Dual Solvent Research Articles

1H,4H-Piperazine-diium Dichlorosulfonate: Structure Elucidation and its Dual Solvent–Catalyst Activity for the Synthesis of New Dihydro-[1,2,4]triazolo[1,5-a]pyrimidine Scaffolds

A new ionic liquid containing a 1H,4H-piperazine-diium ring and chlorosulfonate as a 1,4-dicationic core and counter ion, respectively, was designed and synthesised. The structure elucidation of this ionic liquid was conducted by 1D and 2D NMR, FT-IR, Raman, and mass spectrum analysis. The physical properties of this ionic liquid were determined and reported. Furthermore, the dual solvent–catalyst activity of piperazine-1,4-diium dichlorosulfonate was investigated for the synthesis of new dihydro[1,2,4]triazolo[1,5-a]pyrimidines through a one-pot three-component reaction. The ionic liquid was retrieved and reused several times without reducing its catalytic efficiency.

Deep eutectic solvent promoted tunable synthesis of nitrogen-doped nanoporous carbons from enzymatic hydrolysis lignin for supercapacitors

Dual functional deep eutectic solvent (DES) generated by the complexation of choline chloride and ZnCl2 was applied as both soft template and nitrogen source for the preparation of nanoporous carbons from sustainable lignin resource. Urea was purposely introduced as an additional nitrogen source as well as porogen. The diverse carbons were obtained by thermal treatment of the physical mixtures under N2 atmosphere in one-step. Physico-chemical characterization of the resultant carbons demonstrated that the presence of urea plays a key role in the formation of abundant micropores. With the incorporation of urea into the DES-templated system, the pore structure dominated by small mesopores evolved to a desirable micro-mesoporous hierarchical texture and exhibited a broccoli-like morphology. It has been demonstrated that the broccoli-like carbons exhibit enhanced electrochemical performance when used as electrodes in supercapacitors ascribed to the synergistic effect between rational micro-mesoporous structure and excellent nitrogen-doping efficiency (ca. 4–10 wt%).

Polyoxometalate-Based Metal-Organic Framework Fractal Crystals

Summary Assembling complex hierarchical structures facilely to improve the accessibility of catalytic sites inside bulk catalysts has long been desired but remains challenging. Herein, we fabricate the hierarchical polyoxometalate-based metal-organic framework (POM@MOF) cuboctahedrons by solvent-assisted assembly, and propose a fractal growth mechanism. The great disparity in polarity of the dual solvents used endows them a different strength interaction with the POM. As a result, the polar enriched areas induced by the hydrophilic POM cause diffusion-limited aggregation along with the fractal growth. The obtained POM@MOF fractal crystallites possess an ordered layered surface and mesopores developed from the fractal growth and microscopic separation of the system. The cuboctahedron morphology is directed by the anisotropy of the Keggin units. This is of great significance in constructing hierarchical structures via fractal growth caused by diffusion limit by choosing some solvents with proper polarity disparity, which can be extended to other systems.

Wet-Chemical Tuning of Li3-x PS4 (0≤x≤0.3) Enabled by Dual Solvents for All-Solid-State Lithium-Ion Batteries.

All-solid-state lithium-ion batteries (ASLBs) employing sulfide solid electrolytes are attractive next-generation rechargeable batteries that could offer improved safety and energy density. Recently, wet syntheses or processes for sulfide solid electrolyte materials have opened opportunities to explore new materials and practical fabrication methods for ASLBs. A new wet-chemical route for the synthesis of Li-deficient Li3-x PS4 (0≤x≤0.3) has been developed, which is enabled by dual solvents. Owing to its miscibility with tetrahydrofuran and ability to dissolve elemental sulfur, o-xylene as a cosolvent facilitates the wet-chemical synthesis of Li3-x PS4 . Li3-x PS4 (0≤x≤0.15) derived by using dual solvents shows Li+ conductivity of approximately 0.2 mS cm-1 at 30 °C, in contrast to 0.034 mS cm-1 for a sample obtained by using a conventional single solvent (tetrahydrofuran, x=0.15). The evolution of the structure for Li3-x PS4 is also investigated by complementary analysis using X-ray diffraction, Raman, and X-ray photoelectron spectroscopy measurements. LiCoO2 /Li-In ASLBs employing Li2.85 PS4 obtained by using dual solvents exhibit a reversible capacity of 130 mA h g-1 with good cycle retention at 30 °C, outperforming cells with Li2.85 PS4 obtained by using a conventional single solvent.

