Sustainable Production of Molybdenum Carbide (MXene) from Fruit Wastes for Improved Solar Evaporation.

Invited for the cover of this issue is the group of Edison Huixiang Ang at the National Institute of Education, an institute of Nanyang Technological University, Singapore. The image depicts the sustainable fabrication of two-dimensional MXene sheets from the upcycling of fruit waste for solar desalination. Read the full text of the article at 10.1002/chem.202203184.

Conformal Noble Metal High-Entropy Alloy Nanofilms by Atomic Layer Deposition for an Enhanced Hydrogen Evolution Reaction.

The current synthesis methods of high-entropy alloy (HEA) thin-film coatings face huge challenges in facile preparation, precise thickness control, conformal integration, and affordability. These challenges are more specific and noteworthy for noble metal-based HEA thin films where the conventional sputtering methods encounter thickness control and high-cost issues (high-purity noble metal targets required). Herein, for the first time, we report a facile and controllable synthesis process of quinary HEA coatings consisting of noble metals (Rh, Ru, Pt, Pd, and Ir), by sequential atomic layer deposition (ALD) coupled with electrical Joule heating for post-alloying. Furthermore, the resulting quinary HEA thin film with a thickness of ∼50 nm and an atomic ratio of 20:15:21:18:27 shows promising potential as a platform for catalysis, exhibiting enhanced electrocatalytic hydrogen evolution reaction (HER) performances with lower overpotentials (e.g., from 85 to 58 mV in 0.5 M H2SO4) and higher stability (by retaining more than 92% of the initial current after 20 h with a current density of 10 mA/cm2 in 0.5 M H2SO4) than other noble metal-based structure counterparts in this work. The enhanced material properties and device performances are attributed to the efficient electron transfer of HEA with the increased number of active sites. This work not only presents RhRuPtPdIr HEA thin films as promising HER catalysts but also sheds light on controllable fabrication of conformal HEA-coated complex structures toward a broad range of applications.

Affimer sandwich probes for stable and robust lateral flow assaying.

Lateral flow assays (LFAs) widely deployed for on-site diagnosis have predominantly utilized antibodies as recognition molecules. Antibodies with limited thermal stability deteriorate the performance of the LFA over time. Herein, we demonstrate a stable and robust LFA by utilizing thermally stable peptide-based 12-14 kDa affimers as recognition molecules, in lieu of conventional protein-based antibodies to analyze complex samples with a significantly improved shelf life at room temperature. The model system studied here is that of interleukin-8 (IL8) biomarker for validating the efficacy of the proposed approach, using a pair of affimer probes that demonstrates dual functionality of capturing and reporting. Affimers immobilized on the test zone of LFA serve as capture probes for IL8-affimer-MB complexes. Whereas affimers conjugated with the MBs that enable extraction of IL8 from the sample matrix serve as reporters for visual detection. The MB complexes captured at the test zone resulted in brownish test bands that enable concentration-dependent detection of IL8. The assay yielded sensitive visual detection of IL8 at ng/mL levels (~ 0.1 ng/mL and 1 ng/mL in buffer and human plasma, respectively), within 20 min, using sample volumes of ~ 100 µL. Importantly, the stability of affimer-incorporated LFA improved significantly in contrast to antibody-incorporated LFA over time, even when stored at 4 °C. Therefore, the proposed affimer-based LFA in conjunction with MBs offer stable and reliable detection of biomarkers at clinically relevant concentration ranges in complicated matrices, even without requiring cold storage, hence, offering a promising avenue for on-site diagnosis in resource-limited settings.

Inorganic Photonic Microspheres with Localized Concentric Ordering for Deep Pattern Encoding and Triple Sensory Microsensor.

