Low Vapor Pressure Solvents for Single-Molecule Junction Measurements.

Nonpolar solvents commonly used in scanning tunneling microscope-based break junction measurements exhibit hazards and relatively low boiling points (bp) that limit the scope of solution experiments at elevated temperatures. Here we show that low toxicity, ultrahigh bp solvents such as bis(2-ethylhexyl) adipate (bp = 417 °C) and squalane (457 °C) can be used to probe molecular junctions at ≥100 °C. With these, we extend solvent- and temperature-dependent conductance trends for junction components such as 4,4'-bipyridine and thiomethyl-terminated oligophenylenes and reveal the gold snapback distance is larger at 100 °C due to increased surface atom mobility. We further show the rate of surface transmetalation and homocoupling reactions using phenylboronic acids increases at 100 °C, while junctions comprising anticipated boroxine condensation products form only at room temperature in an anhydrous glovebox atmosphere. Overall, this work demonstrates the utility of low vapor pressure solvents for the comprehensive characterization of junction properties and chemical reactivity at the single-molecule limit.

Temperature-Dependent Rotational Dynamics of Non-Polar Solute in Non-Polar Solvents: Influence of Boundary Conditions.

Rotational dynamics of 3-(benzo[d]thiazol-2-yl)-7-(diethylamino)-2H-chromen-2-one (3BT7D2H-one) non-polar solute in non-polar solvents has been studied by varying temperature to find out how hydrodynamic friction is influenced by solute-size ratio. It has been observed that the rotational dynamics of 3BT7D2H-one follow the Stoke's-Einstein-Debye (SED) model in an n-hexane solvent and it follows the Gierer and Wirtz (GW) model in an n-decane solvent. The probable reason is due to the solute-solvent size ratio which influences boundary conditions parameters and consequently on rotational dynamics of solute.

Preparation of Block Copolymer Self-Assemblies via Pisa in a Non-Polar Medium Based on RCMP.

Polymerization-induced self-assembly (PISA) is conducted in a non-polar medium (n-dodecane) via reversible complexation-mediated polymerization (RCMP). Stearyl methacrylate (SMA) is used to synthesize a macroinitiator, and subsequent block polymerization of benzyl methacrylate (BzMA) from the macroinitiator in n-dodecane afforded a PSMA-PBzMA block copolymer, where PSMA is poly(stearyl methacrylate) and PBzMA is poly(benzyl methacrylate). Because PSMA is soluble but PBzMA is insoluble in n-dodecane, the block copolymer formed a self-assembly during the block polymerization (PISA). Spherical micelles, worms, and vesicles are obtained, depending on the degrees of polymerization of PSMA and PBzMA. "One-pot" PISA is also attained; namely, BzMA is directly added to the reaction mixture of the macroinitiator synthesis, and PISA is conducted in the same pot without purification of the macroinitiator. The spherical micelle and vesicle structures are also fixed using a crosslinkable monomer during PISA. RCMP-PISA is highly attractive as it is odorless and metal-free. The "one-pot" synthesis does not require the purification of the macroinitiator. RCMP-PISA can provide a practical approach to synthesize self-assemblies in non-polar media.

Electrolytic growth of phenyl-modified silica isoporous membrane for non-polar extraction and electrochemical detection of pentachloronitrobenzene.

A phenyl-modified silica isoporous membrane (Ph-SIM) was prepared on the indium-tin-oxide (ITO) electrode using the electrochemically assisted self-assembly (EASA) method. The resulting Ph-SIM preserved vertically ordered nanochannels while exhibiting outstanding hydrophobicity due to the incorporation of phenyl groups within the nanochannels. As a result, the Ph-SIM/ITO sensor exhibited a remarkable affinity for PCNB extraction through hydrophobic interactions, leading to high detection sensitivity. The electrochemical response showed a linear enhancement with the logarithmic concentration of PCNB ranging from 0.1 to 20.0 µM, and the limit of detection was 4.64 nM. Practical results demonstrated that the Ph-SIM/ITO sensor possessed good anti-fouling capability and robust stability, making it a promising candidate for portable detection of non-polar contaminants.

