Norm index in QSTR work for predicting toxicity of ionic liquids on Vibrio fischeri.

Ionic liquids have been becoming new 'green solvent' because of the low saturation vapor pressure, less volatilization and more recycling utilization. Since most ILs are soluble in water, it should be indispensable to evaluate the ecotoxicology effect of ILs on aquatic environment before using them widely. Based on the concept of norm index, a set of norm descriptors were proposed for anions, cations and ILs. The whole IL structure optimization method has been used to build a predictive norm index-based quantitative structure-toxicity relationship model for the toxicity of ILs on Vibrio fischeri. Statistical results indicated that norm descriptors were reliable and robust in expressing the relationship between structural information and toxicity of ILs. Meanwhile, a series of ILs without experimental values were predicted based on this stable QSTR model. The results indicated that for imidazole-based ILs, an increase in the length of substituent in the branch could enhance the toxicity of ILs on Vibrio fischeri, and the branch contains hydroxyl group, double bond or triple bonds might reduce the toxicity of ILs. Results obtained in this present work would be valuable for the molecular design and the toxicity evaluation toward aquatic organism of ILs.

Preparation and evaluation of hydroxyethyl cellulose-based functional polymer for highly efficient utilization of heavy oil under the harsh reservoir environments.

Emulsification viscosity reduction and subsequent demulsification are effective strategies to improve the utilization rate of heavy oil. However, traditional surfactants are challenged by unsatisfactory salt tolerance, inadequate stability in emulsification, difficulty in demulsification and pollution problem of oily wastewater discharge. To realize the feasibility and environment-friendliness of heavy oil utilization in the harsh reservoir environments, we designed a functional polymer and conducted a comprehensive evaluation using heavy oil samples from Chenping oil well in Shengli Oilfield. It was synthesized by grafting two hydrophobic monomers, lauryl methacrylate (LMA) and N, N-Diethylaminomethyl methacrylate (DEAEMA), onto the hydrophilia hydroxyethyl cellulose (HEC) by free-radical polymerization. The viscosity reduction rate can reach 99.57 % even under the high salinity of 26,050 mg/L. The stable oil-in-water (O/W) emulsion can be maintained for >48 h, satisfying the actual requirements for heavy oil recovery. Moreover, the emulsion can be completely demulsified in a CO2 atmosphere within 30 min, suggesting its satisfactory demulsification performance. Our study achieved the one-step transformation of heavy oil emulsion between emulsification and demulsification, which provides a green bio-based material and an ingenious strategy for enhanced oil recovery and other chemical engineering applications including oil/water separation.

Novel Strategy of Polymers in Combination with Silica Particles for Reversible Control of Oil-Water Interface.

Hybrid smart emulsification systems are highly applicable in manipulating oil-in-water (O/W) droplets. Herein, novel switchable block polymers containing both zwitterionic and tertiary amine pendent groups were designed and synthesized to combine with charged silica particles to stabilize the O/W emulsion responsive to pH. This study was carried out in O/W emulsions stabilized with the polymer and silica particles under different pH conditions. The emulsion system was also simulated using molecular dynamics simulation to reveal the mechanism at molecular levels, thus gaining insight into the relationships between the emulsifying properties and the molecular interaction of the mixed system. Upon acidification of the continuous aqueous phase, protonated polymers with excellent hydrophilicity were induced by charged silica particles to cause rapid emulsion coalescence. In alkaline media, the mixed system conversely stabilized the O/W emulsions, cutting polymer consumption by over three-quarters. The emulsification and demulsification can be switched alternately by tuning the pH conditions. The applications exhibited excellent efficiency in separating heavy oil/water emulsions and proved the high conversion rate in emulsion polymerization. Overall, with this novel strategy to relieve tedious modifications on particle surfaces and massive consumption of polymers, the designed responsive emulsification systems can impart intelligent and controllable chemical reactivity to emulsions on demand in a more affordable and sustainable way.

Regenerating cellulose from ionic liquids for an accelerated enzymatic hydrolysis.

