Basic Solvents Research Articles

Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents.

A new long-lived, visible-light-absorbing homoleptic Cu(I) metal-to-ligand charge transfer (MLCT) photosensitizer, [Cu(dchtmp)2]PF6 (dchtmp = 2,9-dicyclohexyl-3,4,7,8-tetramethyl-1,10-phenanthroline), has been synthesized, structurally characterized, and evaluated in terms of its molecular photophysics, electrochemistry, and electronic structure. Static and time-resolved transient absorption (TA) and photoluminescence (PL) spectroscopy measured on the title compound in CH2Cl2 (τ = 2.6 μs, ΦPL = 5.5%), CH3CN (τ = 1.5 μs, ΦPL = 2.6%), and THF (τ = 2.0 μs, ΦPL = 3.7%) yielded impressive photophysical metrics even when dissolved in Lewis basic solvents. The combined static spectroscopic data along with ultrafast TA experiments revealed that the pseudo-Jahn-Teller distortion and intersystem crossing dynamics in the MLCT excited state displayed characteristics of being sterically arrested throughout its evolution. Electrochemical and static PL data illustrate that [Cu(dchtmp)2]PF6 is a potent photoreductant (-1.77 V vs Fc+/0 in CH3CN) equal to or greater than all previously investigated homoleptic Cu(I) diimine complexes. Although we successfully prepared the cyclopentyl analog dcptmp (2,9-dicyclopentyl-3,4,7,8-tetramethyl-1,10-phenanthroline) using the same C-C radical coupling photochemistry as dchtmp, the corresponding Cu(I) complex could not be isolated due to the steric hindrance presented at the metal center. Ultimately, the successful preparation of [Cu(dchtmp)2]+ represents a major step forward for the design and discovery of novel earth-abundant photosensitizers made possible through a newly conceived ligand synthetic strategy.

(Invited) How Does Oxygen Open Up New Horizons at the Interface III-Vs/Liquid Ammonia?

Oxygen is involved in many chemical and electrochemical processes due to its abundance and the difficulty to get rid of it. As a strong oxidizing species, the mechanism of oxygen reduction is significant from both a practical and a fundamental point of view. Depending on the nature of the interface, oxygen can be reduced in aqueous solution either via a two electrons reaction to hydrogen peroxide or a four-electron reaction to water. The electrochemical mechanism is indeed complex considering the large number of electrons involved. As a result, many intermediates are detected. Their chemical nature depends also on the solvent used (pH, stability of radicals...). Among non-aqueous solvents (MeCN, dimethylformamide, dimethyl sulfoxide, pyridine, THF...), liquid ammonia (NH3 liq.) has a unique position.Indeed, in NH3 Liq., the chemical environment is obviously different from water, since their dielectric constants and viscosity coefficients are widely different[1]. Further, at room temperature, ammonia is a very strongly basic solvent (1011 times stronger than water) and a very weak acid (1029 times weaker than water)1. However, there are significant similarities between these two solvents. Both are protic that allows the protonation of oxygen intermediaries. But the strong basicity of NH3 liq avoids the formation of protonated intermediates. Under the atmospheric pressure and low temperature (to –33 ◦C from –78 ◦C), NH3 liq enables to carry out an in-depth study of the oxygen reduction by controlling the pH at many interfaces.In NH3 liq at the dropping mercury electrode, under negative overvoltage, two successive waves from the oxygen reduction were observed[2]. Under illumination and using p-type III-V semiconductors (GaAs and InP), clarification is given on oxygen reaction mechanism. In buffered neutral pH (pH= 16,5 on NH3 scale) a current doubling effect was shown onto p-GaAs an p-InP under illumination[3]. One step is due to photoelectron capture from the conduction band (CB) and another step results from hole injection into the valence band (VB). The first reduction step was monoelectronic and led to the formation of the radical anion superoxide (O2 -). The second step led to the formation of O2 2-. As soon as NH3 liq becomes acidic (pH = 1, on NH3 scale), the current doubling disappeared and it is replaced by a significant decrease of the current in the dark onto p-GaAs. The reduction of oxygen occurs essentially from holes injection in VB. As a consequence, the slope of the Mott/Schottky plots decrease drastically (in the dark) at n- and p-GaAs. When the sample is removed, scratches are observed on GaAs wafers.In acidic aqueous solvent, hydrogen peroxide is produced at the interface with III-V[4]. As a corrosive reactant, H2O2, can be also suggested in acidic NH3 Liq. Is it then possible to monitor the formation of oxide on the III-V in NH3 liq.?[1] J. Jander, Anorganische und allgemeine Chemie in flussigen Ammoniak. Part I, Friedr.;, Vieweg & Sohn, Braunschweig, Germany, 1966.[2] H. A. Laitinen and C. E. Shoemaker, Polarography of Thallium, Copper, Ammonium and Oxygen, J. Am. Soc., 70, 4975 (1950).[3] A-M. Gonçalves, C. Mathieu, M. Herlem, and A. Etcheberry, J. Electroanal. Chem., 462, 88 (1998) [4]J. Jaume, C. Debiemme-Chouvy, J. Vigneron, M. Herlem, E. M. Khoumri, J. L. Sculfort, D. Le Roy, and A. Etcheberry, J. Phys. III Fr., 4, 273 (1994).