Nonpolar Solvent Modulated Inkjet Printing of Nanoparticle Self-Assembly Morphologies.

Patterning of luminescent nanomaterials is critical in the fields of display and information encryption, and inkjet printing technology have shown remarkable significance with the advantage of fast, large-scalable and integrative. However, inkjet printing nanoparticle deposits with high-resolution and well controlled morphology from nonpolar solvent droplets is still challenging. Herein, a facile approach of nonpolar solvent modulated inkjet printing of nanoparticles self-assembly patterns driven by the shrinkage of the droplet and inner solutal convection is proposed. Through regulating the solvent composition and nanoparticle concentration, multicolor light-emissive upconversion nanoparticle self-assembly microarrays with tunable morphologies are achieved, showing the integration of designable microscale morphologies and photoluminescences for multimodal anti-counterfeit. Furthermore, inkjet printing of nanoparticles self-assembled continuous lines with adjustable morphologies by controlling the coalescence and drying of the ink droplets is achieved. The high resolution of inkjet printing microarrays and continuous lines' width < 5 and 10 µm is realized, respectively. This nonpolar solvent-modulated inkjet printing of nanoparticle deposits approach facilitates the patterning and integration of different nanomaterials, and is expected to provide a versatile platform for fabricating advanced devices applied in photonics integration, micro-LED, and near-field display.

Environmental sensitivity of GaN nanofins grown by selective area molecular beam epitaxy.

Nanostructures exhibit a large surface-to-volume ratio, which makes them sensitive to their ambient conditions. In particular, GaN nanowires and nanofins react to their environment as adsorbates influence their (opto-) electronic properties. Charge transfer between the semiconductor surface and adsorbed species changes the surface band bending of the nanostructures, and the adsorbates can alter the rate of non-radiative recombination in GaN. Despite the importance of these interactions with the ambient environment, the detailed adsorption mechanisms are still not fully understood. In this article, we present a systematic study concerning the environmental sensitivity of the electrical conductivity of GaN nanofins. We identify oxygen- and water-based adsorbates to be responsible for a quenching of the electrical current through GaN nanofins due to an increased surface band bending. Complementary contact potential difference measurements in controlled atmospheres on bulkm- andc-plane GaN reveal additional complexity with regard to water adsorption, for which surface dipoles might play an important role besides an increased surface depletion width. The sensitive reaction of the electrical parameters to the environment and surface condition underlines the necessity of a reproducible pre-treatment and/or surface passivation. The presented results help to further understand the complex adsorption mechanisms at GaN surfaces. Due to the sensitivity of the nanofin conductivity on the environment, such structures could perform well as sensing devices.

Demonstration of Solute-specific Synergism in Binary Solvents.

The structure and solvation behavior of binary liquid mixtures of Methanol (MeOH) and N, N-Dimethylformamide (DMF) are explored by ascertaining their intermolecular interactions with either Rhodamine-B (RhB) or Rhodamine101 (Rh101) dye through steady-state absorption, emission, and two-photon induced fluorescence. Specifically, in the present investigation, we examine the strong synergistic solvation observed for the combinations of hydrogen bond donating (MeOH) and accepting (DMF) solvent pairs. Solvatochromism causes the solvatochromic probe molecules to sense increased polarity compared to their bulk counterparts. The origin of synergism was explained in terms of solute-solvent and solvent-solvent interactions in binary solvent mixtures interactions, as evidenced by probe dependence. The solvation behavior of the Methanol and DMF binary solvent mixture shows strong probe dependence, with Rh101 showing synergism while RhB does not.

The Endless World of Carotenoids-Structural, Chemical and Biological Aspects of Some Rare Carotenoids.

