Therapeutic Window of Ligand‐Free Silver Nanoparticles in Agar‐Embedded and Colloidal State: In Vitro Bactericidal Effects and Cytotoxicity

The inhibition of bacterial growth through effective non‐toxic antimicrobial substances is of great importance for the prevention and therapy of implant infections in various medical disciplines. For the evaluation of a therapeutic window of silver nanoparticles (AgNPs), their bactericidal properties were tested in agar composites and colloids on four medical relevant bacteria. Therefore, we produced AgNPs using high‐power nanosecond laser ablation in water showing a log‐normal particle diameter distribution centered at 17 nm. Bacteria were incubated with AgNP concentrations ranging from 5 to 70 µg · mL^?1 and the growth rate was recorded. Additionally, cytotoxic effects of AgNPs on human gingival fibroblasts were examined. The experiments demonstrated that laser‐synthesized AgNPs resulted in a significant bacterial growth inhibition of more than 80% at the indicated concentrations in a solid agar model (Pseudomonas aeruginosa 10 µg · mL^?1, Streptococcus salivarius 10 µg · mL^?1, Escherichia coli 20 µg · mL^?1, Staphylococcus aureus 70 µg · mL^?1). In a planktonic bacteria model, the growth of the tested bacteria was significantly delayed by the addition of AgNPs at a concentration of 35 µg · mL^?1. The cytotoxic assays showed limited adverse effects on human fibroblasts at concentrations of less than 20 µg · mL^?1. The present study illustrates the strong antibacterial effects of ligand‐free, laser‐generated AgNPs that exhibit moderate cytotoxic effects, resulting in a therapeutically applicable concentration of AgNPs for medical purposes between 10 and 20 µg · mL^?1.     

Room‐Temperature Solution‐Synthesized p‐Type Copper(I) Iodide Semiconductors for Transparent Thin‐Film Transistors and Complementary Electronics

Here, room‐temperature solution‐processed inorganic p‐type copper iodide (CuI) thin‐film transistors (TFTs) are reported for the first time. The spin‐coated 5 nm thick CuI film has average hole mobility (µ_FE) of 0.44 cm² V^?1 s^?1 and on/off current ratio of 5 × 10². Furthermore, µ_FE increases to 1.93 cm² V^?1 s^?1 and operating voltage significantly reduces from 60 to 5 V by using a high permittivity ZrO₂ dielectric layer replacing traditional SiO₂. Transparent complementary inverters composed of p‐type CuI and n‐type indium gallium zinc oxide TFTs are demonstrated with clear inverting characteristics and voltage gain over 4. These outcomes provide effective approaches for solution‐processed inorganic p‐type semiconductor inks and related electronics.     

Analytical‐Based Methodologies for Examining the In Vitro Absorption,Distribution, Metabolism,and Elimination (ADME) of Silver Nanoparticles

The clinical applications of silver nanoparticles (AgNPs) remain limited due to the lack of well‐established methodologies for studying their nanokinetics. Hereby, the primary goal is to adapt a suite of analytical‐based methodologies for examining the in vitro absorption, distribution, metabolism, and elimination of AgNPs. Vero 76 and HEK 293 cells are exposed to ≈10‐nm spherical AgNPs⁺ and AgNPs^? at relevant concentrations (0–300 µg mL^?1) and times (4–48 h). Absorption: Inductively coupled plasma optical emission spectroscopy (ICP‐OES) demonstrates that the two AgNP formulations are not bioequivalent. For example, different bioavailabilities (C _maximum < 20.7 ± 4% and 6.82 ± 0.4%), absorption times (T _maximum > 48 and ≈24 h), and absorption rate laws (first‐ and zeroth‐order at 300 µg mL^?1) are determined in Vero 76 for AgNPs⁺ and AgNPs^?, respectively. Distribution: Raman and CytoViva hyperspectral imaging show different cellular localizations for AgNPs⁺ and AgNPs^?. Metabolism: Cloud point extraction (CPE)‐tangential flow filtration (TFF) reveal that ≤ 11% ± 4% of the administered, sublethal AgNPs release Ag⁺ and contribute to the observed cytotoxicity. Elimination: ICP‐OES‐CPE suggests that AgNPs are cleared via exocytosis.     

