Metal ions confinement defines the architecture of G-quartet, G-quadruplex fibrils and their assembly into nematic tactoids.

G-quadruplex, assembled from a square array of guanine (G) molecules, is an important structure with crucial biological roles in vivo but also a versatile template for ordered functional materials. Although the understanding of G-quadruplex structures is the focus of numerous studies, little is known regarding the control of G-quartet stacking modes and the spontaneous orientation of G-quadruplex fibrils. Here, the effects of different metal ions and their concentrations on stacking modes of G-quartets are elucidated. Monovalent cations (typically K+) facilitate the formation of G-quadruplex hydrogels with both heteropolar and homopolar stacking modes, showing weak mechanical strength. In contrast, divalent metal ions (Ca2+, Sr2+, and Ba2+) at given concentrations can control G-quartet stacking modes and increase the mechanical rigidity of the resulting hydrogels through ionic bridge effects between divalent ions and borate. We show that for Ca2+ and Ba2+ at suitable concentrations, the assembly of G-quadruplexes results in the establishment of a mesoscopic chirality of the fibrils with a regular left-handed twist. Finally, we report the discovery of nematic tactoids self-assembled from G-quadruplex fibrils characterized by homeotropic fibril alignment with respect to the interface. We use the Frank-Oseen elastic energy and the Rapini-Papoular anisotropic surface energy to rationalize two different configurations of the tactoids. These results deepen our understanding of G-quadruplex structures and G-quadruplex fibrils, paving the way for their use in self-assembly and biomaterials.

Self-Assembly of Polystyrene-b-poly(2-vinylpyridine)/Chloroauric Acid at the Liquid/Liquid Interface.

The self-assembly of polystyrene-block-poly(2-vinylpyridine) at the liquid/liquid interface has been systematically investigated to develop a series of primary morphologies of the aggregates. The block copolymers self-assembled into large areas of nanodot arrays, parallel nanostrands, layered films, parallel nanobelts, honeycomb monolayers, and foams by reacting with chloroauric acid, depending on the molecular structure of the block copolymers and the amount of chloroauric acid. The formation of the first four ordered structures resulted from interfacial adsorption and self-assembly, and nucleation and epitaxial growth. The latter two structures were attributed to the water hole templating effect and spontaneous interfacial emulsification, respectively. This work provides insight into the self-assembly behavior of block copolymers at the interface and provides a facile approach for fabricating functional structures.

Large-Area Assembly of Metal-Organic Layered Ultrathin Films at the Liquid/Liquid Interface.

Two-dimensional functional metal-organic frameworks and coordination polymers have attracted much attention and have been successfully prepared in solutions and at interfaces through the coordination of ligands to metal ions. However, the preparation of large-area ultrathin ordered films is still a challenge. Here, a modified liquid/liquid interfacial epitaxial growth method has been developed. A planar liquid/liquid interface between a chloroform solution of bipyridine derivatives and pure water was constructed first, and then an aqueous solution of Eu3+ or Cu2+ ions was added dropwise into the water phase. A layered ultrathin film with the size of several hundreds of square micrometers appeared at the liquid/liquid interface after a certain time. The monitoring results showed that the formation of ultrathin films was a result of continuous epitaxial growth of the adsorbed species due to the synergistic effects of hydrophobic effects of the alkyl chains, coordination bonds between the ligands and metal ions, π-π interactions between the ligands, and the restriction of the interface on the vertical growth. This offers a way to fabricate more large-area thin films of amphiphilic molecules.

Lamellar Nanosheets of Water-Insoluble Amphiphiles via Aqueous Solution and Air/Liquid Interface Self-Assembly.

