Fused-Ring-Linked Covalent Organic Frameworks.

The development of linkage chemistry in the research area of covalent organic frameworks (COFs) is fundamentally important for creating robust structures with high crystallinity and diversified functionality. We reach herein a new level of complexity and controllability in linkage chemistry by achieving the first synthesis of fused-ring-linked COFs. A series of bicyclic pyrano[4,3-b]pyridine COFs have been constructed via a cascade protocol involving Schiff-base condensation, intramolecular [4 + 2] cycloaddition, and dehydroaromatization. With a broad scope of Brønsted or Lewis acids as the catalyst, the designed monomers, that is, O-propargylic salicylaldehydes and multitopic anilines, were converted into the fused-ring-linked frameworks in a one-pot fashion. The obtained COFs exhibited excellence in terms of purity, stability, and crystallinity, as comprehensively characterized by solid-state nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction, high-resolution transmission electron microscopy, and so on. Specifically, the highly selective formation (>94%) of pyrano[4,3-b]pyridine linkage was verified by quantitative NMR measurements combined with 13C-labeling synthesis. Moreover, the fused-ring linkage possesses fully locked conformation, which benefits to the high crystallinity observed for these COFs. Advancing the linkage chemistry from the formation of solo bonds or single rings to that of fused rings, this study has opened up new possibilities for the concise construction of sophisticated COF structures with high controllability.

Ionic Exchange of Metal-Organic Frameworks for Constructing Unsaturated Copper Single-Atom Catalysts for Boosting Oxygen Reduction Reaction.

Regulating the coordination environment of atomically dispersed catalysts is vital for catalytic reaction but still remains a challenge. Herein, an ionic exchange strategy is developed to fabricate atomically dispersed copper (Cu) catalysts with controllable coordination structure. In this process, the adsorbed Cu ions exchange with Zn nodes in ZIF-8 under high temperature, resulting in the trapping of Cu atoms within the cavities of the metal-organic framework, and thus forming Cu single-atom catalysts. More importantly, altering pyrolysis temperature can effectively control the structure of active metal center at atomic level. Specifically, higher treatment temperature (900 °C) leads to unsaturated Cu-nitrogen architecture (CuN3 moieties) in atomically dispersed Cu catalysts. Electrochemical test indicates atomically dispersed Cu catalysts with CuN3 moieties possess superior oxygen reduction reaction performance than that with higher Cu-nitrogen coordination number (CuN4 moieties), with a higher half-wave potential of 180 mV and the 10 times turnover frequency than that of CuN4 . Density functional theory calculation analysis further shows that the low N coordination number of Cu single-atom catalysts (CuN3 ) is favorable for the formation of O2 * intermediate, and thus boosts the oxygen reduction reaction.

Abnormal Rheological Phenomena in Newtonian Fluids in Electroosmotic Flows in a Nanocapillary.

Abnormal rheological phenomena arising in Tris-borate-ethylenediaminetetraacetic acid solutions (believed to be Newtonian fluids) were observed in direct current electroosmotic flows within a nanocapillary with a diameter of 200 nm under a low electric field of tens of volts per meter. In solutions with different concentrations and pH values, the flow behavior indices of the power-law fluids were calculated on the basis of current-voltage relations. When the electric field intensity was below a critical value of 6.7 V/m, the fluids exhibited dilatant (shear thickening) effects. Fluid viscosity changed with electric field intensity because the near-wall shear rate of an electroosmotic flow changes with electric field intensity via a power-law relation. When the electric field intensity surpasses the critical electric field, the fluid again becomes Newtonian and has constant viscosity. The investigation shows that in nanocapillaries, fluids commonly believed to be Newtonian can become non-Newtonian near walls as a result of strong nanoscale interfacial effects. The results can also improve our understanding of electroosmosis-related transport phenomena in nanofluidics and biomedical science.

A Fissionable Artificial Eukaryote-like Cell Model.

The use of artificial cells has attracted considerable attention in various fields from biotechnology to medicine. Here, we develop a cell-sized vesicle-in-vesicle (VIV) structure containing a separate inner vesicle (IV) that can be loaded with DNA. We use polymerase chain reaction (PCR) to successfully amplify the amount of DNA confined to the IV. Subsequent osmotic stress-induced fission of a mother VIV into two daughter VIVs successfully divides the IV content while keeping it confined to the IV of the daughter VIVs. The fission rate was estimated to be ∼20% quantified by fluorescence microscope. Our VIV structure represents a step forward toward construction of an advanced, fissionable cell model.