Application of a Dual-Solvent Method in Separating Paraffin from a Shale Oil: A Combined Experimental and DFT Study

An effective dual-solvent (DS) extraction combined with recrystallization was designed for refined paraffin (RP) separation from a shale oil (SO). The content of wax enriched with acetonitrile (AN)/petroleum ether is higher than that with other DSs. The maximum recovery of RP is 22.1 wt % obtained by regulating the DS/SO ratio, extraction time (ET), and extraction times (ETs). The corresponding total relative content of oil obtained by controlling solvent polarity during the recrystallization is 1.9% based on the analysis with a gas chromatograph/mass spectrometer. Long-chain n-alkanes are predominant in RPs, which is consistent with Fourier transform infrared analysis. In addition, the mechanisms for synergic DS extraction were revealed by quantum chemistry calculation with density functional theory, i.e., C–H···π and X–H···Y bonds exist between AN and selected model compounds according to the analyses of electrostatic potential and average local ionization energy. The low boiling point and immiscibility...

Succinimide-Based Ionic Liquids: An Efficient and Versatile Platform for Transformation of CO2 into Quinazoline-2,4(1H,3H)-diones under Mild and Solvent-Free Conditions

Multifunctional succinimide-based ionic liquids (SIILs) were well-designed and synthesized, and they were used as a dual solvent–catalyst for efficient transformation of CO2 and 2-aminobenzonitriles into quinazoline-2,4(1H,3H)-diones under mild conditions. The catalytic behaviors, including the effects of anion–cation structures and reaction parameters, catalyst recyclability, and versatility were thoroughly studied. The optimum [HTMG][Suc] comprising a tetramethylguanidine cation and a succinimide anion showed excellent activity toward various substituted 2-aminobenzonitrile substrates. [HTMG][Suc] was easily recyclable with superior structural integrity. The possible pathways of CO2 and 2-aminobenzonitrile activated by [HTMG][Suc] were investigated in depth, which supported the reaction mechanism well. In comparison with reported catalysts, the protocol herein exhibited comparable catalytic performance under milder and greener conditions without any additional organic solvents.

Transformation of lignosulfonate into graphene-like 2D nanosheets: Self-assembly mechanism and their potential in biomedical and electrical applications.

Facile and controllable synthesis of graphene or graphene-like 2D nanosheets from plentiful and biocompatible materials still remains a great challenge. Herein, a bottom-up and controllable approach was firstly reported to transform earth-abundant lignosulfonate into graphene-like materials, in which lignosulfonate-based 2D nanosheets were fabricated via self-assembly in water/acetone dual solvent system, and then the nanosheets materials were transformed into graphene-like materials by carbonization. The physical properties of obtained lignosulfonate-based nanosheets were characterized, and the formation mechanism of these nanosheets was also elucidated. The thickness of the nanosheets was in the range of 5-20 nm depending on the concentration of lignosulfonate in water. Directed by π - π interactions and hydrogen bonds, the evolution of layered nanosheets seemed to experience from nano-sized rodlikes, a flake with defect holes, and smooth lignosulfonate-based nanosheets. Because of the relatively lower resistance, nano-sized structures and good cytocompatibility, the lignosulfonate-based graphene-like materials exhibited great potential in biomedical energy-related applications.