Vapochromic Luminescent π-Conjugated Systems with Reversible Coordination-Number Control of Hypervalent Tin(IV)-Fused Azobenzene Complexes.

The dynamic and reversible changes of coordination numbers between five and six in solution and solid states, based on hypervalent tin(IV)-fused azobenzene (TAz) complexes, are reported. It was found that the TAz complexes showed deep-red emission owing to the hypervalent bond composed of an electron-donating three-center four-electron (3c-4e) bond and an electron-accepting nitrogen-tin (N-Sn) coordination. Furthermore, hypsochromic shifts in optical spectra were observed in Lewis basic solvents because of alteration of the coordination number from five to six. In particular, vapochromic luminescence was induced by attachment of dimethyl sulfoxide (DMSO) vapor to the coordination point at the tin atom accompanied with a crystal-crystal phase transition. Additionally, the color-change mechanism and degree of binding constants were well explained by theoretical calculation. To the best of our knowledge, this is the first example of vapochromic luminescence by using stable and variable coordination numbers of hypervalent bonds.

Beneficial properties of solvents and ions for lithium ion and post-lithium ion batteries: Implications from charge transfer models

We study the solvation properties of standard lithium salts in various aprotic apolar solvents using conceptual density functional theory. The electronegativity and the chemical hardness of the species are introduced as reliable criteria for identifying suitable solvent-ion combinations. All salt solvation energies reveal positive values as a consequence of the ion association reaction which implies a tendecy for increased ion pair formation. Our findings reveal that frequently used solvents like propylene carbonate, ethylene carbonate, γ-butyrolactone and dimethoxyethane mainly favor the solvation of the lithium ion due to their nucleophilic and thus Lewis-basic properties. The solvation of standard anions like BF4−, PF6− and BOB− is of minor importance in terms of their contribution to the total solvation energy. Based on the values for the electronegativity and the chemical hardness, we show that the increased tendency towards ion pair formation can be avoided by using more acidic and softer anions in combination with more basic and softer solvents. A variation of the cation does not significantly lower the amount of ion pairs. Our results are in qualitative agreement with recent empirical assumptions and shed more light on the underlying interaction patterns.

Can the Lewis Basicity of an Isolated Solvent Molecule be Used for Characterizing Solvent Effects?

Background: The ubiquitous Lewis acid/base interactions are important in solution processes. Analytical chemistry may benefit from a better understanding of the role of Lewis basicity at the molecular level or acting through a bulk solvent effect. Objective: To delineate (i) the basicity at a molecular level, hereafter referred to as solute basicity, and (ii) the solvent basicity, which is a bulk-liquid property. Methods: The literature that relates Lewis basicity scales and solvent effects is analyzed. A special focus is placed on two extensive scales, the Donor Number, DN, and the BF3 Affinity scale, BF3A, which were obtained by calorimetric measurements on molecules as solutes diluted in a quasi-inert solvent, and therefore define a molecular Lewis basicity. We discuss the validity of these solute scales when regarded as solvent scales, in particular when the basicity of strongly associated liquids is concerned. Results: We demonstrate the drawbacks of confusing the Lewis basicity of a solvent molecule, isolated as a solute, and that of the bulk liquid solvent itself. Conclusion: Consequently, we recommend a reasoned use of the concept of Lewis basicity taking clearly into account the specificity of the process for which a Lewis basicity effect may be invoked. In particular, the action of the Lewis base, either as an isolated entity or as a bulk liquid, must be distinguished.