Template-free synthesis of inorganic hollow spheres at water/"water-brother" interfaces as Fenton-like reagents for water treatment.

This paper reports a template-free method to synthesize a series of inorganic hollow spheres (IHSs) including Cu-1, Cu-2, Ni-1, Ni-2 based on mineralization reactions at water/"water-brother" interfaces. "Water-brother" was defined as a solvent which is miscible with water, such as ethanol and acetone. The water/"water-brother" interfaces are very different from water/oil interfaces. The "water-brother" solvent will usually form a homogenous phase with water. Interestingly, in our method, these interfaces can be formed, observed and utilized to synthesize hollow spheres. Utilizing the unique porous properties of the spheres, their potential application in water treatment was demonstrated by using Cu-1 IHSs as Fenton-like reagents for adsorption and decomposition of Congo Red from aqueous solution. The final adsorption equilibrium was achieved after 30min with the maximum adsorption capacity of 86.1mg/g, and 97.3% removal of the dye in 80min after adsorption equilibrium. The IHSs can be reused as least 5 times after treatment by NaOH. This method is facile and suitable for large-scale production, and shows great potential for watertreatment.

High impedance droplet-solid interface lipid bilayer membranes.

A droplet-solid interface lipid bilayer membrane (DSLM) with high impedance was developed through controlling the contact area between an aqueous droplet and electrode. The electrode size can be easily controlled from millimeter to micrometer level. The droplet-solid interface lipid bilayer membranes were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and fluorescence microscopy. The fluorescence recovery after photobleaching (FRAP) was applied to determine the diffusion coefficient of egg PC DSLM to be 2.58 µm(2) s(-1). The DSLM resistance can reach up to 26.3 GΩ, which was then used to study the ion channel behavior of melittin. The resistivity of the bilayer membrane decreased linearly with the increase of melittin concentration in the membrane. The high impedance and fluidity of DSLM makes it an ideal model cell membrane system for ion channel study and high-throughput drug screening.

Palladium nanotubes formed by lipid tubule templating and their application in ethanol electrocatalysis.

Palladium nanotubes were fabricated by using lipid tubules as templates for the first time in a controlled manner. The positively charged lipid 1,2-dioleoyl-3-trimethylammoniumpropane (DOTAP) was doped into lipid tubules to adsorb PdCl4 (2-) on the tubule surfaces for further reduction. The lipid tubule formation was optimized by studying the growing dynamics and ethanol/water ratio. The DOTAP-doped tubules showed pH stability from 0 to 14, which makes them ideal templates for metal plating. The Pd nanotubes are open-ended with a tunable wall thickness. They exhibited good electrocatalytic performance in ethanol. Their electrochemically active surface areas were 6.5, 10.6, and 83.2 m(2) g(-1) for Pd nanotubes with 77, 101, and 150 nm wall thickness, respectively. These Pd nanotubes have great potential in fuel cells. The method demonstrated also opens up a way to synthesize hollow metal nanotubes.

A universal approach for the reversible phase transfer of hydrophilic nanoparticles.

The ability to engineer the surface properties of magnetic nanoparticles is important for their various applications, as numerous physical and chemical properties of nanoscale materials are seriously affected by the chemical constitution of their surfaces. For some specific applications, nanoparticles need to be transferred from a polar to a nonpolar environment (or vice versa) after synthesis. In this work we have developed a universal method for the phase transfer of magnetic nanoparticles that preserves their shape and size. Octadecyltrimethoxysilane was used to cap the surfaces of the aqueous magnetic nanoparticles, thereby allowing their transfer into nonpolar solution. The resulting hydrophobic magnetic nanoparticles were transferred back into aqueous solution by subsequently covering them with an egg-PC lipid monolayer. The superparamagnetic properties of the particles were retained after the phase transfer. The maximum transfer yields are dependent on their particle size with a maximum value of 93.16 ± 4.75% for magnetic nanoparticles with a diameter of 100 nm. The lipid-modified magnetic particles were stable over 1 week, and thus they have potential applications in the field of biomedicine. This work also provides a facile strategy for the controllable engineering of the surface properties of nanoparticles.