The efficient conversion of lignocellulosic materials into fuel ethanol has become a research priority in producing affordable and renewable energy. The pretreatment of lignocelluloses is known to be key to the fast enzymatic hydrolysis of cellulose. Recently, certain ionic liquids (ILs) were found capable of dissolving more than 10wt% cellulose. Preliminary investigations [Dadi, A.P., Varanasi, S., Schall, C.A., 2006. Enhancement of cellulose saccharification kinetics using an ionic liquid pretreatment step. Biotechnol. Bioeng. 95, 904-910; Liu, L., Chen, H., 2006. Enzymatic hydrolysis of cellulose materials treated with ionic liquid [BMIM]Cl. Chin. Sci. Bull. 51, 2432-2436; Dadi, A.P., Schall, C.A., Varanasi, S., 2007. Mitigation of cellulose recalcitrance to enzymatic hydrolysis by ionic liquid pretreatment. Appl. Biochem. Biotechnol. 137-140, 407-421] suggest that celluloses regenerated from IL solutions are subject to faster saccharification than untreated substrates. These encouraging results offer the possibility of using ILs as alternative and non-volatile solvents for cellulose pretreatment. However, these studies are limited to two chloride-based ILs: (a) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), which is a corrosive, toxic and extremely hygroscopic solid (m.p. approximately 70 degrees C), and (b) 1-allyl-3-methylimidazolium chloride ([AMIM]Cl), which is viscous and has a reactive side-chain. Therefore, more in-depth research involving other ILs is much needed to explore this promising pretreatment route. For this reason, we studied a number of chloride- and acetate-based ILs for cellulose regeneration, including several ILs newly developed in our laboratory. This will enable us to select inexpensive, efficient and environmentally benign solvents for processing cellulosic biomass. Our data confirm that all regenerated celluloses are less crystalline (58-75% lower) and more accessible to cellulase (>2 times) than untreated substrates. As a result, regenerated Avicel((R)) cellulose, filter paper and cotton were hydrolyzed 2-10 times faster than the respective untreated celluloses. A complete hydrolysis of Avicel((R)) cellulose could be achieved in 6h given the Trichoderma reesei cellulase/substrate ratio (w/w) of 3:20 at 50 degrees C. In addition, we observed that cellulase is more thermally stable (up to 60 degrees C) in the presence of regenerated cellulose. Furthermore, our systematic studies suggest that the presence of various ILs during the hydrolysis induced different degrees of cellulase inactivation. Therefore, a thorough removal of IL residues after cellulose regeneration is highly recommended, and a systematic investigation on this subject is much needed.

QSAR models for describing the toxicological effects of ILs against Candida albicans based on norm indexes.

The quantitative structure-activity relationship (QSAR) model is an effective alternative to traditional experimental toxicity testing, which is undoubtedly important for modern environmental risk assessment and property prediction. Based on this background, the toxicological effects of ionic liquids (ILs) against Candida albicans (C. albicans) were studied via the QSAR method. A large diverse group of 141 and 85 ILs that have a minimal inhibitory concentration (MIC) and a minimum fungicidal concentration (MBC) against C. albicans were used to obtain multiple linear regression models. These two models were developed based on matrix norm indexes and proposed based on the atomic character and position. Matrix norm indexes proposed in our research group were used to calculate the toxicity of these ILs towards C. albicans for the first time. These two models precisely estimated the toxicity of these ILs towards C. albicans with a square of correlation coefficient (R2) of = 0.930 and a standard error of estimate (SE) of = 0.254 for pMIC, and for pMBC, R2 = 0.873 and SE = 0.243.

QSAR models for describing the toxicological effects of ILs against Staphylococcus aureus based on norm indexes.

The hazardous potential of ionic liquids (ILs) is becoming an issue of great concern due to their important role in many industrial fields as green agents. The mathematical model for the toxicological effects of ILs is useful for the risk assessment and design of environmentally benign ILs. The objective of this work is to develop QSAR models to describe the minimal inhibitory concentration (MIC) and minimal bactericidal concentration (MBC) of ILs against Staphylococcus aureus (S. aureus). A total of 169 and 101 ILs with MICs and MBCs, respectively, are used to obtain multiple linear regression models based on matrix norm indexes. The norm indexes used in this work are proposed by our research group and they are first applied to estimate the antibacterial toxicity of these ILs against S. aureus. These two models precisely and reliably calculated the IL toxicities with a square of correlation coefficient (R2) of 0.919 and a standard error of estimate (SE) of 0.341 (in log unit of mM) for pMIC, and an R2 of 0.913 and SE of 0.282 for pMBC.