Carotenoids are a large and diverse group of compounds that have been shown to have a wide range of potential health benefits. While some carotenoids have been extensively studied, many others have not received as much attention. Studying the physicochemical properties of carotenoids using electron paramagnetic resonance (EPR) and density functional theory (DFT) helped us understand their chemical structure and how they interact with other molecules in different environments. Ultimately, this can provide insights into their potential biological activity and how they might be used to promote health. In particular, some rare carotenoids, such as sioxanthin, siphonaxanthin and crocin, that are described here contain more functional groups than the conventional carotenoids, or have similar groups but with some situated outside of the rings, such as sapronaxanthin, myxol, deinoxanthin and sarcinaxanthin. By careful design or self-assembly, these rare carotenoids can form multiple H-bonds and coordination bonds in host molecules. The stability, oxidation potentials and antioxidant activity of the carotenoids can be improved in host molecules, and the photo-oxidation efficiency of the carotenoids can also be controlled. The photostability of the carotenoids can be increased if the carotenoids are embedded in a nonpolar environment when no bonds are formed. In addition, the application of nanosized supramolecular systems for carotenoid delivery can improve the stability and biological activity of rare carotenoids.

Recent Advances in Polymerization-Induced Self-Assembly (PISA) Syntheses in Non-Polar Media.

It is well-known that polymerization-induced self-assembly (PISA) is a powerful and highly versatile technique for the rational synthesis of colloidal dispersions of diblock copolymer nanoparticles, including spheres, worms or vesicles. PISA can be conducted in water, polar solvents or non-polar media. In principle, the latter formulations offer a wide range of potential commercial applications. However, there has been just one review focused on PISA syntheses in non-polar media and this prior article was published in 2016. The purpose of the current review article is to summarize the various advances that have been reported since then. In particular, PISA syntheses conducted using reversible addition-fragmentation chain-transfer (RAFT) polymerization in various n-alkanes, poly(α-olefins), mineral oil, low-viscosity silicone oils or supercritical CO2 are discussed in detail. Selected formulations exhibit thermally induced worm-to-sphere or vesicle-to-worm morphological transitions and the rheological properties of various examples of worm gels in non-polar media are summarized. Finally, visible absorption spectroscopy and small-angle X-ray scattering (SAXS) enable in situ monitoring of nanoparticle formation, while small-angle neutron scattering (SANS) can be used to examine micelle fusion/fission and chain exchange mechanisms.

Diversity and Biological Activities of Endophytic Fungi from the Flowers of the Medicinal Plant Vernonia anthelmintica.

Secondary metabolites produced by endophytic fungi are an important source of biologically active compounds. The current research was focused on the biological activities of ethyl acetate extracts of fungi, isolated and identified from Vernonia anthelmintica flowers for the first time. In addition, an investigation of the non-polar chemical composition of dichloromethane-ethyl acetate extracts of the most active fungal strain was carried out. The isolates included Ovatospora senegalensis NR-03, Chaetomium globosum NR-04, Thielavia subthermophila NR-06, Aspergillus calidoustus NR-10, Aspergillus keveii XJF-23 and Aspergillus terreus XJF-3 species. Strains were identified by 18S rRNA gene sequencing methods and were registered in GenBank. Crude extracts of the fungi displayed in vitro biological activities, including antimicrobial and cytotoxic activities. A melanin content assay was performed on murine B16 cells. An ethyl acetate extract of O. senegalensis NR-03 showed high anticancer and antimicrobial activity; therefore, we also studied the non-polar chemical composition of the dichloromethane-ethyl acetate fraction and identified 52 non-polar compounds with the different medium. This investigation discovered that the secondary metabolites of the total extract of endophytic fungi could be a potential source of alternative natural antimicrobial, cytotoxic and melanin synthesis activity in their host plant, and the isolation of bioactive metabolites may provide a lead to new compounds of pharmaceutical significance.

A Metal-Organic Framework with Nonpolar Pore Surfaces for the One-Step Acquisition of C2 H4 from a C2 H4 and C2 H6 Mixture.