Two-dimensional (2D) lamellar nanostructures have attracted much interest due to their unique structure and properties. Various fabrication methods have been developed in recent years, including solution self-assembly, exfoliation, and Langmuir monolayer and Langmuir-Blodgett (LB) deposition. In this work, two kinds of facile methods were applied to fabricate lamellar structures of amphiphilic molecules, such as 10,12-pentacosadiynoic acid (PCDA). In method I, the amphiphilic molecules were introduced into aqueous solutions with dimethylformamide (DMF), a solvent miscible with water, through a mass transfer process across a planar liquid/liquid interface; in method II, the DMF solution of the amphiphilic molecules was added directly onto the aqueous solution surface. With the spread and diffusion of DMF, nanosheets with lamellar structures formed in the aqueous solution and at the air/liquid interface, respectively. It is very interesting that the nanosheets obtained through these two methods consist of an even number and odd number of PCDA monolayers, respectively, reflecting different fabrication mechanisms. Method I provides an approach to gently mix organic solutions with aqueous solutions, while method II can be regarded as an extension of the Langmuir monolayer technique, which combines the interfacial assembly with that in solution. These methods have been extended to a series of amphiphilic molecules, and ordered layered structures have been obtained successfully.

A luminescent lyotropic liquid crystal with UV irradiation induced photochromism.

Multicolored photoluminescence induced by UV irradiation in soft materials has invaluable potential in display and detection applications. Here, an ionic liquid (ethylammonium nitrate, EAN)-mediated luminescent lyotropic liquid crystal (LLC) has been fabricated, where an europium complex with two ligands (Eu(DBM)3BQ, DBM = dibenzoylmethane and BQ = 2,2'-biquinoline) was doped. The obtained LLC exhibited enhanced fluorescence intensity and lifetime compared to those of Eu(DBM)3BQ in EAN solution. Interestingly, the luminescent LLC color from the initial red emission of the complex was changed gradually to green when the UV exposure was extended. Though the DBM ligand displayed the typical photo-degradation, the emission intensity of BQ increased drastically. A mechanism based on an UV-induced trans-to-cis isomerization of BQ was proposed to explain such an unusual luminescence phenomenon. Both the experimental and computational results indicated an intra ligand charge transfer (ILCT) accompanied with the BQ isomerization under continuous UV irradiation, which resulted in the enhanced green light emission. The results obtained here are referable for better understanding the interplay between weak interactions and modulation of novel lanthanide-based photochromism systems under UV exposure.

Fabrication of Two-Dimensional Arrays of Diameter-Tunable PS-b-P2VP Nanowires at the Air/Water Interface.

Composite thin films with well-defined and parallel nanowires were fabricated from the binary blends of a diblock copolymer polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) and several homopolystyrenes (h-PSs) at the air/liquid interface through a facile technique, which involves solution self-assembly, interface adsorption, and further self-organization processes. It was confirmed that the nanowires that appeared at the air/water interface came from the cylindrical micelles formed in solution. Interestingly, the diameters of the nanowires are uniform and can be tuned precisely from 45 to 247 nm by incorporating the h-PS molecules into the micellar core. This parallel alignment of the nanowires has potential applications in optical devices and enables the nanowires to be used as templates to prepare functional nanostructures. The extent to which h-PS molecules with different molecular weights are able to influence the diameter control of the nanowires was also systematically investigated.

Influence of gold species (AuCl4(-) and AuCl2(-)) on self-assembly of PS-b-P2VP in solutions and morphology of composite thin films fabricated at the air/liquid interfaces.

Composite thin films doped with Au species were fabricated at an air/liquid interface via a series of steps, including the mass transfer of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) across the liquid/liquid interface between a DMF/CHCl3 solution and an aqueous solution containing either AuCl4(-) or AuCl2(-), self-assembly of PS-b-P2VP in a mixed DMF-water solution, and adsorption and further self-organization of the formed aggregates at the air/liquid interface. This is a new approach for fabricating composite polymer films and can be completed within a very short time. AuCl4(-) and AuCl2(-) ions were found to significantly influence the self-assembly behavior of the block copolymer and the morphologies of the composite films, leading to the formation of nanowire arrays and a foam structure at the air/liquid interface, respectively, which originated from rod-like micelles and microcapsules that had formed in the respective solutions. The effect of the metal complex was analyzed based on the packing parameters of the amphiphilic polymer molecules in different microenvironments and the interactions between the pyridine groups and the metal chloride anions. In addition, these composite thin films exhibited stable and durable performance as heterogeneous catalysts for the hydrogenation of nitroaromatics in aqueous solutions.