Photonic microspheres offer building units with unique topological structures and specific optical functions for diverse applications. Here, a new class of inorganic photonic microspheres with superior robustness, optical and electrical properties is reported by introducing a unique localized concentric ordering architecture and chemical interaction, which further serve as building blocks for deep pattern encoding and multiple sensory optoelectronic devices. Benefiting from localized concentric ordering architecture, the resultant photonic microspheres demonstrate orientation- and angle-independent structural colors. Notably, the formation of well-combined lamellae inorganic layers by chemical interaction grants the microspheres superior mechanical robustness, excellent solvent resistance, thermal stability, and multiple optoelectronic properties simultaneously, rarely seen in previous reports. Owing to these merits, such microspheres are used to construct diverse encoded photonic patterns for anti-counterfeiting applications. Interestingly, cross-communication among neighboring microspheres creates complex photonic sub-patterns, which provide "fingerprint information" with deep encryption security. Moreover, a single photonic microsphere-based optoelectronic microsensor is demonstrated for the first time, which achieves appealing application for real-time health monitoring and safety warning toward triple environmental stimuli. This work not only provides a new kind of robust, multifunctional photonic material, but also opens a new avenue for their uses as complexed pattern encoding and multi-parametric sensing platforms.

Periodic FTO IOs/CdS NRs/CdSe Clusters with Superior Light Scattering Ability for Improved Photoelectrochemical Performance.

Periodic fluorine-doped tin oxide inverse opals (FTO IOs) grafted with CdS nanorods (NRs) and CdSe clusters are reported for improved photoelectrochemical (PEC) performance. This hierarchical photoanode is fabricated by a combination of dip-coating, hydrothermal reaction, and chemical bath deposition. The growth of 1D CdS NRs on the periodic walls of 3D FTO IOs forms a unique 3D/1D hierarchical structure, providing a sizeable specific surface area for the loading of CdSe clusters. Significantly, the periodic FTO IOs enable uniform light scattering while the abundant surrounded CdS NRs induce additional random light scattering, combining to give multiple light scattering within the complete hierarchical structure, significantly improving light-harvesting of CdS NRs and CdSe clusters. The high electron collection ability of FTO IOs and the CdS/CdSe heterojunction formation also contribute to the enhanced charge transport and separation. Due to the incorporation of these enhancement strategies in one hierarchical structure, FTO IOs/CdS NRs/CdSe clusters present an improved PEC performance. The photocurrent density of FTO IOs/CdS NRs/CdSe clusters at 1.23 V versus reversible hydrogen electrode reaches 9.2 mA cm-2 , which is 1.43 times greater than that of CdS NRs/CdSe clusters and 3.83 times of CdS NRs.

Additive-Free Electrophoretic Deposition of Graphene Quantum Dots Thin Films.

The electrophoretic deposition (EPD) of graphene-based materials on transparent substrates is highly potential for many applications. Several factors can determine the yield of the EPD process, such as applied voltage, deposition time and particularly the presence of dispersion additives (stabilisers) in the suspension solution. This study presents an additive-free EPD of graphene quantum dot (GQD) thin films on an indium tin oxide (ITO) glass substrate and studies the deposition mechanism with the variation of the applied voltage (10-50 V) and deposition time (5-25 min). It is found that due to the small size (≈3.9 nm) and high content of deprotonated carboxylic groups, the GQDs form a stable dispersion (zeta-potential of about -35 mV) without using additives. The GQD thin films can be deposited onto ITO with optimal surface morphology at 30 V in 5 min (surface roughness of approximately (3.1±1.3) nm). In addition, as-fabricated GQD thin films also possess some interesting physico-optical properties, such as a double-peak photoluminescence at about λ=417 and 439 nm, with approximately 98 % visible transmittance. This low-cost and eco-friendly GQD thin film is a promising material for various applications, for example, transparent conductors, supercapacitors and heat conductive films in smart windows.

3D FTO/FTO-Nanocrystal/TiO2 Composite Inverse Opal Photoanode for Efficient Photoelectrochemical Water Splitting.

A 3D fluorine-doped SnO2 (FTO)/FTO-nanocrystal (NC)/TiO2 inverse opal (IO) structure is designed and fabricated as a new "host and guest" type of composite photoanode for efficient photoelectrochemical (PEC) water splitting. In this novel photoanode design, the highly conductive and porous FTO/FTO-NC IO acts as the "host" skeleton, which provides direct pathways for faster electron transport, while the conformally coated TiO2 layer acts as the "guest" absorber layer. The unique composite IO structure is fabricated through self-assembly of colloidal spheres template, a hydrothermal method and atomic layer deposition (ALD). Owing to its large surface area and efficient charge collection, the FTO/FTO-NC/TiO2 composite IO photoanode shows excellent photocatalytic properties for PEC water splitting. With optimized dimensions of the SnO2 nanocrystals and the thickness of the ALD TiO2 absorber layers, the 3D FTO/FTO-NC/TiO2 composite IO photoanode yields a photocurrent density of 1.0 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE) under AM 1.5 illumination, which is four times higher than that of the FTO/TiO2 IO reference photoanode.

