Lattice‐Matched Epitaxial Growth of Organic Heterostructures for Integrated Optoelectronic Application

Development of nanowire photonics requires integration of different nanowire components into highly ordered functional heterostructures. Herein, we report a sequential self‐assembly of binary molecular components into branched nanowire heterostructures (BNHs) via lattice‐matched epitaxial growth, in which the microribbon backbone of 2,5‐Bis(5‐tert‐butyl‐2‐benzoxazolyl)thiophene (BBOT) functions as blue‐emitting microlaser source to pump the nanowire branches of BODIPY. By constructing Au electrodes on both branch sides and measuring the photocurrent in them, we successfully realize the integration of an organic laser and a power meter in a single device. This work provides a new insight into the integration of 1D organic nanostructures into BNHs for realizing organic multifunctional photonic devices.     

Whispering‐Gallery‐Mode Microlaser Based on Self‐Assembled Organic Single‐Crystalline Hexagonal Microdisks

Whispering‐gallery‐mode (WGM) resonators of semiconductor microdisks have been applied for achieving low‐threshold and narrow‐linewidth microlasers, but require sophisticated top‐down processing technology. Organic single‐crystalline hexagonal microdisks (HMDs) of p‐distyrylbenzene (DSB) self‐assembled from solution can function as WGM microresonators with a cavity quality factor (Q) of 210. Both multiple‐ and single‐mode lasing had been achieved using DSB HMDs with an edge length of 4.3 and 1.2 μm, respectively. These organic microdisks fabricated by bottom‐up self‐assembly approach may offer potential applications as low‐threshold microlaser sources for photonic circuit integration.     

Nano‐Graphene Oxide Based Multichannel Sensor Arrays towards Sensing of Protein Mixtures

Optical array‐based sensors are attractive candidates for the detection of various bio‐analytes due to their convenient fabrication and measurements. For array‐based sensors, multichannel arrays are more advantageous and used frequently in many electronic sensors. But most reported optically array based sensors are constructed on a single channel array. This difficulty is mainly instigated from the overlap in optical responses. In this report we have used nano‐graphene oxide (nGO) and suitable fluorophores as sensor elements to construct a multichannel sensor array for the detection of protein analytes. By using the optimized multichannel array we are able to detect different proteins and mixtures of proteins with 100 % classification accuracy at sub‐nanomolar concentration. This modified method expedites the sensing analysis as well as minimizes the use of both analyte and sensor elements in array‐based protein sensing. We have also used this system for the single channel array‐based sensing to compare the sensitivity and the efficacy of these two systems for other applications. This work demonstrated an intrinsic trade‐off associated with these two methods which may be necessary to balance for array‐based analyte detections.     

Hydrogen‐Bonding‐Regulated Supramolecular Nanostructures and Impact on Multivalent Binding

Herein we describe the H‐bonding‐regulated nanostructure, thermodynamics, and multivalent binding of two bolaamphiphiles NDI‐1 and NDI‐2 consisting of a hydrophobic naphthalene diimide connected to a hydrophilic wedge by a H‐bonding group and a glucose moiety on its two arms. NDI‐1 and NDI‐2 differ by the single H‐bonding group, namely, hydrazide or amide, which triggers the formation of vesicles and cylindrical micelles, respectively. Although the extended H‐bonding ensures stacking with head‐to‐head orientation and the formation of an array of the appended glucose moieties in both systems, the adaptive cylindrical structure exhibited superior multivalent binding with concanavalin A (ConA) to that of the vesicle. A control amphiphile lacking a H‐bonding group assembled with a random lateral orientation to produce spherical micelles without any notable multivalent binding.     

Integration of Lateral Filter Arrays with Immunoaffinity for Circulating‐Tumor‐Cell Isolation

Circulating tumor cells (CTCs) are an important biomarker for cancer prognosis and treatment monitoring. However, the heterogeneity of the physical and biological properties of CTCs limits the efficiency of various approaches used to isolate small numbers of CTCs from billions of normal blood cells. To address this challenge, we developed a lateral filter array microfluidic (LFAM) device to integrate size‐based separation with immunoaffinity‐based CTC isolation. The LFAM device consists of a serpentine main channel, through which most of a sample passes, and an array of lateral filters for CTC isolation. The unique device design produces a two‐dimensional flow, which reduces nonspecific, geometric capture of normal cells as typically observed in vertical filters. The LFAM device was further functionalized by immobilizing antibodies that are specific to the target cells. The resulting devices captured pancreatic cancer cells spiked in blood samples with (98.7±1.2) % efficiency and were used to isolate CTCs from patients with metastatic colorectal cancer.     