Because C2 H4 plays an essential role in the chemical industry, economical and energy-efficient separation of ethylene (C2 H4 ) from ethane (C2 H6 ) is extremely important. With the exception of energy-intensive cryogenic distillation, there are few one-step methods to obtain polymer-grade (≥99.95 % pure) C2 H4 from C2 H4 /C2 H6 mixtures. Here we report a highly stable metal-organic-framework (MOF) FJI-H11-Me(des) (FJI-H=Hong's group in Fujian Institute of Research on the Structure of Matter) which features one-dimensional hexagonal nonpolar pore surfaces constructed by aromatic rings and alkyl groups. This FJI-H11-Me(des) adsorbs C2 H6 rather than C2 H4 between 273 and 303 K. Practical breakthrough experiments with C2 H4 containing 1 % C2 H6 have shown that FJI-H11-Me(des) can realize the acquisition in one-step of polymer-grade, 99.95 % pure C2 H4 under various conditions including different gas flow rates, temperatures and relative humidity.

Electrostatic Stabilization of Nano Liquid Metals in Doped Nonpolar Liquids.

Liquid metals and alloys are attracting renewed attention owing to their potential for application in various advanced technologies. Eutectic gallium-indium (EGaIn) has been focused on in particular because of its integrated advantages of high conductivity, low melting point, and low toxicity. In this study, the colloidal behavior of nano-dispersed EGaIn in nonpolar oils is investigated. Although the nonpolar oil continuous phase is commonly considered to be free of electric charges, electrostatic repulsion appears to be crucial in the colloidal stabilization of the nano-dispersed EGaIn phases, the modulation of which is possible by doping the oil phases with different types of oil-soluble surfactants. The qualitative correlation between the observed colloidal stabilities and the "zero field" particle mobilities inferred from the field-dependent electrophoretic mobilities indicates that the electric charging of EGaIn particles in surfactant-doped nonpolar oils is a static phenomenon that is maintained in equilibrium, rather than a solely field-induced process. A systematic investigation of the charging properties of these unique biphasic particles, consisting of the liquid Ga-In bulk and the solid Ga2 O3 surface that formed spontaneously, reveals the complicated system-dependent nature of the charging mechanisms mediated by ionic and nonionic surfactants in nonpolar media.

Profiling of non-polar lipids in tears of contact lens wearers during the day.

PURPOSE: This study explored whether the non-polar lipids in the human tear fluid lipidome show diurnal variation with and without contact lens wear. It also addressed the relationship between changes in ocular comfort during the day with the level of non-polar lipids. METHODS: Tear samples were collected in the morning and evening with and without contact lenses using fine glass capillary tubes and were analysed by chip-based nano-electrospray ionization tandem mass spectrometric techniques. Tear levels of cholesteryl esters (CE), wax esters (WE) and triacylglycerides (TAG) were quantified. RESULTS: TAG 48:0, 52:0 and WE 26:0/16:0, and 27:0/17:0 increased from morning to evening. TAG 52:2, WE 21:0/16:0, 21:0/18:1 and 28:0/18:1 decreased during the day when no lenses were worn. CE 21:0 was the only non-polar lipid that increased from morning to evening in contact lens wear. WE 21:0/16:0 and 27:0/17:0 were lower in the morning in contact lens wear compared to no lens wear (p ≤ 0.05). The level of non-polar lipids did not correlate with ocular comfort at the end of the day. CONCLUSION: Even though the level of some of non-polar lipid species changed from morning to evening the total level of major tear non-polar lipids remained unchanged during the day with and without contact lens wear. The effect of change in the quantity and structure of lipid species on tear stability and ocular comfort warrants more investigation.

On-chip mass spectrometric analysis in non-polar solvents by liquid beam infrared matrix-assisted laser dispersion/ionization.

By the on-chip integration of a droplet generator in front of an emitter tip, droplets of non-polar solvents are generated in a free jet of an aqueous matrix. When an IR laser irradiates this free liquid jet consisting of water as the continuous phase and the non-polar solvent as the dispersed droplet phase, the solutes in the droplets are ionized. This ionization at atmospheric pressure enables the mass spectrometric analysis of non-polar compounds with the aid of a surrounding aqueous matrix that absorbs IR light. This works both for non-polar solvents such as n-heptane and for water non-miscible solvents like chloroform. In a proof of concept study, this approach is applied to monitor a photooxidation of N-phenyl-1,2,3,4-tetrahydroisoquinoline. By using water as an infrared absorbing matrix, analytes, dissolved in non-polar solvents from reactions carried out on a microchip, can be desorbed and ionized for investigation by mass spectrometry.

