Ternary Solvent Research Articles

Thermodynamic models for determination of solid–liquid equilibrium of para-tert-butylbenzoic acid in binary and ternary solvent system

Accurate solubility data is essential to make critical decisions from the earliest stage of drug discovery, through the entire process development, formulation, and up to process design. The present research work aims to evaluate the solid–liquid equilibrium data of para-tert-butylbenzoic acid (PTBBA) in binary systems such as acetonitrile + water, isopropyl alcohol + water, and isopropyl alcohol + acetonitrile at 288.15 to 328.15 K and a ternary solvent mixture of isopropyl alcohol + acetonitrile + water system in the temperature range of 298.15 to 323.15 K with varying mass fraction of the binary mixture (isopropyl alcohol + acetonitrile) for a constant mass fraction of water (0.1 and 0.3) using gravimetric and titrimetric methods. It is observed that the solubility of PTBBA increases with an increase in temperature for all the selected solvent systems. Moreover, the solubility of PTBBA in the binary and ternary system is affected by an increase in the mass fraction of water at a given temperature, which acts as an antisolvent. The measured data is correlated with various thermodynamic models such as Van’t Hoff equation, Modified Apelblat equation, Buchowski equation, and Wilson models. It is observed that there is a good agreement between measured and calculated values with an average relative deviation of 0.95 for isopropyl alcohol + acetonitrile system in the case of the modified Apelblat equation.

A new green alternative solvent for extracting echinacoside and acteoside from Cistanche deserticola based on ternary natural deep eutectic solvent

Echinacoside and acteoside, the representative constituents of Cistanche deserticola Y. C. Ma (C. deserticola), are known for its many important biological activities. In this study, a novel ternary natural deep eutectic solvent (NADES) (citric acid, fructose and glucose in a 1:2:1 molar ratio, 30 % water content) was obtained through the adjustment and optimization of single-factor experiments. And through the Box-Behnken design optimization, the optimal extraction conditions were obtained, at the moment, the yields of echinacoside and acteoside were 6.16 and 2.13 mg/g, respectively. In addition, through computer molecular simulation, it was found that there are strong hydrogen bonds and interactions between the molecules of NADES, and the hydrogen bonds, van der Waals forces and π-π interactions played an important role in the extraction of echinacoside and acteoside from C. deserticola by NADES. Finally, compared with the traditional method, NADES ultrasound-assisted extraction of echinacoside and acteoside has a shorter time (15 min), the maximum extraction yield is 1.54–2.86 times and 1.26–2.52 times than that of traditional extraction methods for echinacoside and acteoside, respectively. This study demonstrates that NADES can provides a new direction for developing new sustainable alternatives, improving green extraction process and efficiency for extracting natural active substances.

Miniaturized ternary deep eutectic solvent-based matrix solid-phase dispersion: A green sample preparation method for the determination of chlorophenols in river sediment.

New ternary deep eutectic solvents were prepared and applied as efficient green dispersing solvents in miniaturized matrix solid-phase dispersion to extract chlorophenols from river sediments for the first time. High-performance liquid chromatography coupled with a photodiode array detector was used to analyze the target analytes. The significant factors affecting the extraction were optimized as follows: dispersant (100mg), sample (100mg), ternary eutectic solvents (150μl), grinding for 1min, 450μl of acetonitrile as the elution solvent, and vortex mixing for 20s. Under the optimal conditions, the method exhibited excellent linearity (correlation coefficient>0.9980), low limits of detection between 1.039-2.478μg/g, and extraction recoveries between 93.9% and 99.2%. Furthermore, the method demonstrated excellent precision in the intra- and inter-day analysis with a relative standard deviation below 6%. When compared to conventional extraction techniques, the miniaturized matrix solid-phase dispersion considerably reduced samples and solvent usag, offering important environmental benefits. The green profile of the method was assessed using the complementary green analytical procedure index tool confirming its eco-friendship. The technique was finally employed to evaluate sediment samples from three distinct locations along the Zuibaiji River, indicating its applicability for monitoring environmental samples.