Fabrication of composite polymer foam films at the liquid/liquid interface through emulsion-directed assembly and adsorption processes.

The foam films of polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-b-PAA-b-PS) doped with Cd(II) or Pb(II) species were fabricated at the planar liquid/liquid interfaces between a DMF/chloroform (v/v: 1/1) solution of the polymer and aqueous solutions containing cadmium acetate or lead acetate at ambient temperature. Optical microscopic observation shows the thin film is uniform on a larger length scale. Transmission electron microscopic (TEM) investigations reveal that the foam films are made up of microcapsules with the size of several hundreds of nanometers to micrometers. The walls of the microcapsules have a layered structure decorating with nanofibers and hollow nanospheres, where numerous inorganic fine nanoparticles are dispersed homogeneously. The film formation is a result of emulsion droplet-templated assembly and adsorption of the formed microcapsules at the planar liquid/liquid interface. Because of the miscibility of DMF with chloroform and water, DMF migrates to the aqueous phase while water migrates to the organic phase across the interface, resulting in the formation of a W/O emulsion, as revealed by optical microscopic observation, freeze fracture transmission electron microscopic (FF-TEM) observation, and dynamic laser scattering (DLS) investigation. The triblock copolymer molecules and the inorganic species adsorb and self-assemble around the emulsion drops, leading to the formation of the composite microcapsules. X-ray photoelectron spectroscopic (XPS) and FTIR spectroscopic results indicate that two kinds of Cd(II) or Pb(II) species, metal oxide or hydroxide, resulting from the hydrolysis of the metal ions and the coordinated metal ions to the carboxyl groups coexist in the formed thin films, which transform to metal sulfide completely after treating with hydrogen sulfide to get metal sulfide nanoparticle-doped polymer thin films.

Liquid/Liquid interfacial fabrication of thermosensitive and catalytically active Ag nanoparticle-doped block copolymer composite foam films.

An aqueous solution of AgNO3 (upper phase) and a DMF/CHCl3 solution of polystyrene-b-poly(acryl acid)-b-polystyrene (PS-b-PAA-b-PS) or PS-b-PAA-b-PS/1,6-diaminohexane (DAH) (lower phase) constituted a planar liquid/liquid interface. The lower phase gradually transformed to a water-in-oil (W/O) emulsion via spontaneous emulsification due to the "ouzo effect". Polymer molecules, DAH molecules, and Ag(+) ions assembled into microcapsules around emulsion droplets that adsorbed at the planar liquid/liquid interface, resulting in formation of a foam film. DAH acted as a cross-linker during this process. Transmission electron microscopic observations indicated that Ag nanoclusters that were generated through reduction of Ag(+) ions by DMF were homogeneously dispersed in the walls of the foam structure. X-ray photoelectron spectroscopic investigations revealed that Ag(I) and Ag(0) coexisted in the film, and Ag(I) transformed to Ag(0) after further treatment. The film formed without DAH was not stable, while the film formed with DAH was very stable due to intermolecular attraction between PAA and DAH and formation of amides, as revealed by FTIR spectra. The film formed with DAH exhibited high and durable catalytic activity for hydrogenation of nitro compounds and, very interestingly, exhibited thermoresponsive catalytic behavior.

Highly sensitive plasmonic paper substrate fabricated via amphiphilic polymer self-assembly in microdroplet for detection of emerging pharmaceutical pollutants.

We report an innovative and facile approach to fabricating an ultrasensitive plasmonic paper substrate for surface-enhanced Raman spectroscopy (SERS). The approach exploits the self-assembling capability of poly(styrene-b-2-vinyl pyridine) block copolymers to form a thin film at the air-liquid interface within the single microdroplet scale for the first time and the subsequent in situ growth of silver nanoparticles (AgNPs). The concentration of the block copolymer was found to play an essential role in stabilizing the droplets during the mass transfer phase and formation of silver nanoparticles, thus influencing the SERS signals. SEM analysis of the morphology of the plasmonic paper substrates revealed the formation of spherical AgNPs evenly distributed across the surface of the formed copolymer film with a size distribution of 47.5 nm. The resultant enhancement factor was calculated to be 1.2 × 107, and the detection limit of rhodamine 6G was as low as 48.9 pM. The nanohybridized plasmonic paper was successfully applied to detect two emerging pollutants-sildenafil and flibanserin-with LODs as low as 1.48 nM and 3.45 nM, respectively. Thus, this study offers new prospects for designing an affordable and readily available, yet highly sensitive, paper-based SERS substrate with the potential for development as a lab-on-a-chip device.