Numerical simulation of evaporation with Rayleigh convection using LBM-FDM hybrid method and proposal of the interfacial mass transfer coefficient model

The Rayleigh convection could be induced by solute evaporation in dual solvents, such as acetone-ethyl acetate and isopropanol-water system. The onset of Rayleigh convection and its evolutionary characteristics were simulated using LBM-FDM hybrid method with liquid phase random disturbance model. And the simulation results were in reasonable agreement with experimental measurements in four aspects: Rayleigh convection onset time, concentration field acquired by Schlieren and velocity field acquired by PIV, average mass transfer coefficient, and statistical average velocity distribution along the gravitational direction. It proves that the LBM-FDM hybrid method is effective in capturing the key features in this mesoscale phenomenon. Then three mass transfer model including small eddy model, surface divergence model and the new model based on theoretical parameters concentration variance, its dissipation rate and Reynolds mass flux were proposed to predict the interfacial mass transfer coefficient, and the new developed model had advantages over other two models, in the onset time of Rayleigh convection, the peak of mass transfer coefficient and tackling the non-synchronism between velocity and concentration field in fully developed convective stage. The new developed model shows its strength in determining the mass transfer coefficient in a theoretical way.

Development of a reactive extraction process for isobutyl isobutyrate formation intensified by bifunctional ionic liquid

Isobutyl isobutyrate (IBIBE) is a typical long-chain ester widely used as a solvent, additive, or raw material. To address problems such as acidic waste emission and tedious downstream separation in traditional synthesis routes, a reactive extraction process concept employing the ionic liquid (IL) 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIm][HSO4]) as a dual catalyst and solvent is proposed. To develop such an intensified process, thermodynamic analysis of the reaction system is firstly performed. Liquid-liquid equilibria indicate that [BMIm][HSO4] is a proper extractant that can not only remove the formed IBIBE from the esterification system via phase splitting but also keep the reactants in the IL phase, both facilitating the forward reaction and thus improving the conversion of the reactant and the purity of IBIBE. The kinetics of the esterification is then experimentally determined and fitted using the activity-based kinetic model, which suggests the good catalytic performance of [BMIm][HSO4]. Combining the NRTL model and activity-based kinetic model, a reactive extraction process for IBIBE formation is developed and simulated. High purity of IBIBE (0.9799) and high conversion (0.9931) are obtained.

Sulfination of acetanilide using liquid coordination complexes as dual catalyst and solvent

The Freidel-Crafts sulfination reaction of acetanilide with sulfur dioxide was catalyzed by several AlCl3-based liquid coordination complexes (LCCs), and the results were compared with that catalyzed by traditional ILs. Influences of different catalysts, ligand/AlCl3 molar ratios, and reaction conditions on their catalytic performance were investigated. The optimal result was obtained using acetamide-AlCl3-based LCC (molar ratio of acetamide to AlCl3 was 0.65, marked as 0.65 A A/AlCl3) as the catalyst, giving nearly 100% conversion of acetanilide within 60 min and 94.07% of selectivity to 4-acetamidobenzenesulfinic acid. AA/AlBr3 was synthesized and also showed catalytic activity for the sulfination reaction. Then a plausible reaction mechanism was proposed by investigation through the raman spectra.

Enhancement of Bifunctional Effect of NO3 - Anion By Using Glyme-Based Dual Solvent Electrolytes for Li-Air Batteries

