A Stable Perovskite Sensitized Photonic Crystal P-N Junction with Enhanced Photoelectrochemical Hydrogen Production.

The slow photon effect in inverse opal photonic crystals represents a promising approach to manipulate the interactions between light and matter through the design of material structures. This study introduces a novel ordered inverse opal photonic crystal (IOPC) sensitized with perovskite quantum dots (PQDs), demonstrating its efficacy for efficient visible-light-driven H2 generation via water splitting. The rational structural design contributes to enhanced light harvesting. The sensitization of the IOPC with PQDs improves optical response performance and enhances photocatalytic H2 generation under visible light irradiation compared to the IOPC alone. The designed photoanode exhibits a photocurrent density of 3.42 mA cm-2 at 1.23 V vs RHE. This work advances the rational design of visible light-responsive photocatalytic heterostructure materials based on wide band gap metal oxides for photoelectrochemical applications.

Electric-Field-Assisted Synthesis of Cu/MoS2 Nanostructures for Efficient Hydrogen Evolution Reaction.

Molybdenum sulfide-oxide (MoS2, MS) emerges as the prime electrocatalyst candidate demonstrating hydrogen evolution reaction (HER) activity comparable to platinum (Pt). This study presents a facile electrochemical approach for fabricating a hybrid copper (Cu)/MoS2 (CMS) nanostructure thin-film electrocatalyst directly onto nickel foam (NF) without a binder or template. The synthesized CMS nanostructures were characterized utilizing energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), and electrochemical methods. The XRD result revealed that the Cu metal coating on MS results in the creation of an extremely crystalline CMS nanostructure with a well-defined interface. The hybrid nanostructures demonstrated higher hydrogen production, attributed to the synergistic interplay of morphology and electron distribution at the interface. The nanostructures displayed a significantly low overpotential of -149 mV at 10 mA cm-2 and a Tafel slope of 117 mV dec-1, indicating enhanced catalytic activity compared to pristine MoS2.This research underscores the significant enhancement of the HER performance and conductivity achieved by CMS, showcasing its potential applications in renewable energy.

Advances in All-Solid-State Lithium-Sulfur Batteries for Commercialization.

Solid-state batteries are commonly acknowledged as the forthcoming evolution in energy storage technologies. Recent development progress for these rechargeable batteries has notably accelerated their trajectory toward achieving commercial feasibility. In particular, all-solid-state lithium-sulfur batteries (ASSLSBs) that rely on lithium-sulfur reversible redox processes exhibit immense potential as an energy storage system, surpassing conventional lithium-ion batteries. This can be attributed predominantly to their exceptional energy density, extended operational lifespan, and heightened safety attributes. Despite these advantages, the adoption of ASSLSBs in the commercial sector has been sluggish. To expedite research and development in this particular area, this article provides a thorough review of the current state of ASSLSBs. We delve into an in-depth analysis of the rationale behind transitioning to ASSLSBs, explore the fundamental scientific principles involved, and provide a comprehensive evaluation of the main challenges faced by ASSLSBs. We suggest that future research in this field should prioritize plummeting the presence of inactive substances, adopting electrodes with optimum performance, minimizing interfacial resistance, and designing a scalable fabrication approach to facilitate the commercialization of ASSLSBs.

Emerging potentials of Fe-based nanomaterials for chiral sensing and imaging.

Fe-based nanostructures have possessed promising properties that make it suitable for chiral sensing and imaging applications owing to their ultra-small size, non-toxicity, biocompatibility, excellent photostability, tunable fluorescence, and water solubility. This review summarizes the recent research progress in the field of Fe-based nanostructures and places special emphases on their applications in chiral sensing and imaging. The synthetic strategies to prepare the targeted Fe-based structures were also introduced. The chiral sensing and imaging applications of the nanostructures are discussed in details.

Defect-Engineered Fe3C@NiCo2S4 Nanospike Derived from Metal-Organic Frameworks as an Advanced Electrode Material for Hybrid Supercapacitors.

The rational synthesis and tailoring of metal-organic frameworks (MOFs) with multifunctional micro/nanoarchitectures have emerged as a subject of significant academic interest owing to their promising potential for utilization in advanced energy storage devices. Herein, we explored a category of three-dimensional (3D) NiCo2S4 nanospikes that have been integrated into a 1D Fe3C microarchitecture using a chemical surface transformation process. The resulting electrode materials, i.e., Fe3C@NiCo2S4 nanospikes, exhibit immense potential for utilization in high-performance hybrid supercapacitors. The nanospikes exhibit an elevated specific capacity (1894.2 F g-1 at 1 A g-1), enhanced rate capability (59%), and exceptional cycling stability (92.5% with 98.7% Coulombic efficiency) via a charge storage mechanism reminiscent of a battery. The augmented charge storage characteristics are attributed to the collaborative features of the active constituents, amplified availability of active sites inherent in the nanospikes, and the proficient redox chemical reactions of multi-metallic guest species. When using nitrogen-doped carbon nanofibers as the anode to fabricate hybrid supercapacitors, the device exhibits high energy and power densities of 62.98 Wh kg-1 and 6834 W kg-1, respectively, and shows excellent long-term cycling stability (95.4% after 5000 cycles), which affirms the significant potential of the proposed design for applications in hybrid supercapacitors. The DFT study showed the strong coupling of the oxygen from the electrolyte OH- with the metal atom of the nanostructures, resulting in high adsorption properties that facilitate the redox reaction kinetics.

Rugged Forest Morphology of Magnetoplasmonic Nanorods that Collect Maximum Light for Photoelectrochemical Water Splitting.

