Adjustable object floating states based on three-segment three-phase contact line evolution.

SignificanceAdjusting the floating states when objects float on water shows great potential for assembly, mineral flotation, nanostructured construction, and floating robot design, but the real-time regulation of floating states is challenging. Inspired by the different floating states of a falling fruit, we propose a facile strategy to transform the object between different floating states based on a three-segment three-phase contact line evolution. In addition, the potential of floating state transformation in solar-powered water evaporation, interface catalysis, and drug delivery is demonstrated. These findings provide insights into floating regulation and show great potential for floating-related applications.

Machine Learning-Assisted High-Throughput Identification and Quantification of Protein Biomarkers with Printed Heterochains.

Advanced in vitro diagnosis technologies are highly desirable in early detection, prognosis, and progression monitoring of diseases. Here, we engineer a multiplex protein biosensing strategy based on the tunable liquid confinement self-assembly of multi-material heterochains, which show improved sensitivity, throughput, and accuracy compared to standard ELISA kits. By controlling the material combination and the number of ligand nanoparticles (NPs), we observe robust near-field enhancement as well as both strong electromagnetic resonance in polymer-semiconductor heterochains. In particular, their optical signals show a linear response to the coordination number of the semiconductor NPs in a wide range. Accordingly, a visible nanophotonic biosensor is developed by functionalizing antibodies on central polymer chains that can identify target proteins attached to semiconductor NPs. This allows for the specific detection of multiple protein biomarkers from healthy people and pancreatic cancer patients in one step with an ultralow detection limit (1 pg/mL). Furthermore, rapid and high-throughput quantification of protein expression levels in diverse clinical samples such as buffer, urine, and serum is achieved by combining a neural network algorithm, with an average accuracy of 97.3%. This work demonstrates that the heterochain-based biosensor is an exemplary candidate for constructing next-generation diagnostic tools and suitable for many clinical settings.

Spatiotemporal-Dependent Confinement Effect of Bubble Swarms Enables a Fractal Hierarchical Assembly with Promoted Chirality.

The submarine-confined bubble swarm is considered an important constraining environment for the early evolution of living matter due to the abundant gas/water interfaces it provides. Similarly, the spatiotemporal characteristics of the confinement effect in this particular scenario may also impact the origin, transfer, and amplification of chirality in organisms. Here, we explore the confinement effect on the chiral hierarchical assembly of the amphiphiles in the confined bubble array stabilized by the micropillar templates. Compared with the other confinement conditions, the assembly in the bubble scenario yields a fractal morphology and exhibits a unique level of the chiral degree, ordering, and orientation consistency, which can be attributed to the characteristic interfacial effects of the rapidly formed gas/water interfaces. Thus, molecules with a balanced amphiphilicity can be more favorable for the promotion. Not limited to the pure enantiomers, chiral amplification of the enantiomer-mixed assembly is observed only in the bubble scenario. Beyond the interfacial mechanism, the fast formation kinetics of the confined liquid bridges in the bubble scenario endows the assembly with the tunable hierarchical morphology when regulating the amphiphilicity, aggregates, and confined spaces. Furthermore, the chiral-induced spin selectivity (CISS) effect of the fractal hierarchical assembly was systematically investigated, and a strategy based on photoisomerization was developed to efficiently modulate the CISS effect. This work provides insights into the robustness of confined bubble swarms in promoting a chiral hierarchical assembly and the potential applications of the resulting chiral hierarchical patterns in solid-state spintronic and optical devices.

Ultrasensitive Detection of Cancer Biomarkers Using Photonic-Crystal-Enhanced Single-Molecule Imaging.

The rapid and sensitive quantification of low-abundance protein markers holds immense significance in early disease diagnosis and treatment. Single-molecule fluorescence imaging exhibits very high detection sensitivity and thus has great application potential in this area. The single-molecule signal, however, is often susceptible to interference from background noise due to its inherently weak intensity. A variety of signal amplification techniques based on cascading reactions have been developed to improve the signal-to-noise ratio of single-molecule imaging. Nevertheless, the operation of these methods is typically complicated and time-consuming, which limits the clinical application. Herein, we introduce an enzyme-free, photonic-crystal-based single-molecule (PC-SM) biochip for cost-effective, time-efficient, and ultrasensitive detection of disease markers. The PC-SM biochip can enhance the signal-to-noise ratio of single molecules by nearly 3-fold compared with unamplified samples, through coupling of the single-molecule photon energy with the optical band gap of the photonic crystal. We used the PC-SM biochip to detect the low-abundance leukemia inhibitory factor in the blood of pancreatic cancer patients and healthy people and achieved a detection limit of 2.0 pg/L and an AUC of 0.9067. The method exhibits exceptional sensitivity and specificity, showing great application potential in various clinical settings.