High‐Throughput,Protein‐Targeted Biomolecular Detection Using Frequency‐Domain Faraday Rotation Spectroscopy

A clinically relevant magneto‐optical technique (fd‐FRS, frequency‐domain Faraday rotation spectroscopy) for characterizing proteins using antibody‐functionalized magnetic nanoparticles (MNPs) is demonstrated. This technique distinguishes between the Faraday rotation of the solvent, iron oxide core, and functionalization layers of polyethylene glycol polymers (spacer) and model antibody–antigen complexes (anti‐BSA/BSA, bovine serum albumin). A detection sensitivity of ≈10 pg mL^?1 and broad detection range of 10 pg mL^?1 ? c_BSA ? 100 µ g mL^?1 are observed. Combining this technique with predictive analyte binding models quantifies (within an order of magnitude) the number of active binding sites on functionalized MNPs. Comparative enzyme‐linked immunosorbent assay (ELISA) studies are conducted, reproducing the manufacturer advertised BSA ELISA detection limits from 1 ng mL^?1 ? c_BSA ? 500 ng mL^?1. In addition to the increased sensitivity, broader detection range, and similar specificity, fd‐FRS can be conducted in less than ≈30 min, compared to ≈4 h with ELISA. Thus, fd‐FRS is shown to be a sensitive optical technique with potential to become an efficient diagnostic in the chemical and biomolecular sciences.     

Sensitive Detection of Carcinoembryonic Antigen Using Stability‐Limited Few‐Layer Black Phosphorus as an Electron Donor and a Reservoir

The instability of few‐layer black phosphorus (FL‐BP) hampers its further applications. Here, it can be demonstrated that the instability of FL‐BP can also be the advantage for application in biosensor. First, gold nanoparticle/FL‐BP (BP‐Au) hybrid is facilely synthesized by mixing Au precursor with FL‐BP. BP‐Au shows outstanding catalytic activity (K = 1120 s^?1 g^?1) and low activation energy (17.53 kJ mol^?1) for reducing 4‐nitrophenol, which is attributed to the electron‐reservoir and electron‐donor properties of FL‐BP, and synergistic interaction of Au nanoparticles and FL‐BP. Oxidation of FL‐BP after catalytic reaction is further confirmed by transmission electron microscope, X‐ray photoelectron spectroscopy, and zeta potentials. Second, the catalytic activity of BP‐Au can be reversibly switched from “inactive” to “active” upon treatment with antibody and antigen in solution, thus providing a versatile platform for label‐free colorimetric detection of biomarkers. The sensor shows a wide detection range (1 pg mL^?1 to –10 µg mL^?1), high sensitivity (0.20 pg mL^?1), and selectivity for detecting carcinoembryonic antigen (CEA). Finally, the biosensor has been used to detect CEA in colon and breast cancer clinical samples with satisfactory results. Therefore, the instability of BP can also be the advantage for application in detecting cancer biomarker in clinic.     

Aggregation‐Induced Electrochemiluminescence by Metal‐Binding Protein Responsive Hydrogel Scaffolds

Functionalized hydrogels have aroused general interest due to their versatile applications in biomaterial fields. This work reports a hydrogel network composed of gold nanoclusters linked with bivalent cations such as Ca²⁺, Mg²⁺, and Zn²⁺. The hydrogel exhibits both aggregation‐induced emission (AIE) and aggregation‐induced electrochemiluminescence (AIECL) effects. Most noteworthy, the AIECL effect (≈50‐fold enhancement) is even more significant than the corresponding AIE effect (approximately fivefold enhancement). Calmodulin, a Ca²⁺ binding protein, may efficiently regulate the AIECL dynamics after specific binding of the Ca²⁺ linker, with the linear range from 0.3 to 50 µg mL^?1 and a limit of detection of 0.1 µg mL^?1. Considering the important roles of bivalent cations in the life system, these results may pave a new avenue for the design of a biomolecule‐responsive AIECL‐type hydrogel with multifunctional biomedical purposes.     