Efficient continuous dehydration of fructose to 5-hydroxymethylfurfural in ternary solvent system

Biomass-derived 5-hydroxymethylfurfural (HMF) has been identified as a versatile precursor for clean fuels and degradable polymers. Here, we developed an efficient flow-through system to continuously produce HMF in high selectivity from fructose dehydration. Effects of solvent, the relative ratio of aqueous to organic phase, the proportion of different cosolvents in the organic phase as well as the reaction variables on reactivity of fructose dehydration to HMF were comprehensively investigated to obtain the optimal results. The conduction of a H2O/dioxane/methyl isobutyl ketone (MIBK) ternary solvent system in combination with Amberlyst 70 as catalyst contributed to 93 % selectivity and 84 % yield of HMF in residence time as short as 1.6 min. The strengthened hydrogen bonding interactions by the addition of dioxane accounted for an increase in the interactions of fructose with water and cosolvent molecules, accelerating the dehydration rate. Meanwhile, the in-situ extraction of HMF from active aqueous phase to organic phase by MIBK protected it from unfavorable side reactions. The reaction system exhibited good stability without significant change on the catalytic performance over 10 h reaction. Additionally, fructose was selectively dehydrated from fructose-glucose mixtures, holding great promises for the integration with the industrial operations producing mixture of sugars (such as fructose corn syrup).

Hydrogen bonding boosted oxidative desulfurization by ZnCl2/boric acid/polyethylene glycol-based ternary deep eutectic solvents

Deep eutectic solvents, as the novel and green solvents, are widely applied in various fields because of its unique and excellent quality, such as simple synthesis, non-toxic, biodegradable, wide range of liquids and strong solvation ability. In this work, a series of ternary deep eutectic solvents were synthesized using ZnCl2, boric acid (BA) and polyethylene glycol (PEG) with appropriate molar ratios by hydrogen bonds. Compared with binary DESs, ZnCl2/2BA/2PEG showed a better desulfurization performance, and 98.7 % sulfur removal was achieved. The hydrogen bonding interaction is considered as the key factor to the formation of DES and to promote the desulfurization reaction. In addition, BA and ZnCl2 play a synergistic and positive role in the desulfurization system. The DES was immiscible with fuel and could be reused for six cycles without a significant reduction in activity. The possible mechanism of the positive effect of hydrogen bonding interaction and O2•− free radicals was proposed. This work offers more possibility for designing new types of DESs for deep desulfurization of fuel oils and other applications in relation to extraction or catalysis.

Salt-free reactive dyeing of cotton fibers in a ternary solvent system with different reactive dye chemistries

Salt-free reactive dyeing of cotton fibers in a ternary solvent system with different reactive dye chemistries

One-pot synthesis of 5-Hydroxymethylfurfural from glucose and corn stover in an aqueous choline chloride/ acetone ternary solvent

Aqueous choline chloride/acetone was developed as a green ternary solvent for catalytic conversion of glucose and raw corn stover into 5-HMF. The results illustrated that acidic ChCl solution played a vital role in promoting the tandem isomerization/dehydration reaction of glucose to 5-HMF, while acetone was identified as an efficient extracting solvent to simultaneously remove 5-HMF from the aqueous phase. The composition of the ternary solvent system was found to have a significant impact on the 5-HMF yield, reaction selectivity, and preventing the further degradation of 5-HMF. A competitive 5-HMF yield of 73.3 mol% was achieved from glucose catalyzed by an ultra-low H2SO4 loading of 2 mmol at 190 °C for 10 min in the ternary ChCl-H2O-acetone solvent with a mass ratio of 1:2:3. This novel solvent system exhibited good stability, high efficiency, and excellent recyclability, employing in catalytic conversion of both glucose and lignocellulose to produce 5-HMF.

Multimode ultrasound and ternary deep eutectic solvent sequential pretreatments enhanced the enzymatic saccharification of corncob biomass