Nanoscale Control of Homoepitaxial Growth on a Two‐Dimensional Zeolite

Nanoscale crystal growth control is crucial for tailoring two‐dimensional (2D) zeolites (crystallites with thickness less than two unit cells) and thicker zeolite nanosheets for applications in separation membranes and as hierarchical catalysts. However, methods to control zeolite crystal growth with nanometer precision are still in their infancy. Herein, we report solution‐based growth conditions leading to anisotropic epitaxial growth of 2D zeolites with rates as low as few nanometers per day. Contributions from misoriented surface nucleation and rotational intergrowths are eliminated. Growth monitoring at the single‐unit‐cell level reveals novel nanoscale crystal‐growth phenomena associated with the lateral size and surface curvature of 2D zeolites.     

Organic Printed Core–Shell Heterostructure Arrays: A Universal Approach to All‐Color Laser Display Panels

A universal approach is demonstrated for realizing dual‐wavelength lasing in organic core–shell structured microlaser arrays, which show great promise in serving as all‐color laser display panels. By alternately printing hydrophilic and hydrophobic laser dye solutions on preprocessed substrates, precisely patterned core–shell heterostructure arrays were obtained. The spatially separated core and shell independently function as optical resonators to support dual‐wavelength tunable lasing in each heterostructure. Such a general method enables to flexibly control the lasing wavelength of the core–shell microlasers across a wide spectral range by systematically designing the gain media. Using as‐prepared microlaser arrays as display panels, full‐color laser displays were achieved with a color gamut much larger than that of standard RGB space. These results provide insights for design concepts and device construction for novel optoelectronic applications.     

插层型NBR/膨润土混杂材料及其对PVC增韧作用的研究

研究了胶乳插层法制备的丁腈橡胶 /有机改性膨润土 (NBR/OMB)混杂材料的力学性能和微观结构及其对聚氯乙烯 (PVC)的增韧作用。结果表明 :胶乳插层法制备的NBR/OMB混杂材料具有优异的力学性能 ;TEM和XRD结果表明 ,有部分NBR大分子嵌入到膨润土层间 ,形成较均匀、细致的分散。NBR/OMB混杂材料增韧PVC的效果明显优于NBR ,增韧后拉伸强度和弯曲强度的保持率明显提高     

Atomically Dispersed Nickel(I) on an Alloy‐Encapsulated Nitrogen‐Doped Carbon Nanotube Array for High‐Performance Electrochemical CO2 Reduction Reaction

Single‐atom catalysts (SACs) show great promise for electrochemical CO₂ reduction reaction (CRR), but the low density of active sites and the poor electrical conduction and mass transport of the single‐atom electrode greatly limit their performance. Herein, we prepared a nickel single‐atom electrode consisting of isolated, high‐density and low‐valent nickel(I) sites anchored on a self‐standing N‐doped carbon nanotube array with nickel–copper alloy encapsulation on a carbon‐fiber paper. The combination of single‐atom nickel(I) sites and self‐standing array structure gives rise to an excellent electrocatalytic CO₂ reduction performance. The introduction of copper tunes the d‐band electron configuration and enhances the adsorption of hydrogen, which impedes the hydrogen evolution reaction. The single‐nickel‐atom electrode exhibits a specific current density of ?32.87 mA cm^?2 and turnover frequency of 1962 h^?1 at a mild overpotential of 620 mV for CO formation with 97 % Faradic efficiency.     

NBR/ORGANOMODIFIED BENTONITE INTERCALATED HYBRIDS AND THEIR EFFECTS ON THE TOUGHNESS OF PVC

Hybrids of intercalative nitrile-butadiene rubber/organomodified bentonite (NBR/OMB) were prepared by thelatex intercalation technique. Investigation of their mechanical properties and the microstructore of NBR/OMB showed thatthe organomodified bentonite is an effective toughener for NBR. Transmission electronic microscopy (TEM) and X-rnydiffraction (XRD) tests showed that the NBR macromolecule could be intercalated into the galleries of bentonite.Incorporation of NBR/OMB hybrids as tougheners into poly(vinyl chloride) (PVC) results in a substantial increase in theimpact strength of PVC, but little decrease in its tensile strength and flexural strength, compared to the unmodified PVC.     