In recent years, non-aqueous type rechargeable Li-air (O2) batteries (LABs) have attracted much attention as large-scale energy storage devices for electric vehicles because of the high energy density over 5 times larger than that of the conventional Li-ion batteries (LIBs) [1]. However, there are some problems to be solved for the practical use such as smooth deposition/decomposition reaction of Li2O2 at air electrode and suppression of Li dendrite growth at Li metal negative electrode (NE). To address these problems, we selected 1.0 M LiNO3/tetraglyme(G4) electrolyte and added acetonitrile (AN) or dimethyl sulfoxide (DMSO) with both high dielectric constant ε and low viscosity η to enhance the Li salt dissociation and lowering the electrolyte viscosity. Namely, the NO3 - anion was reported to work as a mediator to decompose the Li2O2 product at air electrode [2] and to form Li2O layer on the surface of Li metal NE to suppress the Li dendrite growth [3,4] and extra electrolyte decomposition. In this study, we investigated the bifunctional effects of NO3 - anion and its enhancement by using the dual solvent system for electrolyte. As a reference, 1.0 M LiOTf/G4 was also examined in the same way. Figure 1 shows the η values for 1.0 M LiNO3/G4+X and 1.0 M LiOTf/G4+X (X= DMSO, AN) electrolytes. The both η values decreased with an increase in the content of mixed solvents especially for AN because of one tenth lower η (0.37 mPas) than G4. As a result, the σ value was drastically improved (Fig. 2). For the addition of DMSO, the decrease in the η was not so big. However, the σ value effectively increased as well as those for the AN. This indicates that the relative high ε (47) of DMSO enhanced to dissociate the Li salts and improved the σ value by increasing the number of carrier ions. In fact, the effect was confirmed by Raman spectra and Walden plots. Figure 3 shows the discharge/charge curves for the LAB cells using the dual solvent electrolytes at the applied current of 0.20 mA cm-2. By mixing DMSO, the overpotential was drastically reduced especially during discharge process. This effect was enhanced at a higher rate operation. In addition, Li deposition/dissolution tests using Li foil | Cu mesh cell also exhibited improved performances for the 1.0 M LiNO3/G4 electrolytes. The effects for the dual solvent system will be reported in more detail at the meeting. This study was supported by JST Project “ALCA-SPRING”, Japan. [1] P. G. Bruce et al., Nature materials, 11, 19 (2012). [2] D. Sharon, et al., ACS App. Mater. & Int., 7, 16590 (2015). [3] J. Uddin, et al., J. Phy. Chem. Lett., 4, 3760 (2013). [4] M. Saito et al., J. Electrochem. Soc., 164(12), A2872 (2017). Figure 1

Effects of Dual Solvents on the Electrolyte Properties of LiNO3/G4-Based Electrolyte for Li-Air Batteries

Lithium (Li)-air (O2) batteries (LABs) have been expected to be used for electric vehicles because of the high theoretical energy density of ca. 3500 Wh kg-1. However, there are some problems in the practical use, i.e. Li dendrite growth at Li metal negative electrode (NE), high overpotential during discharge process, etc. Recently, to solve these problems, LiNO3/ tetraglyme (G4)-based electrolytes were studied because of the bi-functional effects of surface oxidation for Li metal NE [1] and Li2O2 decomposition mediator at air electrode [2] by the NO3 -. However, the LiNO3 salt is quite low dissociation degree in G4 solvent, which causes to low ionic conductivity. In this study, we mixed dimethyl sulfoxide (DMSO) or acetonitrile (AN) with high dielectric constant e and low viscosity h as binary solvent to 1.0 M LiNO3/G4 electrolyte and investigated the effects on the electrolyte properties and LAB cell performance. G4 (< 30 ppm H2O) and AN or DMSO were mixed at the volume ratio of 9:1, 7:3 and 5:5, and 1.0 M LiNO3/G4+X (X =DMSO, AN) was prepared by dissolution of LiNO3 as supporting salt in an Ar filled dry box. The viscosity η and ionic conductivity σ were measured. The self-diffusion coefficient D of ions and solvents were evaluated by a PGSE-NMR [3]. The dissociation degree of Li salt was evaluated by using a Raman spectroscopy and Walden plot. Discharge/charge properties were also tested by using LAB cells using the electrolytes to discuss the effect of dual solvent. The η values of 1.0 M LiNO3/G4+X (DMSO, AN) decreased with increase in the content of dual solvents especially for AN because of the lower viscosity (0.37 mPa s) than that of DMSO (2.0 mPa s). However, DMSO-mixed electrolytes exhibited a similar increase in the σ value as well as AN mixed ones. Namely, the Li salt dissociation was assumed to be enhanced by the high e value (47) of DMSO. Fig. 1 shows the Raman spectra for the dual solvent electrolytes. In fact, the peak corresponding [Li+-(G4)] complex, i.e. Li+ solvation structure of G4, at 870 cm-1 disappeared for the DMSO-mixed electrolyte, indicating the strong interaction with DMSO solvent molecules compared with G4 ones. Walden plots exhibited and supported the enhancement of Li salt dissociation. Therefore, the DMSO and AN mixing as binary solvent was effective to increase in the number and mobility of carrier ions, respectively. Fig. 2 shows the discharge/charge properties of LAB cells using the 1.0 M LiNO3/G4+X (X = DMSO, AN, vol. ratio = 5:5). The both dual electrolytes successfully reduced the overpotential during discharge process. Especially for the DMSO-mixing a significant effect was achieved owing to the good supplying rate of NO3 - as mediator to the air-electrode. The effects for the dual solvent system in more detail, e.g. stability of the DMSO and AN in the dual electrolytes will be also reported at the meeting. This study was supported by JST Project “ALCA-SPRING”, Japan. [1] J. Uddin et al., J. Phys. Chem., 4, 3760 (2013). [2] D. Sharon et al., ACS Appl. Mater. Interfaces, 7, 16590, (2015). [3] M. Saito et al., RSC Adv., 7, 49031-49040 ,(2017). Figure 1