Selection of Mixed Amines in the CO2 Capture Process

In order to select the best mixed amines in the CO2 capture process, the absorption of CO2 in mixed amines was explored at the required concentrations by using monoethanolamine (MEA) as a basic solvent, mixed with diisopropanolamine (DIPA), triethanolamine (TEA), 2-amino-2-methyl-1-propanol (AMP), and piperazine (PZ). Here, a bubble column was used as the scrubber, and a continuous operation was adopted. The Taguchi method was used for the experimental design. The conditional factors included the type of mixed amine (A), the ratio of the mixed amines (B), the liquid feed flow (C), the gas-flow rate (D), and the concentration of mixed amines (E). There were four levels, respectively, and a total of 16 experiments. The absorption efficiency (EF), absorption rate (RA), overall mass transfer coefficient (KGa), and scrubbing factor (ϕ) were used as indicators and were determined in a steady-state by the mass balance and two-film models. According to the Taguchi analysis, the importance of the parameters and the optimum conditions were obtained. In terms of the absorption efficiency (EF), the absorption rate (absorption factor) (RA/ϕ), and the overall mass transfer coefficient (KGa), the order of importance is D > E > A > B > C, D > E > C > B > A, and D > E > C > A > B, respectively, and the optimum conditions are A1B4C4D3E3, A1B3C4D4E2, A4B2C3D4E4, and A1B1C1D4E1. The optimum condition validation results showed that the optimal values of EF, RA, and KGa are 100%, 30.69 × 10−4 mol/s·L, 1.540 l/s, and 0.269, respectively. With regard to the selection of mixed amine, it was found that the mixed amine (MEA + AMP) performed the best in the CO2 capture process.

Introduction of a Recyclable Basic Ionic Solvent with Bis-(NHC) Ligand Property and The Possibility of Immobilization on Magnetite for Ligand- and Base-Free Pd-Catalyzed Heck, Suzuki and Sonogashira Cross-Coupling Reactions in Water

A new versatile and recyclable NHC ligand precursor has been developed with ligand, base, and solvent functionalities for the efficient Pd-catalyzed Heck, Suzuki and Sonogashira cross-coupling reactions under mild conditions. Furthermore, NHC ligand precursor was immobilized on magnetite and its catalytic activity was also evaluated towards the coupling reactions as a heterogeneous catalyst. The NHC ligand precursor was prepared with imidazolium functionalization of TCT followed by a simple ion exchange by hydroxide ions. However, the results revealed an excellent catalytic activity for the both homogeneous and heterogeneous catalytic systems. 1.52 g.cm−3 and 1194 cP was obtained for the density and viscosity of the NHC ligand precursor respectively. On the other hand, the heterogeneous type could be readily recovered from the reaction mixture and reused for several times while preserving its properties. Heterogeneous nature of the magnetic catalyst was studied by hot filtration, mercury poisoning, and three-phase tests. High to excellent yields were obtained for all entries for the both homogeneous and heterogeneous catalysts, which reflects the high consistency of the catalyst.

Insights into the charge-transfer character of electronic transitions in RCp2Ti(C2Fc)2 complexes using solvatochromism, resonance Raman spectroscopy, and TDDFT.

A series of complexes with low-energy FeII to TiIV metal-to-metal charge-transfer (MMCT) transitions, Cp2Ti(C2Fc)2, Cp*2Ti(C2Fc)2, and MeOOCCp2Ti(C2Fc)2, was investigated using solvatochromism and resonance Raman spectroscopy (RRS) augmented with time-dependent density functional theory (TDDFT) calculations in order to interrogate the nature of the CT transitions. Computational models were benchmarked against the experimental UV-Vis spectra and B3LYP/6-31G(d) was found to most faithfully represent the spectra. The energy of the MMCT transition was measured in 15 different solvents and a multivariate fit to the Catalán solvent parameters - solvent polarizability (SP), solvent dipolarity (SdP), solvent basicity (SB), and solvent acidity (SA) - was performed. The effect of SP indicates a greater degree of electron delocalization in the excited state (ES) than the ground state (GS). The small negative solvatochromism with respect to SdP indicates a smaller dipole moment in the ES than the GS. The effect of SB is consistent with charge-transfer to Ti. Upon excitation into the MMCT absorption band, the RRS data show enhancement of the alkyne stretching modes and of the out-of-plane bending modes of the cyclopentadienyl ring connected to Fe and the alkyne bridge. This is consistent with changes in the oxidation states of Ti and Fe, respectively. The higher-energy transitions (350-450 nm) show enhancement of vibrational modes consistent with ethnylcyclopentadienyl to Ti ligand-to-metal charge transfer (LMCT). The RRS data is consistent with the TDDFT predicted character of these transitions. TDDFT suggests that the lowest-energy transition in Cp2Ti(C2Fc)2CuI, where CuI is coordinated between the alkynes, retains its FeII to TiIV MMCT character, in agreement with the RRS data, but that the lowest-energy transitions have significant CuI to Ti character. For Cp2Ti(C2Fc)2CuI, excitation into the low-energy MMCT absorption band results in selective enhancement of the symmetric alkynyl stretching mode.

