Rice Husk, Brewer's Spent Grain, and Vine Shoot Trimmings as Raw Materials for Sustainable Enzyme Production.

Solid by-products with lignocellulosic structures are considered appropriate substrates for solid-state fermentation (SSF) to produce enzymes with diverse industrial applications. In this work, brewer's spent grain (BSG), rice husk (RH), and vine shoot trimmings (VSTs) were employed as substrates in SSF with Aspergillus niger CECT 2088 to produce cellulases, xylanases, and amylases. The addition of 2% (NH4)2SO4 and 1% K2HPO4 to by-products had a positive effect on enzyme production. Substrate particle size influenced enzyme activity and the overall highest activities were achieved at the largest particle size (10 mm) of BSG and RH and a size of 4 mm for VSTs. Optimal substrate composition was predicted using a simplex centroid mixture design. The highest activities were obtained using 100% BSG for ß-glucosidase (363 U/g) and endo-1,4-ß-glucanase (189 U/g), 87% BSG and 13% RH for xylanase (627 U/g), and 72% BSG and 28% RH for amylase (263 U/g). Besides the optimal values found, mixtures of BSG with RH or VSTs proved to be alternative substrates to BSG alone. These findings demonstrate that SSF bioprocessing of BSG individually or in mixtures with RH and VSTs is an efficient and sustainable strategy to produce enzymes of significant industrial interest within the circular economy guidelines.

Highly efficient grafting of hetero-complementary amidinium and carboxylate hydrogen-bonding/ionic pairs onto polymer surfaces.

We describe a grafting methodology, based on thiol-fluoroarene chemistry, to efficiently incorporate complementary hydrogen-bonding carboxylate and amidinium groups into polymer backbones. The process was optimized both in solution and on the surface of processed films, with the aim to produce materials showing hetero-complementary adhesion.

New Vascular Graft Using the Decellularized Human Chorion Membrane.

The increase of both arterial occlusive diseases and coronary heart diseases leads to a higher demand for small-diameter vascular grafts (<6 mm). The gold standard for small-diameter vessel replacement is the use of autologous veins. Nevertheless, up to 30% of these patients need to use vascular grafts. Although synthetic polymers have been successfully used for the replacement of large-diameter vascular grafts (>6 mm), they are associated with thrombosis, intimal hyperplasia, calcification, and chronic inflammation when used as small-diameter vascular grafts. Therefore, natural materials have been studied for this application. In this study, a decellularized human chorion membrane (dHCM) vascular graft with a 3-4 mm diameter was created. Herein, the biocompatibility of dHCM with endothelial cells was demonstrated in vitro and ex ovo. Blood biocompatibility of dHCM was also shown by studying plasma protein adsorption, platelet adhesion and activation, and its hemolytic potential. Furthermore, dHCM antibacterial properties against Staphylococcus aureus were also studied. In summary, the dHCM reticular layer side presented all the needed characteristics to be used in the inner side of a vascular graft. Additionally, the mechanical properties of the dHCM tubular construct were studied, being similar to the ones of the saphenous vein, the gold standard for autologous small-diameter vessel replacement.

Sorting pain out of salience: assessment of pain facial expressions in the human fetus.