Effects of polyurethane foam carrier addition on anoxic/aerobic membrane bioreactor (A/O-MBR) for coal gasification wastewater (CGW) treatment: Performance and microbial community structure.

Coal gasification wastewater (CGW) is a typical toxic and refractory industrial wastewater with abundant phenols contained. Two identical anoxic/aerobic membrane bioreactors (with (R2) and without (R1) polyurethane (PU) foam) were carried out in parallel to investigate the role of PU foam addition in enhancing pollutants removal in CGW. Results showed that both systems exhibited effective removal of chemical oxygen demand (>93%) and total phenols (>97%) but poor ammonia nitrogen removal (<35%) constrained by ammonia oxidation process. GC-MS analysis revealed that aromatic and other refractory intermediates were dramatically reduced in R2. Moreover, the PU addition had negligible influence on the total soluble microbial products and extracellular polymeric substances contents but significantly alleviated membrane fouling with the operating time 33% prolonged. Microbial community revealed that Flavobacterium, Holophaga, and Geobacter were enriched on PU. Influent type might be a main driver for microbial community succession.

Occupational stressors, mental health, and sleep difficulty among nurses during the COVID-19 pandemic: The mediating roles of cognitive fusion and cognitive reappraisal.

This study aimed to examine the relationships between occupational stressors, mental health problems, and sleep difficulty, and the mediating roles of cognitive fusion and cognitive reappraisal on the relationships in Chinese nurses. A total of 323 nurses (mean age = 32.11 ± 6.75 years) from 25 hospitals in China participated a cross-sectional online survey. Participants were asked to refer to the period during the severest time of the COVID-19 pandemic in China (January to March 2020) when assessing the psychological variables. The direct links from occupational stressors to cognitive fusion, cognitive reappraisal, mental health and sleep difficulty were significant. Cognitive fusion and cognitive reappraisal mediated the links from occupational stressors to mental health problems, while cognitive fusion and mental health problems mediated the links from occupational stressors to sleep difficulty. The sequential mediation via cognitive fusion and mental health problems as well as via cognitive reappraisal and mental health problems on the links from occupational stressors to sleep difficulty were also significant. Findings from the current study indicate that intervention strategies focusing on the reduction of cognitive fusion and improvement of cognitive reappraisal could help better prepare nurses to alleviate mental health problems and sleep difficulties that are related to COVID-19 and potentially similar pandemics in the future.

One-step synthesis and assembly of two-dimensional arrays of mercury sulfide nanocrystal aggregates at the air/water interface.

Ordered two-dimensional (2D) arrays of ß-HgS nanocrystal aggregates were prepared successfully at the air/water interface through the interfacial reaction between Hg(2+) ions in the subphase and H(2)S in the gaseous phase under the direction of liquid-expanded monolayers of arachidic acid (AA). These 2D arrays are composed of hexagonal or quasi-hexagonal aggregates with the size of several hundreds of nanometers that consist of several tens of HgS nanocrystals with the size of several nanometers. The formed HgS nanocrystals together with AA molecules self-assembled into round aggregates due to the interactions between the species, and the aggregates self-assembled into 2D arrays further due to the attractions between them. During the self-assembly process, the soft round aggregates transformed into hexagonal or quasi-hexagonal ones. The experimental conditions, especially the phase states of the AA monolayers and temperature, have great influences on the formation of the 2D arrays. To the best of our knowledge, this is the first case to get 2D ordered arrays at the air/water interface through a one-step synthesis and assembly process.

A new approach to construct and modulate G-quadruplex by cationic surfactant.

