Phenyl Borate Research Articles

A Transient Iron Carbide Generated by Cyaphide Cleavage.

Despite their potential relevance as molecular models for industrial and biological catalysis, well-defined mononuclear iron carbide complexes are unknown, in part due to the limited number of appropriate C1 synthons. Here, we show the ability of the cyaphide anion (C≡P-) to serve as a C1 source. The high spin (S = 2) cyaphide complex PhB(tBuIm)3Fe-C≡P (PhB(tBuIm)3- = phenyl(tris(3-tert-butylimidazol-2-ylidene)borate) is readily accessed using the new cyaphide transfer reagent [Mg(DippNacNac)(CP)]2 (DippNacNac = CH{C(CH3)N(Dipp)}2 and Dipp = 2,6-di(iso-propyl)phenyl). Phosphorus atom abstraction is effected by the three-coordinate Mo(III) complex Mo(NtBuAr)3 (Ar = 3,5-Me2C6H3), which produces the known phosphide (tBuArN)3Mo≡P along with a transient iron carbide complex PhB(tBuIm)3Fe≡C. Electronic structure calculations reveal that PhB(tBuIm)3Fe≡C adopts a doublet ground state with nonzero spin density on the carbide ligand. While isolation of this complex is thwarted by rapid dimerization to afford the corresponding diiron ethynediyl complex, the carbide can be intercepted by styrene to provide an iron alkylidene.

A novel AIE fluorescent probe for the detection and imaging of hydrogen peroxide in living tumor cells and in vivo

Hydrogen peroxide (H2O2), a key reactive oxygen species (ROS), plays crucial roles in redox signaling pathways and immune responses associated with cell proliferation, differentiation, migration, and disease progression. The selective monitoring of overproduced H2O2 is important for understanding the diagnosis and pathogenesis of diseases such as cardiovascular disease, cancers, diabetes, Parkinson’s disease, Alzheimer’s disease, and inflammation. In this paper, an AIE fluorescent probe BQM-H2O2 was developed by connecting phenyl borate with the fluorophore BQM-PNH for selective detection of H2O2. In the presence of H2O2 at fw = 99% (pH = 7.4, 1% DMSO), the probe BQM-H2O2 could generate strong fluorescent signals due to the oxidation of the borate ester. The probe exhibited high selectivity and a low detection limit toward H2O2 with the calculated LOD of 112.6 nM. Importantly, it was employed in the detection of exogenous and endogenous hydrogen peroxide in 4T1 cells with low cytotoxicity. This probe has also been successfully applied to imaging of H2O2 in Blab/c mice bearing 4T1 graft tumors.

Macrocyclization of Dienes under Confinement with Cationic Tungsten Imido/Oxo Alkylidene N‐Heterocyclic Carbene Complexes

AbstractMacrocyclization reactions are still challenging due to competing oligomerization, which requires the use of small substrate concentrations. Here, the cationic tungsten imido and tungsten oxo alkylidene N‐heterocyclic carbene complexes [[W(N‐2,6‐Cl2‐C6H3)(CHCMe2Ph(OC6F5)(pivalonitrile)(IMes)+ B(ArF)4−] (W1) and [W(O)(CHCMe2Ph(OCMe(CF3)2)(IMes)(CH3CN)+ B(ArF)4−] (W2) (IMes=1,3‐dimesitylimidazol‐2‐ylidene; B(ArF)4−=tetrakis(3,5‐bis(trifluoromethyl)phenyl borate) have been immobilized inside the pores of ordered mesoporous silica (OMS) with pore diameters of 3.3 and 6.8 nm, respectively, using a pore‐selective immobilization protocol. X‐ray absorption spectroscopy of W1@OMS showed that even though the catalyst structure is contracted due to confinement by the mesopores, both the oxidation state and structure of the catalyst stayed intact upon immobilization. Catalytic testing with four differently sized α,ω‐dienes revealed a dramatically increased macrocyclization (MC) and Z‐selectivity of the supported catalysts compared to the homogenous progenitors, allowing high substrate concentrations of 25 mM. With the supported complexes, a maximum increase in MC‐selectivity from 27 to 81 % and in Z‐selectivity from 17 to 34 % was achieved. In general, smaller mesopores exhibited a stronger confinement effect. A comparison of the two supported tungsten‐based catalysts showed that W1@OMS possesses a higher MC‐selectivity, while W2@OMS exhibits a higher Z‐selectivity which can be rationalized by the structures of the catalysts.

