Spatially Mediated Paper Reactors for On-Site Multicoded Encryption.

This report develops a point-of-use chemical trigger and applies it to a dual-functional chemical encryption chip that enables manual and digital identification with enhanced coding security levels suitable for on-site information verification. The concept relies on conducting continuous chemical synthesis and chromatographic separation of specified compounds on a paper device in a straightforward sketch. In addition to single-step chemical reactions, cascade syntheses and operations involving components of distinct mobilities are also demonstrated. The condensation of dione and hydrazine is first demonstrated on a linear paper reactor, where precursors can mix to react, followed by final product separation under optimized conditions. This linear paper reactor design can also support a multistep cascade Wittig reaction by controlling the relative mobility of reactants, intermediates, and final products. Furthermore, a three-dimensional paper reactor with appropriate mobile phases helps to initiate complex solvent system-driven azide-alkyne cycloaddition. By the use of a three-dimensional device design for spatially limited interdevice reactant transportation, reactants crossing designated boundaries trigger confined chemical reactions at specific positions. Accumulation of repetitive reactions leads to successful product gradient generation and mixing effects, representing a fully controllable intersubstrate chemical operation on the platform. Standing on initiating desired chemical reactions at particular interface regions, integration of appropriate selective reaction area, numerical digits overlay, color diversity, and mobile recognition realizes this dual-functional multicoding encryption process.

Effects of chain-chain interaction on the configuration of short-chain alkanethiol self-assembled monolayers on a metal surface.

Surface-specific sum frequency generation vibrational spectroscopy is applied to study the molecular configuration of short-chain n-alkanethiol self-assembled monolayers (SAMs with n = 2-6) on the Au surface. For monolayers with n≥ 3, the alkanethiols are upright-oriented, with the CH3 tilt angle varying between ∼33° and ∼46° in clear even-odd dependency. The ethanethiol monolayer (n = 2) is, however, found to exhibit a distinct lying-down configuration with a larger methyl tilt angle (67°-79°) and a smaller CH2 tilt angle (56°-68°). Such a unique configurational transition from n = 2 to n≥ 3 discloses the steric effect owing to chain-chain interaction among neighboring molecules. Through density functional theory calculations, the transition is further confirmed to be energetically favorable for thiols on a defective reconstructed Au(111) surface but not on the pristine one. Our study highlights the roles of the chain-chain interaction and the substrate surface atomic structure when organizing SAMs, offering a strategic pathway for exploiting their applications.

Specializing Carbon Nanozyme Active Sites for Sensitive Alkaline Phosphatase Activity Metal-Free Detection.

As biological enzymes regulate metabolic processes, alkaline phosphatase (ALP) is a critical diagnostic indicator associated with many diseases. To accurately measure the enzyme activity, nanozymactic materials can offer sensitive strategies for ALP detection. However, nanozymes often lack specific target binding sites, and the presence of common co-components, e. g., metal ions, may cause false-positive or false-negative results in enzyme activity determination. Herein, we developed a colorimetric assay for ALP detection using metal-free nanozymatic carbon dots (CDs). The ALP hydrolysis of pyrophosphate ions (PPi) to phosphate ions (Pi) induces a "turn-on" response based on the nanozyme activity. This PPi-induced inhibition mechanism is extensively studied via the Michaelis-Menten model, revealing that PPi acts as a noncompetitive inhibitor for CDs at a binding site distinct from the common nanozyme active site. With superior responses to ALP substrates, a highly sensitive and selective method is established for sensing ALP activity with a linear range of 0.010-0.200 U/L and a detection limit of 0.009 U/L. This finding explores the recognition and binding behavior of nanozymes, allowing for precise and reliable measurements even in complex samples, and represents a significant breakthrough for nanozyme-based assays in biological analysis.

Guiding Metal Organic Framework Morphology via Monolayer Artificial Defect-Induced Preferential Facet Selection.

