Laccases hold great potential for biotechnological applications, particularly in environmental pollutant remediation. Laccase activity is governed by the solvent environment, and ionic liquids (ILs) emerge as a versatile solvent for activation or stabilization of enzymes. Herein, effects of cholinium-based ILs formulated with carboxylic acids, inorganic acid, and amino acids as anionic species, on the catalytic activity of laccase from Trametes versicolor were investigated by experimental and computational approaches. Experimental results showed that laccase activity was enhanced by 21.39 % in 0.5 M cholinium dihydrogen citrate ([Cho][DHC]), in relation to the laccase activity in phosphate buffer medium. However, cholinium aminoate ILs negatively affected laccase activity, as evidenced by the partial deactivation of laccase in both cholinium glycinate and cholinium phenylalaninate, at concentrations of 0.1 M and 0.5 M, respectively. Molecular dynamics studies revealed that the enhancement of laccase activity in [Cho][DHC] might be attributed to the highly stabilized and compact structure of laccase, facilitating a better internal electron transfer during the laccase-substrate interactions. Enhanced catalytic performance of laccase in [Cho][DHC] was postulated to be driven by the high accumulation level of dihydrogen citrate anions around laccase's surface. [Cho][DHC] holds great promise as a cosolvent in laccase-catalyzed biochemical reactions.
The mobility of (14)C-chlorpyrifos using soil TLC was investigated in this study. It was found that chlorpyrifos was not mobile in clay, clay loam and peat soil. The mobility of (14)C-chlorpyrifos and non-labelled chlorpyrifos was also tested with silica gel TLC using three types of developing solvent hexane (100%), hexane:ethyl acetate (95:5, v/v); and hexane:ethyl acetate (98:2, v/v). The study showed that both the (14)C-labelled and non-labelled chlorpyrifos have the same Retardation Factor (Rf) for different developing solvent systems. From the soil column study on mobility of chlorpyrifos, it was observed that no chlorpyrifos residue was found below 5 cm depth in three types of soil at simulation rainfall of 20, 50 and 100 mm. Therefore, the soil column and TLC studies have shown similar findings in the mobility of chlorpyrifos.
The rate of formation and disappearance of phthalic anhydride (PAn) intermediate in the aqueous cleavage of N-methoxyphthalamic acid (NMPA) under acidic pH was studied spectrophotometrically in mixed CH3CN-H2O solvents. The rate of formation of PAn from NMPA is almost independent of the change in acetonitrile content from 20 to 70% v/v in mixed aqueous solvents. The rate constants for the formation of PAn from NMPA are approximately 10-fold smaller than the corresponding rate constants for the formation of PAn from o-carboxybenzohydroxamic acid (OCBA). These observations are ascribed to the consequence of the occurrence of slightly different mechanisms in these reactions.
In the crystal of the title complex, [Co(C(9)H(6)NO)(3)].C(2)H(5)OH, the central Co atom has a distorted octahedral coordination comprised of three N atoms and three O atoms from the three 8-quinolinolato ligands. The three Co-O bond distances are in the range 1.887 (2)-1.910 (2) A, while the three Co-N bond distances range from 1.919 (2) to 1.934 (2) A. The solvent ethanol molecule forms an intermolecular O-H.O hydrogen bonding with a quinolinolato ligand.
In this study, the role of manganese precursors in mesoporous (meso) MnOx/γ-Al2O3 catalysts was examined systematically for toluene oxidation under ozone at ambient temperature (20 °C). The meso MnOx/γ-Al2O3 catalysts developed with Mn(CH3COO)2, MnCl2, Mn(NO3)2.4H2O and MnSO4 were prepared by an innovative single step solvent-deficient method (SDM); the catalysts were labeled as MnOx/Al2O3(A), MnOx/Al2O3(C), MnOx/Al2O3(N), and MnOx/Al2O3(S), respectively. Among all, MnOx/Al2O3(C) showed superior performance both in toluene removal (95%) as well as ozone decomposition (88%) followed by acetate, nitrate and sulphated precursor MnOx/Al2O3. The superior performance of MnOx/Al2O3(C) in the oxidation of toluene to COx is associated with the ozone decomposition over highly dispersed MnOx in which extremely active oxygen radicals (O2-, O22- and O-) are generated to enhance the oxidation ability of the catalysts greatly. In addition, toluene adsorption over acid support played a vital role in this reaction. Hence, the properties such as optimum Mn3+/Mn4+ ratio, acidic sites, and smaller particle size (≤2 nm) examined by XPS, TPD of NH3, and TEM results are playing vital role in the present study. In summary, the MnOx/Al2O3 (C) catalyst has great potential in environmental applications particularly for the elimination of volatile organic compounds with low loading of manganese developed by SDM.