Oxidation of the acridine by peroxy acids in various organic solvents

The rate of oxidation reaction of the acridine with peroxy acids in various organic solvents was studied. It has been found the effective rate constants ( k ) and the activation energy ( E a ) of studied process. The rate of oxidation acridine does not depend on the nature of peroxy acid. Between the parameters of the transition state Δ Н ≠ and Δ Ѕ ≠ is some linear relationship, indicating on the presence of the counteraction effect in our series of experiments. The rate of oxidation and activation energy inflation of solvation peroxy acid and acridine was calculated. The reaction medium affects the rate of oxidation. Correlation equations between the rate constants of the reactions in study and the physicochemical parameters of the solvents were proposed. The correlation equation for effective rate constants and the basic physicochemical parameters of solvents at 318 K has the form: lg k =4,37169+ (14,7818 ±1,9305 ) f ( n ) - (3,4465 ±0,6137) f ( ε ) + + ( 0,0035 ± 0,0005) B - (0,1005 ± 0,0150) E T - ( 0,0488 ± 0.0052 ) V M . N=8; R=0, 9755; S= 0, 0678; F=66,9699. The polarizability, polarization , basicity V M and of solvent have effect on the oxidation process. Correlation equations for effective rate constants for other temperatures are similar. The correlation equation for effective energies ( E a ) of activation and the basic physicochemical parameters of solvents has the form: lgE ак =2,4901+(0,0006 ±0,0001) B - (0,0013 ±0,0002 δ 2 -(0,0058 ±0,0009) V M N=8; R= 0,9984; S=0,0054; F=4909,8110. The basicity, molar volume and Hildebrand's function of solvent have effect on the energy of activation process. The proposed correlation equations relate the parameters of the transition state of the oxidation process and the physic-chemical parameters of solvents. Keywords: acridine, oxidation reaction, peroxy acids, activation energy, correlation equation.

Extending the chemistry of weakly basic ligands: solvates of Ag+ and Cu+ stabilized by [Al{OC(CF3)3}4]- anion as model examples in the screening of useful weakly interacting solvents.

Weakly Coordinating Anions (WCAs) facilitate the formation of exotic "naked" cationic species. However, the feasibility of the respective synthesis approaches may be limited by the basicity of the solvent utilized, as the latter is one of the most important factors determining the solvation ability. In this work, we focus on a series of novel complexes of Ag(i) and Cu(i) with weakly basic ligands such as CH2Cl2, Cl3CCN and SO2 stabilized by perfluorinated alkoxyaluminate, Al[(ORF)4]-, RF = C(CF3)3. The discussion includes their synthesis protocols, crystal structures, vibrational spectra and thermal stability (TGA/DSC/EGA). We show that the Cu-SO2 adducts present exceptional stability in relation to other metal-SO2 complexes. To broaden the scope of weakly basic ligands which could prove helpful in the development of chemistry with WCAs, the screening of potential candidates based on DFT calculations is presented.