Guiding metal organic framework (MOF) morphology, especially without the need for chemical additives, still remains a challenge. For the first time, we report a unique surface guiding approach in controlling the crystal morphology formation of zeolitic imidazole framework-8 (ZIF-8) and HKUST-1 MOFs on disrupted alkanethiol self-assembled monolayer (SAM)-covered Au substrates. Selective molecule removal is applied to generate diverse SAM matrices rich in artificial molecular defects in a monolayer to direct the dynamic crystal growth process. When a 11-mercaptoundecanol alkanethiol monolayer is ruptured, the hydroxyl tail groups of surface residue molecules act as nucleating sites by coordination with precursor metal ions. Meanwhile, the exposed alkane chain backbones stabilize a particular facet of MOF nuclei in the dynamic growth by slowing down their crystal growth rates along a specific direction. The competitive formation between the [110] and [100] planes of ZIF-8 ultimately regulates the crystal shapes from rhombic dodecahedron, truncated rhombic dodecahedron, and truncated cube to cube. Similarly, changeable morphologies of HKUST-1 crystals are also achieved from cube and tetrakaidekahedron to octahedron, originating from the competitive selection between the [100] and [111] planes. In addition to the artificial matrix preferred orientation of initial nucleation, parameters such as temperature also play a crucial role in the resulting crystal morphology. Standing on the additive-free MOF crystal morphology growth control, porous architectures prepared in this approach can act as templates for ligand-free metal (Au, Ag, and Cu) nanocluster synthesis. The nanocluster-embedded MOF structures represent distinct crystal morphology-dependent optical properties, and interestingly, their fluorescence emission can be highly enhanced by facet-induced nanocluster packing alignments. These findings not only provide a unique thought on MOF crystal morphology guidance but also pave a new route for the accompanied property investigation and further application.

Gap-directed chemical lift-off lithographic nanoarchitectonics for arbitrary sub-micrometer patterning.

We introduce a unique soft lithographic operation that exploits stamp roof collapse-induced gaps to selectively remove an alkanethiol self-assembled monolayer (SAM) on Au to generate surface patterns that are orders of magnitude smaller than structures on the original elastomer stamp. The smallest achieved feature dimension is 5 nm using a micrometer-scale structured stamp in a chemical lift-off lithography (CLL) process. Molecular patterns retained in the gaps between stamp features and their circumscribed or inscribed circles follow mathematical predictions, and their sizes can be tuned by altering the stamp structure dimensions, including height, pitch, and shape. These generated surface molecular patterns can function as biorecognition arrays or be transferred to the underneath Au layer for metallic structure creation. By combining CLL process with this gap phenomenon, soft material properties that are previously thought as demerits can be used to achieve sub-10 nm features in a straightforward sketch.

Metal-Free Transparent Three-Dimensional Flexible Electronics by Selective Molecular Bridges.

Flexible and transparent electronics is a new generation of device enabling modern interactive designs, which facilitates the recent development of low-cost, lightweight, and flexible materials. Although conventional indium tin oxide material still dominates the major market, its brittleness and steadily increasing price drive scientists to search for other alternatives. To meet the high demand, numerous metallic or organic conductive materials have been developed, but their poor adhesion toward supporting substrates and the subsequent circuit patterning approach remains problematic. In this study, a robust metal-free flexible conductive film fabrication strategy is introduced. The flexible polyethylene terephthalate (PET) film is utilized as the base, where a poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) conductive layer is tightly linked onto this supporting substrate. An interface activation process, i.e., oxygen plasma treatment, generates PET surface active spots to react with the subsequently introduced poly(vinyl alcohol) (PVA) molecule functional groups. This spatially selective PVA molecular bridge therefore acts as a dual-function intermediate layer through covalent bonding toward PET and hydrogen bonding toward PEDOT:PSS to conjugate two distinct materials. This PEDOT:PSS/PVA/PET film delivers superior physical properties, such as a high conductivity of 38.2 Ω/sq and great optical transmittance of 84.1%, which are well tunable under conductive polymer thickness controls. The film is also durable and can maintain original electrical properties even under serious bending for hundreds of cycles. Relying on these outstanding performances, arbitrary conductive circuits are built on this flexible substrate and can function as normal electronics when integrated with multiple electronic parts, e.g., light-emitting diodes (LEDs). Superior electrical signal outputs are achieved when complicated stereo structures including folding, splicing, interlacing, and braiding are incorporated, enabling the use of these films for flexible three-dimensional electronics assembling. Space identifying smart key and lock pair, origami rabbit-carrot touch response, pressure-stimulated jumping frog, and moving dinosaur recognition designs realize these PEDOT:PSS/PVA/PET film-based human-machine interactive devices. This flexible, transparent, and conductive film generation approach by molecular bridge creation should facilitate future development of flexible or foldable devices with complex circuits.