INTRODUCTION: The question of whether the human fetus experiences pain has received substantial attention in recent times. With the advent of high-definition 4-dimensional ultrasound (4D-US), it is possible to record fetal body and facial expressions. OBJECTIVE: To determine whether human fetuses demonstrate discriminative acute behavioral responses to nociceptive input. METHODS: This cross-sectional study included 5 fetuses with diaphragmatic hernia with indication of intrauterine surgery (fetoscopic endoluminal tracheal occlusion) and 8 healthy fetuses, who were scanned with 4D-US in 1 of 3 conditions: (1) acute pain group: Fetuses undergoing intrauterine surgery were assessed in the preoperative period during the anesthetic injection into the thigh; (2) control group at rest: Facial expressions at rest were recorded during scheduled ultrasound examinations; and (3) control group acoustic startle: Fetal facial expressions were recorded during acoustic stimulus (500-4000 Hz; 60-115 dB). RESULTS: Raters blinded to the fetuses' groups scored 65 pictures of fetal facial expressions based on the presence of 12 items (facial movements). Analyses of redundancy and usefulness excluded 5 items for being of low discrimination capacity (P>0.2). The final version of the pain assessment tool consisted of a total of 7 items: brow lowering/eyes squeezed shut/deepening of the nasolabial furrow/open lips/horizontal mouth stretch/vertical mouth stretch/neck deflection. Odd ratios for a facial expression to be detected in acute pain compared with control conditions ranged from 11 (neck deflection) to 1,400 (horizontal mouth stretch). Using the seven-item final tool, we showed that 5 is the cutoff value discriminating pain from nonpainful startle and rest. CONCLUSIONS: This study inaugurates the possibility to study pain responses during the intrauterine life, which may have implications for the postoperative management of pain after intrauterine surgical interventions.

The Parkinson disease pain classification system: results from an international mechanism-based classification approach.

ABSTRACT: Pain is a common nonmotor symptom in patients with Parkinson disease (PD) but the correct diagnosis of the respective cause remains difficult because suitable tools are lacking, so far. We developed a framework to differentiate PD- from non-PD-related pain and classify PD-related pain into 3 groups based on validated mechanistic pain descriptors (nociceptive, neuropathic, or nociplastic), which encompass all the previously described PD pain types. Severity of PD-related pain syndromes was scored by ratings of intensity, frequency, and interference with daily living activities. The PD-Pain Classification System (PD-PCS) was compared with classic pain measures (ie, brief pain inventory and McGill pain questionnaire [MPQ], PDQ-8 quality of life score, MDS-UPDRS scores, and nonmotor symptoms). 159 nondemented PD patients (disease duration 10.2 ± 7.6 years) and 37 healthy controls were recruited in 4 centers. PD-related pain was present in 122 patients (77%), with 24 (15%) suffering one or more syndromes at the same time. PD-related nociceptive, neuropathic, or nociplastic pain was diagnosed in 87 (55%), 25 (16%), or 35 (22%), respectively. Pain unrelated to PD was present in 35 (22%) patients. Overall, PD-PCS severity score significantly correlated with pain's Brief Pain Inventory and MPQ ratings, presence of dyskinesia and motor fluctuations, PDQ-8 scores, depression, and anxiety measures. Moderate intrarater and interrater reliability was observed. The PD-PCS is a valid and reliable tool for differentiating PD-related pain from PD-unrelated pain. It detects and scores mechanistic pain subtypes in a pragmatic and treatment-oriented approach, unifying previous classifications of PD-pain.

Sequencing batch airlift reactors (SBAR): a suitable technology for treatment and valorization of mineral oil wastewaters towards lipids production.

Produced water (PW) and spent oil-based wastewaters are some of the largest mineral oil wastewaters produced. Due to the high toxicity of hydrocarbons, several countries set stringent discharge limits and its treatment is compulsory before discharge. In this work, biological treatment of mineral oil wastewaters coupled with the production of bacterial lipids is demonstrated in sequential batch airlift reactors (SBAR). Two SBAR (2 L working volume) were used for treatment of PW and lubricant-based wastewater (LW), inoculated with Alcanivorax borkumensis SK2 (SBARAb+PW) and Rhodococcus opacus B4 (SBARR.o+LW), respectively. A total petroleum hydrocarbon removal (TPH) efficiency up to 96% and 80% were achieved for SBARAb+PW and SBARR.o+LW, respectively. Intracellular lipids production in SBARAb+PW increased when lower TPH/N ratios and higher feast stage duration were applied (up to 0.74 g g-1 cell dry weight (CDW)), whereas in SBARR.o+LW higher lipids production was observed for higher TPH/N ratios (0.94 g g-1 in CDW). Triacylglycerols (TAG) were the main intracellular lipid accumulated in both SBARAb+PW and SBARR.o+LW operations, while wax ester (WE) production was only observed extracellularly in the SBARAb+PW.

Ion speciation: a key for the understanding of the solution properties of ionic liquid mixtures.

