Study of Green Solvents for Ruthenium Alkylidene Mediated Ring-Opening Metathesis Polymerization

Hyun Gyu Shin,Hyun Sub Lee,Eun Ji Hong,김정곤 대한화학회 2021 Bulletin of the Korean Chemical Society Vol.42 No.3

Ruthenium alkylidene mediated ring-opening metathesis polymerizations (Ru-ROMP) are evaluated in green chemical solvents to increase their green metrics. The Ru-ROMP of representative monomers of norbornene, oxa-norbornene, and cyclooctadiene were compared in reference solvents (tetrahydrofuran and chloroform) and green solvents (2-methyl tetrahydrofuran, ethyl acetate, dimethyl carbonate, and acetone). The results showed that the use of a green solvent is promising. All green solvents exhibited excellent Ru-ROMP efficiency while their chain length controls were sensitive to solvents and monomers. Among the candidates, dimethyl carbonate expressed the general applicability of various combinations of monomers and solvents.

2P-122 The strategy for Green Solvent Processing and Application to Hole Transport Materials for Perovskite Solar Cells

최현태,이준우,류승운,박상아,최경원,박태호 한국공업화학회 2017 한국공업화학회 연구논문 초록집 Vol.2017 No.1

The concept of asymmetry in the monomer leads to irregularity despite being a homopolymer. Green processing was approached with asymmetric alkoxy substitution, resulted in high efficient HTMs. Using applicable green solvents from Hansen parameter fitting, we characterize asymmetric polymer and fabricate hole transport layers. 2-methyl anisole is the green solvent that is used in food additives, which is edible and no harmful in human body. High absolute solubility in green solvent was exhibited by asymmetric structure named asy-PBTBDT, which induces the irregularity. The perovskite HTM using asy-PBTBDT demonstrates high PCE with chlorobenzene and 2-methyl anisole which is eco-friendly solvent. As it has not only environmental friendly processibility but also sufficient photochemical and device stability, it is expected to be an industrial material.

Green-Solvent-Processable High-Mobility Semiconducting Copolymers with Engineered Oligo(Ethylene Glycol) Side Chains

강보석,김민제,( Ziang Wu ),우한영,조정호 한국공업화학회 2019 한국공업화학회 연구논문 초록집 Vol.2019 No.1

Replacement of toxic chlorinated solvents with eco- and humanfriendly green solvents is an important task for the successful implemention of next-generation polymer electronics technology. Herein, we synthesized five aqueous-solvent-processable conjugated copolymers by incorporating linear or branched oligo(ethylene glycol) side chains and systematically investigated their material and electronic properties. The resulting benzothiadiazole-based copolymers were well-soluble in both an ethanol/water mixed solvent, and their thin films showed distinct morphologies and crystalline characteristics that resulted from the self-assembling properties of the engineered side chains. Moreover, the copolymers showed excellent electrical characteristics with high hole mobilities of up to 0.1 ㎠ V^-1 s^-1. These results clearly demon strate the immense potential of branched oligo(ethylene glycol) side chains for application in green electronics. Keywords: oligoethylene glycol, side-chain engineering

A Comparative Study on the Stability and Structure of Two Different Green Fluorescent Proteins in Organic Co-solvent Systems

Govindan Raghunathan,Sriram Sokalingam,Nagasundarapandian Soundrarajan,Ganapathiraman Munussami,Bharat Madan,이선구 한국생물공학회 2013 Biotechnology and Bioprocess Engineering Vol.18 No.2

Green fluorescent protein (GFP) has been used as a reporter marker in a wide range of biological and bioengineering studies. The expanded use of GFP in the field of biosensors, biochips and bio-conjugations requires the stability of GFP in organic co-solvent systems. This prompted us to examine the kinetic stability of two different GFP sequences, n-GFP and s-GFP, showing different folding robustness and thermodynamic stability, under a range of organic co-solvent systems. n-GFP and s-GFP are variants whose biophysical properties are comparable to wild type and super folder GFPs, respectively. The stability of n-GFP and s-GFP in 50% water-miscible organic solvents showed that s-GFP with higher thermodynamic stability exhibited much higher stability against organic solvents than n-GFP, which has lower thermodynamic stability. s-GFP was quite stable even in 90% organic solvents. Circular dichroism analysis confirmed that s-GFP maintained its native structure in organic co-solvent systems, whereas n-GFP showed structural variations under these conditions. Four highly fluctuating loop regions were identified from molecular dynamic simulations under the organic cosolvent conditions. A structural comparison of n-GFP and s-GFP suggested that the improved kinetic stability of s-GFP was due to its larger number of hydrogen bonds and salt-bridges that were present in four loop regions. This study suggests that thermodynamically stable s-GFP can be a good choice for use under harsh organic co-solvent conditions.