Corncob (CB) is a valuable agricultural waste in high abundance. It is mainly composed of cellulose, hemicellulose and lignin that link in a complex interlocking matrix. The key to its utilization depends on separating cellulose from lignin and hemicellulose using an environment-friendly and effective pretreatment method to improve glucose yield. The study aimed to investigate the effect of sequential pretreatment of CB with ultrasound (US) in conjunction with ternary deep eutectic solvent (TDES). The US, type and molar ratio of TDES, temperature, and time were optimized. The results showed that under the optimum conditions, US (40 +60 kHz, 60 min) + TDES (ChCl-Gly-LA, 1:1:2, 120 ℃, 3 h), the removal of lignin and hemicellulose were 87.54 % and 67.00 %, respectively, and the recovery of cellulose was 82.18 %. After 72 h of enzymatic hydrolysis , the yield of glucose and xylose were 76.94 % and 41.26 %, respectively. Comparatively, pretreated CB yielded 61.58 % glucose and 26.90 % xylose higher than the untreated. Scanning electron microscopy revealed that the surface of the CB became cracked and rugged. X-ray diffraction showed that the CrI increased significantly from 36 % to 59 %. Fourier transform mid-infrared spectroscopy indicated significant changes in the characteristic functional groups of lignin and hemicellulose. Increases in Tonset, Tendset, Tp, Vmax and decreases in Char at 600 °C all corresponded to increases in thermal stability. These results further confirmed that TDES combined with ultrasonic pretreatment effectively removed lignin and hemicellulose. In conclusion, this approach could greenly and efficiently pretreat CB as a new method for biomass pretreatment. • Double hydrogen bond acceptor (donor) ternary pretreatment DES was studied. • The lignin removal efficiency of ternary DES was higher than binary DES. • TDES containing lactic acid reduced significantly the lignin content. • TDES combined with ultrasonic pretreatment increased lignin removal rate. • TDES combined with ultrasonic pretreatment enhanced sugar yields.

Improved glucose yield and concentration of sugarcane bagasse by the pretreatment with ternary deep eutectic solvents and recovery of the pretreated liquid

In this study, a novel ternary deep eutectic solvents (DES) consisting of choline chloride/PEG/hydroxyethyl sulfonic acid (HSA) was developed to effectively improve glucose yield and concentration of sugarcane bagasse, and the conditions of the pretreatment were optimized by response surface method (RSM). Under the optimal conditions, the maximum glucose concentration (GC) could reach 12.39 g/L (HSA concentration 1.34 %, PEG400, 2.3 h, 150 °C), and the maximum glucose yield (GY) was 0.2497 g/g (HSA concentration 1.41 %, PEG400, 2.1 h, 150 °C). Hemicellulose was completely removed, and the maximum lignin removal rate was 86.89 %. After pretreatment, 95 % of the pretreated liquid can be recycled. Finally, the structural and morphological changes of bagasse before and after pretreatment were investigated by scanning electron microscopy (SEM), Fourier Transform infrared analyzer (FT-IR) and X-ray diffraction (XRD).

Preparation, characterization of light-colored lignin from corn stover by new ternary deep eutectic solvent extraction

The industrial lignin has shown great potential to replace some of petrochemical. But the deep color of lignin limits their application in high-value field. The extraction of light-colored lignin from lignocellulose still remains challenging. Here, we reported a strategy for rapid extraction of lignin from corn stover by using a new ternary deep eutectic solvent (TDES) composed of choline chloride (ChCl), formic acid (FA) and maleic acid (MA). The color feature and structural characterization of obtained lignin was comprehensively elucidated. The results revealed that the lignin streams had light color (brightness ISO 23.44 %) with a high yield (76.3 %), purity (93.5 %), low molecular weight (Mw 1544–2040 g/mol), and low polydispersity (PDI ≤ 1.76). The introduction of MA could reduce the destruction of lignin substructure during the treatment process and avoid the deepening of lignin color. Quantitative analysis of conjugated carbonyl and quinone carbonyl and semi-quantitative analysis of lignin by 2D NMR showed that temperature had a great influence on its structure.

Poly(methylene blue)-ternary deep eutectic solvent/Au nanoparticle modified electrodes as novel electrochemical sensors: Optimization, characterization and application

A new electrochemical sensor based on a nanocomposite formed by the electroactive redox polymer poly(methylene blue) (PMB) formed in a ternary deep eutectic solvent (DES) mixture, and gold nanoparticles (AuNP) was developed. The polymerisation of MB was carried out by potential cycling in ternary DES formed by choline chloride, ethylene glycol and fructose, containing 84% of the choline chloride: ethylene glycol mixture, in the presence of an acid dopant. The composition of the AuNP-chitosan dispersion was optimized by studying the effect of different concentrations of the nanoparticles and the polymer in the dispersion on the PMB film growth. The nanocomposite films obtained under different conditions were characterized by cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy. The nanocomposite with the best characteristics was also obtained in aqueous media for comparison. The nanocomposite-based sensor formed by AuNP and PMB in DES was used for determining ascorbic acid (AA) and 5-aminosalicylic acid (5-ASA) by fixed potential amperometry at +0.20 V in 0.10 mol L−1 KCl and at +0.40 V in Britton-Robinson buffer at pH 7, respectively. Limits of detection of 0.40 μmol L−1 and 0.064 μmol L−1 were obtained for AA and 5-ASA, respectively, with the PMBDES/AuNP/GCE. The sensor was successfully applied to determine both analytes in pharmaceutical samples.