Recently, combinations of two (or more) ionic liquids, known as ionic liquid mixtures, have become popular and have a broad range of applications. However, the fundamental knowledge on the molecular interactions that exist in ionic liquid mixtures is far from being understood. In this work, the experimental measurement of the water activity coefficient and computational modelling using Conductor-like Screening Model for Real Solvent (COSMO-RS) were carried out to get an insight into the molecular interactions that are present in ionic liquid mixtures in aqueous solution. The results show that the combination of two ionic liquids of different basicity in aqueous solution allows fine tuning of the water activities, covering a wide range of values that could replace several pure fluids. This is an important feature resulting from the unexpected ion speciation of the ionic liquid mixtures in aqueous solution.

A Triple Salting-Out Effect is Required for the Formation of Ionic-Liquid-Based Aqueous Multiphase Systems.

Novel aqueous multiphase systems (MuPSs) formed by quaternary mixtures composed of cholinium-based ionic liquids (ILs), polymers, inorganic salts, and water are reported herein. The influence of several ILs, polymers, and salts was studied, demonstrating that a triple salting-out is a required phenomenon to prepare MuPSs. The respective phase diagrams and "tie-surfaces" were determined, followed by the evaluation of the effect of temperature. Finally, the remarkable ability of IL-based MuPSs to selectively separate mixtures of textile dyes is shown.

Toward an Understanding of the Mechanisms behind the Formation of Liquid-liquid Systems formed by Two Ionic Liquids.

Biphasic systems composed of aprotic ionic liquids (ILs) allow the development of new separation processes constituted only by nonvolatile solvents. Six pairs of cholinium- and phosphonium-based ILs were found to be able to form biphasic systems, and the respective liquid-liquid phase diagrams were determined. Although IL anions do not seem to control the phase separation phenomenon, they play an important role in defining the size of the biphasic region. A linear dependence of the ILs mutual solubilities with the IL anions volume was found, supporting the relevance of the entropy of mixing. With the exception of the system formed by ILs with a common anion, the remaining liquid-liquid systems display a significant ion exchange extent between the phases, which inversely depends on the ILs cohesive energy. It is finally shown that four-phase systems with a remarkable performance in the separation of mixtures of dyes can be prepared.

Understanding M-ligand bonding and mer-/fac-isomerism in tris(8-hydroxyquinolinate) metallic complexes.

Tris(8-hydroxyquinolinate) metallic complexes, Mq3, are one of the most important classes of organic semiconductor materials. Herein, the nature of the chemical bond in Mq3 complexes and its implications on their molecular properties were investigated by a combined experimental and computational approach. Various Mq3 complexes, resulting from the alteration of the metal and substitution of the 8-hydroxyquinoline ligand in different positions, were prepared. The mer-/fac-isomerism in Mq3 was explored by FTIR and NMR spectroscopy, evidencing that, irrespective of the substituent, mer- and fac-are the most stable molecular configurations of Al(iii) and In(iii) complexes, respectively. The relative M-ligand bond dissociation energies were evaluated experimentally by electrospray ionization tandem mass spectrometry (ESI-MS-MS), showing a non-monotonous variation along the group (Al > In > Ga). The results reveal a strong covalent character in M-ligand bonding, which allows for through-ligand electron delocalization, and explain the preferred molecular structures of Mq3 complexes as resulting from the interplay between bonding and steric factors. The mer-isomer reduces intraligand repulsions, being preferred for smaller metals, while the fac-isomer is favoured for larger metals where stronger covalent M-ligand bonds can be formed due to more extensive through-ligand conjugation mediated by metal "d" orbitals.

Diarylferrocene tweezers for cation binding.