Abstract 3482: Cachexia has profound metabolic consequences in the heart and skeletal muscle

Abstract Cachexia is an underexplored and yet devastating consequence of cancer that is the cause of 20% of all cancer related deaths [1]. Cachexia is associated with poor treatment outcome [3], fatigue, and extremely poor quality of life [2, 3]. Tissue wasting is one of the characteristics associated with cachexia syndrome. Here we have used 1H MRS to characterize the metabolic profile of skeletal muscle and heart muscle obtained from normal mice and noncachexia (Panc1) and cachexia inducing (Pa04C) human pancreatic cancer xenograft bearing mice to further understand this syndrome. Male severe combined immunodeficient (SCID) mice were inoculated in the right flank with cancer cells (2 × 106) and in the right hind leg muscle with cachexia reporter myoblasts (2×106) [4]. Mice were sacrificed once tumors were ~400 mm3, and the heart and skeletal muscle were harvested for dual phase solvent extraction. 1H magnetic resonance (MR) spectra of the water phase were acquired with a 750 MHz MR spectrometer. Quantitative changes in metabolite levels were obtained from 1H MR spectra. Leucine, creatine, lactate and glucose were significantly lower, and acetate and formate were significantly higher, in the muscle of cachectic mice compared to non-cachetic mice. Cachectic mice had significantly lower alanine, succinate, glycine, lipid and PUFA (poly unsaturated fatty acids), and significantly higher acetate, pyruvate, and formate compared to normal mice. Non-cachectic mice had significantly lower alanine, succinate, phosphocreatine, and glycine, and significantly higher leucine, isoleucine, valine, pyruvate, creatine, taurine and glucose compared to normal mice. In the heart, leucine, isoleucine, valine, aspartate, glucose, lipid and PUFA were significantly lower, and glutamine was significantly higher, in cachectic mice compared to non-cachetic mice. Cachectic mice had significantly lower leucine, isoleucine, valine, lactate, alanine, glutamate, and PUFA, and significantly higher glutamine and glucose compared to normal mice. Non-cachectic mice had significantly lower alanine, and significantly higher glucose and lipid compared to normal mice. These data highlight, for the first time, the profound metabolic changes that occur in skeletal muscle and the heart with cachexia, identifying potential in vivo 1H MRS indices to detect the onset of cachexia from changes in branched chain amino acids, glucose, and PUFAs. Our data also provide new insights into the effects of cachexia as well as noncachexia inducing tumors on skeletal muscle and heart metabolism that may lead to metabolic interventions in ‘metabolotheranostic' strategies to reduce the morbidity associated with cancer and cachexia. Supported by NIH R01CA193365, R35CA209960, and P30CA06973. Ref. 1. Argiles et al: Nat. Rev. Can 2014, 14(11):754 2. Fearon et al: HPB (Oxford) 2010, 12(5):323 3. Ozola et al: Pancreatology 2015, 15(1):19 4. Winnard et al: Can Res. 2016, 76(6):1441 Citation Format: Santosh Kumar Bharti, Paul Winnard, Yelena Mironchik, Marie-France Penet, Zaver M. Bhujwalla. Cachexia has profound metabolic consequences in the heart and skeletal muscle [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2018; 2018 Apr 14-18; Chicago, IL. Philadelphia (PA): AACR; Cancer Res 2018;78(13 Suppl):Abstract nr 3482.