HYPOTHESIS: G-quadruplex structure has raised increasing attention in supramolecular chemistry as an effective template for ordered functional materials. Thus, it is of practical significance to advance our understanding regarding G-quadruplex structures. Typically, G-quadruplex structures are formed in the presence of suitable metal ions. New methods to construct such structures need to be explored. EXPERIMENTS: The supramolecular assembly between CTAB and a guanosine derivative at different molar ratios was systematically studied, including assembly mechanisms, morphology, and macroscopic properties. Cationic surfactants with different alkyl chains were studied as control experiments. FINDINGS: A novel strategy to construct G-quadruplex with the promotion of the cationic surfactant CTAB is presented in this work. The structure-property relationships of G-quadruplex gels are characterized by rheology and shrinkage ratio experiments. MacKintosh's theory was used to rationalize the relationship between gel elasticity and water content. The transition of G-quadruplex structures could be easily enabled by modulating CTAB concentration, which promotes the phase transition from gel/sol biphase to homogeneous sol phase. This work will provide a new viewpoint for the construction and modulation of G-quadruplex structures.

Stable porphyrin vesicles formed in non-aqueous media and dried to produce hollow shells.

Stable vesicles of an amphiphilic manganese complex of 5,10,15,20-tetrakis-4-oxy(2-stearic acid)phenylporphyrin [Mn(iii)TPP(COOH)] were formed in non-aqueous solution (CHCl(3) + CH(3)OH, 4 : 1 v/v); the vesicles can be dried to produce hollow shells.

Fabricating highly catalytically active block copolymer/metal nanoparticle microstructures at the liquid/liquid interface.

HYPOTHESIS: Our previous studies have shown that the metal nanoparticle/polymer composite structures fabricated at the liquid/liquid interface have good reusability but lower catalytic activity for heterogeneous reactions in aqueous solutions. This should be attributed to the poor water wettability and more compact structure of the polymer matrices. Therefore, it should be possible to improve the catalytic activity through designing and fabricating a porous composite structure with good water wettability. EXPERIMENTS: A modified liquid/liquid interface adsorption and fabrication method was used. An aqueous solution of copper acetate and a chloroform/DMF mixed solution of PS-b-PAA acted as the two phases. Through spontaneous emulsification, self-assembly of the polymer molecules with Cu2+ ions in the droplets, and adsorption of the formed spherical micelles and nanofibers to the planar liquid/liquid interface, a porous composite microstructure was formed. FINDINGS: This structure consisted of nanofiber-connected nanospheres which have a PS core and a PAA corona. Tiny and well-dispersed Cu nanoparticles were embedded in the hydrophilic corona and were adsorbed on the nanofibers surface as well. After physical cross-linking with 1,6-diaminohexane, the composite material exhibited high catalytic activity and good reusability for the reactions in aqueous solutions. For example, the rate constant for the reduction of p-nitroaniline reached 1965 s-1 g-1.

Highly selective and sensitive fluorogenic ferric probes based on aggregation-enhanced emission with -SiMe3 substituted polybenzene.

In this study, thiophene was linked to polybenzene to generate novel fluorescent probes, namely 3,4-diphenyl-2,5-di(2-thienyl)phenyl-trimethylsilane (DPTB-TMS) with a -SiMe3 substituent and 3,4-diphenyl-2,5-di(2-thienyl)phenyl (DPTB) without the -SiMe3 substituent, respectively. Both of the two compounds exhibit aggregation-enhanced emission (AEE) properties in tetrahydrofuran/water mixtures due to restricted intramolecular rotation of the peripheral groups, which make the two compounds good candidates for the detection of Fe3+ ions in aqueous-based solutions. The fluorescence intensity of the two compounds decreases immediately and obviously upon addition of a trace amount of Fe3+, and decreases continuously as the amount of Fe3+ increases. The fluorescence was quenched to 92% of its initial intensity when the amount of Fe3+ ions reached 6µmol for DPTB-TMS and to 80% for DPTB in the systems, indicating that the compound with the -SiMe3 group is a more effective probe. The detection limit was found to be 1.17µM (65ppb). The detection mechanism is proposed to be static quenching. DPTB-TMS is highly efficient for the detection of ferric ions even in the presence of other metal ions. In addition, the method is also successfully applied to the detection of ferric ions in water, blood serum, or solid films. This indicates that these polybenzene compounds can be applied as low-cost, high selectivity, and high efficiency Fe3+ probes in water or in clinical applications.