The host-guest chemistry of ferrocene derivatives was explored by a combined experimental and theoretical study. Several 1-arylferrocenes and 1,1'-diarylferrocenes were synthesized by the Suzuki-Miyaura cross-coupling reaction. The ability of these compounds to bind small cations in the gas phase was investigated experimentally by electrospray ionization mass spectrometry (ESI-MS). The results evidenced a noticeable ability of all 1,1'-diarylferrocenes studied to bind cations, while the same was not observed for the corresponding 1-arylferrocenes nor ferrocene. The 1,1'-diarylferrocenecation relative interaction energies were evaluated by ESI-MS and quantum chemical calculations and showed that cation binding in these systems follows electrostatic trends. It was found that, due to their unique molecular shape and smooth torsional potentials, 1,1'-diarylferrocenes can act as molecular tweezers of small-sized cations in the gas phase.

From polymer latexes to multifunctional liquid marbles.

A simple method to prepare multifunctional liquid marbles and dry water with magnetic, color, and fluorescent properties is presented. Multifunctional liquid marbles were prepared by encapsulation of water droplets using flocculated polymer latexes. First, the emulsion polymerization reaction of polystyrene and poly(benzyl methacrylate) was carried out using cheap and commercially available cationic surfactants. Subsequently, flocculation of the latex was provoked by an anion-exchange reaction of the cationic surfactant by the addition of lithium bis(trifluoromethanesulfonyl)imide salt. The flocculated polymer latex was filtered and dried, leading to very hydrophobic micronanoparticulated powders. These powders showed a great ability to stabilize the air/water interface. Stable liquid marbles were obtained by rolling water droplets onto the hydrophobic powders previously prepared. The use of very small polystyrene nanoparticles led us to the preparation of very stable and the biggest known liquid marbles up to 2.5 mL of water. Furthermore, the introduction of fluorescent comonomer dyes into the polymer powders allowed us to obtain new morphological images and new knowledge about the structure of liquid marbles by confocal microscopy. Furthermore, the introduction of magnetic nanoparticles into the polymer latex led to magnetic responsive liquid marbles, where the iron oxide nanoparticles are protected within a polymer. Altogether this method represents an accessible and general platform for the preparation of multifunctional liquid marbles and dry water, which may contribute to extending of their actual range of applications.

Novel 2-alkyl-1-ethylpyridinium ionic liquids: synthesis, dissociation energies and volatility.

This work presents the synthesis, volatility study and electrospray ionization mass spectrometry with energy-variable collision induced dissociation of the isolated [(cation)2(anion)](+) of a novel series of 2-alkyl-1-ethyl pyridinium based ionic liquids, [(2)CN-2(1)C2Py][NTf2]. Compared to the imidazolium based ionic liquids, the new ionic liquid series presents a higher thermal stability and lower volatility. The [(cation)2(anion)](+) collision induced dissociation energies of both [(2)CN-2(1)C2Py][NTf2] and [CNPy][NTf2] pyridinium series show an identical trend with a pronounced decrease of the relative cation-anion interaction energy towards an almost constant value for N = 6. It was found that the lower volatility of [(2)CN-2(1)C2Py][NTf2] with a shorter alkyl chain length is due to its higher enthalpy of vaporization. Starting from [(2)C3(1)C2Py][NTf2], the lower volatility is governed by the combination of slightly lower entropies and higher enthalpies of vaporization, an indication of a higher structural disorder of the pyridinium based ionic liquids than the imidazolium based ionic liquids. Dissociation energies and volatility trends support the cohesive energy interpretation model based on the overlapping of the electrostatic and van der Waals functional interaction potentials.

Cation alkyl side chain length and symmetry effects on the surface tension of ionic liquids.