Abstract 3483: 1H MRS characterization of the cachetic brain metabolome induced by human pancreatic pancer xenografts

Abstract The uncontrollable extreme weight loss due to cachexia results in a particularly poor quality of life causing profound weakness, listlessness, and an inability to function. A major characteristic of cachexia is accelerated skeletal muscle and fat storage wasting causing nutrient mobilization both directly as lipid and amino acids, and indirectly as ketone bodies and glucose derived from liver keto- and gluconeogenesis with systemic distribution including to the tumor through the bloodstream. Previously, we have reported the initial characterization of a myoblast optical imaging reporter that allowed real-time longitudinal monitoring of the early onset of cancer induced wasting and measured plasma metabolic changes associated with pancreatic ductal adenocarcinoma (PDAC)-induced cachexia. Here, for the first time, we have performed high-resolution quantitative 1H MR spectroscopy (MRS) of brain tissue to characterize the brain metabolome of normal mice and mice with human PDAC xenografts that induce cachexia (Pa04C cells) or are noncachectic (Panc1 cells). Male severe combined immunodeficient mice were inoculated in the right flank with cancer cells (2×106) and in the right hind leg muscle with reporter myoblasts (2×106). Once the mice were sacrificed, brains were harvested, freeze clamped and stored in -80°C until 1H MRS analysis. Dual phase solvent extraction was performed on brain tissues and MR spectra were acquired on 750 MHz (17.6T) spectrometer. As anticipated, mice with cachexia-inducing Pa04C tumors showed significant weight loss with time. For the first time, we found that brains from Pa04C tumor bearing mice exhibited a profound reduction in water soluble metabolites as compared to Panc1 and nontumor bearing normal mice. Significant decreases in neurotransmitters: γ-aminobutyric acid (GABA), N-acetyl aspartate (NAA), and taurine as well as lactate, myo-inositol, phosphocholine, glycerophosphocholine, creatine, formate, and essential amino acids: Leu, ILe, Val, and Phe were observed in brains from cachectic mice compared to noncachectic and healthy mice. Non-cachexia inducing Panc1 tumors also induced a significant decrease of brain GABA, glutamate, aspartate, total choline and tyrosine compared to normal brains. These results provide new insights into profound changes in brain metabolism during cachexia that are likely indicative of compromised CNS function and may be a major contributing factor to the systemic control of cachectic wasting. These data provide strong evidence to support investigating new metabolic interventions to reverse CNS injury and cachexia. and provide new CNS targets for early detection using in vivo MRS techniques. Acknowledgement: This work was supported by NIH R01CA193365, R35CA209960, and P30CA06973. Citation Format: Santosh Kumar Bharti, Paul T. Winnard, Yelena Mironchik, Marie-France Penet, Anirban Maitra, Zaver M. Bhujwalla. 1H MRS characterization of the cachetic brain metabolome induced by human pancreatic pancer xenografts [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2018; 2018 Apr 14-18; Chicago, IL. Philadelphia (PA): AACR; Cancer Res 2018;78(13 Suppl):Abstract nr 3483.

Abstract 1571: Benign lipomatous lesions and liposarcomas have metabolic differences as identified in a high-resolution 1H and 31P MRS pilot study