Manipulating Chemical Processes by Pseudosolid Spatial Limitation.

It is always preferred to perform chemical processes in liquid or gas phases because of the merits of operation convenience, reaction efficiency, and component homogeneity. However, tremendous efforts have to be made to purify the final product and minimize procedure losses unless a well-defined chemical mechanism is found. Herein, an unconventional chemical functioning system accommodating molecule-in-pseudosolid manipulation is reported. It entails the properties of enhanced molecular effective collision and directional guidance for delicate chemical reaction spatial controls. This design achieves facilitated rates on multicomponent chemical reactions with pros of unique simultaneous final product separation through intrapseudosolid spatial limitation. Localized homogeneous component mixing, pronounced molecular collision, and pure product separation happening in this action surmount the obstacles of conventional chemical operation with a straightforward sketch. A path toward fine chemistry is therefore paved, where traditional thoughts on beneficial reaction environments may be reconsidered.

Ultrasensitive and Low-Cost Paper-Based Graphene Oxide Nanobiosensor for Monitoring Water-Borne Bacterial Contamination.

Water-borne pathogens are mostly generated due to poor sanitation, industrial effluents, and sewage sludge, leading to a significant increase in mortality rate. To prevent this, we need a simple, user-friendly, and rapid on-site detection tool of pathogens, i.e., a biosensor. As contaminated water mainly contains (80%) coliform bacteria, of which Escherichia coli is the major species, we have developed a screen-printed paper-based, label-free biosensor for the detection of E. coli in water. A nanoarchitectured graphene oxide (GO), as a fast electron-transfer flatland, was deposited on the screen-printed graphene (G) on a hydrophobic paper, followed by the immobilization of lectin Concanavalin A (ConA) as a biorecognition element for a GGO_ConA-biosensing electrode. The electrochemical characterization of GGO_ConA shows fast electron transfer with a calculated electroactive surface area of 0.16 cm2. The biosensor performance was tested in the sludge water and beach water (real sample) as an analyte using the electrochemical impedance spectroscopy (EIS) technique. The charge-transfer resistance (Rct) of GGO_ConA increases linearly with the bacterial concentration in the range of 10-108 CFU mL-1 with an estimated limit of detection (LOD) of 10 CFU mL-1, which indicates the ultrasensitivity of our biosensor, with 100 times more sensitivity than previous studies. Our reported biosensor, being cost-effective, eco-friendly, and ultrasensitive, may serve greatly as a portable monitoring kit for checking water-borne bacterial contamination.

Enclosed paper-based analytical devices: Concept, variety, and outlook.

Paper-based analytical devices possess desirable properties such as low cost, convenient production, and rapid output. These advantages over conventional analytical devices have attracted tremendous attention in recent years, and an abundance of fabrication techniques have been achieved with different designs. Related approaches are adopted by scientists and engineers from different research fields to create practical devices tailored for various applications. Among a diverse selection of strategies, paper-based analytical devices featuring enclosed channels can protect its contents from environmental harm, which is helpful in designing paper-based devices aimed toward practical use. However, superior properties of enclosed device designs have often been neglected when a paper-based platform is selected, and related discussion is still lacking in the field. To fill this empty space in the relevant literature, important issues are highlighted and recent research achievements are included in this article, which should have implication for scientists interested in sensing technology, analytical chemistry, material science, and miniaturized devices. For the convenience of reader's understanding, this article provides a general introduction to the basic properties and concepts of paper-based analytical devices. Firstly, commonly used fabrication strategies and detection methods are mentioned, with an in-depth emphasis on paper-based devices with enclosed channels, including breakthroughs in device types, thoughts on novel fabrication, and practical application examples. Subsequently, other important topics related to enclosed paper-based device design are summarized, and future challenges and opportunities in the field are also discussed.

