65%–80%). Full article
(This article belongs to the Special Issue Greener and Sustainable Chemistry)

Review

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Open AccessReview Sustainable Utility of Magnetically Recyclable Nano-Catalysts in Water: Applications in Organic Synthesis
Appl. Sci. 2013, 3(4), 656-674; doi:10.3390/app3040656
Received: 20 June 2013 / Revised: 2 October 2013 / Accepted: 17 October 2013 / Published: 25 October 2013
Cited by 31 | PDF Full-text (956 KB) | HTML Full-text | XML Full-text
Abstract
Magnetically recyclable nano-catalysts and their use in aqueous media is a perfect combination for the development of greener sustainable methodologies in organic synthesis. It is well established that magnetically separable nano-catalysts avoid waste of catalysts or reagents and it is possible to recover
[...] Read more.
Magnetically recyclable nano-catalysts and their use in aqueous media is a perfect combination for the development of greener sustainable methodologies in organic synthesis. It is well established that magnetically separable nano-catalysts avoid waste of catalysts or reagents and it is possible to recover >95% of catalysts, which is again recyclable for subsequent use. Water is the ideal medium to perform the chemical reactions with magnetically recyclable nano-catalysts, as this combination adds tremendous value to the overall benign reaction process development. In this review, we highlight recent developments inthe use of water and magnetically recyclable nano-catalysts (W-MRNs) for a variety of organic reactions namely hydrogenation, condensation, oxidation, and Suzuki–Miyaura cross-coupling reactions, among others. Full article
(This article belongs to the Special Issue Greener and Sustainable Chemistry)
Figures

Open AccessReview Glycerol: A promising Green Solvent and Reducing Agent for Metal-Catalyzed Transfer Hydrogenation Reactions and Nanoparticles Formation
Appl. Sci. 2013, 3(1), 55-69; doi:10.3390/app3010055
Received: 19 December 2012 / Revised: 15 January 2013 / Accepted: 21 January 2013 / Published: 23 January 2013
Cited by 30 | PDF Full-text (220 KB) | HTML Full-text | XML Full-text
Abstract
Glycerol is a non-toxic, non-hazardous, non-volatile, biodegradable, and recyclable liquid that is generated as a byproduct in the manufacture of biodiesel fuel from vegetable oils. Due to its easy availability, along with its unique combination of physical and chemical properties, glycerol has recently
[...] Read more.
Glycerol is a non-toxic, non-hazardous, non-volatile, biodegradable, and recyclable liquid that is generated as a byproduct in the manufacture of biodiesel fuel from vegetable oils. Due to its easy availability, along with its unique combination of physical and chemical properties, glycerol has recently emerged as an economically appealing and safe solvent for organic synthesis. Recent works have also demonstrated that glycerol can be used as a hydrogen source in metal-catalyzed transfer hydrogenation of organic compounds, such as aldehydes, ketones, olefins and nitroarenes. Herein, the advances reached in this emerging field are reviewed. The utility of glycerol as solvent and reducing agent for the generation of metal nanoparticles is also briefly discussed. Full article
(This article belongs to the Special Issue Greener and Sustainable Chemistry)

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