Effect of pyrolysis temperature on characteristics and aromatic contaminants adsorption behavior of magnetic biochar derived from pyrolysis oil distillation residue.

The magnetic biochars were easily fabricated by thermal pyrolysis of Fe(NO3)3 and distillation residue derived from rice straw pyrolysis oil at 400, 600 and 800°C. The effects of pyrolysis temperature on characteristics of magnetic biochars as well as adsorption capacity for aromatic contaminants (i.e., anisole, phenol and guaiacol) were investigated carefully. The degree of carbonization of magnetic biochars become higher as pyrolysis temperature increasing. The magnetic biochar reached the largest surface area and pore volume at the pyrolysis temperature of 600°C due to pores blocking in biochar during pyrolysis at 800°C. Based on batch adsorption experiments, the used adsorbent could be magnetically separated and the adsorption capacity of anisole on magnetic biochars was stronger than that of phenol and guaiacol. The properties of magnetic biochar, including surface area, pore volume, aromaticity, grapheme-like-structure and iron oxide (γ-Fe2O3) particles, showed pronounced effects on the adsorption performance of aromatic contaminants.

Thermogravimetric investigation of the co-combustion between the pyrolysis oil distillation residue and lignite.

Co-combustion of lignite with distillation residue derived from rice straw pyrolysis oil was investigated by non-isothermal thermogravimetric analysis (TGA). The addition of distillation residue improved the reactivity and combustion efficiency of lignite, such as increasing the weight loss rate at peak temperature and decreasing the burnout temperature and the total burnout. With increasing distillation residue content in the blended fuels, the synergistic interactions between distillation residue and lignite firstly increased and then decreased during co-combustion stage. Results of XRF, FTIR, (13)C NMR and SEM analysis indicated that chemical structure, mineral components and morphology of samples have great influence on the synergistic interactions. The combustion mechanisms and kinetic parameters were calculated by the Coats Redfern model, suggesting that the lowest apparent activation energy (120.19kJ/mol) for the blended fuels was obtained by blending 60wt.% distillation residue during main co-combustion stage.

Facile pretreatment of lignocellulosic biomass using deep eutectic solvents.

In this work, three kinds of deep eutectic solvents (DESs) were facilely prepared and used in the pretreatment of corncob, including monocarboxylic acid/choline chloride, dicarboxylic acid/choline chloride and polyalcohol/choline chloride. The enhanced delignification and subsequent enzymatic hydrolysis efficiency were found to be related to the acid amount, acid strength and the nature of hydrogen bond acceptors. The XRD, SEM and FT-IR results consistently indicated that the structures of corncob were disrupted by the removal of lignin and hemicellulose in the pretreatment process. In addition, the optimal pretreatment temperature and time were 90°C and 24h, respectively. This study explored the roles of various DESs combinations, pretreatment temperature and time to better utilize the DESs in the pretreatment of lignocellulosic biomass.

Topological study on the toxicity of ionic liquids on Vibrio fischeri by the quantitative structure-activity relationship method.

As environmentally friendly solvents, ionic liquids (ILs) are unlikely to act as air contaminants or inhalation toxins resulting from their negligible vapor pressure and excellent thermal stability. However, they can be potential water contaminants because of their considerable solubility in water; therefore, a proper toxicological assessment of ILs is essential. The environmental fate of ILs is studied by quantitative structure-activity relationship (QSAR) method. A multiple linear regression (MLR) model is obtained by topological method using toxicity data of 157 ILs on Vibrio fischeri, which are composed of 74 cations and 22 anions. The topological index developed in our research group is used for predicting the V. fischeri toxicity for the first time. The MLR model is precise for estimating LogEC50 of ILs on V. fischeri with square of correlation coefficient (R(2)) = 0.908 and the average absolute error (AAE) = 0.278.

Quantitative Structure-Activity Relationship for High Affinity 5-HT1A Receptor Ligands Based on Norm Indexes.