Printable Smart Materials and Devices: Strategies and Applications.

Smart materials are a kind of functional materials which can sense and response to environmental conditions or stimuli from optical, electrical, magnetic mechanical, thermal, and chemical signals, etc. Patterning of smart materials is the key to achieving large-scale arrays of functional devices. Over the last decades, printing methods including inkjet printing, template-assisted printing, and 3D printing are extensively investigated and utilized in fabricating intelligent micro/nano devices, as printing strategies allow for constructing multidimensional and multimaterial architectures. Great strides in printable smart materials are opening new possibilities for functional devices to better serve human beings, such as wearable sensors, integrated optoelectronics, artificial neurons, and so on. However, there are still many challenges and drawbacks that need to be overcome in order to achieve the controllable modulation between smart materials and device performance. In this review, we give an overview on printable smart materials, printing strategies, and applications of printed functional devices. In addition, the advantages in actual practices of printing smart materials-based devices are discussed, and the current limitations and future opportunities are proposed. This review aims to summarize the recent progress and provide reference for novel smart materials and printing strategies as well as applications of intelligent devices.

Spin population determines whether antiaromaticity can increase or decrease radical stability.

Aromaticity, as a classical and fundamental concept in chemistry, can enhance thermodynamic stability. In sharp contrast, a previous study showed that antiaromaticity rather than aromaticity can enhance the radical stability of α-methyl heterocyclic compounds. Here, we demonstrate a similar antiaromaticity-promoted radical stability when the methyl group is replaced by five-membered (alkyl)(amino)cyclics (AACs). More interestingly, when an AAC is fused with an antiaromatic ring, the radical stability could be either reduced or enhanced, depending on the spin population. Specifically, when the spin density is populated on an incoming antiaromatic 1,4-dihydro-1,4-diborinine moiety, the radical stability is enhanced whereas when the spin density is maintained on the original five-membered ring, the radical stability is reduced. Our findings highlight the importance of spin density in tuning the radical stability, inviting experimental chemists' verification.

Lead-Chelating Intermediate for Air-Processed Phase-Pure FAPbI3 Perovskite Solar Cells.

Formamidinium-lead triiodide (FAPbI3) perovskite holds promise as a prime candidate in the realm of perovskite photovoltaics. However, the photo-active α-FAPbI3 phase, existing as a metastable state, is observable solely at elevated temperatures and is susceptible to degradation into the δ-phase in ambient air. Therefore, the attainment of phase-stable α-FAPbI3 in ambient conditions has become a crucial objective in perovskite research. Here, we proposed an efficient conversion process of PbI2 into the α-FAPbI3 perovskites in ambient air. This conversion was facilitated by the introduction of chelating molecules, which interacted with PbI2 to form an intermediate phase. Due to the reduced formation barrier resulting from the altered reaction pathway, this stable intermediate phase transitioned directly into α-FAPbI3 upon the deposition of the organic cation solution, effectively bypassing the formation of δ-FAPbI3. Consequently, the ambient-fabricated FAPbI3 perovskite solar cells (PSCs) exhibited an outstanding power conversion efficiency of 25.08 %, along with a high open-circuit voltage of 1.19 V. Furthermore, the unencapsulated devices demonstrated remarkable environmental stability. Notably, this innovative approach promises broad applicability across various chelating molecules, opening new avenues for further progress in the ambient air fabrication of FAPbI3 PSCs.

2,2'-Bipyridyl-4,4'-Dicarboxylic Acid Modified Buried Interface of High-Performance Perovskite Solar Cells.