Solvent Influence on Selectivity in α-Pinene Oxide Isomerization Using MoO3-Modified Zeolite BETA

Natural source turpentine is an available source of α-pinene oxide. This compound’s value is especially given by the possibility of producing important compounds campholenic aldehyde and trans-carveol. In this work, we would like to present the usage of MoO3-modified zeolite BETA in α-pinene oxide isomerization concerning campholenic aldehyde and trans-carveol formation using a wide range of solvents. Catalyst calcination temperature also influenced the reaction course (selectivity to desired compounds and reaction rate). MoO3-zeolite BETA was prepared by the wet impregnation method and characterized by different techniques. The use of polar aprotic solvents had the most positive effect on the reaction course. Solvent basicity and polarity considerably influenced the reaction rate and selectivity to particular products. The combination of high basicity and the high polarity was the most suitable for the studied reaction from the reaction rate point of view. Selectivity to campholenic aldehyde and trans-carveol was the most influenced by solvent basicity. Higher solvent basicity caused the preferential formation of trans–carveol, influence on selectivity to campholenic aldehyde formation was the opposite. The described catalyst may be used for α-pinene oxide rearrangement to both desired products dependently on the used solvent. Molybdenum offers an exciting alternative for previously described modifications of zeolites for this reaction.

Effective Sample Preparation of Polyphenols in Wine Using Deep Eutectic Solvent‐based Dispersive Liquid–Liquid Microextraction HPLC‐UV Determination

Polyphenols are phytochemicals that exist in grapes and are beneficial to human health. In this study, resveratrol, oxyresveratrol, and piceatannol in wine were extracted by deep eutectic solvent dispersive liquid–liquid microextraction (DES‐DLLME), and a method was established for quantifying these polyphenols by high‐performance liquid chromatography‐UV/Vis (HPLC‐UV/Vis). Several parameters pertaining to sample extraction, clean‐up, and concentration were optimized and verified with central composite design (CCD) using Design Expert 11. The optimized sample preparation parameters are as follows: the DES extraction solvent, tributylmethylammonium chloride/decanoic acid (1:3 M ratio); basic solvent, 1.3 mL of 5% potassium bicarbonate; volume of acetic anhydride, 250 μL; derivatization time, 5 min; dispersive solvent, methanol; ratio of extraction and dispersive solvents, 1:5.5; and salt, 1.0 g. Chromatographic separation by HPLC/UV–Vis was performed on an ACME C18 (4.6 mm id × 150 mm length, 5 μm particle size) column in gradient elution mode using water and 70% methanol. Under the established extraction and HPLC‐UV conditions, the limit of detection (LOD) and limit of quantitation (LOQ) of the three analytes in spiked samples ranged from 1.69 to 2.53 μg/L and 5.64 to 8.42 μg/L, respectively. Recovery studies were performed in low, medium, and high concentration ranges to establish a calibration curve, and the accuracy and precision in the working range were 95.1–108.0% and 1.3–6.7 RSD%, respectively. The calibration curves for quantitative analysis were obtained in the concentration ranges 5.6–56.4, 8.3–82.6, and 8.4–84.2 μg/L, with correlation coefficients (r2) ranging from 0.9947 to 0.9967. The proposed method was applied to the determination of polyphenols in wine samples.

Facile preparation of core-shell Ag@SiO2 nanoparticles and their application in spectrally splitting PV/T systems

Several researchers have demonstrated that plasmonic nanofluids based filters can potentially enhance hybrid solar photovoltaic/thermal (PV/T) systems performance. In this work, we report a facile process for achieving silica-coated silver (Ag) nanoparticles using dimethylamine (DMA) as a basic solvent to induce tetraethyl orthosilicate (TEOS) hydrolysis. Then, the prepared Ag@SiO2 nanoparticles which have a controllable silica shell thickness are suspended in propylene glycol-CoSO4 hybrid fluid. Finally, the characteristics of the PV/T system filtered by the Ag@SiO2/CoSO4-PG nanofluids are evaluated based on the indoor test and photo-thermal conversion model. The results show that the nanoparticles prepared under optimized conditions, i.e., pH value of 8–9, water: ethanol volume ratio of 1:4, temperature of 25 °C, TEOS volume of 0.05 mL, and reaction time of 12 h, exhibit an absorption peak at 474 nm. Further, this study reveals that Ag@SiO2/CoSO4-PG nanofluid filter with concentration of 25.4 mg/L gives a reasonable spectral match with silicon concentrator solar cell according to the measured optical transmittance and the calculated filtering efficiency of 39.3%. The use of 25.4 mg/L Ag@SiO2/CoSO4-PG nanofluid filter produces a higher total efficiency of 63.3% and yields economic value enhancement of 67.8% compared to the PV only system when worth factor (w) is 3.