Arylpiperazine derivatives are promising 5-hydroxytryptamine (5-HT) receptor ligands which can inhibit serotonin reuptake effectively. In this work, some norm index descriptors were proposed and further utilized to develop a model for predicting 5-HT1A receptor affinity (pKi) of 88 arylpiperazine derivatives. Results showed that this new model could provide satisfactory predictions with the square of the correction coefficient (R(2)) of 0.8891 and the squared correlation coefficient of cross-validation (Q(2)) of 0.8082, respectively. In addition, the applicability domain of this model was validated by using the leverage approach and results which suggested potential large scale for further utilization of this model. The results of statistical values and validation tests demonstrated that our proposed norm index based model could be successfully applied for predicting the affinity 5-HT1A receptor ligands of arylpiperazine derivatives.

Aqueous Ionic Liquids and Deep Eutectic Solvents for Cellulosic Biomass Pretreatment and Saccharification.

Ionic liquids (ILs) have proven effective solvents for pretreating lignocellulose, leading to the fast saccharification of cellulose and hemicellulose. However, the high current cost of most ILs remains a major barrier to commercializing this recent approach at a practical scale. As a strategic detour, aqueous solutions of ILs are also being explored as less costly alternatives to neat ILs for cellulose pretreatment. However, limited studies on a few select IL systems are known and there remains no systematic survey of various ILs, eluding an in-depth understanding of pretreatment mechanisms afforded by aqueous IL systems. As a step toward filling this gap, this study presents results for Avicel cellulose pretreatment by neat and aqueous solutions (1.0 and 2.0 M) of 20 different ILs and three deep eutectic solvents, correlating enzymatic hydrolysis rates of pretreated cellulose with various IL properties such as hydrogen-bond basicity, polarity, Hofmeister ranking, and hydrophobicity. The pretreatment efficiencies of neat ILs may be loosely correlated to the hydrogen-bond basicity of the constituent anion and IL polarity; however, the pretreatment efficacies for aqueous ILs are more complicated and cannot be simply related to any single IL property. Several aqueous IL systems have been identified as effective alternatives to neat ILs in lignocellulose pretreatment. In particular, this study reveals that aqueous solutions of 1-butyl-3-methylimidazolium methanesulfonate ([BMIM][MeSO3]) are effective for pretreating switchgrass (Panicum virgatum), resulting in fast saccharification of both cellulose and hemicellulose. An integrated analysis afforded by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis and cellulase adsorption isotherm of lignocellulose samples is further used to deliver a more complete view of the structural changes attending aqueous IL pretreatment.

Quantitative structure-toxicity relationship of the aquatic toxicity for various narcotic pollutants using the norm indexes.

The aquatic toxicity value of hazardous contaminants plays an important role in the risk assessments of aquatic ecosystems. The following study presents a stable and accurate structure-toxicity relationship model based on the norm indexes for the prediction of toxicity value (log(LC50)) for 190 diverse narcotic pollutants (96 h LC50 data for Poecilia reticulata). Research indicates that this new model is very efficient and provides satisfactory results. The suggested prediction model is evidenced by R(2) (square correlation coefficient) and ARD (average relative difference) values of 0.9376 and 10.45%, respectively, for the training set, and 0.9264 and 13.90% for the testing set. Comparison results with reference models demonstrate that this new method, based on the norm indexes proposed in this work, results in significant improvements, both in accuracy and stability for predicting aquatic toxicity values of narcotic pollutants.

SO3H-functionalized acidic ionic liquids as catalysts for the hydrolysis of cellulose.

The conversion of cellulose into valuable chemicals to deal with the depletion of fossil fuel has got much attention. Completing the hydrolysis of cellulose under mild conditions is the key step. In this study, six kinds of SO(3)H-functionalized acidic ionic liquids were used as acid catalyst to promote the hydrolysis of cellulose in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl). All of them were efficient for the hydrolysis of cellulose, with the maximum total reducing sugars (TRS) yields over 83% at 100 °C. Acidic ionic liquids with analogous structures showed similar catalytic activities. Triethyl-(3-sulfo-propyl)-ammonium hydrogen sulfate (IL-5 in this study) was the optimum ionic liquid for cellulose hydrolysis, with the maximum TRS yield at 100 °C up to 99% when the dosage used was 0.2g. In addition, the water in [BMIM]Cl had negative effect on cellulose hydrolysis. Therefore, controlling the content of water in a comparatively low level is quite necessary.