The regulation of interfaces remains a critical and challenging aspect in the pursuit of highly efficient and stable perovskite solar cells (PSCs). Here, 2,2'-bipyridyl-4,4'-dicarboxylic acid (HBPDC) is incorporated as an interfacial layer between SnO2 and perovskite layers in PSCs. The two carboxylic acid moieties on HBPDC bind to SnO2 through esterification, while its nitrogen atoms, possessing lone electron pairs, interact with uncoordinated lead (Pb2+) atoms through Lewis acid-base interactions. This dual functionality enables simultaneous passivation of surface defects on both the SnO2 and buried perovskite layers. In addition, the electron-deficient nature of HBPDC enhances interfacial energy band alignment and facilitates electron transfer from the perovskite to SnO2. Furthermore, the incorporation of HBPDC strengthens the interfacial adhesion, improving mechanical reliability. As a result, the PSCs exhibited an impressive power conversion efficiency (PCE) of 25.41 % under standard AM 1.5G conditions, along with remarkable environmental stability.

In-Situ Cyclized Polyacrylonitrile as an Electron Selective Layer for n-i-p Perovskite Solar Cell with Enhanced Efficiency and Stability.

In situ cyclized polyacrylonitrile (CPAN) is developed to replace n-type metal oxide semiconductors (TiO2 or SnO2) as an electron selective layer (ESL) for highly efficient and stable n-i-p perovskite solar cells (PSCs). The CPAN layer is fabricated via facile in situ cyclization reaction of polyacrylonitrile (PAN) coated on a conducting glass substrate. The CPAN layer is robust and insoluble in common solvents, and possesses n-type semiconductor properties with a high electron mobility of 4.13×10-3 cm2 V-1 s-1. With the CPAN as an ESL, the PSC affords a power conversion efficiency (PCE) of 23.12 %, which is the highest for the n-i-p PSCs with organic ESLs. Moreover, the device with the CPAN layer holds superior operational stability, maintaining over 90 % of their initial efficiency after 500 h continuous light soaking. These results confirm that the CPAN layer would be a desirable low-cost and efficient ESL for n-i-p PSCs and other photoelectronic devices with high performance and stability.

Orientation-Controlled Ultralong Assembly of Janus Particles Induced by Bubble-Driven Instant Quasi-1D Interfaces.

Constructing precisely oriented assemblies and exploring their orientation-dependent properties remain a challenge for Janus nanoparticles (JNPs) due to their asymmetric characteristics. Herein, we propose a bubble-driven instant quasi-1D interfacial strategy for the oriented assembly of JNP chains in a highly controllable manner. It is found that the rapid formation of templated bubbles can promote the interfacial orientation of JNPs kinetically, while the confined quasi-1D interface in the curved liquid bridge can constrain the disordered rotation of the particles, yielding well-oriented JNP chains in a long range. During the evaporation process, the interfacial orientation of the JNPs can be transferred to the assembled chains. By regulating the amphiphilicity of the JNPs, both heteraxial and coaxial JNP assemblies are obtained, which show different polarization dependences on light scattering, and the related colorimetric logic behaviors are demonstrated. This work demonstrates the great potential of patterned interfacial assembly with a manageable orientation and shows the broad prospect of asymmetric JNP assembly in constructing novel optoelectronic devices.

Molecular Recognition-Modulated Hetero-Assembly of Nanostructures for Visualizable and Portable Detection of Circulating miRNAs.

Biomolecular markers, particularly circulating microRNAs (miRNAs) play an important role in diagnosis, monitoring, and therapeutic intervention of cancers. However, existing detection strategies remain intricate, laborious, and far from being developed for point-of-care testing. Here, we report a portable colorimetric sensor that utilizes the hetero-assembly of nanostructures driven by base pairing and recognition for direct detection of miRNAs. Following hybridization, two sizes of nanoparticles modified with single-strand DNA can be robustly assembled into heterostructures with strong optical resonance, exhibiting distinct structure colors. Particularly, the large nanoparticles are first arranged into nanochains to enhance scattering signals of small nanoparticles, which allows for sensitive detection and quantification of miRNAs without the requirement of target extraction, amplification, and fluorescent labels. Furthermore, we demonstrate the high specificity and single-base selectivity of testing different miRNA samples, which shows great potential in the diagnosis, staging, and monitoring of cancers. These heterogeneous assembled nanostructures provide an opportunity to develop simple, fast, and convenient tools for miRNAs detection, which is suitable for many scenarios, especially in low-resource setting.

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

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

Supramolecular Photonic Hydrogel for High-Sensitivity Alkaline Phosphatase Detection via Synergistic Driving Force.