Aiming at providing a comprehensive study of the influence of the cation symmetry and alkyl side chain length on the surface tension and surface organization of ionic liquids (ILs), this work addresses the experimental measurements of the surface tension of two extended series of ILs, namely R,R'-dialkylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C(n)C(n)im][NTf2]) and R-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C(n)C(1)im][NTf2]), and their dependence with temperature (from 298 to 343 K). For both series of ILs the surface tension decreases with an increase in the cation side alkyl chain length up to aliphatic chains no longer than hexyl, here labeled as critical alkyl chain length (CACL). For ILs with aliphatic moieties longer than CACL the surface tension displays an almost constant value up to [C12C12im][NTf2] or [C16C1im][NTf2]. These constant values further converge to the surface tension of long chain n-alkanes, indicating that, for sufficiently long alkyl side chains, the surface ordering is strongly dominated by the aliphatic tails present in the IL. The enthalpies and entropies of surface were also derived and the critical temperatures were estimated from the experimental data. The trend of the derived thermodynamic properties highlights the effect of the structural organization of the IL at the surface with visible trend shifts occurring at a well-defined CACL in both symmetric and asymmetric series of ILs. Finally, the structure of a long-alkyl side chain IL at the vacuum-liquid interface was also explored using Molecular Dynamics simulations. In general, it was found that for the symmetric series of ILs, at the outermost polar layers, more cations point one of their aliphatic tails outward and the other inward, relative to the surface, than cations pointing both tails outward. The number of the former, while being the preferred conformation, exceeds the latter by around 75%.

Inclusion complexes of ionic liquids and cyclodextrins: are they formed in the gas phase?

The interaction of imidazolium-based ionic liquids with α- and ß-cyclodextrins was investigated by electrospray ionization mass spectrometry with variable collision induced dissociation energy and quantum chemical gas-phase calculations. The center-of-mass energy at which 50% of a precursor ion decomposes (Ecm,1/2) was determined for the isolated [cyclodextrin + cation](+) or [cyclodextrin + anion](-) adduct ions of imidazolium-based ionic liquids with different alkyl chain lengths combined with a large set of anions, such as chloride, bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, methanesulfonate, dicyanamide, and hydrogensulfate. Moreover, both symmetric and asymmetric imidazolium cationic cores were evaluated. The relative interaction energies in the adduct ions were interpreted in terms of the influence of cation/anion structures and their inherent properties, such as hydrophobicity and hydrogen bond accepting ability, in the complexation process with the cyclodextrins. The trends observed in the mass spectral data together with quantum-chemical calculations suggest that in the gas phase, cations and anions will preferentially interact with the lower or upper rim of the cyclodextrin, respectively, as opposed to what has been reported in condensed phase where the formation of an inclusion complex between ionic liquid and cyclodextrin is assumed.

Evaluation of cation-anion interaction strength in ionic liquids.

Electrospray ionization mass spectrometry with variable collision induced dissociation of the isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) ions of imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ionic liquids (ILs) combined with a large set of anions, such as chloride, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and bis[(trifluoromethyl)sulfonyl]imide, was used to carry out a systematic and comprehensive study on the ionic liquids relative interaction energies. The results are interpreted in terms of main influences derived from the structural characteristics of both anion and cation. On the basis of quantum chemical calculations, the effect of the anion upon the dissociation energies of the ionic liquid pair, and isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) aggregates, were estimated and are in good agreement with the experimental data. Both experimental and computational results indicate an energetic differentiation between the cation and the anion to the ionic pair. Moreover, it was found that the quantum chemical calculations can describe the trend obtained for the electrostatic cation-anion attraction potential. The impact of the cation-anion interaction strengths in the surface tension of ionic liquids is further discussed. The surface tensions dependence on the cation alkyl chain length, and on the anion nature, follows an analogous pattern to that of the relative cation-anion interaction energies determined by mass spectrometry.

Hydrolysis of tetrafluoroborate and hexafluorophosphate counter ions in imidazolium-based ionic liquids.

Controversy behind the postulation that ionic liquids (ILs) are entirely green materials emerged a few years ago. This statement is not always valid, and properties such as toxicity and chemical/thermal stability of ILs should be fully characterized to evaluate their potential use as green solvents. Therefore, in this work, the thermal and chemical decompositions of hexafluorophosphate- and tetrafluoroborate-based ILs in aqueous solutions were evaluated. The experimental conditions employed allowed the study of the possible decomposition of both anions, the effect of the cation side alkyl chain length, the influence of the pH of the aqueous solutions, as well as the temperature influence. Three experimental techniques were employed to fully characterize those anions' stability, electrospray mass spectrometry, nuclear magnetic resonance spectroscopy, and pH measurements of the equilibrium aqueous solutions. The results noticeably indicate that it is suitable to use aqueous solutions of hexafluorophosphate-based ILs at moderate temperatures while acidic conditions promote the anion hydrolysis, even at low temperatures. On the other hand, the tetrafluoroborate-based ILs are not water-stable compounds since they hydrolyze under all of the conditions tested and the hydrolysis extent is markedly dependent on the temperature.