Soybean oil extraction using ethyl acetate and 1-butanol: From solvent selection to thermodynamic assessment

Henrique Gasparetto,Ana Luiza Barrachini Nunes,Fernanda de Castilhos,Nina Paula Gonçalves Salau 한국공업화학회 2022 Journal of Industrial and Engineering Chemistry Vol.113 No.-

Soybean oil extraction using two green solvents was investigated from solvent selection to thermodynamics:ethyl acetate and 1-butanol. The screening of the solvents was performed using the Hansenparameters and Infinite Dilution Activity Coefficient (IDAC) obtained through the COnductor-likeScreening MOdels – Segment Activity Coefficient (COSMO-SAC) theory. The solvent selection was performedon ethyl acetate and 1-butanol in comparison with ethanol, a well-studied green solvent, andhexane, a non-renewable and industrially used solvent. The effects of temperature and solvent/solid ratioon the yield of soybean oil extraction were investigated through response surface methodology (RSM). The RSM obtained satisfactory statistical results, with R2adj of 0.9958 for ethyl acetate and 0.9729 for 1-butanol. The kinetic of the extractions were evaluated using two different models: mass transfer kineticand So and Macdonald. The last one obtained the best correlation to the data (R2 > 0.9964). The thermodynamicassessment showed endothermic, and spontaneous processes for both solvents. 1-Butanol, ethylacetate, and hexane have a better performance on the yield of soybean oil extraction than using ethanol;however, ethyl acetate is the best candidate to replace the industrial use of hexane due to its highest rateof soybean oil extraction at the process beginning.

An effective combination of reusable Pd@MOF catalyst and deep eutectic solvents for high-performance C–C coupling reaction

Minh-Huy Dinh Dang,Trang Thi Thu Nguyen,Bao Quang Gia Le,Linh Ho Thuy Nguyen,Ngoc Xuan Dat Mai,My Van Nguyen,Phuong Hoang Tran,Tan Le Hoang Doan 한국공업화학회 2022 Journal of Industrial and Engineering Chemistry Vol.111 No.-

Pd-incorporated Zr-based metal–organic framework containing sulfone groups, named Pd(II)BUT-11, wassuccessfully prepared by dispersing the sulfone-functionalized MOF in Pd(OAc)2 solution. X-ray diffraction,scanning electron microscopy, N2 isotherm sorption, X-ray photoelectron spectroscopy, and thermogravimetricanalysis were applied to determine the features of the Pd-incorporated MOF. In the catalyticstudies, Pd(II)@BUT-11 was shown to be an efficient heterogeneous catalyst for synthesizing various stilbenederivatives via the cross-coupling Heck reaction with DABCO-derived deep eutectic solvent (DES) asa green solvent. Notably, the catalyst and the solvent could be recovered and reused, with their activityand structure remaining stable throughout several trials. The method provides an alternative solution tothe conventional catalysts and solvents, resulting in a green and efficient stilbene synthesis process. Furthermore, the stilbenes were separated by extraction with ethyl acetate due to the low solubility ofDES with this solvent.

Environmentally friendly and non-polluting solvent pretreatment of palm samples for polyphenol analysis using choline chloride deep eutectic solvents

Fu, N.,Lv, R.,Guo, Z.,Guo, Y.,You, X.,Tang, B.,Han, D.,Yan, H.,Row, K.H. Elsevier 2017 Journal of chromatography Vol.1492 No.-

<P>In this work, choline chloride (ChCI) deep eutectic solvents (DESs) were evaluated for the pretreatment of palm samples in the analysis of polyphenols, such as protocatechuic acid, catechins, epicatechin, and caffeic acid. During the enrichment step of the pretreatment, eight DESs comprising ChCI with ethylene glycol (EG), glycerol (Gly), xylitol (Xyl), phenol (Ph), formic acid (FA), citric acid (CiA), oxalic acid (OA), or malonic acid (MA), were prepared and applied to the reflux extraction of polyphenols from palm samples. All the DESs exhibited higher polyphenol extraction efficiency than methanol, and the highest extraction efficiency was obtained using ChCI-FA (1:1, mole ratio). For the purification step of the pretreatment, eight ChCI DES-modified adsorbents were prepared by hydrothermal polymerization and packed into solid phase extraction (SPE) cartridges, and ChCI-Urea, ChCI-Gly, ChCI-FA, and water, were used as eluents. The ChCI DES-modified adsorbents were characterized by Fourier transform infrared spectroscopy, thermal gravimetric analysis, scanning electron microscopy, and Brunauer-Emmett-Teller surface analysis, and the polyphenols were analyzed by mass spectrometry and high-performance liquid chromatographultraviolet detection. The highest purification efficiency was obtained using the ChCI-Ph DES-modified adsorbent as the SPE packing material and ChCI-Urea-H2O (1:1:5, mole ratio), ChCI-Gly (1:1, mole ratio), ChCI-FA-H2O (1:1:5, mole ratio), and H2O as the eluents. Compared to conventional purification processes that employ commercial C-18 or C-8 SPE columns with organic solvents as eluents, the ChCI DES-based SPE purification process successfully avoided the use of expensive commercial SPE columns and organic solvents. Furthermore, it isolated a larger amount of the target compounds under the same experimental conditions, and could be applied over five cycles with good reversibility. This work indicates that DESs as green solvents have great potential for the totally green pretreatment of samples during the enrichment and purification processes. (C) 2017 Elsevier B.V. All rights reserved.</P>