Structurally-colored photonic hydrogels which are fabricated by introducing hydrogels into thin films or photonic crystal structures are promising candidates for biosensing. Generally, the design of photonic hydrogel biosensors is based on the sensor-analyte interactions induced charge variation within the hydrogel matrix, or chemically grafting binding sites onto the polymer chains, to achieve significant volume change and color variation of the photonic hydrogel. However, relatively low anti-interference capability or complicated synthesis hinder the facile and low-cost fabrication of high-performance photonic hydrogel biosensors. Here, a facilely prepared supramolecular photonic hydrogel biosensor is developed for high-sensitivity detection of alkaline phosphatase (ALP), which is an extensively considered clinical biomarker for a variety of diseases. Responding to ALP results in the broken supramolecular crosslinking and thus increased lattice distancing of the photonic hydrogel driven by synergistic repulsive force between nanoparticles embedded in photonic crystal structure and osmotic swelling pressure. The biosensor shows sensitivity of 7.3 nm spectral shift per mU mL-1 ALP, with detection limit of 0.52 mU mL-1 . High-accuracy colorimetric detection can be realized via a smartphone, promoting point-of-care sensing and timely diagnosis of related pathological conditions.

At-Home COVID-19 Rapid Antigen Test Down to 0.03 pg mL-1 of Nucleocapsid Protein.

Rapid and ultra-sensitive detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is critical for early screening and management of COVID-19. Currently, the real-time reverse transcription polymerase chain reaction (rRT-PCR) is the primary laboratory method for diagnosing SARS-CoV-2. It is not suitable for at-home COVID-19 diagnostic test due to the long operating time, specific equipment, and professional procedures. Here an all-printed photonic crystal (PC) microarray with portable device for at-home COVID-19 rapid antigen test is reported. The fluorescence-enhanced effect of PC amplifies the fluorescence intensity of the labeled probe, achieving detection of nucleocapsid (N-) protein down to 0.03 pg mL-1 . A portable fluorescence intensity measurement instrument gives the result (negative or positive) by the color of the indicator within 5 s after inserting the reacted PC microarray test card. The N protein in inactivated virus samples (with cycle threshold values of 26.6-40.0) can be detected. The PC microarray provides a general and easy-to-use method for the timely monitoring and eventual control of the global coronavirus pandemic.

Humidity-Controlled Molecular Assembly and Photoisomerization Behavior with a Bubble-Assisted Patterning Approach.

Precise control of molecular assembly is of great significance in the application of functional molecules. This work has systematically investigated the humidity effect in bubble-assisted molecular assembly. This work finds humidity is critical in the evolution of the soft confined space, leading to the formation of microscale liquid confined space under high humidity, and nanoscale liquid confined space under low humidity. It is also revealed that the differences in surface wettability and adhesion play the key role. Consequently, a flat pattern with thermodynamically favorable ordered structure and a sharp pattern with dynamically favorable disordered structure are achieved, which show different solid-state photoisomerization behaviors and photoresponsiveness. Interestingly, conductivity of sharp pattern with disordered structure is higher than that of flat pattern with layered ordered structure due to electronic transport mechanism of different spatial dimensions. This work opens a new way for manipulating the molecular self-assembly to control the morphology and function of molecular patterns.

FP(µ-N)2 S: A Sulfur-Pnictogen Four-Membered Ring with 6π Electrons.

The new 6π-electron four-membered ring compound 3-fluoro-1λ2 ,2,4,3λ3 -thiadiazaphosphetidine, FP(µ-N)2 S, has been generated in the gas phase through high-vacuum flash pyrolysis (HVFP) of thiophosphoryl diazide, FP(S)(N3 )2 , at 1000 K. Subsequent isolation of FP(µ-N)2 S in cryogenic matrices (Ar, Ne, and N2 ) allows its characterization with matrix-isolation IR and UV-vis spectroscopy by combination with 15 N-isotope labeling and computations at the CCSD(T)-F12a/VTZ-F12 level of theory. Upon visible-light irradiation at 550 nm, this cyclic compound undergoes ring-opening to the thiazyl isomer FPNSN, followed by dissociation to FP and SN2 under subsequent UV-irradiation at 365 nm. In sharp contrast to the square planar structure for the isolobal four-membered ring S2 N2 , a puckered structure with significant biradical character has been found for FP(µ-N)2 S.