Electrochemical Sensing of Nitrofurazone and Semicarbazide on an Au-Ag Film Fabricating from a Deep Eutectic Solvent

A facile electrochemical sensor is reported for the highly selective and sensitive detection of nitrofurazone (NFZ) and its metabolites, semicarbazide (SC), by using an Au-Ag modified electrode. The Au-Ag film was produced on a Cu foil by electrodeposition in a choline chloride-urea-glycerol ternary deep eutectic solvent containing gold (III) ions and silver (I) ions. Cyclic voltammetry (CV) indicates that the co-deposition of Au-Ag would be feasible. The morphology, crystallinity, and composition of Au-Ag deposits were characterized via scanning electron microscopy (SEM), powder X-ray diffractometer, and X-ray photoelectron spectroscopy (XPS). Under the optimal condition, the Au-Ag modified electrode shows a wider linear concentration range of 1.99–643.49 μM with a low detection limit of 0.2 μM for NFZ. The corresponding linear range of SC is 7.94 to 482 μM, and the detection limit is 1.01 μM. It also demonstrated good anti-interference ability against various common interfering substances. Finally, the modified electrode was successfully applied in the real samples, and the average recoveries for NFZ and SC were 100.59% and 101.01%, respectively. The present electrochemical strategy is promising to broaden the practical electrochemical application in the environment.

Dermal Delivery of Diclofenac Sodium-In Vitro and In Vivo Studies.

Previously, we reported the use of confocal Raman spectroscopy (CRS) as a novel non-invasive approach to determine drug disposition in the skin in vivo. Results obtained by CRS were found to correlate with data from the well-established in vitro permeation test (IVPT) model using human epidermis. However, these studies used simple vehicles comprising single solvents and binary or ternary solvent mixtures; to date, the utility of CRS for monitoring dermal absorption following application of complex marketed formulations has not been examined. In the present work, skin delivery of diclofenac sodium (DFNa) from two topical dermatological drug products, namely Diclac® Lipogel 10 mg/g and Primofenac® Emulsion gel 1%, was determined by IVPT and in vivo by both CRS and tape stripping (TS) methodologies under similar experimental conditions. The in vivo data were evaluated against the in vitro findings, and a direct comparison between CRS and TS was performed. Results from all methodologies showed that Diclac promoted significantly greater DFNa delivery to the skin (p < 0.05). The cumulative amounts of DFNa which permeated at 24 h in vitro for Diclac (86.5 ± 9.4 µg/cm2) were 3.6-fold greater than the corresponding amounts found for Primofenac (24.4 ± 2.7 µg/cm2). Additionally, total skin uptake of DFNa in vivo, estimated by the area under the depth profiles curves (AUC), or the signal intensity of the drug detected in the upper stratum corneum (SC) (4 µm) ranged from 3.5 to 3.6-fold greater for Diclac than for Primofenac. The shape of the distribution profiles and the depth of DFNa penetration to the SC estimated by CRS and TS were similar for the two methods. However, TS data indicated a 4.7-fold greater efficacy of Diclac relative to Primofenac, with corresponding total amounts of drug penetrated, 94.1 ± 22.6 µg and 20.2 ± 7.0 µg. The findings demonstrate that CRS is a methodology that is capable of distinguishing skin delivery of DFNa from different formulations. The results support the use of this approach for non-invasive evaluation of topical products in vivo. Future studies will examine additional formulations with more complex compositions and will use a wider range of drugs with different physicochemical properties. The non-invasive nature of CRS coupled with the ability to monitor drug permeation in real time offer significant advantages for testing and development of topical dermatological products.