Detection of Matrilysin Activity Using Polypeptide Functionalized Reduced Graphene Oxide Field-Effect Transistor Sensor.

A novel approach for rapid and sensitive detection of matrilysin (MMP-7, a biomarker involved in the degradation of various macromolecules) based on a polypeptide (JR2EC) functionalized reduced graphene oxide (rGO) field effect transistor (FET) is reported. MMP-7 specifically digests negatively charged JR2EC immobilized on rGO, thereby modulating the conductance of rGO-FET. The proposed assay enabled detection of MMP-7 at clinically relevant concentrations with a limit of detection (LOD) of 10 ng/mL (400 pM), attributed to the significant reduction of the net charge of JR2EC upon digestion by MMP-7. Quantitative detection of MMP-7 in human plasma was further demonstrated with a LOD of 40 ng/mL, illustrating the potential for the proposed methodology for tumor detection and carcinoma diagnostic (e.g., lung cancer and salivary gland cancer). Additionally, excellent specificity of the proposed assay was demonstrated using matrix metallopeptidase 1 (MMP-1), a protease of the same family. With appropriate selection and modification of polypeptides, the proposed assay could be extended for detection of other enzymes with polypeptide digestion capability.

Improved synthesis and growth of graphene oxide for field effect transistor biosensors.

Reduced graphene oxide (RGO) has many advantages over graphene such as low-cost, aqueous processable and industrial-scalable. However, two main limitations that prevent the use of RGO in electronics are the high electrical resistance and large electrical resistance deviation between fabricated devices. This limits RGO's use in biosensors, capacitors and other electronic devices. Herein, we present (1) a modified Hummer's method to obtain large RGO flakes via in-situ size fractionation and (2) the novel growth of RGO which can bridge the gaps in-between existing RGO flakes. Together, these two processes reduced the electrical resistance drastically from 1.99E + 06 to 4.68E + 03 Ω/square and the standard deviation decreased from 80.5 % to 16.5 %. The RGO was then fabricated into a field-effect transistor biosensor. A 1 pmol to 100 nmol change in Cytochrome C protein corresponded to a 3 % change in electrical resistance. The reported improved RGO synthesis method and subsequent growth enable large-scale application of RGO in practical electronic devices such as biosensors.

A review on electronic bio-sensing approaches based on non-antibody recognition elements.

In this review, recent advances in the development of electronic detection methodologies based on non-antibody recognition elements such as functional liposomes, aptamers and synthetic peptides are discussed. Particularly, we highlight the progress of field effect transistor (FET) sensing platforms where possible as the number of publications on FET-based platforms has increased rapidly. Biosensors involving antibody-antigen interactions have been widely applied in diagnostics and healthcare in virtue of their superior selectivity and sensitivity, which can be attributed to their high binding affinity and extraordinary specificity, respectively. However, antibodies typically suffer from fragile and complicated functional structures, large molecular size and sophisticated preparation approaches (resource-intensive and time-consuming), resulting in limitations such as short shelf-life, insufficient stability and poor reproducibility. Recently, bio-sensing approaches based on synthetic elements have been intensively explored. In contrast to existing reports, this review provides a comprehensive overview of recent advances in the development of biosensors utilizing synthetic recognition elements and a detailed comparison of their assay performances. Therefore, this review would serve as a good summary of the efforts for the development of electronic bio-sensing approaches involving synthetic recognition elements.

Applications of atomic layer deposition in solar cells.

Atomic layer deposition (ALD) provides a unique tool for the growth of thin films with excellent conformity and thickness control down to atomic levels. The application of ALD in energy research has received increasing attention in recent years. In this review, the versatility of ALD in solar cells will be discussed. This is specifically focused on the fabrication of nanostructured photoelectrodes, surface passivation, surface sensitization, and band-structure engineering of solar cell materials. Challenges and future directions of ALD in the applications of solar cells are also discussed.