One-Pot Self-Assembly of Dual-Color Domes Using Mono-Sized Silica Nanoparticles.

Spots with dual structural colors on the skin of some organisms in nature are of tremendous interest due to the unique function of their dye-free colors. However, imitation of them requires complicated manufacturing processes, expensive equipment, and multiple predesigned building blocks. In this work, a one-pot strategy based on the phase-separation-assisted nonuniform self-assembly of monosized silica nanoparticles is developed to construct domes with dual structural colors. In drying poly(ethylene glycol)-dextran-based (PEG-DEX) droplets, monosized nanoparticles distribute nonuniformly in two compartments due to the droplet inner flow and different nanoparticle compatibility with the two phases. The dome colors are derived from the self-assembled nanoparticles and are programmable by regulating the assembly conditions. The one-pot strategy enables the preparation of multicolor using only one type of building block. With the dual-color domes, encrypted patterns with a high volume of contents are designed, showing promising applications in information delivery.

Reconfigurable Magnetic Liquid Metal Robot for High-Performance Droplet Manipulation.

Droplet manipulation is crucial for diverse applications ranging from bioassay to medical diagnosis. Current magnetic-field-driven manipulation strategies are mainly based on fixed or partially tunable structures, which limits their flexibility and versatility. Here, a reconfigurable magnetic liquid metal robot (MLMR) is proposed to address these challenges. Diverse droplet manipulation behaviors including steady transport, oscillatory transport, and release can be achieved by the MLMR, and their underlying physical mechanisms are revealed. Moreover, benefiting from the magnetic-field-induced active deformability and temperature-induced phase transition characteristics, its droplet-loading capacity and shape-locking/unlocking switching can be flexibly adjusted. Because of the fluidity-based adaptive deformability, MLMR can manipulate droplets in challenging confined environments. Significantly, MLMR can accomplish cooperative manipulation of multiple droplets efficiently through on-demand self-splitting and merging. The high-performance droplet manipulation using the reconfigurable and multifunctional MLMR unfolds new potential in microfluidics, biochemistry, and other interdisciplinary fields.

Dredging the Charge-Carrier Transfer Pathway for Efficient Low-Dimensional Ruddlesden-Popper Perovskite Solar Cells.

Low-dimensional Ruddlesden-Popper (LDRP) perovskites still suffer from inferior carrier transport properties. Here, we demonstrate that efficient exciton dissociation and charge transfer can be achieved in LDRP perovskite by introducing γ-aminobutyric acid (GABA) as a spacer. The hydrogen bonding links adjacent spacing sheets in (GABA)2 MA3 Pb4 I13 (MA=CH3 NH3 + ), leading to the charges localized in the van der Waals gap, thereby constructing "charged-bridge" for charge transfer through the spacing region. Additionally, the polarized GABA weakens dielectric confinement, decreasing the (GABA)2 MA3 Pb4 I13 exciton binding energy as low as ≈73 meV. Benefiting from these merits, the resultant GABA-based solar cell yields a champion power conversion efficiency (PCE) of 18.73 % with enhanced carrier transport properties. Furthermore, the unencapsulated device maintains 92.8 % of its initial PCE under continuous illumination after 1000 h and only lost 3 % of its initial PCE under 65 °C for 500 h.

Volatile Dual-Solvent Assisted Intermediate Phase Regulation for Anti-Solvent-Free Perovskite Photovoltaics.

The unprecedented development of perovskite solar cells (PSCs) makes them one of the most promising candidates for terawatt-scale green energy production with low cost. However, the high boiling point solvents during the solution-processed film deposition cause anisotropic crystal growth and toxic solvent vapor during high-throughput manufacturing. Here, a dual-component green solvent consisting of isopropyl acetate and acetonitrile is proposed to form a volatile perovskite precursor, which can realize the high-quality perovskite thin film deposition by intermediate phase regulation. A room-temperature stable perovskite intermediate phase is constructed with the engagement of isopropyl acetate as co-solvent, which suppresses the exploding nucleation rate in volatile perovskite precursor, providing a fine grain growth rate and wide processing window in scalable film deposition. The corresponding PSCs fabricated by blade coating without anti-solvents or gas quenching achieve power conversion efficiency (PCE) of 16.37 % and 15.29 % for the areas of 14.08 cm2 and 37.83 cm2 , respectively.