Influence of Guest Exchange on the Magnetization Dynamics of Dilanthanide Single‐Molecule‐Magnet Nodes within a Metal–Organic Framework

Multitopic organic linkers can provide a means to organize metal cluster nodes in a regular three‐dimensional array. Herein, we show that isonicotinic acid N‐oxide (HINO) serves as the linker in the formation of a metal–organic framework featuring Dy₂ single‐molecule magnets as nodes. Importantly, guest solvent exchange induces a reversible single‐crystal to single‐crystal transformation between the phases Dy₂(INO)₄(NO₃)₂?2 solvent (solvent=DMF (Dy₂‐DMF), CH₃CN (Dy₂‐CH₃CN)), thereby switching the effective magnetic relaxation barrier (determined by ac magnetic susceptibility measurements) between a negligible value for Dy₂‐DMF and 76 cm^?1 for Dy₂‐CH₃CN. Ab initio calculations indicate that this difference arises not from a significant change in the intrinsic relaxation barrier of the Dy₂ nodes, but rather from a slowing of the relaxation rate of incoherent quantum tunneling of the magnetization by two orders of magnitude.     

Stress‐Transfer‐Induced In Situ Formation of Ultrathin Nickel Phosphide Nanosheets for Efficient Hydrogen Evolution

Ultrathin two‐dimensional (2D) nanostructures have attracted increasing research interest for energy storage and conversion. However, tackling the key problem of lattice mismatch inducing the instability of ulreathin nanostructures during phase transformations is still a critical challenge. Herein, we describe a facile and scalable strategy for the growth of ultrathin nickel phosphide (Ni₂P) nanosheets (NSs) with exposed (001) facets. We show that single‐layer functionalized graphene with residual oxygen‐containing groups and a large lateral size contributes to reducing the lattice strain during phosphorization. The resulting nanostructure exhibits remarkable hydrogen evolution activity and good stability under alkaline conditions.     

Simultaneous Dual Encoding of Three‐Dimensional Structures by Light‐Induced Modular Ligation

A highly efficient strategy for the simultaneous dual surface encoding of 2D and 3D microscaffolds is reported. The combination of an oligo(ethylene glycol)‐based network with two novel and readily synthesized monomers with photoreactive side chains yields two new photoresists, which can be used for the fabrication of microstructures (by two‐photon polymerization) that exhibit a dual‐photoreactive surface. By combining both functional photoresists into one scaffold, a dual functionalization pattern can be obtained by a single irradiation step in the presence of adequate reaction partners based on a self‐sorting mechanism. The versatility of the approach is shown by the dual patterning of halogenated and fluorescent markers as well as proteins. Furthermore, we introduce a new ToF–SIMS mode (“delayed extraction”) for the characterization of the obtained microstructures that combines high mass resolution with improved lateral resolution.     

A Concentric Ring Electrode for a Wall‐jet Cell in a Microfluidic Device

A concentric ring array electrode that amplifies the current signal without redox cycling has been developed for highly sensitive electrochemical detection at a single potential in a microfluidic platform. Herein, the effect of ring‐electrode width on the current and current density was examined. A ring‐array electrode with widths that decrease from the inner to the outer ring was shown to exhibit the highest sensitivity. This electrode delivered a current density that was approximately 50 % higher than that of a conventionally used disc electrode. We used numerical simulations to further optimize this type of array electrode, which led to a limit of detection for catechol of 6.2 nmol/L. This ring array electrode has great potential for use in a variety of applications because it can be used to detect irreversible targets with a simple apparatus at a single potential and requires no electrode modification to achieve high sensitivity.     

Single‐Crystalline Ultrathin Nickel Nanosheets Array from In Situ Topotactic Reduction for Active and Stable Electrocatalysis

Simultaneously synthesizing and structuring atomically thick or ultrathin 2D non‐precious metal nanocrystal may offer a new class of materials to replace the state‐of‐art noble‐metal electrocatalysts; however, the synthetic strategy is the bottleneck which should be urgently solved. Here we report the synthesis of an ultrathin nickel nanosheet array (Ni‐NSA) through in situ topotactic reduction from Ni(OH)₂ array precursors. The Ni nanosheets showed a single‐crystalline lamellar structure with only ten atomic layers in thickness and an exposed (111) facet. Combined with a superaerophobic (low bubble adhesive) arrayed structure the Ni‐NSAs exhibited a dramatic enhancement on both activity and stability towards the hydrazine‐oxidation reaction (HzOR) relative to platinum. Furthermore, the partial oxidization of Ni‐NSAs in ambient atmosphere resulted in effective water‐splitting electrocatalysts for the hydrogen‐evolution reaction (HER).     

A simple electrical approach to monitor dielectrophoretic focusing of particles flowing in a microchannel

This paper reports an impedance‐based system for the quantitative assessment of dielectrophoretic (DEP) focusing of single particles flowing in a microchannel. Particle lateral positions are detected in two electrical sensing zones placed before and after a DEP‐focusing region, respectively. In each sensing zone, particle lateral positions are estimated using the unbalance between the opposite pulses of a differential current signal obtained with a straightforward coplanar electrode configuration. The system is used to monitor the focusing of polystyrene beads of 7 or 10 μm diameter, under various conditions of DEP field intensities and flow rates that produce different degrees of focusing. This electrical approach represents a simple and valuable alternative to optical methods for monitoring of particle focusing systems.     