Novel spectrofluorometric method utilizing functionalized carbon quantum dots for determining histamine levels in nasal secretions: Implications for allergic rhinitis

Histamine plays a crucial role in regulating various physiological functions and is significantly involved in the development of allergic rhinitis. Accurately measuring histamine levels in nasal secretions can serve as a specific indicator for studying mast cell activation and diagnosing allergic reactions. However, the controversy surrounding histamine levels in nasal secretions during allergenic stimulation suggests potential inaccuracies and imprecision in the analytical methods used, as well as the presence of substances that may interfere with the determination of histamine. In this study, a sensitive and selective spectrofluorometric method was developed using carbon quantum dots (CQDs) derived from beetroot slices, which are non-toxic and eco-friendly materials. These CQDs were functionalized with histamine tetra phenyl borate to determine histamine levels in nasal secretions. Various characterization techniques were employed to confirm the successful synthesis and functionalization of the CQDs. The functionalized CQDs demonstrated enhanced fluorescence and selective interaction with histamine, leading to concentration-dependent fluorescence quenching. The developed method was successfully utilized to compare histamine levels in nasal secretions of healthy individuals and patients with allergic rhinitis. The results showed that the histamine level was significantly higher in patients with allergic rhinitis than in healthy individuals, suggesting a potential association between allergic rhinitis and histamine, (normal vs. patient: 350 ± 20 ng/mL vs. 2520 ± 37 ng/mL, p < 0.05). Furthermore, the proposed spectrofluorometric method exhibited improved linearity range, dynamic range, and detection limit compared to a previously reported spectrophotometric method.

Stimulation-responsive mucoadhesive probiotics for inflammatory bowel disease treatment by scavenging reactive oxygen species and regulating gut microbiota

Inflammatory bowel disease (IBD) is characterized by the high level of reactive oxygen species (ROS) and highly dysfunctional intestinal flora. Here, a stimulation-responsive mucoadhesive probiotic Lac@HDP was rationally constructed for achieving specific adhesion of colitis site and depleting high level of ROS in inflammatory site. Briefly, Lac is Lactobacillus acidophilus, HDP is obtained by hyaluronic acid grafted with dopamine protected by phenylboric acid. Specifically, by consuming a large amount of ROS, phenyl borate group of Lac@HDP is oxidized and fractured, thus exposing the catechol hydroxyl group and obtaining strong mucosal adhesion ability, thereby significantly prolong the retention time of Lac in the inflammatory site. In the murine model of acute and chronic colitis, the stimulation-responsive mucoadhesive probiotics were significantly more effective in alleviating colitis symptoms than antioxidants and probiotics alone. In addition, the abundance and diversity of intestinal flora were increased after treatment with Lac@HDP, which was helpful to alleviate IBD. Importantly, the stimulation-responsive mucoadhesive probiotics have good biological safety in vivo, which provides the prospect of clinical application in the future.

Novel (E)−2-((1-(thiophen-2-yl)ethylidene)-amino) phenol Manganese(II) as an Ionophore Based on Thiocyanate-Selective Electrodes and Its Applications