Abstract Adipocytic tumors present a spectrum of neoplastic disease including benign lipomas, atypical lipomatous tumors (ALTs), and malignant liposarcomas. Liposarcomas are the most common soft tissue sarcoma, accounting for approximately 20% of all adult soft tissue sarcomas [1]. Some liposarcomas are suspected to arise through dedifferentiation of ALTs, a process that is not well understood. Pleomorphic liposarcomas are high-grade, aggressive tumors with high metastatic potential and overall 5-year survival rate of 20-30% [3]. Distinguishing high-grade liposarcomas from benign and atypical lipomatous tumors can be a diagnostic challenge with implications for surgical and clinical management. The rate of misdiagnosis is approximately 30–40% following radiological detection [4], and 7–17% on histological evaluation [5]. De-identified human surgical samples were collected from the Dept. of Orthopaedic Surgery, JHU, School of Medicine Baltimore, MD. One tissue specimen from a benign pleomorphic lipoma and two tissue specimens from a pleomorphic liposarcoma were examined using 1H and 31P magnetic resonance spectroscopy (MRS) on 750 MHz MR spectrometer. Dual phase solvent extraction was performed to obtain aqueous and lipid phase spectra. Metabolites were quantified and changes were reported in terms of percentage change compared to levels in pleomorphic lipoma set to 100%. Depletion in branched chain amino acids (-10%), tyrosine (-15%), phenylalanine (-25%), lactate (-45%), pyruvate (-35-50%), acetate (-5-25%), and elevation in alanine (40%), succinate (35-60%), glycine (400-500%), histidine (15-25%), glucose (100%), glutamine (50%), glutamate (75%), and myo-inositol (300%) were observed in pleomorphic liposarcoma. 31P MRS of the aqueous phase revealed high levels of phosphocholine in the pleomorphic liposarcoma as compared to the lipoma (not detected). MRS analysis of the lipid phase identified depletion in lipid (-65%, CH3 peak at 0.9 ppm was quantified) and an increase in phosphatidylethanolamine (75%) and phosphatidylcholine (30%). Visible variations in TAG glycerol backbone (4.2-4.3ppm) and -CH=CH- peaks from polyunsaturated fatty acids at 2.8ppm and 5.3ppm were also observed. We are currently analyzing additional samples from several types of sarcomas to expand this study. Our preliminary data support investigating the use of 1H and 31P MRS of liposarcomas for differentiation between subtypes.

Conversion of Biomass and Its Derivatives to Levulinic Acid and Levulinate Esters via Ionic Liquids

Biomass has emerged as an abundant and relatively low cost carbon resource alternative to fossil fuel resources in the sustainable production of specialty chemicals and biofuel. Levulinic acid is an attractive platform chemical. Upgrading of levulinic acid produces levulinate esters, which serve as a transportation fuel and fuel additive. The present review focuses on the development of sustainable conversion of biomass into levulinic acid and levulinate esters via ionic liquids dual solvent–catalysts. The synthesis routes of levulinic acid and levulinate esters and the corresponding ionic liquids are introduced. The biomass pretreament, as well as the conversions of lignocellulosic biomass and their derivatives into levulinic acid and levulinate esters, are detailed in relation to the catalytic role, properties, and performance of acidic ionic liquids. Finally, the operating conditions affecting the ionic liquids catalytic conversions are discussed as part of a comprehensive review of this topic.

Research on a Dual Solvent To Separate Olefin/Aromatic–Sulfide from Heavy Fluid Catalytic Cracking Naphtha

The separation of olefin from heavy FCC naphtha is benefit to avoid the loss of octane number during the desulfurization process. Extractive distillation is a promising alternative to separate olefin and enrich sulfide at the same time, in which the solvent is crucial for the process feasibility. The property of single solvent is unilateral to separate olefin or enrich sulfide in most instances. With the aim to study a dual-solvent, the vapor-liquid equilibrium (VLE) of heavy FCC naphtha with single solvents were obtained experimentally. Sulfolane showed best ability to separate olefin among six single solvents, which displayed a selectivity coefficient θ of 2.81. N-methyl-pyrrolidone showed best ability to concentrate sulfide with the selectivity coefficient β up to 2.07. On these bases, a series of dual-solvents were designed to study the separation performance. Selectivity coefficients θ and β grew to 4.01 and 1.97, respectively, with the volume ratio of sulfolane to N-methyl-pyrrolidone at 85:15. In a...