Force driven separation of drops by deterministic lateral displacement

We investigate the separation of drops in force-driven deterministic lateral displacement (f-DLD), a promising high-throughput continuous separation method in microfluidics. We perform scaled-up macroscopic experiments in which drops settle through a square array of cylindrical obstacles. These experiments demonstrate the separation capabilities-and provide insight for the design-of f-DLD for drops of multiple sizes, including drops that are larger than the gaps between cylinders and exhibit substantial deformation as they move through the array. We show that for any orientation of the driving force relative to the array of obstacles, the trajectories of the drops follow selected locking directions in the lattice. We also found that a simple collision model accurately describes the average migration angles of the drops for the entire range of sizes investigated here, and for all forcing directions. In addition, we found a difference of approximately 20° between the critical angles at which the smallest and largest drops first move across a line of obstacles (column) in the array, a promising result in terms of potential size resolution of this method. Finally, we demonstrate that a single line of cylindrical obstacles rotated with respect to the driving force is capable of performing binary separations. The critical angles obtained in such single line experiments, moreover, agree with those obtained using the full array, thus validating the assumption in which the trajectory (and average migration angle) of the drops is calculated from individual obstacle-drop collisions.     

Topology variation and loop structural homology in crystal and simulated structures of a bimolecular DNA quadruplex

The topology of DNA quadruplexes depends on the nature and number of the nucleotides linking G-quartet motifs. To assess the effects of a three-nucleotide TTT linker, the crystal structure of the DNA sequence d(G(4)T(3)G(4)) has been determined at 1.5 A resolution, together with that of the brominated analogue d(G(4)(Br)UTTG(4)) at 2.4 A resolution. Both sequences form bimolecular intermolecular G-quadruplexes with lateral loops. d(G(4)(Br)UTTG(4)) crystallized in the monoclinic space group P2(1) with three quadruplex molecules in the asymmetric unit, two associating together as a head-to-head stacked dimer, and the third as a single head-to-tail dimer. The head-to-head dimers have two lateral loops on the same G-quadruplex face and form an eight-G-quartet stack, with a linear array of seven K(+) ions between the quartets. d(G(4)T(3)G(4)) crystallized in the orthorhombic space group C222 and has a structure very similar to the head-to-tail dimer in the P2(1) unit cell. The sequence studied here is able to form several different folds; however, all four quadruplexes in the two structures have lateral loops, in contrast to the diagonal loops reported for the analogous quadruplex with T(4) loops. A total of seven independent T(3) loops were observed in the two structures. These can be classified into two discrete conformational classes, suggesting that these represent preferred loop conformations that are independent of crystal-packing forces.     

Amperometric Flow‐Injection Determination of Phenolic Compounds Using a Biosensor with Immobilized Laccase,Peroxidase and Tyrosinase

A screen‐printed four‐electrode sensor based on immobilization of laccase (Coriolus hirsutus), peroxidase (horseradish) and tyrosinase (mushroom) in the same array was developed for monitoring of phenols. The enzymes were immobilized onto a self‐assembled monolayer (4‐mercapto‐1‐butanol) modified gold surface via covalent attachment by epichlorohydrin coupling. The experimental conditions for simultaneous operation of the three enzymes were optimized based on catechol determination. The sensors were further applied for the amperometric detection of several substituted phenolic compounds, carried out using a single line flow‐injection system. Hydrogen peroxide served as co‐substrate for peroxidase. The limits of detection for phenols in aqueous solutions were in the micromolar range, one assay was completed in less than 5 min. The preliminary studies showed that the compatibility of the above mentioned enzyme array enabled the multielectrode biosensor to be applied to real samples including industrial wastewaters and surface waters.     

Hydrophilic strips for preventing air bubble formation in a microfluidic chamber

In a microfluidic chamber, unwanted formation of air bubbles is a critical problem. Here, we present a hydrophilic strip array that prevents air bubble formation in a microfluidic chamber. The array is located on the top surface of the chamber, which has a large variation in width, and consists of a repeated arrangement of super‐ and moderately hydrophilic strips. This repeated arrangement allows a flat meniscus (i.e. liquid front) to form when various solutions consisting of a single stream or two parallel streams with different hydrophilicities move through the chamber. The flat meniscus produced by the array completely prevents the formation of bubbles. Without the array in the chamber, the meniscus shape is highly convex, and bubbles frequently form in the chamber. This hydrophilic strip array will facilitate the use of a microfluidic chamber with a large variation in width for various microfluidic applications.