The title compound, {[Zn(C9H11N2S2)2]·0.5C6H7N} n , comprises two independent, but chemically similar, Zn[S2CN(Et)CH2py]2 residues and a 4-methyl-pyridine solvent mol-ecule in the asymmetric unit. The Zn-containing units are connected into a one-dimensional coordination polymer (zigzag topology) propagating in the [010] direction, with one di-thio-carbamate ligand bridging in a μ2-κ(3) mode, employing one pyridyl N and both di-thio-carbamate S atoms, while the other is κ(2)-chelating. In each case, the resultant ZnNS4 coordination geometry approximates a square pyramid, with the pyridyl N atom in the apical position. In the crystal, the chains are linked into a three-dimensional architecture by methyl- and pyridyl-C-H⋯S, methyl-ene-C-H⋯N(pyrid-yl) and pyridyl-C-H⋯π(ZnS2C) inter-actions. The connection between the chain and the 4-methyl-pyridine solvent mol-ecule is of the type pyridyl-C-H⋯N(4-methyl-pyridine).
In the title cluster complex hexane solvate, [Ru6(C30H32P2)(CO)22]·C6H14, two Ru3(CO)11 fragments are linked by a Ph2P(CH2)6PPh2 bridge with the P atoms equatorially disposed with respect to the Ru3 triangle in each case; the hexane solvent mol-ecule is statistically disordered. The Ru⋯Ru distances span a relatively narrow range, i.e. 2.8378 (4) to 2.8644 (4) Å. The hexyl chain within the bridge has an all-trans conformation. In the mol-ecular packing, C-H⋯O inter-actions between cluster mol-ecules, and between cluster and hexane solvent mol-ecules lead to a three-dimensional architecture. In addition, there are a large number of C≡O⋯π(arene) inter-actions in the crystal. The importance of the carbonyl groups in establishing the packing is emphasized by the contribution of 53.4% to the Hirshfeld surface by O⋯H/H⋯O contacts.
Deep eutectic solvent (DES) affinities with cellular membranes structures dictate the degree of cytotoxicity that results from these interactions. The physicochemical properties of choline chloride (ChCl)-DESs suggest non-negligible cytotoxicities that were attested by published researches. In this study, the profiles of novel N,N-diethylammonium chloride (DAC)-based-deep eutectic solvents (DESs) prepared with various hydrogen bond donors (urea, glycerol, ethylene glycol, malonic acid, and zinc chloride) were compared to those of ChCl-DESs by using HelaS3, AGS, MCF-7, and WRL-68 cancer cell lines. The molecular interactions between salts and cellular membranes were investigated to explain the observed cytotoxicity. The results show that ChCl-based DESs (279 ≤ IC50 ≥ 1260 mM) were less toxic than DAC-based DESs (37 ≤ IC50 ≥ 109 mM). COSMO-RS analysis emphasized the importance of salt hydrophobicity with regards to DESs cytotoxicity. Malonic acid increased hydrophobicity and cytotoxicity in general, thus highlighting the potential of ammonium salt-based DESs as anticancer agents.
The binding characteristics of DNA in deep eutectic solvents (DESs), particularly the binding energy and interaction mechanism, are not widely known. In this study, the binding of tetrabutylammonium bromide (TBABr) based DES of different hydrogen bond donors (HBD), including ethylene glycol (EG), glycerol (Gly), 1,3-propanediol (1,3-PD) and 1,5-pentanediol (1,5-PD), to calf thymus DNA was investigated using fluorescence spectroscopy. It was found that the shorter the alkyl chain length (2 carbons) and higher EG ratios of TBABr:EG (1:5) increased the binding constant (Kb) between DES and DNA up to 5.75 × 105 kJ mol-1 and decreased the binding of Gibbs energy (ΔGo) to 32.86 kJ mol-1. Through displacement studies, all synthesised DESs have been shown to displace DAPI (4',6-diamidino-2-phenylindole) and were able to bind on the minor groove of Adenine-Thymine (AT)-rich DNA. A higher number of hydroxyl (OH) groups caused the TBABr:Gly to form more hydrogen bonds with DNA bases and had the highest ability to quench DAPI from DNA, with Stern-Volmer constants (Ksv) of 115.16 M-1. This study demonstrated that the synthesised DESs were strongly bound to DNA through a combination of electrostatic, hydrophobic, and groove binding. Hence, DES has the potential to solvate and stabilise nucleic acid structures.
3-Nitro-2-phenoxypyridine and 3-nitro-2-(4-methyl)phenoxypyridine were obtained when 2-chloro-3-nitropyridine was treated with phenol and p-cresol, respectively. Fluorescence studies were carried out in various solvents, in capped and uncapped conditions and for differing concentrations. Both 3-nitro-2-phenoxypyridine and 3-nitro-2-(4-methyl)phenoxypyridine were fluorescent compounds but 3-Nitro-2-(4-methyl)phenoxypyridine was more fluorescent than 3-nitro-2-phenoxypyridine in all the solvents used. The fluorescence intensity decreased with concentration and time.