Boosted light absorption by WO3-x/Ag/PbS heterostructure for high-efficiency interfacial solar steam generation.

Interfacial solar steam generation is considered a promising approach to address energy and drinking water shortages. However, designing efficient light-absorbing and photothermal-converting materials remains challenging. In this study, we describe a detailed method for synthesising a three-dimensional (3D) hierarchical oxygen defect-rich WO3/Ag/PbS/Ni foam (termed WO3-x/Ag/PbS/NF) composite to realise efficient exciton separation and enhanced photothermal conversion. The 3D heterogeneous ternary photothermal material combines the individual benefits of WO3-x, Ag and PbS, improving charge transfer and promoting photogenerated electron-hole pairs. This enhances light absorption and energy conversion. Theoretical calculations indicate that the increased photothermal conversion efficiency primarily results from the heterojunction between Ag, WO3-x and PbS, facilitating exciton separation and electron transfer. Consequently, the WO3-x/Ag/PbS/NF solar evaporator exhibits exceptional light absorption (98% within the sunlight spectrum), a high evaporation rate of 1.90 kg m-2h-1 under 1 sun and a light-to-heat conversion efficiency of 94%. The WO3-x/Ag/PbS/NF evaporator also exhibits excellent capabilities in seawater desalination and wastewater treatment. This approach introduces a synergistic concept for creating novel multifunctional light-absorbing materials suitable for various energy-related applications.

An Ultraviolet-Lithography-Assisted Sintering Method for Glass Microlens Array Fabrication.

Glass microlens arrays (MLAs) have tremendous prospects in the fields of optical communication, sensing and high-sensitivity imaging for their excellent optical properties, high mechanical robustness and physicochemical stability. So far, glass MLAs are primarily fabricated using femtosecond laser modification assisted etching, in which the preparation procedure is time-consuming, with each concave-shaped microlens being processed using a femtosecond laser point by point. In this paper, a new method is proposed for implementing large-scale glass MLAs using glass particle sintering with the assistance of ultraviolet (UV) lithography. The glass particles are dispersed into the photoresist at first, and then immobilized as large-scaled micropillar arrays on quartz glass substrate using UV lithographing. Subsequently, the solidified photoresist is debinded and the glass particles are melted by means of sintering. By controlling the sintering conditions, the convex microlens will be self-assembled, attributed to the surface tension of the molten glass particles. Finally, MLAs with different focal lengths (0.12 to 0.2 mm) are successfully fabricated by utilizing different lithography masks. Meanwhile, we also present the optimization of the sintering parameter for eliminating the bubbles in the microlenses. The main factors that affect the focal length of the microlens and the image performance of the MLAs have been studied in detail.

Comparison of various pretreatment methods for biohydrogen production from cornstalk.

To establish high-efficiency pretreatments of cornstalk (CS) for hydrogen fermentative production, various pretreatment strategies have been investigated and contrasted in this work. Five pretreatment methods, including acid-soaking pretreatment, base-soaking pretreatment, high-temperature-assisted acid pretreatment, high-temperature-assisted base pretreatment and ultrasonic-assisted acid pretreatment (UAP), were performed on CS. The results showed that UAP significantly promoted the hydrogen production by CS compared with other pretreatments. The optimum UAP process, pretreating substrate with ultrasonication in 2.0% sulfuric acid solution for 1.5 h at the liquid-solid ratio of 20:1, obtained the maximum specific hydrogen accumulation of 142.59 mL g(-1)-CS and an average hydrogen production rate of 17.03 mL g(-1)-CS h(-1). Furthermore, the scanning electron microscope analysis of CS samples supports the hydrogen production results as well. The present work demonstrates that UAP is an efficient and practical CS pretreatment for hydrogen production from agricultural waste straws.

Three-dimensional hierarchical oxygen vacancy-rich WO3-decorated Ni foam evaporator for high-efficiency solar-driven interfacial steam generation.