Reporter-encapsulated liposomes on graphene field effect transistors for signal enhanced detection of physiological enzymes.

A novel approach for enzymatic assay using reporter-encapsulated liposomes on graphene field effect transistors (FET) is proposed. This approach involves real time monitoring of drain current (Id) of reduced graphene oxide (rGO) upon rupture of reporter-encapsulated 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC) liposomes triggered by enzymes. For validation of the proposed approach, 2,4,6-trinitrophenol (TNP) is used as the reporter for specific detection of phospholipase A2 (PLA2), a key enzyme in various membrane related physiological processes. Experimental results revealed that Id increased with PLA2 concentration, which is attributed to the interaction between released TNP and rGO. The limit of detection (LOD) achieved by the proposed approach was 80 pM, which is superior to most assays reported previously and much lower than the cut-off level of circulating secretory PLA2 (2.07 nM). Besides the high accuracy of the electronic detection methodology, the signal enhancement effect realized by the excess concentration of TNP (approximately 1 mM) in liposomes is believed to be the main reason for the significantly enhanced sensitivity of the proposed assay, indicating great potential for further improvement in the sensitivity by increasing the concentration of TNP. In addition, the proposed approach is rapid (incubation time ≤ 10 min) and label-free, thus showing great potential for practical applications in the future.

Synergetically enhanced near-infrared photoresponse of reduced graphene oxide by upconversion and gold plasmon.

A new route to improve responsivity of reduced graphene oxide (rGO)-based near-infrared photodetectors is reported by coupling upconversion and gold plasmon. Near-infrared light is converted by upconversion nanoparticle into shorter wavelengths that can readily be absorbed by rGO. Further coupling of plasmonic layer increased upconversion emissions and rGO absorption, resulting in an overall enhancement of photo-responsivity by 10 times.

Surfactant-thermal syntheses, structures, and magnetic properties of Mn-Ge-sulfides/selenides.

Although either surfactants or amines have been investigated to direct the crystal growth of metal chalcogenides, the synergic effect of organic amines and surfactants to control the crystal growth has not been explored. In this report, several organic bases (hydrazine monohydrate, ethylenediamine (en), 1,2-propanediamine (1,2-dap), and 1,3-propanediamine (1,3-dap)) have been employed as structure-directing agents (SDAs) to prepare four novel chalcogenides (Mn3Ge2S7(NH3)4 (1), [Mn(en)2(H2O)][Mn(en)2MnGe3Se9] (2), (1,2-dapH)2{[Mn(1,2-dap)2]Ge2Se7} (3), and (1,3-dapH)(puH)MnGeSe4(4) (pu = propyleneurea) under surfactant media (PEG-400). These as-prepared new crystalline materials provide diverse metal coordination geometries, including MnS3N tetrahedra, MnGe2Se7 trimer, and MnGe3Se10 T2 cluster. Compounds 1-3 have been fully characterized by single-crystal X-ray diffraction (XRD), powder XRD, UV-vis spectra, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Moreover, magnetic measurements for compound 1 showed an obvious antiferromagnetic transition at ~9 K. Our research not only enriches the structural chemistry of the transitional-metal/14/16 chalcogenides but also allows us to better understand the synergic effect of organic amines and surfactants on the crystallization of metal chalcogenides.

Kinetically controlling phase transformations of crystalline mercury selenidostannates through surfactant media.

Herein we report the surfactant-thermal method to prepare two novel one-dimensional mercury selenidostannates, [DBUH]2[Hg2Sn2Se6(Se2)] (1) and [DBUH]2[Hg2Sn2Se7] (2), where DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene, by applying PEG-400 as the reaction medium. It is worth noting that 1 is kinetically stable and can be transformed into thermodynamically stable phase 2 under a longer reaction time. Our strategy "growing crystalline materials in surfactants" could open a new door to preparing novel crystals with diverse structures and interesting properties.

Enhanced far infrared emissivity, UV protection and near-infrared shielding of polypropylene composites via incorporation of natural mineral for functional fabric development.