A horizontal-type scanning near-field optical microscope with torsional mode operation toward high-resolution and non-destructive imaging of soft materials.

We design and build a horizontal-type aperture based scanning near-field optical microscope (a-SNOM) with superior mechanical stability toward high-resolution and non-destructive topographic and optical imaging. We adopt the torsional mode in AFM (atomic force microscopy) operation to achieve a better force sensitivity and a higher topographic resolution when using pyramidal a-SNOM tips. The performance and stability of the AFM are evaluated through single-walled carbon nanotube and poly(3-hexyl-thiophene) nanowire samples. An optical resolution of 93 nm is deduced from the a-SNOM imaging of a metallic grating. Finally, a-SNOM fluorescence imaging of soft lipid domains is successfully achieved without sample damage by our horizontal-type a-SNOM instrument with torsional mode AFM operation.

Metal-Free Colorimetric Detection of Pyrophosphate Ions by Inhibitive Nanozymatic Carbon Dots.

The pyrophosphate ion (P2O74-, PPi) plays a critical role in various biological processes and acts as an essential indicator for physiological mechanism investigations and disease control monitoring. However, most of the currently available approaches for PPi species detection for practical usage still lack appropriate indicator generation, straightforward detection requirements, and operation convenience. In this study, a highly sensitive and selective PPi detection approach via the use of nanozymatic carbon dots (CDs) is introduced. This strategy eliminates the common need for metal ions in the detection process, where a direct indicator-PPi interaction is adopted to provide straightforward signal reports, and importantly, through a green indicator preparation. The preparation of this nanozymatic CDs' indicator utilizes an aqueous solution refluxing, employing galactose and histidine as the precursor materials. The mild conditions of the solution refluxing produce fluorescent CDs exhibiting peroxidase-mimic properties, which can catalyze the o-phenylenediamine oxidation under the presence of H2O2. The introduction of PPi species, interestingly, inhibits this process very efficiently, the extent of which can be colorimetrically monitored by the generated yellow product 2,3-diaminophenazine. Spectroscopic results point to CD surface functional groups' selective binding toward PPi species, which severely interferes with the electron transfer process in the enzymatic catalysis. Relying on this CD peroxidase-mimetic property inhibition, sensitive and selective recognition of PPi reaches a detection limit of 4.29 nM, enabling practical usage in complex matrixes. Owing to the superior compatibility and high stability of nanozymatic CDs, they can also be inkjet-printed on paper-based devices to create a portable and convenient platform for PPi detection. Both the solution and the paper-device-based selective recognitions confirm this unique and robust metal-free inhibitive PPi detection, which is supported by a convenient green preparation of nanozymatic CDs.

Multilayered Ag NP-PEDOT-Paper Composite Device for Human-Machine Interfacing.

Flexible pressure sensors have attracted increasing interest because of their potential applications on wearable sensing devices for human-machine interface connections, but challenges regarding material cost, fabrication robustness, signal transduction, sensitivity improvement, detection range, and operation convenience still need to be overcome. Herein, with a simple, low-cost, and scalable approach, a flexible and wearable pressure-sensing device fabricated by utilizing filter paper as the solid support, poly(3,4-ethylenedioxythiophene) to enhance conductivity, and silver nanoparticles to provide a rougher surface is introduced. Sandwiching and laminating composite material layers with two thermoplastic polypropylene films lead to robust integration of sensing devices, where assembling four layers of composite materials results in the best sensitivity toward applied pressure. This practical pressure-sensing device possessing properties such as high sensitivity of 0.119 kPa-1, high durability of 2000 operation cycles, and an ultralow energy consumption level of 10-5 W is a promising candidate for contriving point-of-care wearable electronic devices and applying it to human-machine interface connections.