Reappraisal of Empirical Solvent Polarity Scales for Organic Solvents

AbstractCorrelations of Reichardt'sET(30), the CatalánSdP(solvent dipolarity),SP(solvent polarizability),SA(solvent acidity),SB(solvent basicity), Kamlet‐Taftπ* (dipolarity/polarizability),α(hydrogen bond donating ability) andβ(hydrogen bond accepting ability) polarity parameters with the molar concentration of 161 pure organic solvents are presented. Mostly, linear relationships of the polarity parameter as a function of molar concentration are obtained as long as each individual solvent class is considered separately. A physically different interpretation of theET(30), Kamlet‐Taftπ* andαas well as CatalánSAandSBparameters has been proposed. Furthermore, the Hildebrand solubility parameter in combination with the diffraction index is used for the correlation analysis with the above‐mentioned solvent parameters. It can be concluded that empirical polarity parameters derived from solvatochromic UV/Vis measurements are inherently a function of the molecular structure of the probe.

Calculation of donor numbers: Computational estimates for the Lewis basicity of solvents

Donor numbers are important reference values for classifying the Lewis basicity of solvents. We present a conceptual density functional theory (DFT) formalism for the calculation of Donor numbers in order to overcome experimental challenges. Our results reveal a high degree of agreement with the experimental values for distinct protic and aprotic solvents. With the help of simplified chemical reactions, we examine various levels of approximations and the outcomes reveal that even the simplest approaches provide reasonable results. The proposed theoretical framework allows us to replace time-consuming and challenging experiments and highlights the importance of local molecular interactions.

Equilibrium solubility of 7-amino-4-methylcoumarin in several aqueous co-solvent mixtures revisited: Transfer property, solute-solvent and solvent-solvent interactions and preferential solvation

The preferential solvation analysis was carried out by the inverse Kirkwood–Buff integrals method on available solubility data of 7-amino-4-methylcoumarin in four aqueous co-solvent mixtures of ethylene glycol (EG, 1) + water (2), isopropanol (1) + water (2), ethanol (1) + water (2) and DMF (1) + water (2). Results show that the drug is preferentially surrounded by water in water-rich regions, and by organic solvents in other composition ranges. Among these binary mixtures, the highest preferential solvation magnitude was recorded for isopropanol solutions. Selective solvation of the drug by organic solvents may be owing to the higher basicity of solvents that facilitates interactions with the Lewis acidic groups of 7-amino-4-methylcoumarin. A solvent effect analysis was performed by using the linear solvation energy relationships to unravel the relative importance of solute-solvent and solvent-solvent interactions on the solubility variation. In addition, the transfer properties, e.g. transfer Gibbs free energy (ΔtrGo), transfer enthalpy (ΔtrHo) and transfer entropy (ΔtrSo) were derived in terms of the accessible solubility data, indicating more favorable solubilization ability in the intermediate compositions of co-solvents.

Deep eutectic solvents-assisted synthesis of ZnCo2O4 nanosheets as peroxidase-like nanozyme and its application in colorimetric logic gate

Pyrophosphate (PPi) and pyrophosphatase (PPase) play a significant role in the therapy of arthritic and clinical diagnosis. In this study, we quickly synthesized ZnCo2O4 nanosheets (NSs) with excellent peroxidase catalytic activity in basic deep eutectic solvent (DES). It was found that PPi could inhibit the catalytic capability of ZnCo2O4 NSs transforming colorless o-phenylenediamine (OPD) into yellow oxidized OPD (oxOPD), and the absorbance falls down at 420 nm. However, if PPase was simultaneously present in the system, PPi would be hydrolyzed, leading to the restoration of peroxidase activity of ZnCo2O4 NSs. Therefore, paving a way for colorimetric analysis of PPi as well as PPase. Furthermore, on the basis of above colorimetric assay, an IMPLICATION logic gate was legitimately designed. With the advantages of fast-speed, low-cost and simplification, we firmly believe that our proposed system has a good potential for simple and fast clinic diagnosis of arthritic diseases, even has great significance in the fields of life sciences, environmental measurement and food safety.

The Administration Matrix Modifies the Beneficial Properties of a Probiotic Mix of Bifidobacterium animalis subsp. lactis BB-12 and Lactobacillus acidophilus LA-5.