Synthesis of one-dimensional silver oxide nanoparticle arrays and silver nanorods templated by Langmuir monolayers.

One-dimensional (1D) silver oxide nanoparticle arrays were synthesized by illuminating the composite Langmuir-Blodgett monolayers of porphyrin derivatives/Ag(+) and n-hexadecyl dihydrogen phosphate (n-HDP)/Ag(+) deposited on carbon-coated copper grids with daylight and then exposing them to air. Transmission electron microscopy (TEM) observation shows that the nanoparticle size is around 3 nm, with the separation of about 2-3 nm. High-resolution TEM (HRTEM) investigation indicates that the particles are made up of Ag(2)O. Ag nanorods with the width of 15-35 nm and the length of several hundreds of nanometers were synthesized by irradiating the composite Langmuir monolayers of porphyrin derivatives/Ag(+) and n-HDP/Ag(+) by UV-light directly at the air/water interface at room temperature. HRTEM image and selected-area electron diffraction (SAED) pattern indicate that the nanorods are single crystals with the (110) face of the face-centered cubic (fcc) silver parallel to the air/water interface. The formation of the 1D arrays and the nanorods should be attributed to the templating effect of the linear supramolecules formed by porphyrin derivative or n-HDP molecules in Langmuir monolayers through non-covalent interactions.

Metal-cation-mediated nanocrystal arrays of sandwich-type (phthalocyaninato) [tetrakis(4-pyridyl)porphyrinato] cerium complex formed at the water-chloroform interface.

Regular square, wirelike, quadrate, and rodlike nanocrystal arrays of Cd2+, Hg2+, or Ag+ metal-cation-mediated sandwich-type mixed (phthalocyaninato) [5,10,15,20-tetrakis(4-pyridyl)poprhyrinato] cerium(III) double-decker complex Ce(Pc)(TPyP) have been successfully prepared at the water-chloroform interface. The nanocrystal growth processes were monitored by transmission electron microscopy (TEM), which reveals that different morphologies of nanocrystals have been fabricated from double-decker molecules connected by different kinds of metal cations, forming coordination polymers. These nanoscaled coordination polymers were characterized by FT-IR spectra and energy-dispersive X-ray spectra (EDS). EDS results clearly revealed the elements of the nanocrystals and the FT-IR spectra give evidence for the coordination interaction between the double-decker molecules and metal cations. The UV-vis absorption spectrum indicates the formation of J-aggregates of the double-decker molecules in the nanocrystals formed.

Two-dimensional "nano-ring and nano-crystal" morphologies in Langmuir monolayer of phthalocyaninato nickel complexes.

Three 1,8,15,22-tetrasubstituted phthalocyaninato nickel complexes Ni[Pc(alpha-OR)(4)] [H(2)Pc(alpha-OC(5)H(11))(4) = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine; H(2)Pc(alpha-OC(7)H(15))(4) = 1,8,15,22-tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyanine; H(2)Pc(alpha-OC(10)H(7))(4) = 1,8,15,22-tetrakis(2-naphthyloxy)phthalocyanine] (1-3) have been prepared by treating the corresponding metal-free phthalocyanines H(2)Pc(alpha-OR)(4) with Ni(acac)(2)2H(2)O in refluxing n-pentanol. Structures of the Langmuir monolayers of these compounds at different temperature have been investigated. Compound 1 formed nano-ring structures with the outer diameter of 70-150 nm and inner diameter of 50 nm at 25.0 degrees C while 2 and 3 formed round particles. This difference can be ascribed to the different substituents at alpha position. The morphologies of the aggregates of 1 in monolayers have been found to change with temperature. Decreasing in temperature induced the formation of regular quadrate crystals. UV-vis absorption spectra revealed strong intermolecular interactions in the nano-ring aggregates. Polarized UV-vis absorption spectra suggest a titled orientation with respect to the surface of substrate for phthalocyanine macrocycles in the nano-ring aggregates.