Solar steam generation is considered to be an effective strategy to alleviate the global water shortage problem. Therefore, exploring highly efficient and thermal stability photothermal conversion materials is highly essential and urgent. In this work, we develop a three-dimensional (3D) oxygen vacancy-rich WO3 with ''nanorod array grown on nanosheet array" unique architecture decorated on Ni foam (denoted as WO3-x/NF) through a simple and effective hydrothermal method followed by an annealing route, which is applied as light-absorbing material. The 3D hierarchical porous unique structure of the WO3-x/NF evaporator can supply a channel steam escaping and enhance the light trapping due to the multi-scattering effect, and the localized surface plasmon resonance (LSPR) effects of WO3-x also contribute to increase the light absorption in the full solar spectrum. The as-prepared WO3-x/NF evaporator reveals a high solar absorption (95%), an evaporation rate of 1.50 kg m-2 h-1 under one sun illumination, and a light-to-heat conversion efficiency of about 88%, as well as stable salt-resistance performance. The water purification results show that WO3-x/NF evaporator has a significant effect on seawater desalination without significant salt accumulation and purification of heavy metal wastewater. Furthermore, the first-principles calculations reveal that WO3 with oxygen vacancies has a narrower bandgap, which is more conducive to absorb solar energy from the whole spectrum. This work can provide a new avenue toward the design of other high photothermal conversion system.

A graphene assembled porous fiber-based Janus membrane for highly effective solar steam generation.

Owing to the shortage of clean water as the global problem, the exploration of photothermal substances with high performance solar steam generation for sustainable water purification is essential and urgent. Herein, we demonstrate the assembly of two-dimensional graphene into one-dimensional rough, loose, and porous fibers and further use the assembled fibers to fabricate Janus membrane evaporator. The specific configuration guarantees an enhanced light harvesting property through multiple reflections, and improves the vapor transport ability through the constructed interlaced network. As a result, the as-obtained evaporator exhibits high solar absorbance, superior photothermal property and energy conversion efficiency, which is much higher than those of other reported Janus membrane evaporators and also better than the fabricated carbon nanotube-, and graphene sheet-based Janus membrane evaporator. The water purification results indicate that the fabricated graphene fiber-based Janus membrane is highly effective in seawater desalination without obvious salt accumulation and heavy metal wastewater purification. This study proposes a neotype graphene assembly for the fabrication of Janus membrane evaporator, which has potential applications in desalination and wastewater decontamination.

Anion Relay Enabled [3 + 3]-Annulation of Active Methylene Isocyanides and Ene-Yne-Ketones.

A new anion relay enabled [3 + 3]-annulation of active methylene isocyanides and conjugated ene-yne-ketones was developed for the efficient and straightforward synthesis of biologically valuable furo[3,2-c]pyridine derivatives. In this transformation, a sequential through-bond and through-space anion relay chemistry cascade is involved, which is initiated by an intermolecular Michael addition. Three new bonds and two rings are sequentially constructed from readily available acyclic precursors.

Magnetically triggered drug release from biocompatible microcapsules for potential cancer therapeutics.

This paper demonstrates that magnetic field triggered drug release from magnetic lipid microcapsules (MLMs) in a controlled manner. Two types of MLMs were fabricated, i.e., MLMs with negatively charged magnetic nanoparticles (MNPs) inside and MLMs with positively charged MNPs on their surfaces. The release of carboxyfluorescein (CF) and the chemotherapy drug doxorubicin (Dox) induced by the AC magnetic field (AMF) was investigated in detail both experimentally and theoretically. Although the drug release of these two types of MLMs synchronizes the switch of the AMF, they exhibited different mechanisms. The magnetic heating effect dominates the release of MLMs with MNPs inside, while both magnetic heating and oscillation effects play important roles in the release of MLMs with MNPs on the surfaces. The in vitro cytotoxicity experiments of Dox loaded microcapsules toward HeLa cells were further performed, which confirmed that these magnetic responsive drug carriers had obvious effects on cell death triggered by the external non-invasive AMF.

Electroformation of giant unilamellar vesicles in saline solution.