Gas-phase dissociation of ionic liquid aggregates studied by electrospray ionisation mass spectrometry and energy-variable collision induced dissociation.

Positive singly charged ionic liquid aggregates [(C(n)mim)(m+1)(BF(4))(m)](+) (mim = 3-methylimidazolium; n = 2, 4, 8 and 10) and [(C(4)mim)(m+1)(A)(m)](+) (A = Cl(-), BF(4) (-), PF(6) (-), CF(3)SO(3) (-) and (CF(3)SO(2))(2)N(-)) were investigated by electrospray ionisation mass spectrometry and energy-variable collision induced dissociation. The electrospray ionisation mass spectra (ESI-MS) showed the formation of an aggregate with extra stability for m = 4 for all the ionic liquids with the exception of [C(4)mim][CF(3)SO(3)]. ESI-MS-MS and breakdown curves of aggregate ions showed that their dissociation occurred by loss of neutral species ([C(n)mim][A])(a) with a >or= 1. Variable-energy collision induced dissociation of each aggregate from m = 1 to m = 8 for all the ionic liquids studied enabled the determination of E(cm, 1/2) values, whose variation with m showed that the monomers were always kinetically much more stable than the larger aggregates, independently of the nature of cation and anion. The centre-of-mass energy values correlate well with literature data on ionic volumes and interaction and hydrogen bond energies.

Mutual solubilities of water and hydrophobic ionic liquids.

The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties that produces increasing interest in the research of these fluids as environmentally friendly "neoteric" solvents. One of the main research fields is their exploitation as solvents for liquid-liquid extractions, but although ILs cannot vaporize leading to air pollution, they present non-negligible miscibility with water that may be the cause of some environmental aquatic risks. It is thus important to know the mutual solubilities between ILs and water before their industrial applications. In this work, the mutual solubilities of hydrophobic yet hygroscopic imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ILs in combination with the anions bis(trifluoromethylsulfonyl)imide, hexafluorophosphate, and tricyanomethane with water were measured between 288.15 and 318.15 K. The effect of the ILs structural combinations, as well as the influence of several factors, namely cation side alkyl chain length, the number of cation substitutions, the cation family, and the anion identity in these mutual solubilities are analyzed and discussed. The hydrophobicity of the anions increases in the order [C(CN)(3)] < [PF(6)] < [Tf(2)N] while the hydrophobicity of the cations increases from [C(n)mim] < [C(n)mpy] < or = [C(n)mpyr] < [C(n)mpip] and with the alkyl chain length increase. From experimental measurements of the temperature dependence of ionic liquid solubilities in water, the thermodynamic molar functions of solution, such as Gibbs energy, enthalpy, and entropy at infinite dilution were determined, showing that the solubility of these ILs in water is entropically driven and that the anion solvation at the IL-rich phase controls their solubilities in water. The COSMO-RS, a predictive method based on unimolecular quantum chemistry calculations, was also evaluated for the description of the water-IL binary systems studied, where it showed to be capable of providing an acceptable qualitative agreement with the experimental data.

Surface tensions of imidazolium based ionic liquids: anion, cation, temperature and water effect.

This work addresses the experimental measurements of the surface tension of eight imidazolium based ionic liquids (ILs) and their dependence with the temperature (288-353 K) and water content. The set of selected ionic liquids was chosen to provide a comprehensive study of the influence of the cation alkyl chain length, the number of cation substitutions and the anion on the properties under study. The influence of water content in the surface tension was studied for several ILs as a function of the temperature as well as a function of water mole fraction, for the most hydrophobic IL investigated, [omim][PF(6)], and one of the more hygroscopic IL, [bmim][PF(6)]. The surface thermodynamic functions such as surface entropy and enthalpy were derived from the temperature dependence of the surface tension values.