Aligning Solution‐Derived Carbon Nanotube Film with Full Surface Coverage for High‐Performance Electronics Applications

The main challenge for application of solution‐derived carbon nanotubes (CNTs) in high performance field‐effect transistor (FET) is how to align CNTs into an array with high density and full surface coverage. A directional shrinking transfer method is developed to realize high density aligned array based on randomly orientated CNT network film. Through transferring a solution‐derived CNT network film onto a stretched retractable film followed by a shrinking process, alignment degree and density of CNT film increase with the shrinking multiple. The quadruply shrunk CNT films present well alignment, which is identified by the polarized Raman spectroscopy and electrical transport measurements. Based on the high quality and high density aligned CNT array, the fabricated FETs with channel length of 300 nm present ultrahigh performance including on‐state current I_on of 290 µA µm^?1 (V_ds = ?1.5 V and V_gs = ?2 V) and peak transconductance g_m of 150 µS µm^?1, which are, respectively, among the highest corresponding values in the reported CNT array FETs. High quality and high semiconducting purity CNT arrays with high density and full coverage obtained through this method promote the development of high performance CNT‐based electronics.     

Microtubular Fuel Cell with Ultrahigh Power Output per Footprint

A novel realization of microtubular direct methanol fuel cells (µ DMFC) with ultrahigh power output is reported by using “rolled‐up” nanotechnology. The microtube (Pt‐RuO₂‐RUMT) is prepared by rolling up Ru₂O layers coated with magnetron‐sputtered Pt nanoparticles (cat‐NPs). The µ DMFC is fabricated by embedding the tube in a fluidic cell. The footprint of per tube is as small as 1.5 × 10^?4 cm². A power density of ≈257 mW cm^?2 is obtained, which is three orders of magnitude higher than the present microsized DFMCs. Atomic layer deposition technique is applied to alleviate the methanol crossover as well as improve stability of the tube, sustaining electrolyte flow for days. A laminar flow driven mechanism is proposed, and the kinetics of the fuel oxidation depends on a linear‐diffusion‐controlled process. The electrocatalytic performance on anode and cathode is studied by scanning both sides of the tube wall as an ex situ working electrode, respectively. This prototype µ DFMC is extremely interesting for integration with micro‐ and nanoelectronics systems.     

Ultrastiff,Strong, and Highly Thermally Conductive Crystalline Graphitic Films with Mixed Stacking Order

A macroscopic film (2.5 cm × 2.5 cm) made by layer‐by‐layer assembly of 100 single‐layer polycrystalline graphene films is reported. The graphene layers are transferred and stacked one by one using a wet process that leads to layer defects and interstitial contamination. Heat‐treatment of the sample up to 2800 °C results in the removal of interstitial contaminants and the healing of graphene layer defects. The resulting stacked graphene sample is a freestanding film with near‐perfect in‐plane crystallinity but a mixed stacking order through the thickness, which separates it from all existing carbon materials. Macroscale tensile tests yields maximum values of 62 GPa for the Young's modulus and 0.70 GPa for the fracture strength, significantly higher than has been reported for any other macroscale carbon films; microscale tensile tests yield maximum values of 290 GPa for the Young's modulus and 5.8 GPa for the fracture strength. The measured in‐plane thermal conductivity is exceptionally high, 2292 ± 159 W m^?1 K^?1 while in‐plane electrical conductivity is 2.2 × 10⁵ S m^?1. The high performance of these films is attributed to the combination of the high in‐plane crystalline order and unique stacking configuration through the thickness.     

A Chemically Doped Naphthalenediimide‐Bithiazole Polymer for n‐Type Organic Thermoelectrics

The synthesis of a novel naphthalenediimide (NDI)‐bithiazole (Tz2)‐based polymer [P(NDI2OD‐Tz2)] is reported, and structural, thin‐film morphological, as well as charge transport and thermoelectric properties are compared to the parent and widely investigated NDI‐bithiophene (T2) polymer [P(NDI2OD‐T2)]. Since the steric repulsions in Tz2 are far lower than in T2, P(NDI2OD‐Tz2) exhibits a more planar and rigid backbone, enhancing π–π chain stacking and intermolecular interactions. In addition, the electron‐deficient nature of Tz2 enhances the polymer electron affinity, thus reducing the polymer donor–acceptor character. When n‐doped with amines, P(NDI2OD‐Tz2) achieves electrical conductivity (≈0.1 S cm^?1) and a power factor (1.5 µW m^?1 K^?2) far greater than those of P(NDI2OD‐T2) (0.003 S cm^?1 and 0.012 µW m^?1 K^?2, respectively). These results demonstrate that planarized NDI‐based polymers with reduced donor–acceptor character can achieve substantial electrical conductivity and thermoelectric response.     