Ionization of Volatile Organics and Nonvolatile Biomolecules Directly from a Titanium Slab for Mass Spectrometric Analysis.

Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) and electrospray ionization (ESI)-MS can cover the analysis of analytes from low to high polarities. Thus, an ion source that possesses these two ionization functions is useful. Atmospheric surface-assisted ionization (ASAI), which can be used to ionize polar and nonpolar analytes in vapor, liquid, and solid forms, was demonstrated in this study. The ionization of analytes through APCI or ESI was induced from the surface of a metal substrate such as a titanium slab. ASAI is a contactless approach operated at atmospheric pressure. No electric contacts nor any voltages were required to be applied on the metal substrate during ionization. When placing samples with high vapor pressure in condensed phase underneath a titanium slab close to the inlet of the mass spectrometer, analytes can be readily ionized and detected by the mass spectrometer. Furthermore, a sample droplet (~2 µL) containing high-polarity analytes, including polar organics and biomolecules, was ionized using the titanium slab. One titanium slab is sufficient to induce the ionization of analytes occurring in front of a mass spectrometer applied with a high voltage. Moreover, this ionization method can be used to detect high volatile or polar analytes through APCI-like or ESI-like processes, respectively.

Triple-Knockout, Synuclein-Free Mice Display Compromised Lipid Pattern.

Recent studies have implicated synucleins in several reactions during the biosynthesis of lipids and fatty acids in addition to their recognised role in membrane lipid binding and synaptic functions. These are among aspects of decreased synuclein functions that are still poorly acknowledged especially in regard to pathogenesis in Parkinson's disease. Here, we aimed to add to existing knowledge of synuclein deficiency (i.e., the lack of all three family members), with respect to changes in fatty acids and lipids in plasma, liver, and two brain regions in triple synuclein-knockout (TKO) mice. We describe changes of long-chain polyunsaturated fatty acids (LCPUFA) and palmitic acid in liver and plasma, reduced triacylglycerol (TAG) accumulation in liver and non-esterified fatty acids in plasma of synuclein free mice. In midbrain, we observed counterbalanced changes in the relative concentrations of phosphatidylcholine (PC) and cerebrosides (CER). We also recorded a notable reduction in ethanolamine plasmalogens in the midbrain of synuclein free mice, which is an important finding since the abnormal ether lipid metabolism usually associated with neurological disorders. In summary, our data demonstrates that synuclein deficiency results in alterations of the PUFA synthesis, storage lipid accumulation in the liver, and the reduction of plasmalogens and CER, those polar lipids which are principal compounds of lipid rafts in many tissues. An ablation of all three synuclein family members causes more profound changes in lipid metabolism than changes previously shown to be associated with γ-synuclein deficiency alone. Possible mechanisms by which synuclein deficiency may govern the reported modifications of lipid metabolism in TKO mice are proposed and discussed.

Hydrogen-Bond-Driven Synergistically Enhanced Hyperpolarizability: Chiral Coordination Polymers with Nonpolar Structures Exhibiting Unusually Strong Second-Harmonic Generation.

Four chiral coordination polymers (CPs), M[(S,S)-C14 H14 N2 O6 ] and M[(R,R)-C14 H14 N2 O6 ] (M=Zn or Cd), have been exclusively synthesized in high yields with the aid of newly designed chiral ligand under hydrothermal condition. The CPs crystallizing in the orthorhombic nonpolar space group, C2221 , reveal three-dimensional framework structures composed of MO4 tetrahedra and the corresponding homochiral linkers. Powder second-harmonic generation (SHG) measurements indicate that the nonpolar CPs reveal very strong SHG efficiency of ca. 5-9 times that of KH2 PO4 and exhibit type-I phase-matching behavior. Density functional theory calculations suggest that the unusually large SHG efficiency found from the nonpolar CPs should be attributable to the synergistic effect of polarizable metal cations and enhanced hyperpolarizability in the donor-acceptor system originating from the hydrogen bonding in the coordinated linkers.