Novel highly selective potentiometric sensor based on aquadichloro(E)−2-((1-(thiophen-2-yl)ethylidene)-amino)phenol manganese(II)trihydrate as an anion carrier. The thiocayanate electrode displayed a very high selectivity compared with others inorganic anions. Different sensors with plasticized PVC membranes have been investigated. The sensors construction containing different amounts of ionophore with and without additives. The pH over 3.5–6.5 range has been studied. Optimized membrane electrode included 66 mg PVC, 132 mg o-nitrophenyloctylether, 10 mol % tetrakis(trifluoromethyl)phenyl borate and 2% [Mn(C12H11NOS)(Cl2)(H2O)]· 3H2O. The optimized sensors exhibit Nernstian response for thiocyanate through a linear concentration ranging from (5 × 10−8 to 9.06 × 10−1 M) with a detection limit of 3 × 10−8 M and a slope of −57.7 mV decade−1, the measurement carried out in acetate buffer pH 4.7. The response time of electrode <10 s and the lifetime of the sensor more than 6 weeks. The proposed electrode was effectively utilized to estimation of thiocyanate in saliva sample, the results revealed a valid agreement with reference colorimetric method.

Synergistic wound repair effects of a composite hydrogel for delivering tumor-derived vesicles and S-nitrosoglutathione.

Treating chronic wounds requires transition from proinflammatory M1 to anti-inflammatory M2 dominant macrophages. Based on the role of tumor extracellular vesicles (tEVs) in regulating the phenotypic switching from M1 to M2 macrophages, we propose that tEVs may have a beneficial impact on alleviating the overactive inflammatory microenvironment associated with refractory wounds. On the other hand, as a nitric oxide donor, S-nitrosoglutathione (GSNO) can regulate inflammation, promote angiogenesis, enhance matrix deposition, and facilitate wound healing. In this study, a guar gum-based hydrogel with tEVs and GSNO was designed for the treatment of diabetic refractory wounds. This hybrid hydrogel was formed through the phenyl borate bonds, which can automatically disintegrate in response to the high reactive oxygen species (ROS) level at the site of refractory diabetic wounds, releasing tEVs and GSNO. We conducted a comprehensive evaluation of this hydrogel in vitro, which demonstrated excellent performance. Meanwhile, using a full-thickness excision model in diabetic mice, the wounds exposed to the therapeutic hydrogel healed completely within 21 days. The increased closure rate was associated with macrophage polarization and collagen deposition, accelerated fibroblast proliferation, and increased angiogenesis in the regenerating tissues. Therefore, this multifunctional hybrid hydrogel appears to be promising for clinical applications.

Potentiometric determination of mebeverine hydrochloride antispasmodic drug based on molecular docking with different ionophores host-guest inclusion as a theoretical study.

The scientific community has continued to pay particular attention to potentiometric sensors based on ion-selective membrane sensors as an energy-efficient, easy-to-use method suitable for microfabrication. To this end, potentiometric ion-selective sensors were used as an alternative green analytical instrument. Three distinct sensors relying on various ionophores were built and assessed. A cationic exchanger, tetra phenyl borate, was used in the polyvinyl chloride polymeric plasticized matrix using di octyl phthalate, where α, β, and γ cyclodextrins were utilized as ionophores. A comparative potentiometric analysis was carried out using three ion-selective sensor designs: α, β, and γ cyclodextrins sensors. β-Cyclodextrin significantly reduced the detection limit and improved the discriminative performance of mebeverine hydrochloride (MBV) in the pharmaceutical dosage form over α- and γ-cyclodextrins in the presence of other interfering chemicals. Additionally, a significant connection was made between the practical perspective and a theoretical investigation based on computational research. Nernstian potentiometric results for the optimum sensor were obtained for MBV in the range of concentrations 1.0 × 10-2 to 1.0 × 10-6 M, its slope was -58.70 ± 0.12 mV per decade with lower detection limits 4.50 × 10-7 M. This computational molecular docking investigation clarified that the binding sites and modes were in good agreement with the experiment results. This investigation was applied to expect the interaction between MBV and the proposed sensors to ensure which ionophores were the best for MBV.

Synthesis of siloxane nanogel with phenylboronic functional groups

In this work, a siloxane nanogel containing phenyl borate functional groups was obtained consistently by condensation of the sodium salt of methyltriethoxysilane in acetic acid and further functionalization with 4,4,5,5-tetramethyl-2-styryl-1,3,2-dioxaborolane (St-BPin) by hydrosilylation reaction. The obtained nanogel was investigated by NMR and IR spectroscopy, element analysis, and GPC.