Sensitive and Reversible Detection of Methanol and Water Vapor by In Situ Electrochemically Grown CuBTC MOFs on Interdigitated Electrodes

The in situ electrochemical growth of Cu benzene‐1,3,5‐tricarboxylate (CuBTC) metal–organic frameworks, as an affinity layer, directly on custom‐fabricated Cu interdigitated electrodes (IDEs) is described, acting as a transducer. Crystalline 5–7 µm thick CuBTC layers are grown on IDEs consisting of 100 electrodes with a width and a gap of both 50 µm and a height of 6–8 µm. These capacitive sensors are exposed to methanol and water vapor at 30 °C. The affinities show to be completely reversible with higher affinity toward water compared to methanol. For exposure to 1000 ppm methanol, a fast response is observed with a capacitance change of 5.57 pF at equilibrium. The capacitance increases in time followed diffusion‐controlled kinetics (k = 2.9 mmol s^?0.5 g^?1_CuBTC). The observed capacitance change with methanol concentration follows a Langmuir adsorption isotherm, with a value for the equilibrium affinity K _e = 174.8 bar^?1. A volume fraction f _MeOH = 0.038 is occupied upon exposure to 1000 ppm of methanol. The thin CuBTC affinity layer on the Cu‐IDEs shows fast, reversible, and sensitive responses to methanol and water vapor, enabling quantitative detection in the range of 100–8000 ppm.     

Vertically Aligned Niobium Nanowire Arrays for Fast‐Charging Micro‐Supercapacitors

Planar micro‐supercapacitors are attractive for system on chip technologies and surface mount devices due to their large areal capacitance and energy/power density compared to the traditional oxide‐based capacitors. In the present work, a novel material, niobium nanowires, in form of vertically aligned electrodes for application in high performance planar micro‐supercapacitors is introduced. Specific capacitance of up to 1 kF m^?2 (100 mF cm^?2) with peak energy and power density of 2 kJ m^?2 (6.2 MJ m^?3 or 1.7 mWh cm^?3) and 150 kW m^?2 (480 MW m^?3 or 480 W cm^?3), respectively, is achieved. This remarkable power density, originating from the extremely low equivalent series resistance value of 0.27 Ω (2.49 µΩ m² or 24.9 mΩ cm²) and large specific capacitance, is among the highest for planar micro‐supercapacitors electrodes made of nanomaterials.     

All‐Solution‐Processed Pure Formamidinium‐Based Perovskite Light‐Emitting Diodes

All‐solution‐processed pure formamidinium‐based perovskite light‐emitting diodes (PeLEDs) with record performance are successfully realized. It is found that the FAPbBr₃ device is hole dominant. To achieve charge carrier balance, on the anode side, PEDOT:PSS 8000 is employed as the hole injection layer, replacing PEDOT:PSS 4083 to suppress the hole current. On the cathode side, the solution‐processed ZnO nanoparticle (NP) is used as the electron injection layer in regular PeLEDs to improve the electron current. With the smallest ZnO NPs (2.9 nm) as electron injection layer (EIL), the solution‐processed PeLED exhibits a highest forward viewing power efficiency of 22.3 lm W^?1, a peak current efficiency of 21.3 cd A^?1, and an external quantum efficiency of 4.66%. The maximum brightness reaches a record 1.09 × 10⁵ cd m^?2. A record lifetime T₅₀ of 436 s is achieved at the initial brightness of 10 000 cd m^?2. Not only do PEDOT:PSS 8000 HIL and ZnO NPs EIL modulate the injected charge carriers to reach charge balance, but also they prevent the exciton quenching at the interface between the charge injection layer and the light emission layer. The subbandgap turn‐on voltage is attributed to Auger‐assisted energy up‐conversion process.     