Finely Tunable Surface Wettability by Two-Dimensional Molecular Manipulation.

Local molecular environment governs material interface properties, especially the substrate's exposing behavior and overall functionality expression. Although current techniques can provide efficient surface property modification, challenges in molecule spatial distribution and composition controls limited the generation of homogeneous and finely tunable molecular environment. In this study, Au-thiolate rupturing operation in chemical lift-off lithography (CLL) is used to manipulate the substrate interface molecular environment. The creation of randomly distributed artificial self-assembled monolayer defects generates vacancies for substrate property modification through back-insertion of molecules with opposite functionalities. Surface wettability adjustment is utilized as an example, where well-controllable molecule distribution provides finely tunable substrate affinity toward liquids with different physical properties. The distinct property difference between two surface regions assists microdroplet formation when liquids flow through, not only water solution but also low-surface-tension organic liquids. These microdroplet arrays become a template to guide material assembly in its formation process and act as pH-sensitive platforms for high-throughput detection. Furthermore, the tunability of the molecular pattern in this approach helps minimize the coffee-ring effect and the sweet-spot issue in matrix-assisted laser desorption/ionization mass spectrometry. Two-dimensional molecular manipulation in the CLL operation, therefore, holds the capability toward controlling homogeneous material surface property and toward exhibiting behavior adjustments.

Low-voltage driven portable paper bipolar electrode-supported electrochemical sensing device.

Aiming to overcome the obstacles of power supply requirement and chip usefulness in practice, a low-cost and convenient portable electrochemical sensing device is introduced for the first time, featuring bipolar electrode system, LED read-out, laminated paper-based devices, and low-voltage button cells. The electric circuits of this practical device are constructed on laminating films with copper and conductive carbon tapes, and the reservoirs facilitating chemical reactions are made with chromatography paper. The device is sensitive to electrochemical responses, validated by the demonstrative hydrogen peroxide and enzyme-assisted glucose detection. The business-card-size chip achieves sensitive analyte detection by naked eyes as well as further image processing in both laboratory samples and human serum samples testing, featuring detection limit as low as 1.79 µM and a dynamic range from 10 µM to 10 mM. This new practical design of point-of-care sensing chip entails the properties of facile fabrication, simple usage, high robustness, low power consumption, and accurate sensing showing the attainability of fabricating a useful and portable analytical device.

Wafer-scale bioactive substrate patterning by chemical lift-off lithography.

The creation of bioactive substrates requires an appropriate interface molecular environment control and adequate biological species recognition with minimum nonspecific attachment. Herein, a straightforward approach utilizing chemical lift-off lithography to create a diluted self-assembled monolayer matrix for anchoring diverse biological probes is introduced. The strategy encompasses convenient operation, well-tunable pattern feature and size, large-area fabrication, high resolution and fidelity control, and the ability to functionalize versatile bioarrays. With the interface-contact-induced reaction, a preformed alkanethiol self-assembled monolayer on a Au surface is ruptured and a unique defect-rich diluted matrix is created. This post lift-off region is found to be suitable for insertion of a variety of biological probes, which allows for the creation of different types of bioactive substrates. Depending on the modifications to the experimental conditions, the processes of direct probe insertion, molecular structure change-required recognition, and bulky biological species binding are all accomplished with minimum nonspecific adhesion. Furthermore, multiplexed arrays via the integration of microfluidics are also achieved, which enables diverse applications of as-prepared substrates. By embracing the properties of well-tunable pattern feature dimension and geometry, great local molecular environment control, and wafer-scale fabrication characteristics, this chemical lift-off process has advanced conventional bioactive substrate fabrication into a more convenient route.

Laminated Copper Nanocluster Incorporated Antioxidative Paper Device with RGB System-Assisted Signal Improvement.