Controlling morphology of [formula omitted] perovskite film by dual solvent elimination method

Uniform CH3NH3PbI3 perovskite film with lower surface roughness was fabricated by tuning the dielectric constant (εr) of the precursor solvents. The extraction of highly polar solvent over localized area in this dual solvent elimination method (DSEM) leads to larger grain size and better crystallinity at room temperature. The correlated confocal PL and scanning electron microscopy (SEM) depicts minimal distribution in local PL intensity across this uniform film. Photoluminescence spectroscopy and fluorescence microscopy were utilized to probe the underlying photophysics of the perovskite film. The photovoltaic device fabricated in ambient air was found to have efficiency of 6% with JSC value of 12.5 mA and VOC of 900 mV.

Dual Alkali Solvent System for CO2 Capture from Flue Gas.

A novel two-aqueous-phase CO2 capture system, namely the dual alkali solvent (DAS) system, has been developed. Unlike traditional solvent-based CO2 capture systems in which the same solvent is used for both CO2 absorption and stripping, the solvent of the DAS system consists of two aqueous phases. The upper phase, which contains an organic alkali 1-(2-hydroxyethyl) piperazine (HEP), is used for CO2 absorption. The lower phase, which consists of a mixture of K2CO3/KHCO3 aqueous solution and KHCO3 precipitate, is used for CO2 stripping. Only a certain kind of amine (such as HEP) is able to ensure the phase separation, satisfactory absorption efficiency, effective CO2 transfer from the upper phase to the lower phase, and regeneration of the upper phase. In the meantime, due to the presence of K2CO3/KHCO3 in the lower phase, HEP in the upper phase is capable of being regenerated from its sulfite/sulfate heat stable salt, which enables the simultaneous absorption of CO2 and SO2/SO3 from the flue gas. Preliminary experiments and simulations indicate that the implementation of the DAS system can lead to 24.0% stripping energy savings compared to the Econamine process, without significantly lowering the CO2 absorption efficiency (∼90%).

Abstract 2510: Interrogating liver metabolic stress due to cancer-induced cachexia

Abstract Cancer-induced cachexia accounts for approximately 20% of all cancer deaths 1. In pancreatic cancer, the syndrome affects nearly 80% of patients 2,3. Cachectic patients experience a wide range of symptoms affecting the function of several organs such as muscle, liver, brain, and heart, that decrease quality of life and worsen prognosis. A major characteristic of cachexia is the accelerated skeletal muscle and fat storage wasting causing nutrient mobilization both directly as lipid and amino acids, and indirectly as glucose derived from the exploitation of liver gluconeogenesis that reaches the tumor through the bloodstream4. Patients with cachexia develop a wide range of metabolic stress from increased proteins and fat tissue burning resulting in increased energy expenditure. Here, for the first time, we have performed high-resolution quantitative 1H magnetic resonance spectroscopy (MRS) of liver tissue obtained from normal, noncachectic and cachectic mice bearing PDAC that are cachectic (Pa04C) and noncachectic (Panc1). A significant reduction in liver weight and significant changes in 1H MRS derived metabolite profiles were detected with cachexia. Human pancreatic cancer cell lines, Panc1 and Pa04C, were used for the study. Six to 8 week old male severe combined immunodeficient mice were inoculated in the right flank with cancer cells (5×106) and in the right hind leg muscle with reporter myoblasts (2×106) to monitor the development of cachexia in mice5. Live animal optical imaging was done using a Xenogen IVIS® Spectrum (PerkinElmer) optical scanner. Dual phase solvent extraction was performed on liver tissue to extract water soluble metabolites. All 1H MR spectra were acquired on an Avance 750 MHz Bruker NMR spectrometer. We found, for the first time, that the liver in Pa04C tumor bearing mice underwent a profound weight loss; although Panc1 tumor bearing mice showed some liver weight loss this was not as profound as observed with Pa04C tumors. Significant decreases in lactate, glucose and glutathione were observed in cachectic mouse liver compared to noncachectic mouse liver, and the liver from healthy control mice. The significant decrease of these metabolites in cachectic livers may reflect increased utilization of glucose, lactate and glutathione by the tumor or other organs during the cachexia cascade4. These results provide new insights into changes in liver metabolism during cachexia, and support investigating metabolic strategies such as supplementing glutathione or glucose to reduce cachexia associated morbidity.