High Amplification of the Antiviral Activity of Curcumin through Transformation into Carbon Quantum Dots

It is demonstrated that carbon quantum dots derived from curcumin (Cur‐CQDs) through one‐step dry heating are effective antiviral agents against enterovirus 71 (EV71). The surface properties of Cur‐CQDs, as well as their antiviral activity, are highly dependent on the heating temperature during synthesis. The one‐step heating of curcumin at 180 °C preserves many of the moieties of polymeric curcumin on the surfaces of the as‐synthesized Cur‐CQDs, resulting in superior antiviral characteristics. It is proposed that curcumin undergoes a series of structural changes through dehydration, polymerization, and carbonization to form core–shell CQDs whose surfaces remain a pyrolytic curcumin‐like polymer, boosting the antiviral activity. The results reveal that curcumin possesses insignificant inhibitory activity against EV71 infection in RD cells [half‐maximal effective concentration (EC₅₀) >200 µg mL^?1] but exhibits high cytotoxicity toward RD cells (half‐maximal cytotoxic concentration (CC₅₀) <13 µg mL^?1). The EC₅₀ (0.2 µg mL^?1) and CC₅₀ (452.2 µg mL^?1) of Cur‐CQDs are >1000‐fold lower and >34‐fold higher, respectively, than those of curcumin, demonstrating their far superior antiviral capabilities and high biocompatibility. In vivo, intraperitoneal administration of Cur‐CQDs significantly decreases mortality and provides protection against virus‐induced hind‐limb paralysis in new‐born mice challenged with a lethal dose of EV71.     

Scalable Design of Two‐Dimensional Oxide Nanosheets for Construction of Ultrathin Multilayer Nanocapacitor

Large size of capacitors is the main hurdle in miniaturization of current electronic devices. Herein, a scalable solution‐based layer‐by‐layer engineering of metallic and high‐κ dielectric nanosheets into multilayer nanosheet capacitors (MNCs) with overall thickness of ≈20 nm is presented. The MNCs are built through neat tiling of 2D metallic Ru_0.95O₂^0.2? and high‐κ dielectric Ca₂NaNb₄O₁₃^? nanosheets via the Langmuir–Blodgett (LB) approach at room temperature which is verified by cross‐sectional high‐resolution transmission electron microscopy (HRTEM). The resultant MNCs demonstrate a high capacitance of 40–52 µF cm^?2 and low leakage currents down to 10^?5–10^?6 A cm^?2. Such MNCs also possess complimentary in situ robust dielectric properties under high‐temperature measurements up to 250 °C. Based on capacitance normalized by the thickness, the developed MNC outperforms state‐of‐the‐art multilayer ceramic capacitors (MLCC, ≈22 µF cm^?2/5 × 10⁴ nm) present in the market. The strategy is effective due to the advantages of facile, economical, and ambient temperature solution assembly.     

3D Anisotropic Thermal Conductivity of Exfoliated Rhenium Disulfide

ReS₂ represents a different class of 2D materials, which is characterized by low symmetry having 1D metallic chains within the planes and extremely weak interlayer bonding. Here, the thermal conductivity of single‐crystalline ReS₂ in a distorted 1T phase is determined at room temperature for the in‐plane directions parallel and perpendicular to the Re‐chains, and the through‐plane direction using time‐domain thermoreflectance. ReS₂ is prepared in the form of flakes having thicknesses of 60–450 nm by micromechanical exfoliation, and their crystalline orientations are identified by polarized Raman spectroscopy. The in‐plane thermal conductivity is higher along the Re‐chains, (70 ± 18) W m^?1 K^?1, as compared to transverse to the chains, (50 ± 13) W m^?1 K^?1. As expected from the weak interlayer bonding, the through‐plane thermal conductivity is the lowest observed to date for 2D materials, (0.55 ± 0.07) W m^?1 K^?1, resulting in a remarkably high anisotropy of (130 ± 40) and (90 ± 30) for the two in‐plane directions. The thermal conductivity and interface thermal conductance of ReS₂ are discussed relative to the other 2D materials.     