Giant unilamellar vesicle (GUV) formation on indium tin oxide (ITO) electrodes in saline solution and from charged lipids has proven to be difficult in the past. Yet the best cell membrane models contain charged lipids and require physiological conditions. We present a way to overcome this problem by using plasma cleaned ITO electrodes. GUVs from zwitterionic lipids, lipid mixtures and even pure charged lipids could be electroformed under physiological conditions and even higher concentrations of NaCl. The hydrophilic ITO surface may facilitate the hydration of the solid lipid film and the formation of lipid bilayers that subsequently bend and form vesicles. The formation of GUVs in saline solution is influenced by different parameters. The influences of the amplitude and frequency of the used AC field, the NaCl concentration, and the temperature were investigated. Finite element analysis simulating the effect of the electric field on GUV formation in saline solution could well explain the experimental results. Frequencies in the kHz-range favored for GUVs formation in saline solution, as they suppress the formation of electric double layer, while higher frequencies could again impair the effect of electric field and impede GUV formation. The diameters of the GUVs increased gradually with NaCl concentration from 0mM to 200mM and subsequently decreased from 200mM to 2M. High yields of GUVs were also formed in PBS solution and cell culture medium, which indicates this method is a promising way to prepare GUVs on a large scale in physiological relevant conditions.

Fabrication of Thickness-Controllable Micropatterned Polyelectrolyte-Film/Nanoparticle Surfaces by Using the Plasma Oxidation Method.

We have demonstrated a novel way to form thickness-controllable polyelectrolyte-film/nanoparticle patterns by using a plasma etching technique to form, first, a patterned self-assembled monolayer surface, followed by layer-by-layer assembly of polyelectrolyte-films/nanoparticles. Octadecyltrimethoxysilane (ODS) and (3-aminopropyl)triethoxysilane (APTES) self-assembled monolayers (SAMs) were used for polyelectrolyte-film and nanoparticle patterning, respectively. The resolution of the proposed patterning method can easily reach approximately 2.5 µm. The height of the groove structure was tunable from approximately 2.5 to 150 nm. The suspended lipid membrane across the grooves was fabricated by incubating the patterned polyelectrolyte groove arrays in solutions of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) giant unilamellar vesicles (GUVs). The method demonstrated here reveals a new path to create patterned 2D or 3D structures.

A novel electrochemiluminescent immunosensor based on CdS-coated ZnO nanorod arrays for HepG2 cell detection.

In this work, the highly oriented CdS-coated-ZnO nanorod arrays have been fabricated. The CdS-coated-ZnO nanorod arrays show high electrochemiluminescence intensity, fast response and good stability. All of the desirable properties spur the development of an ECL immunosensor for the detection of the liver cancer cell line (HepG2 cells). Two successive modification steps of 3-aminopropyltriethoxysilane and gold nanoparticles onto the CdS-coated-ZnO nanorod arrays not only offer the substrates for conjugation of antibody, but also effectively enhance the ECL signal, resulting in production of the high performance ECL immunosensor. The ECL immunosensor exhibits a sensitive response to HepG2 cells in a linear range of 300-10,000 cells mL(-1) with a detection limit of 256 cells mL(-1). The proposed sensor characteristics of high specificity, good reproducibility and remarkable stability will provide a sensitive, selective, and convenient approach for the clinical detection of cancer cells.

Electrochemiluminescent TiO2/CdS nanocomposites for efficient immunosensing of HepG2 cells.

An electrochemiluminescence (ECL) immunosensor for HepG2 cells (human liver hepatocellular carcinoma cells) was fabricated based on CdS-capped TiO2 hybrid nanoparticles. The CdS-capped TiO2 was obtained by immersing TiO2 nanoparticles into separate Cd2+ and S2- solutions successively 10 times. The hybrid nanoparticles have excellent ECL intensity after coating with 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid (IL) and 3-aminopropyl-triethoxysilane (APTES). The viscous IL is helpful to immobilize the hybrid nanoparticles on the electrode as well as for the electron transfer from nanoparticles to the electrode, which is advantageous to the ECL immunosensor. APTES was used to attach gold nanoparticles onto the electrode surface. The HepG2 antibodies were then immobilized onto the electrode surface via the interaction between their amine groups and gold nanoparticles. A wide detection range from 400 to 10 000 cells per mL was achieved. The detection limit was determined to be 396 cells per mL. Using HeLa cells as interferences, the excellent selectivity of this sensor has been demonstrated using both confocal fluorescence microscopy and ECL techniques. Due to its good sensitivity, selectivity and stability, the sensor has great potential in medical diagnosis.