Consumption of dairy products is one of the most natural ways to introduce probiotics. However, the beneficial effects of the probiotics might depend on the administration form. The aim of this study was to investigate the beneficial properties of two probiotic strains: Bifidobacterium animalis subsp. lactis (BB-12) and Lactobacillus acidophilus (LA-5) in different administration forms (capsules and yogurt). First, in vitro resistance to gastrointestinal condition, surface properties, and immunomodulation capacities were determined. Then, the anti-inflammatory properties of the probiotic strains administrated on yogurt or capsules were tested in a dinitrobenzene sulfonic acid (DNBS)-induced colitis mouse model. The survival rates of BB-12 and LA-5 strains to gastrointestinal conditions were slightly higher when yogurt was used as carrier. They showed most affinity to hexane (no-polar basic solvent) than ethyl-acetate (polar basic solvent). BB-12 showed the higher binding capacity to HT-29, Caco-2, and mucin. Both probiotic candidates suppress the secretion of IL-8 secretion by HT-29-TNF-α stimulated cells. Finally, administration of BB-12 and LA-5 strains improve colitis in mice. They protect against weight loss, inflammation, and hyperpermeability induced by DNBS. However, these anti-inflammatory effects were limited when mice were treated with the probiotic strain on a yogurt matrix. Overall results indicate that BB-12 and LA-5 positive properties are compromised depending on the matrix. Consequently, the selection of an appropriate matrix is an important criterion to conserve the positive benefits of these probiotic strains.

Ir(I)‐Catalyzed Synthesis of (E)‐4‐Benzylidenylacridines and (E)‐2‐Styrylquinoline‐3‐carboxamide through Sequential Suzuki–Miyaura Coupling, Dehydrogenative Friedländer Reaction, and sp3‐C–H Activation

An efficient one‐pot strategy evolved in the synthesis of (E)‐4‐benzylidenylacridin‐1(2H)‐ones, (4 or 9) (E)‐2‐styryl quinoline‐3‐carboxamides (5 or 10) by sequential Suzuki–Miyaura coupling‐dehydrogenative Friedländer‐sp3 C–H activation. The 2‐amino‐5‐chloro benzhydrol 1, aromatic alcohol 2 or 6 ketones 3 or 3', and phenylboronic acid 7 underwent a smooth reaction in a basic deep eutectic solvent consisting of K2CO3 and ethylene glycol (DES‐1,1:1). DES‐1 could enable the Pd‐catalyzed Suzuki coupling reaction of 6, as well as the rapid oxidation of primary, secondary, and Suzuki coupled primary alcohols (2, 1, and 8) in the presence of an iridium catalyst and 1,10‐phenanthroline. The acidic DES‐2 (dimethyl urea/tartaric acid, 7:3) assists the Friedländer annulation and subsequent sp3‐C–H functionalization resulting in (E)‐4‐benzylidenylacridin‐1(2H)‐ones (4 or 9) and (E)‐2‐styryl quinoline‐3‐carboxamides (5 or 10).

Feasibility and the Mechanism of Desorption of Phenolic Compounds from Activated Carbons

The desorption efficiency (DE) of phenols, including p-nitrophenol, p-chlorophenol, p-hydroxybenzoic acid, phenol, and hydroquinone, from activated carbons (ACs), has been investigated with a variety of solvents to gain insight into the feasibility and mechanism of phenols desorption. Ultrasound (US), microwaves (MW), and flow mode have been used to facilitate phenols desorption. It was found that the basicity, polarity, and hydrogen bonds of solvents synergistically affected phenols desorption. The preferred solvents (Lewis basic solvents, acetic acid, and alcohols) gave highly efficient elution. Increasing the alkaline or/and hydrogen bonding interactions, by adding ammonia or urea, enhanced desorption in most solvents. Moreover, although US and MW heating slightly improved desorption, complete desorption was easily achieved in a flow mode. It is demonstrated, herein, that phenols adsorption on the ACs is a reversible physical process, thus proving the feasibility of phenols desorption with proper solvents. Comparison of diffuse reflectance infrared Fourier transform (DRIFT) spectra and porosity property measurements of pristine, loaded, and eluted ACs confirmed our results. It can, therefore, be stated that our procedure can be used to dispose of secondary pollution while cutting post-treatment costs, thanks to the recovery of valuable compounds and AC recycling.