Fabry–Pérot Oscillation and Room Temperature Lasing in Perovskite Cube‐Corner Pyramid Cavities

Recently, organometal halide perovskite‐based optoelectronics, particularly lasers, have attracted intensive attentions because of its outstanding spectral coherence, low threshold, and wideband tunability. In this work, high‐quality CH₃NH₃PbBr₃ single crystals with a unique shape of cube‐corner pyramids are synthesized on mica substrates using chemical vapor deposition method. These micropyramids naturally form cube‐corner cavities, which are eminent candidates for small‐sized resonators and retroreflectors. The as‐grown perovskites show strong emission ≈530 nm in the vertical direction at room temperature. A special Fabry–Pérot (F–P) mode is employed to interpret the light confinement in the cavity. Lasing from the perovskite pyramids is observed from 80 to 200 K, with threshold ranging from ≈92 µJ cm^?2 to 2.2 mJ cm^?2, yielding a characteristic temperature of T₀ = 35 K. By coating a thin layer of Ag film, the threshold is reduced from ≈92 to 26 µJ cm^?2, which is accompanied by room temperature lasing with a threshold of ≈75 µJ cm^?2. This work advocates the prospect of shape‐engineered perovskite crystals toward developing micro‐sized optoelectronic devices and potentially investigating light–matter coupling in quantum optics.     

Zn‐Ion Hybrid Micro‐Supercapacitors with Ultrahigh Areal Energy Density and Long‐Term Durability

On‐chip micro‐supercapacitors (MSCs), as promising power candidates for microdevices, typically exhibit high power density, large charge/discharge rates, and long cycling lifetimes. However, as for most reported MSCs, the unsatisfactory areal energy density (<10 µWh cm^?2) still hinders their practical applications. Herein, a new‐type Zn‐ion hybrid MSC with ultrahigh areal energy density and long‐term durability is demonstrated. Benefiting from fast ion adsorption/desorption on the capacitor‐type activated‐carbon cathode and reversible Zn stripping/plating on the battery‐type electrodeposited Zn‐nanosheet anode, the fabricated Zn‐ion hybrid MSCs exhibit remarkable areal capacitance of 1297 mF cm^?2 at 0.16 mA cm^?2 (259.4 F g^?1 at a current density of 0.05 A g^?1), landmark areal energy density (115.4 µWh cm^?2 at 0.16 mW cm^?2), and a superb cycling stability without noticeable decay after 10 000 cycles. This work will inspire the fabrication and development of new high‐performance microenergy devices based on novel device design.     

Isoindigo‐Based Polymers with Small Effective Masses for High‐Mobility Ambipolar Field‐Effect Transistors

So far, most of the reported high‐mobility conjugated polymers are p‐type semiconductors. By contrast, the advances in high‐mobility ambipolar polymers fall greatly behind those of p‐type counterparts. Instead of unipolar p‐type and n‐type materials, ambipolar polymers, especially balanced ambipolar polymers, are potentially serviceable for easy‐fabrication and low‐cost complementary metal‐oxide‐semiconductor circuits. Therefore, it is a critical issue to develop high‐mobility ambipolar polymers. Here, three isoindigo‐based polymers, PIID‐2FBT , P1FIID‐2FBT , and P2FIID‐2FBT are developed for high‐performance ambipolar organic field‐effect transistors. After the incorporation of fluorine atoms, the polymers exhibit enhanced coplanarity, lower energy levels, higher crystallinity, and thus increased µ _e. P2FIID‐2FBT exhibits n‐type dominant performance with a µ _e of 9.70 cm² V^?1 s^?1. Moreover, P1FIID‐2FBT exhibits a highly balanced µ _h and µ _e of 6.41 and 6.76 cm² V^?1 s^?1, respectively, which are among the highest values for balanced ambipolar polymers. Moreover, a concept “effective mass” is introduced to further study the reasons for the high performance of the polymers. All the polymers have small effective masses, indicating good intramolecular charge transport. The results demonstrate that high‐mobility ambipolar semiconductors can be obtained by designing polymers with fine‐tuned energy levels, small effective masses, and high crystallinity.