Far infrared radiation in the range of 4-20 µm has been showed to have biological and health benefits to the human body. Therefore, incorporating far-infrared emissivity additives into polymers and/or fabrics hold promise for the development of functional textiles. In this study, we incorporated nine types of natural minerals into polypropylene (PP) film and examined their properties to identify potential candidates for functional textiles and apparels. The addition of 2% mineral powders into PP film increased the far-infrared emissivity (5-14 µm) by 7.65%-14.48%. The improvement in far-infrared emissivity within the range of 5-14 µm, which overlaps with the peak range of human skin radiation at 8-14 µm, results in increased absorption efficiency, and have the potential to enhance thermal and biological effects. Moreover, the incorporation of mineral powders in PP films exhibited favorable ultraviolet (UV) protection and near-infrared (NIR) shielding properties. Two films, specifically those containing red ochre and hematite, demonstrated excellent UV protection with a UPF rating of 50+ and blocked 99.92% and 98.73% of UV radiation, respectively. Additionally, they showed 95.2% and 93.2% NIR shielding properties, compared to 54.1% NIR shielding properties of PP blank films. The UV protection and NIR shielding properties offered additional advantages for the utilization of polymer composite with additives in the development of sportswear and other outdoor garments. The incorporation of minerals could absorb near-IR radiation and re-emit them at longer wavelength in the mid-IR region. Furthermore, the incorporation of minerals significantly improved the heat retention of PP films under same heat radiation treatment. Notably, films with red ochre and hematite exhibited a dramatic temperature increase, reaching 2.5 and 3.2 times the temperature increase of PP films under same heat radiation treatment, respectively (46.8 °C and 59.9 °C higher than the temperature increase of 20.9 °C in the PP film). Films with additives also demonstrated lower thermal effusivity than PP blank films, indicating superior heat insulation properties. Therefore, polypropylene films with mineral additives, particularly those containing red ochre and hematite, showed remarkable heat capacity, UV-protection, NIR-shielding properties and enhanced far infrared emissivity, making them promising candidates for the development of functional textiles.

Bacterial cellulose impregnated with andaliman (Zanthoxylum acanthopodium) microencapsulation as diabetic wound dressing.

Diabetic foot ulcer (DFU) is a common complication of diabetes mellitus which can cause infection, amputation and even death. One of many treatments that can be applied to support the DFU healing processes is by using wound dressings. Bacterial cellulose (BC) is a good material to be used as a wound dressing. However, some of the limitations of BC to be applied as wound dressing are does not possess antibacterial properties and support the healing process. Andaliman (Zanthoxylum acanthopodium) is known to have antioxidant, antibacterial and anti-inflammatory abilities that can support BC as a wound dressing. This research focused on the manufacture of BC/Z. acanthopodium microencapsulated wound dressing composites and evaluate their potential as a DFU wound dressing with a variety of gelatin composition in microencapsulation. The results of FTIR and SEM analysis showed that the Z. acanthopodium impregnation process in BC was successful. The variation of gelatine that used in microencapsulation affected the morphological and effectiveness of the wound dressing. However, overall, the wound dressings showed good antibacterial effect on E. coli and S. aureus bacteria and accelerating the wound closure process 8 times faster (BCAMc12) on the 17th day compared to wounds that did not receive any treatment.

Photocatalytic Degradation of Methylene Blue Using N-Doped ZnO/Carbon Dot (N-ZnO/CD) Nanocomposites Derived from Organic Soybean.