Fabrication of Heavy Metal Ion FET Based Sensor for Detecting Arsenite

Arsenic is one of the toxic chemical among heavy metals. It is mostly present in ground waters at higher levels. The long term exposure of food or water to arsenic leads to cancer and heart diseases. Arsenic occurs in two oxidation states, Arsenite (As2O3, As (III)) a trivalent form and Arsenate (As2O5, As (V)) a pentavalent form. As (III) is an inorganic form which is more toxic than As (V). The detection of arsenic ion in drinking water or in any liquid form of food can be done with several laboratory equipments such as ICP-MS. The detection limit of ICP-MS for Arsenic is 0.05μg/L (10^-10M). Though these laboratory methods can be used for detecting the arsenic ion but it is very complex, costly and time consuming. In this research, we developed a methodology for detecting Arsenite ion (As2O3, As (III)). FET based ion sensor is fabricated where the gate pulse is characterized with 1500 μs pulse width and amplitude of 1 V is connected to one electrode. A steady DC bias of 2 V is applied as the drainsource voltage. The Ion Selective Membrane(ISM) is used which is immobilized on the sensing areas. This ISM contains Ionophore, Potassium tetra phenyl borate, Poly vinyl chloride, 2-Nitrophenyl octyl ether and this ISM components mixture is dissolved in Tetrahydrofuran. Sodium Arsenite (NaAsO2) is the inorganic compound which is used for detection of As (III). This solution is dropped on the sensing area which covers both ISM and gate. When Vd is supplied, we temporarily apply Vg of 0V and 1V which causes a change in current level, we define it as gain and is used as our measurement signal. The concentration range from 10^-10 M to 10^-4 M of arsenite ion can be detected. This sensor is easy to fabricate, smaller in size, high sensitivity and takes less time for detecting Arsenite. This FET based ion sensor has same detection limit comparable to ICP-MS and this sensor shows higher sensitivity than the Nernstian slope. The sensing characteristics are not affected by the interfering ions. Figure 1

Fabrication of β cyclodextrin containing AIE-active polymeric composites through formation of dynamic phenylboronic borate and their theranostic applications

Since the first discovery by Tang in 2001, aggregation-induced emission (AIE) phenomenon has attracted considerable research interest in various fields. In this contribution, AIE-active composites (named as An-HPG-β-CD) have been fabricated via conjugation of AIE-active compound An-B(OH)2 and hyperbranched polyglycerol functionalized β cyclodextrin (HPG-β-CD) based on dynamic phenyl borate for the first time. The potential biomedical applications of these AIE-active composites for biological imaging and drug delivery applications were further explored. The successful preparation of An-HPG-β-CD composites was confirmed through a series of characterization techniques. The An-HPG-β-CD composites possess great water dispersibility, low cytotoxicity, excellent fluorescence properties and uniform size and morphology, which make them promising for cell imaging. Furthermore, the cavities of An-HPG-β-CD composites could be utilized for loading with doxorubicin for drug delivery applications. In conclusion, we have developed a novel method for fabrication of AIE-active An-HPG-β-CD composites through formation of dynamic phenylboronic borate between β cyclodextrin containing hyperbranched polyglycerol and phenylboronic containing AIE dye. These AIE-active composites are of great potential in biological imaging and drug delivery applications.

Ecofriendly Long Life Nanocomposite Sensors for Determination of Carbachol in Presence of Choline: Application in Ophthalmic Solutions and Biological Fluids.