The rate of aqueous cleavage of N-(2’-hydroxyphenyl)phthalimide (A), monitored at 320 nm, 1.0 10–3 M NaOH, 35ºC and within CH3CN content range 1% – 80% v/v in mixed aqueous solvents, follows the reaction scheme: A + HO-/H2O ➝ B + HO-/H2O ➝ P1 + P2 where B, P1 and P2 represent N-(2’-hydroxyphenyl)phthalamic acid, phthalic acid and 2-hydroxyaniline, respectively. The values of k1 and k2 at different content of CH3CN have been calculated from a kinetic equation based upon a reaction scheme with two irreversible pseudo-first-order consecutive reaction paths. The values of k1/k2 are > 104 within CH3CN content range 1% – 80% v/v in mixed aqueous solvents. The intermediate hydrolysis product (B) exists in 72% dianionic, 27.9% monoanionic and 0.1% nonionic form under the present experimental conditions. Both dianionic and monoanionic forms of B are non-reactive while the nonionic form of B is reactive towards hydrolysis under such conditions.
The objective of this study was to evaluate the effects of solid-to-solvent ratio (1:5. 1:10, 1:15 and 1:20) on the extraction of phenolic compounds (TPC and TFC) and antioxidant capacity (ABTS and DPPH radical scavenging capacity) of P. niruri. Solid-to-solvent ratio showed a significant effect for both phenolic compounds (TPC and TFC) and antioxidant capacity (ABTS and DPPH radical scavenging capacity) with 1:20 was the condition for extracting the highest of phenolic compounds (TPC and TFC) with a value of 5788.7 mg GAE/100 g DW and 1906.5 mg CE/100 g DW, respectively and exhibited high antioxidant capacities (ABTS and DPPH radical scavenging capacities) with a value of 0.820 mM and 1.598 mM, respectively among the four levels studied. TPC was positively and significantly correlated with ABTS and DPPH (r=0.999 and r=0.999) under the effects of solid-to-solvent ratio as compared to TFC, positively and strongly correlated (r=0.865 and r=0.868) with ABTS and DPPH.
Solvent-extracted Moringa oleifera seed oil was transesterified using immobilized lipase (Lipozyme IM 60) (Novozymes Bagsvaerd Denmark) at 1% (w/w) concentration, shaken at 60oC and 200 rpm for up to 24h. After transesterification, the oil was fractionated with acetone at -18oC and without acetone at 10oC to obtain two fractions, stearin and olein fractions. Incubation of the transesterified oil at 10oC for 24 h resulted in the formation of fat crystals, which settled at the bottom of the flask in sample transesterified for 24 h, while the control (0 h) sample became rather viscous with fat crystals in suspension. Transesterification resulted in a change in the triacylglycerol (TAG) profile of the oil, which in turn affected its solid fat content (SFC) and thermal behavior. The SFC value at 0oC after 24 h of reaction was 10.35% and significantly (P
Exposure to organic solvent during work activities has been known to be associated with significant clinical conditions such as peripheral neuropathy and neurobehavioral changes. Three reported cases of peripheral neuropathy most likely due to exposure to chronic organic solvent were reported recently in Bentong Malaysia. These cases showed a compatible clinical history, occupational history, examination and neurological study that link with peripheral neuropathy due to organic solvent poisoning. Proper education and training with review of engineering control measures are among preventive and corrective measures recommended. More comprehensive study in order to establish significant causal-effect relationship as documented evidence is recommended.
We have designed new derivatives of naphtha [2 ,1-b:6 ,5-13V difuran as DPNDF-CN1 and DPNDF-CN2. The molecular structures of DPNDF, its derivatives DPNDF-CN1 and DPNDF-CN2 have been optimized at the ground (So) and first excited (S1) states using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively. Then the highest occupied molecular orbitals (HOMOs), the lowest unoccupied molecular orbitals (Lumos), photoluminescence properties, electron affinities (EELS), reorganization energies (.1.$) and ionization potentials (iPs) have been investigated. The balanced A(h) and A(e) showed that DPNDF, DPNDF-CN1 and DPNDF-CN2 would be better charge transport materials for both hole and electron. The effect of attached acceptors on the geometrical parameters, electronic, optical and charge transfer properties have also been investigated.
In this study, a novel Type II deep eutectic solvent (DES) namely, choline chloride:copper(II) chloride dihydrate (ChCl:CuCl2·2H2O) was used to pretreat oil palm fronds (OPFs). The sequential pretreatment with alkaline hydrogen peroxide (0.25 vol%, 90 min) at ambient conditions and a Type II DES (90 °C, 3 h) at a later stage resulted in a delignification of 55.14% with high xylan (80.79%) and arabinan (98.02%) removals. The characterizations of pretreated OPFs confirmed the excellent performance of DES in OPF fractionation. Thus, the application of a Type II DES at ambient pressure and relatively lower temperature was able to improve the lignin and hemicellulose removals from OPFs.