Autonomous optimization of non-aqueous Li-ion battery electrolytes via robotic experimentation and machine learning coupling

Developing high-energy and efficient battery technologies is a crucial aspect of advancing the electrification of transportation and aviation. However, battery innovations can take years to deliver. In the case of non-aqueous battery electrolyte solutions, the many design variables in selecting multiple solvents, salts and their relative ratios make electrolyte optimization time-consuming and laborious. To overcome these issues, we propose in this work an experimental design that couples robotics (a custom-built automated experiment named "Clio”) to machine-learning (a Bayesian optimization-based experiment planner named "Dragonfly”). An autonomous optimization of the electrolyte conductivity over a single-salt and ternary solvent design space identifies six fast-charging non-aqueous electrolyte solutions in two work-days and forty-two experiments. This result represents a six-fold time acceleration compared to a random search performed by the same automated experiment. To validate the practical use of these electrolytes, we tested them in a 220 mAh graphite∣∣LiNi0.5Mn0.3Co0.2O2 pouch cell configuration. All the pouch cells containing the robot-developed electrolytes demonstrate improved fast-charging capability against a baseline experiment that uses a non-aqueous electrolyte solution selected a priori from the design space.

A novel ternary deep eutectic solvent for efficient recovery of critical metals from spent lithium-ion batteries under mild conditions

In terms of environmental pollution and the shortage of resources, an efficient recovery of valuable metals in spent lithium-ion batteries (LIBs) is currently the most promising measure to achieve green sustainability of cathode materials. In this study, an choline chloride (ChCl)/ benzenesulfonic acid (BSA)/ ethanol ternary deep eutectic solvent (e.g., ChCl:BSA:Ethanol = 1:1:2 in molar ratio) was designed and applied to efficiently leach lithium (Li) and cobalt (Co) from spent LIBs under mild conditions. The experimental results show that the leaching efficiencies of Li and Co can reach 99% and 98%, respectively, under the optimal conditions: (i) a reaction temperature of 90 °C, (ii) a Solid/Liquid ratio of 20 g L−1, (iii) ChCl:BSA:Ethanol with a molar ratio of 1:1:2 and (iv) a reaction time of 2 h. The kinetics of the leaching process shows that the leaching is controlled by a surface chemical reaction. Furthermore, the Co2+ in the leachate can be directly converted into Co3O4 via precipitation of H2C2O4 and NaOH and calcination. The recovered high-value product Co3O4 can regenerate the LiCoO2 cathode material. This study provides a new method for the green recovery of spent LIB cathode materials with high efficiency and low energy consumption.

Molecular dynamics simulation on the crystal morphology of β-HMX affected by binary and ternary solvent systems

Based on the effect of different solvents on the growth rate of crystal surfaces, the binary and ternary systems exhibited the advantage of controlling the morphology of the crystals by adjusting the solvent ratio. Inspired by this idea, the crystal morphologies of β-HMX in the binary systems (propylene carbonate-water, acetone–water, dimethyl sulfoxide-water) and ternary systems (propylene carbonate-acetone–water, propylene carbonate-dimethyl sulfoxide-water) are predicted based on the modified attachment energy (MAE) model. The morphological simulation results of β-HMX were in good agreement with the microscopic morphologies obtained by SEM. The σ-profile peaks of HMX are distributed in the HB-donor and the nonpolar regions, and indicates HMX can provide hydrogen bonding. The radial distribution function (RDF) analysis shows that solvent molecule adsorption on β-HMX molecules is via solvent-crystal face interactions of van der Waals interaction, hydrogen bonding and electrostatic interaction.

A gel polymer electrolyte based on ternary deep eutectic solvent for flexible, wide-temperature tolerant zinc-ion hybrid supercapacitors

Aqueous zinc ion hybrid supercapacitor (ZIHS) is attracting considerable interest due to its noticeable safety, low cost, and high theoretical energy density. However, the widely used hydrogel electrolytes suffer from freeze and evaporation issues, which hinder the practical applications of ZIHS over a wide temperature range. Herein, we develop a gel polymer electrolyte (GPE) based on a ternary deep eutectic solvent (DES) with a low eutectic point (<-90 °C). The optimal GPE not only shows excellent flexibility and satisfactory mechanical properties in the temperature from −40 °C to room temperature, but also exhibits high ionic conductivity of 7.3 mS cm−1 at −40 °C. When it is served as the electrolyte in a ZIHS, it endows the ZIHS with an energy density of 66.83 Wh kg−1 at a power density of 187.96 W kg−1 and outstanding cycling stability with ∼95.5% capacitance retention after 20000 cycles. Furthermore, the assembled flexible device indicates favorable bendability and outstanding wide-temperature adaptability from −40 to 60 °C. More importantly, the flexible device still works well under various harsh conditions, such as pressing, bending, puncturing, and cutting. The obtained results can provide new guidance and insight for exploring wide-temperature tolerant GPEs for ZIHS.