Several emerging nano scale forms of carbon are showing great promise in electrochemical sensing such as graphene and multi-walled carbon nanotubes (MWCNTs). Herein we present an ecofriendly method to fabricate long life and sensitive ion selective sensors based on graphene and MWCNTs nanocomposites with no need for volatile organic solvents. Both sensors were fabricated, for the analysis of carbachol in ophthalmic solutions, plasma and urine where ion- association complex was formed between cationic carbachol and anionic Sodium tetra phenyl borate (NaTBP) in a ratio 1:1. Both sensors were evaluated according to the IUPAC recommendation data, revealing linear response in the concentration range 10−7 M to 10−2 M with near Nernstian slopes 50.80 ± 5 and 58.14 ± 3 mV/decade and correlation coefficients 0.9992 and 0.9998 for graphene and MWCNTs based sensors, respectively. Both sensors were successfully applied as stability indicating method for the analysis of carbachol in presence of its metabolite choline, in ophthalmic preparations, in plasma and urine showing good recovery percentage values. MWCNTs based sensor showed some advantages over graphene sensor regarding lower limit of detection (LOD), longer life time and higher selectivity towards carbachol. Statistical comparison of the proposed sensors with the official method showed no significant difference for accuracy and precision.

Peroxynitrite Activatable NIR-II Fluorescent Molecular Probe for Drug-Induced Hepatotoxicity Monitoring.

Drug-induced hepatotoxicity represents an important challenge for safety in drug development. The production of peroxynitrite (ONOO-) is proposed as an early sign in the progression of drug-induced hepatotoxicity. Currently, reported ONOO- probes mainly emit in the visible range or the first NIR window, which have limited in vivo biosensing application due to the autofluorescence and photon scattering. Herein, we developed a peroxynitrite activatable second near-infrared window (NIR-II) molecular probe for drug-induced hepatotoxicity monitoring, based on the fusion of an NIR-II fluorescence turn-on benzothiopyrylium cyanines skeleton and the phenyl borate. In the presence of ONOO-, the probe IRBTP-B can turn on its NIR-II fluorescence by yielding its fluorophore IRBTP-O and display good linear response to ONOO-. Tissue phantom study confirmed reliable activated signals could be acquired at a penetration depth up to 5 mm. Using this probe, we disclose the upregulation of ONOO- in a preclinical drug-induced liver injury model and the remediation with N-acetyl cysteine (NAC) in vivo. We expect that this strategy will serve as a general method for the development of an activatable NIR-II probe based on the hydroxyl functionalized reactive sites by analyte-specific triggering.

Seventeen-electron chromium(i)tricarbonyltris(phosphine) complexes supported by tris(phosphinomethyl)phenylborates.

The inaugural crystallographic characterization of chromium(i)tricarbonyltris(phosphine) radicals has been achieved. Oxidation of [PPN][Cr(CO)3(PhBP)] (PhBP = [PhB(CH2PPh2)3]-) and analogous Cr(0) complexes featuring 3,5-dimethylphenyl and 3,5-bis(trifluoromethyl)phenyl borate substituents affords charge-neutral Cr(CO)3(PhBP) zwitterions, containing the first fully characterized [Cr(CO)3P3]+ units. The stabilization affected by the intramolecular charge separation established by PhBP ligands dramatically increases the robustness of these seventeen-electron Cr(i) complexes. Previous attempts to isolate salts of mer/fac-[Cr(CO)3P3]+ were frustrated by the thermal instability of these cations. The EPR spectroscopic data of Cr(CO)3(PhBP) supports Rieger's hypothesized low temperature preparation of fac-[Cr(CO)3{CH3C(CH2PPh2)3}]+. The robust [Cr(CO)3P3]+ unit of Cr(CO)3(PhBP) motivated the preparation of structurally characterized Cr(0)/Cr(i) (Cr(CO)3{η6-(PhBP)Cr(CO)3}, Cr(CO)3{η6-(((3,5-CH3)C6H3)BP)Cr(CO)3}) and W(0)/Cr(i) (W(CO)3{η6-(((3,5-CH3)C6H3)BP)Cr(CO)3}) complexes. While these bimetallics feature classical κ3-phosphine and η6-arene metal-binding, they are noteworthy since all other reported mixed-valent Cr(0)/Cr(i) complexes exhibit (a) significant thermal instability that has precluded their isolation and (b) greater uncertainty regarding the presence of distinct Cr(i) and Cr(0) centers. This work illustrates the utility of tris(phosphino)borates for the stabilization of cationic metal fragments within zwitterions that are inaccessible or difficult to characterize independently.