Pomegranate fruit is the most studied part of punica granatum shrub. The fruit contains enormous
amount of polyphenol compounds in the peel and arils (flesh) which are responsible for its antioxidant
activity. The polyphenols present are of varying degree of lipophilicity and thus would require solvents
of varying polarity to extract them. In this study, the effects of solvent type and homogenisation on
extraction yield were considered. The fruit was first separated into peel and flesh and subsequently, one
half of each of the peel and flesh were separately homogenised. Ethanol, ethylacetate and hexane were
used to extract the polyphenol content of each of the four samples; non-homogenised peel (NP), nonhomogenised flesh (NF), homogenised peel (HP) and homogenised flesh (HF) in decreasing order of
polarity using maceration method. The extraction was carried out successively using the residue
recovered from previous extraction. Ethanol was used for a second time to complete the extraction
process. The total extractive yield from the four samples were 27.19, 26.04, 25.03 and 15.61 for HP,
NP, HF and NF respectively. The experiment has demonstrated that maceration process can be used to
extract compounds from pomegranate to give a yield similar to more sophisticated method and ethanol
is a suitable solvent for extracting hydrophilic compounds from the fruit.
Lipase-catalyzed production of palm esters was performed via alcoholysis of palm oil and oleyl alcohol in solvent and solvent-free systems using a 2 L stirred tank reactor (STR). Two immobilized lipases were tested and Lipozyme RM IM exhibited superior performance in both reaction systems. Reusability studies of the enzymes in a solvent-free system also demonstrated the high stability of Lipozyme RM IM as shown by its ability to yield more than 70% palm esters with up to 19 cycles of reusing the same enzymes. Modification of the enzyme washing process improved the stability of Lipozyme TL IM in a solvent system as demonstrated by maintaining 65% yield after 5 times of repeated enzyme use. The scale up process for both lipases was conducted in the presence of solvents by using the impeller tip speed approach. Lipozyme RM IM-catalyzed reaction in a 15 L STR produced 85.7% yield and there was a significant drop to 60.7% in the 300 L STR, whereas Lipozyme TL IM had a lower yield (65%) when the reaction volume was increased to 15 L. The low yields could be due to the accumulation of enzymes at the bottom of the vessel. Purification of palm esters via solvent-solvent extraction revealed that more than 90% of oleyl alcohol was extracted after the third extraction cycle at 150 rpm impeller speed with reduced palm esters: ethanol ratio (v/v) from 1:4 to 1:3.
The high dependence on crude oil for energy utilization leads to a necessity of finding alternative sustainable resources. Solvents are often employed in valorizing the biomass into bioproducts and other value-added chemicals during treatment stages. Unfortunately, despite the effectiveness of conventional solvents, hindrances such as expensive solvents, unfavourable environmental ramifications, and complicated downstream separation systems often occur. Therefore, the scientific community has been actively investigating more cost-effective, environmentally friendly alternatives and possess the excellent dissolving capability for biomass processing. Generally, 'green' solvents are attractive due to their low toxicity, economic value, and biodegradability. Nonetheless, green solvents are not without disadvantages due to their complicated product recovery, recyclability, and high operational cost. This review summarizes and evaluates the recent contributions, including potential advantages, challenges, and drawbacks of green solvents, namely ionic liquids, deep eutectic solvents, water, biomass-derived solvents and carbon dioxide in transforming the lignocellulosic biomass into high-value products. Moreover, research opportunities for future developments and potential upscale implementation of green solvents are also critically discussed.
The effect of carbon black on the mechanical properties of elastomers is of great interest, because the filler is one of principal ingredients for the manufacturing of rubber products. While fillers can be used to enhance the properties of elastomers, including stress-free swelling resistance in solvent, it is widely known that the introduction of fillers yields significant inelastic responses of elastomers under cyclic mechanical loading, such as stress-softening, hysteresis and permanent set. When a filled elastomer is under mechanical deformation, the filler acts as a strain amplifier in the rubber matrix. Since the matrix local strain has a profound effect on the material's ability to absorb solvent, the study of the effect of carbon black content on the swelling characteristics of elastomeric components exposed to solvent in the presence of mechanical deformation is a prerequisite for durability analysis. The aim of this study is to investigate the effect of carbon black content on the swelling of elastomers in solvent in the presence of static mechanical strains: simple extension and simple torsion. Three different types of elastomers are considered: unfilled, filled with 33 phr (parts per hundred) and 66 phr of carbon black. The peculiar role of carbon black on the swelling characteristics of elastomers in solvent in the presence of mechanical strain is explored.