Green solvent-processed complementary-like inverters based on ambipolar organic thin-film transistors

Minjeong Lee,윤승재,Dongil Ho,Taeshik Earmme,Assunta Marrocchi,Luigi Vaccaro,김충익 한국공업화학회 2022 Journal of Industrial and Engineering Chemistry Vol.105 No.-

In the trends of ever-growing worldwide interest for the environment/health and the corresponding legalregulations, there have been various studies to replace toxic halogenated/aromatic hydrocarbon organicsolvents commonly used in the solution-processing of organic semiconductors (OSCs) with more sustainablegreen solvents. In this paper, we fabricated ambipolar organic thin-film transistors (OTFTs) andcomplementary-like inverters by blending a p-type OSC (6,13-bis(triisopropylsilylethynyl)pentacene;TIPS-pentacene) and a n-type OSC (N,N’-di-n-octyl-3,4,9,10-perylenetetracarboxylic diimide; PTCDI-C8)in a single green solvent anisole. In particular, shellac was employed as green dielectric materials andthe electrical performance of the resulting devices were compared with those fabricated using toxic solventsor commonly used oxide-based dielectrics. The bulk-heterojunction (BHJ)-structured OTFTs in theoptimized condition exhibited typical ambipolar characteristics with relatively balanced charge carriermobilities as high as 0.042 and 0.14 cm2 V 1s 1 for hole and electron, respectively. Additionally,complementary-like inverters based on the two optimized ambipolar OTFTs showed a decent transfergain as high as 21 at negative supply voltages of 60 V. Thus, by demonstrating the applicability of greensolvents not only for OTFTs but also in the implementation of circuit devices, we expect that the resultsobtained will spark more interest for the more sustainable fabrication of OSC-based electronic devicesand their commercialization/mass-production in the relevant industrial real cases.

9-Phenyl-5,5'-Diphenyl-3,3'-Bis-(3-sulfopropy)-Benzoxazolo Carbocyanine Triethyl Ammonium Salt의 용매에 대한 안정성

김영찬,Kim, Yeoung-Chan 한국정보기술전략혁신학회 2004 情報學硏究 Vol.7 No.2

The symmetric 9-phenyl-5,5'-diphenyl-3,3'-bis-(3-sulfopropyl)-benzoxazolo carbocyanine triethyl ammonium salt is of industrial importance as green-sensitizing dye in the spectral sensitization of emulsion microcrystals in negative film and positive paper-making. The stability on the solvents of benzoxazolo carbocyanine dye was measured by UV-Vis spectrophotometer, and then dye was stabilized in various solvents. The maximum absorption peak range in various solvents was 507nm~515nm. It was identified that the solvents can be used to photographic emulsion.

Understanding the non-solvent induced phase separation (NIPS) effect during the fabrication of microporous PVDF membranes via thermally induced phase separation (TIPS)

Jung, J.T.,Kim, J.F.,Wang, H.H.,di Nicolo, E.,Drioli, E.,Lee, Y.M. Elsevier Scientific Pub. Co 2016 Journal of membrane science Vol.514 No.-

The thermally induced phase separation (TIPS) method is regaining momentum as a competitive platform to fabricate highly porous microporous membranes. In membrane technology, there has been an active search for more sustainable ways to fabricate polymeric membranes using green solvents. Rhodiasolv PolarClean® is a recently identified environmentally friendly TIPS solvent that shows high potential for the preparation of microporous PVDF membranes. Interestingly, its high miscibility with water induces a nonsolvent-induced phase separation (NIPS) effect on the membrane surface and this simultaneous NIPS-TIPS effect is referred to as the combined NIPS-TIPS (N-TIPS) method. In this work, a thorough investigation was carried out to understand the underlying phenomena in the membrane formation kinetics during the N-TIPS process. It was found that the NIPS and TIPS morphology can be tailored to control the mechanical properties, pore size distribution, and flux of the prepared membranes. For instance, increasing the coagulation bath solvent concentration facilitated the formation of a spherulitic morphology, whereas increasing the bath temperature induced the formation of a bicontinuous morphology free of macrovoids. It was determined that by controlling the phase separation kinetics, the mechanical properties of the prepared PVDF membranes could be remarkably improved from 0.9MPa to 6.1MPa. Several pore-forming additives including polyvinylpyrrolidone, Pluronics F-127, LiCl, and glycerol were employed to induce surface pores and their effects were thoroughly characterized. The membranes prepared with Pluronic additives exhibited high water permeabilities up to 2800Lm<SUP>-2</SUP>h<SUP>-1</SUP>bar<SUP>-1</SUP> with narrow pore size distributions.