The Effect of Acidic Ternary Deep Eutectic Solvent Treatment on Native Lignin

Ternary deep eutectic solvents (DESs) are gaining increased attention to serve as a cheap green alternative medium for the processing of lignocellulosic biomass. For example, mixtures of choline chloride (ChCl), ethylene glycol (EG), and oxalic acid (OA) were recently explored for the fractionation of lignocellulosic biomass into its main components. Interestingly, during this processing, the recovered lignin was structurally modified by incorporation of EG, which altered its solubility properties and led to the need for different lignin recovery strategies. This offers an excellent starting point for a deeper investigation of the effect of acidic DES systems on the structure of lignin. In particular, native-like residual enzyme lignins (RELs) that are hard to completely dissolve in organic solvents are specifically suitable for this task. Here, a ternary DES is used consisting of ChCl/EG with OA or trifluoromethanesulfonic acid (HOTf) as a third component. The results showed that both solvent systems led to high EG incorporation into REL. The HOTf system showed a lesser extent of lignin depolymerization at similar modification levels as it already induced modification at lower temperature (25–30 °C). Low recovery yields from typical acidic precipitation were observed for treatment with both acidic DES systems. Analysis of THF and DCM extracts showed that the products in the water phase included small EG modified lignin fragments and aromatic monomers released from lignin aryl ether linkage cleavage. This analysis details the types of other products that can be expected and where these will end up during fractionation. These results show that the treatment of lignin with acidic DES in the presence of alcohols leads to low- and high-molecular-weight products that are not effectively recovered by typical precipitation procedures.

Low-condensed lignin and high-purity cellulose production from poplar by synergistic deep eutectic solvent-hydrogenolysis pretreatment

This paper presented a green and environmentally friendly method to obtain lignin with a structure similar to milled wood lignin (MWL) and high-purity cellulose from biomass in a two-step process. The first step, maleic acid (MA), choline chloride (ChCl), and ethylene glycol (EG) ternary deep eutectic solvent (DES) pretreatment was performed to obtain lignin with less-condensed structure. The results showed that the obtained lignin had similar properties to MWL under the condition (MA/ChCl/EG = 1:5:15, 80°C, 10 h). The DES recovered still had good cycle performance. The second step, the cellulose-rich residue was hydrogenated with isopropanol-water solvent and Raney nickel to obtain high-purity cellulose. The results showed that the purity of cellulose obtained by catalytic hydrogenolysis was > 94%. The glucose yield after enzymatic hydrolysis was 243.72 mg/g, which was 14.7 times higher than the untreated poplar. Overall, this work was of great significance for the effective separation of biomass.

Enabling the drug combination of celecoxib through a spherical co-agglomeration strategy with controllable and stable drug content and good powder properties

Combining celecoxib with other chemopreventive drugs is a promising method of chemoprevention for cancer, especially for colorectal cancer. However, the traditional drug combination approaches are restricted with high-cost apparatus, complex and numerous unit operations. This work aims to develop an efficient spherical co-agglomeration strategy for celecoxib in combination with lovastatin, which can achieve drug combination in a single crystallization unit. The ternary solvent system was determined based on molecular simulation, and then a stable spherical agglomeration process was developed through the design of molar fraction of anti-solvent (MFA) and stirring rate to produce spherical agglomerates with high sphericity (84.2–89.9 %) and narrow size distribution. On this basis, celecoxib-benzoic acid spherical co-agglomerates were designed to form a complete spherical co-agglomeration strategy, which includes solvent system selection, spherical agglomeration and spherical co-agglomeration. Finally, celecoxib-lovastatin spherical co-agglomerates with synergistic efficacy were successfully produced by this strategy, with controllable and stable drug content (fluctuation < 2.7 %), good powder properties, and improved tabletability.