Facile fabrication of luminescent hyaluronic acid with aggregation-induced emission through formation of dynamic bonds and their theranostic applications

Aggregation-induced emission (AIE) is an abnormal phenomenon, which has been extensively explored for various applications. Taken advantage of the unique AIE feature, a number of luminescent nanoprobes with strong fluorescence intensity could thus be fabricated through different strategies; however, the fabrication of AIE-active carbohydrate polymers is still challenge owing to the poor solubility of carbohydrate polymers in most of organic solvents. In this work, a rather facile strategy has been developed for fabricating AIE-active sodium hyaluronate (Sh) through the formation of dynamic phenyl borate between the phenylboronic acid groups of AIE dye (An-B(OH)2)) and Sh in a “one-pot” route. This reaction could occur under low temperature, air atmosphere and in the present water. The physicochemical properties, biocompatibility, biological imaging and drug delivery performance of the final An-Sh fluorescent organic nanoparticles (FNPs) were confirmed by different characterization techniques. Results suggested that An-Sh FNPs possess high water dispersibility, strong fluorescence, and good biocompatibility. These excellent properties make An-Sh FNPs great potential for biological imaging and controlled drug delivery applications. In conclusion, we have developed a facile one-pot strategy for the preparation of AIE-active FNPs through the formation of dynamic bonds in rather mild experimental conditions. The outstanding properties and performance of An-Sh FNPs make them promising candidates for biological imaging and controlled drug delivery applications.

PVC membrane, coated-wire, and carbon-paste ion-selective electrodes for potentiometric determination of galantamine hydrobromide in physiological fluids

We report on highly-sensitive ion-selective electrodes (ISEs) for potentiometric determining of galantamine hydrobromide (GB) in physiological fluids. Galantamine hydrobromide (GB) was selected for this study due to its previous medical importance for treating Alzheimer's disease. Three different types of ISEs were investigated: PVC membrane electrode (PVCE), carbon-paste electrode (CPE), and coated-wire electrode (CWE). In the construction of these electrodes, galantaminium–reineckate (GR) ion-pair was used as a sensing species for GB in solutions. The modified carbon-paste electrode (MCPE) was prepared using graphene oxide (MCPE-GO) and sodium tetrakis (trifluoromethyl) phenyl borate (MCPE-STFPB) as ion-exchanger. The potentiometric modified CPEs (MCPE-GO and MCPE-STFPB) show an improved performance in term of Nernstian slope, selectivity, response time, and response stability compared to the unmodified CPE. The prepared electrodes PVCE, CWE, CPE, MCPE-GO and MCPE-STFPB show Nernstian slopes of 59.9, 59.5, 58.1, 58.3 and 57.0 mV/conc. decade, and detection limits of 5.0 × 10−6, 6.3 × 10−6, 8.0 × 10−6, 6.0 × 10−6 and 8.0 × 10−6 mol L−1, respectively. The prepared ISEs also show high selectivity against cations (i.e. Na+, K+, NH4+, Ca2+, Al3+, Fe3+), amino acids (i.e. glycine, L-alanine alanine), and sugars (i.e. fructose, glucose, maltose, lactose). The prepared ISEs are applicable for determining GB in spiked serums, urines, and pharmaceutical preparations, using a standard addition and a direct potentiometric method. The fast response time (<10 s), long lifetime (1–5 weeks), reversibility and stability of the measured signals facilitate the application of these sensors for routine analysis of the real samples.

POTENTIOMETRIC DETERMINATION OF GLYCOPYRRONIUM BROMIDE IN BINARY MIXTURE WITH INDACATEROL MALEATE USING POLYVINYL CHLORIDE (PVC) MEMBRANE, COATED GRAPHITE AND CARBON PASTE SENSORS