Electronic structure variations of polar and nonpolar ZnO lattices with nitrogen-ion bombardment using synchrotron-based in situ photoemission and X-ray absorption spectroscopy.

Surface polarity with different crystal orientations has been demonstrated as a crucial parameter in determining the physical properties and device applications in many transition metal oxide and semiconductor compound systems. The influences of surface polarity on electronic structures in nitrogen-incorporated ZnO lattices have been investigated in the present work. The successful doping of nitrogen atoms in ZnO lattices is suggested by the existence of N-related chemical bonds obtained from X-ray photoelectron spectroscopy analysis where a pronounced N-Zn peak intensity has been observed in the (000\bar 1)-terminated polar ZnO compound compared with the (10\bar 10)-terminated nonpolar ZnO compound. An energy shift of the valence band maximum towards the Fermi level has been resolved for both polar and nonpolar ZnO lattices, whereas a charge redistribution of the O 2p hybridized states is only resolved for o-plane ZnO with a polar surface. Angular-dependent X-ray absorption analyses at the O K-edge reveal enhanced surface-state contributions and asymmetric O 2p orbital occupations in the (000\bar 1)-terminated o-plane ZnO compound. The results shed light on the efficient nitrogen doping in ZnO lattices with polar surfaces. The comprehensive electronic structure investigations of correlations between impurity doping and surface polarity in ZnO lattices may also offer guidance for the material design in other transition metal oxide and semiconductor systems.

Nonaqueous electrophoresis on microchips: A review.

The use of organic solvents as electrolytic medium in electrophoresis has become an important alternative for the analysis of compounds that exhibit low or no solubility in water. In recent years, nonaqueous electrophoresis has been extensively explored in conventional capillary systems for different applications. On the other hand, this separation strategy is still not as popular as free solution electrophoresis on chip-based platforms due to the effects of solvent in the background electrolyte on the sample injection, detection performance, and microfluidic platform compatibility. In this way, this review summarizes the main achievements on nonaqueous microchip electrophoresis (NAME). To the best of our knowledge, this is the first review dedicated to discuss exclusively nonaqueous electrophoresis on chip-based systems. For this purpose, some important theoretical aspects involved when separations are performed in organic medium, such as equilibrium, interactions and electrophoretic considerations, are included in the review. In addition, the main challenges, advantages and influences of nonaqueous media on the sample injection, detection as well as the choice of the substrate to fabricate chip-based electrophoresis devices are highlighted. Last, examples showing the feasibility of nonaqueous microchip electrophoresis for applications exploiting different methodologies, operational, and instrumental conditions are summarized and discussed. We hope this review can be useful to spread the huge potential of nonaqueous electrophoresis on microfluidic platforms.

Two-Photon-Induced Fluorescence Study of Rhodamine-6G Dye in Different Sets of Binary Solvents.

This study deals with the effects of different sets of binary solvents on the Two-Photon Induced Fluorescence (TPIF), a non-linear process, of the Rhodamine-6G (Rh6G) dye, which is a well-known xanthene dye. This work examines the importance of inter-molecular interactions, which results in the modulation of the TPIF of the Rh6G. In this work, we have investigated three binary solvent mixtures representing varying polarity and intermolecular interactions. Specific solvent mixtures used are methanol-water, methanol-dimethyl formamide, and methanol-chloroform. Since the solvent polarity across these binary solvents differs, there are significant intermolecular interactions in the binary mixture solvents, which modulate the two-photon process of Rh6G when irradiated with high-intensity laser light at 780 nm. In our studies, we find that Rh6G in the MeOH-H2O binary solvent has maximum red-shift and minimum intensity as compared to other pairs of binary liquids when the volume fraction of methanol decreases due to more extensive hydrogen bonding between the two components. Additionally, at 1:1 ratio of binary mixtures, Rh6G is found to have the highest TPEACS value for methanol-chloroform binary solvent and reason for that is related to the formation of weak H-bond networks between proton donor chloroform and proton acceptor methanol.