This study reports on successful synthesis of carbon dots (CDs), nitrogen-doped zinc oxide (N-ZnO), and N-ZnO/CD nanocomposites as photocatalysts for degradation of methylene blue. The first part was the synthesis of CDs utilizing a precursor from soybean and ethylenediamine as a dopant by a hydrothermal method. The second part was the synthesis of N-ZnO with urea as the nitrogen dopant carried out by a calcination method in a furnace at 500 °C for 2 h in an N2 atmosphere (5 °C min-1). The third part was the synthesis of N-ZnO/CD nanocomposites. The characteristics of CDs, N-ZnO, and N-ZnO/CD nanocomposites were analyzed through Fourier transform infrared (FTIR), UV-vis absorbance, photoluminescence (PL), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), thermal gravimetry analysis (TGA), field-emission scanning electron microscopy energy-dispersive spectroscopy (FESEM EDS), X-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) analysis. Based on the HR-TEM analysis, the CDs had a spherical shape with an average particle size of 4.249 nm. Meanwhile, based on the XRD and HR-TEM characterization, the N-ZnO and N-ZnO/CD nanocomposites have wurtzite hexagonal structures. The materials of N-ZnO and N-ZnO/CD show increased adsorption in the visible light region and low energy gap E g. The E g values of N-ZnO and N-ZnO/CDs were found to be 2.95 and 2.81 eV, respectively, whereas the surface area (S BET) values 3.827 m2 g-1 (N-ZnO) and 3.757 m2 g-1(N-ZnO/CDs) belonged to the microporous structure. In the last part, the photocatalysts of CDs, N-ZnO, and N-ZnO/CD nanocomposites were used for degradation of MB (10 ppm) under UV-B light irradiation pH = 7.04 (neutral) for 60 min at room temperature. The N-ZnO/CD nanocomposites showed a photodegradation efficiency of 83.4% with a kinetic rate of 0.0299 min-1 higher than N-ZnO and CDs. The XRD analysis and FESEM EDS of the N-ZnO/CDs before and after three cycles confirm the stability of the photocatalyst with an MB degradation of 58.2%. These results have clearly shown that the N-ZnO/CD nanocomposites could be used as an ideal photocatalytic material for the decolorization of organic compounds in wastewater.

The New Materials for Battery Electrode Prototypes.

In this article, we present the performance of Copper (Cu)/Graphene Nano Sheets (GNS) and C-π (Graphite, GNS, and Nitrogen-doped Graphene Nano Sheets (N-GNS)) as a new battery electrode prototype. The objectives of this research are to develop a number of prototypes of the battery electrode, namely Cu/GNS//Electrolyte//C-π, and to evaluate their respective performances. The GNS, N-GNS, and primary battery electrode prototypes (Cu/GNS/Electrolyte/C-π) were synthesized by using a modified Hummers method; the N-doped sheet was obtained by doping nitrogen at room temperature and the impregnation or the composite techniques, respectively. Commercial primary battery electrodes were also used as a reference in this research. The Graphite, GNS, N-GNS, commercial primary batteries electrode, and battery electrode prototypes were analyzed using an XRD, SEM-EDX, and electrical multimeter, respectively. The research data show that the Cu particles are well deposited on the GNS and N-GNS (XRD and SEM-EDX data). The presence of the Cu metal and electrolytes (NH4Cl and MnO2) materials can increase the electrical conductivities (335.6 S cm-1) and power density versus the energy density (4640.47 W kg-1 and 2557.55 Wh kg-1) of the Cu/GNS//Electrolyte//N-GNS compared to the commercial battery (electrical conductivity (902.2 S cm-1) and power density versus the energy density (76 W kg-1 and 43.95 W kg-1). Based on all of the research data, it may be concluded that Cu/GNS//Electrolyte//N-GNS can be used as a new battery electrode prototype with better performances and electrical activities.

Lanthanide-doped Na(x)ScF(3+x) nanocrystals: crystal structure evolution and multicolor tuning.

Rare-earth-based nanomaterials have recently drawn considerable attention because of their unique energy upconversion (UC) capabilities. However, studies of Sc(3+)-based nanomaterials are still absent. Herein we report the synthesis and fine control of Na(x)ScF(3+x) nanocrystals by tuning of the ratio of oleic acid (OA, polar surfactant) to 1-octadecene (OD, nonpolar solvent). When the OA:OD ratio was increased from low (3:17) to high (3:7), the nanocrystals changed from pure monoclinic phase (Na(3)ScF(6)) to pure hexagonal phase (NaScF(4)) via a transition stage at an intermediate OA:OD ratio (3:9) where a mixture of nanocrystals in monoclinic and hexagonal phases was obtained and the coexistence of the two phases inside individual nanocrystals was also observed. More significantly, because of the small radius of Sc(3+), Na(x)ScF(3+x):Yb/Er nanocrystals show different UC emission from that of NaYF(4):Yb/Er nanocrystals, which broadens the applications of rare-earth-based nanomaterials ranging from optical communications to disease diagnosis.