A novel approach was conducted in this article for the determination of glycopyrronium bromide (GLY) in binary mixture with indacaterol maleate using ion selective electrodes for its selective determination in pure form and pharmaceutical formulation. Four ion selective electrode sensors were designed for determination of glycopyrronium bromide namely; glycopyrronium bromide-polyvinyl chloride (GLY-PVC) membrane, GLY-Coated graphite sensor and GLY-modified carbon paste sensors. The sensors are based on the ion association complexes of GLY cation with sodium tetra phenyl borate (GLY-TPB) and phosphomolybidic acid (GLY-PMA) counter anions as ion exchange sites using dioctylphthalate (DOP) as plasticizer. Validation of the method shows suitability of the proposed sensors for use in the quality control assessment of GLY and for its routine analysis. The results obtained were statistically compared to reported method and there was no significant difference between the proposed methods and the reported method regarding the accuracy and precision. The method was validated according to International Conference on Harmonization (ICH) guidelines and the results were satisfactory.

Synthesis and application of new surface active poly (ionic liquids) based on 1,3-dialkylimidazolium as demulsifiers for heavy petroleum crude oil emulsions

Application of ionic liquids (ILs) and their polymers (PILs) as green chemicals in the petroleum industry is an original area of the research study. This work aims to synthesize new amphiphilic ILs based on dialkyl substituted imidazolium cations as a head groups combine with acetate and 4-(trifluoromethoxy) phenyl borate anions. Their surface activity and aggregation behaviors, in toluene and aqueous medium, have been investigated by surface tension, particle size distribution and zeta potentials measurements. The sizes of aggregates in water and toluene solvents have been investigated from the dynamic light scattering (DLS) measurements. The demulsification mechanism for the heavy crude oil/water emulsions at low water contents has been estimated from the fluorescent optical microscope in the presence of the prepared ILs and PILs. The demulsification performance of ILs and PILs demulsifiers was found to be considerably improved with incorporation of oxyethylene units into hydrophobic imidazolium cations, and increment the content of 4-(trifluoromethoxy)phenyl borate anions. The results confirmed that the PIL has stronger adsorption for asphaltene molecules facilitated the distortion of the asphaltene protective film that stabilized the water-in-oil emulsion and thus promoting the water droplets coalescence to realize the separation of water from oil.

Ion Transfer Voltammetry at Thin Films Based on Functionalized Cationic [6]Helicenes

AbstractWe describe a new family of molecular ion‐to‐electron redox probes based on cationic diaza, azaoxa, and dioxa [6]helicenes and their derivatives. Their unique structure combines, in a single framework, two privileged families of molecules – helicenes and triaryl methyl carbenium moieties. These cationic [6]helicenes exhibit reversible and reproducible oxidation/reduction behavior and facilitate the ion transfer into thin layer sensing films composed of bis(2‐ethylhexyl)sebacate (DOS), polyurethane (PU), sodium tetrakis 3.5‐bis(trifluoromethyl)phenyl borate, sodium ionophore X and diaza+(C8)2Br2 for cation transfer. Cyclic voltammetry is used to interrogate the thin films. The cationic response can be tuned by adjusting the membrane loading. Addition of lipophilic cation exchanger into the membrane film results in transfer waves of Gaussian shape for cations. A peak separation of 60 mV and peak width of 110 mV are near the theoretical values for a surface confined process. While Nernstian shifts of the peak potentials with analyte concentration is obtained for membranes based on cationic [6]helicenes and doped with sodium‐selective ionophore X, this ionophore was found to promote a gradual loss of redox active species from the ionophore‐based membranes into the sample solution.

Anions for Near-Infrared Selective Organic Salt Photovoltaics

Organic molecular salts are an emerging and highly tunable class of materials for organic and transparent photovoltaics. In this work, we demonstrate novel phenyl borate and carborane-based anions paired with a near-infrared (NIR)-selective heptamethine cation. We further explore the effects of anion structures and functional groups on both device performance and physical properties. Changing the functional groups on the anion significantly alters the open circuit voltage and yields a clear dependence on electron withdrawing groups. Anion exchange is also shown to selectively alter the solubility and film surface energy of the resulting molecular salt, enabling the potential fabrication of solution-deposited cascade or multi-junction devices from orthogonal solvents. This study further expands the catalog and properties of organic salts for inexpensive, and stable NIR-selective molecular salt photovoltaics.