Paper-based analytical devices are an emerging class of lightweight and simple-to-use analytical platform. However, challenges such as instrumental requirements and chemical reagents durability, represent a barrier for less-developed countries and markets. Herein, we report an advanced laminated device using red emitting copper nanocluster and RGB digital analysis for signal improvement. Upon RGB system assistance, the device signal-to-background ratio and the calibration sensitivity are highly enhanced under a filter-free setup. In addition, the calibration sensitivity, limit of detection, and coefficient of determination are on par with those determined by instrumental fluorescence analysis. Moreover, the limitation of using oxidation-susceptible fluorescent nanomaterials is overcome by the introduction of protecting tape barriers, antioxidative sheets, and lamination enclosing. The robustness of device is highly advanced, and the durability is prolonged to more than tenfold.

Large Area Nanoparticle Alignment by Chemical Lift-Off Lithography.

Nanoparticle alignment on the substrate attracts considerable attention due to its wide application in different fields, such as mechanical control, small size electronics, bio/chemical sensing, molecular manipulation, and energy harvesting. However, precise nanoparticle positioning and deposition control with high fidelity are still challenging. Herein, a straightforward strategy for high quality nanoparticle-alignment by chemical lift-off lithography (CLL) is demonstrated. This technique creates high resolution self-assembled monolayer (SAM) chemical patterns on gold substrates, enabling nanoparticle-selective deposition and precise alignment. The fabricated nanoparticle arrangement geometries and dimensions are well-controllable in a large area. With proper nanoparticle surface functionality control and adequate substrate molecular manipulation, well-defined nanoparticle arrays with single-particle-wide alignment resolution are achieved.

Surface functional DNA density control by programmable molecular defects.

Programmable surface-patterned functional DNA density is achieved via manipulation of molecular-level defects through chemical lift-off lithography. Artificial SAM defects are well-tunable by a contact-induced reaction, enabling molecular environment guidance and DNA insertion to be spatially and quantitatively addressable. This straightforward molecular density control creates an advanced avenue toward fabricating multiplexed bioactive substrates.

Self-standing aptamers by an artificial defect-rich matrix.

The classical alkanethiol post-passivation can prevent nonspecific binding of nucleotide bases onto supporting substrates and help aptamers transition from a "lying down" to a "standing up" orientation. However, the surface probes display lower binding affinity towards targets than those in bulk solutions due to unsatisfied hybridization spaces on the alkanethiol passivated substrate. To overcome this challenge, an artificial defect-rich matrix possessing an aptamer "self-standing" property created by chemical lift-off lithography (CLL) is demonstrated. This approach provided artificial defects on a hydroxyl-terminated alkanethiol self-assembled monolayer (SAM), which allowed the insertion of thiolated aptamers. The diluted surface molecular environment assisted aptamers not only to "self-stand" on the surface, but also to separate from each other, providing a suitable surface aptamer density and sufficient space for capturing targets. With this approach, the binding affinity of the aptamer towards a target was comparable to solution-type probes, showing higher recognition efficiency than that in conventional methods.

Multicolor Functional Carbon Dots via One-Step Refluxing Synthesis.

Carbon dots are admirable fluorescent nanomaterials due to their low cost, high photostability, excellent biocompatibility, and environmental friendliness. Most conventional carbon dot fabrication approaches produce single-colored fluorescent material in the preparation process; different methods are therefore required to synthesize distinct carbon dots for specific optical applications. In this study, carbon dots carrying different emission colors are prepared through a one-step refluxing process. The emission of these materials can be well-tuned by sodium hydroxide content in the precursor solution. The carbon dots produced are used as sensing probes based on the spectrofluorometric inner filter effect for target molecule detection. Three sensing categories that combine carbon dots and inner filter effect are demonstrated, including direct, metal nanoparticle-assisted, and enzymatic reaction-supported detection. Caffeine, melamine, and fenitrothion are selected as targets to demonstrate the strategies, respectively. These multifunctional carbon dot-based sensors achieve comparable sensitivity toward analytes with a much more convenient preparation route.