A feasible nanoscale framework of heterogeneous plasmonic materials and proper surface engineering can enhance photoelectrochemical (PEC) water-splitting performance owing to increased light absorbance, efficient bulk carrier transport, and interfacial charge transfer. This article introduces a new magnetoplasmonic (MagPlas) Ni-doped Au@Fex Oy nanorods (NRs) based material as a novel photoanode for PEC water-splitting. A two stage procedure produces core-shell Ni/Au@Fex Oy MagPlas NRs. The first-step is a one-pot solvothermal synthesis of Au@Fex Oy . The hollow Fex Oy nanotubes (NTs) are a hybrid of Fe2 O3 and Fe3 O4 , and the second-step is a sequential hydrothermal treatment for Ni doping. Then, a transverse magnetic field-induced assembly is adopted to decorate Ni/Au@Fex Oy on FTO glass to be an artificially roughened morphologic surface called a rugged forest, allowing more light absorption and active electrochemical sites. Then, to characterize its optical and surface properties, COMSOL Multiphysics simulations are carried out. The core-shell Ni/Au@Fex Oy MagPlas NRs increase photoanode interface charge transfer to 2.73 mAcm-2 at 1.23 V RHE. This improvement is made possible by the rugged morphology of the NRs, which provide more active sites and oxygen vacancies as the hole transfer medium. The recent finding may provide light on plasmonic photocatalytic hybrids and surface morphology for effective PEC photoanodes.

3D hierarchically porous magnetic molybdenum trioxide@gold nanospheres as a nanogap-enhanced Raman scattering biosensor for SARS-CoV-2.

The global pandemic of COVID-19 is an example of how quickly a disease-causing virus can take root and threaten our civilization. Nowadays, ultrasensitive and rapid detection of contagious pathogens is in high demand. Here, we present a novel hierarchically porous 3-dimensional magnetic molybdenum trioxide-polydopamine-gold functionalized nanosphere (3D mag-MoO3-PDA@Au NS) composed of plasmonic, semiconductor, and magnetic nanoparticles as a multifunctional nanosculptured hybrid. Based on the synthesized 3D mag-MoO3-PDA@Au NS, a universal "plug and play" biosensor for pathogens is proposed. Specifically, a magnetically-induced nanogap-enhanced Raman scattering (MINERS) detection platform was developed using the 3D nanostructure. Through a magnetic actuation process, the MINERS system overcomes Raman signal stability and reproducibility challenges for the ultrasensitive detection of SARS-CoV-2 spike protein over a wide dynamic range up to a detection limit of 10-15 g mL-1. The proposed MINERS platform will facilitate the broader use of Raman spectroscopy as a powerful analytical detection tool in diverse fields.

Photodynamic therapy characteristics of phthalocyanines in the presence of boron doped detonation nanodiamonds: Effect of symmetry and charge.

The synthesis, photophysicochemical and photodynamic therapy (PDT) activities of benzothiazole substituted zinc phthalocyanine (Pc): 1 (asymmetrically substituted and composed of no charges), 2 (asymmetrically substituted and composed of three positive charges), and 3 (symmetrically substituted and composed of four positive charges), are presented. The triplet and singlet oxygen quantum yields were highest for complex 2 showing the importance of asymmetry and charge. The complexes are covalently and non-covalently linked to B doped detonation nanodiamonds (B@DNDs) to yield nanohybrids (B@DNDs-1, B@DNDs-2, B@DNDs-3). The presence of B@DNDs, asymmetry and positive charge resulted in improved PDT with the lowest cell viability being observed for B@DNDs-2 at 5%. The cell viability ranged from 5% to 7% for the nanohybrids compared to 19-26% for Pcs alone.

One-Pot Synthesis of One-Dimensional Multijunction Semiconductor Nanochains from Cu1.94S, CdS, and ZnS for Photocatalytic Hydrogen Generation.

Chains of alternating semiconductor nanocrystals are complex nanostructures that can offer control over photogenerated charge carriers dynamics and quantized electronic states. We develop a simple one-pot colloidal synthesis of complex Cu1.94S-CdS and Cu1.94S-ZnS nanochains exploiting an equilibrium driving ion exchange mechanism. The chain length of the heterostructures can be tuned using a concentration dependent cation exchange mechanism controlled by the precursor concentrations, which enables the synthesis of monodisperse and uniform Cu1.94S-CdS-Cu1.94S nanochains featuring three epitaxial junctions. These seamless junctions enable efficient separation of photogenerated charge carriers, which can be harvested for photocatalytic applications. We demonstrate the superior photocatalytic activity of these noble metal free materials through solar hydrogen generation at a hydrogen evolution rate of 22.01 mmol g-1 h-1, which is 1.5-fold that of Pt/CdS heterostructure photocatalyst particles.

Light- and Melanin Nanoparticle-Induced Cytotoxicity in Metastatic Cancer Cells.

Melanin nanoparticles are known to be biologically benign to human cells for a wide range of concentrations in a high glucose culture nutrition. Here, we show cytotoxic behavior at high nanoparticle and low glucose concentrations, as well as at low nanoparticle concentration under exposure to (nonionizing) visible radiation. To study these effects in detail, we developed highly monodispersed melanin nanoparticles (both uncoated and glucose-coated). In order to study the effect of significant cellular uptake of these nanoparticles, we employed three cancer cell lines: VM-M3, A375 (derived from melanoma), and HeLa, all known to exhibit strong macrophagic character, i.e., strong nanoparticle uptake through phagocytic ingestion. Our main observations are: (i) metastatic VM-M3 cancer cells massively ingest melanin nanoparticles (mNPs); (ii) the observed ingestion is enhanced by coating mNPs with glucose; (iii) after a certain level of mNP ingestion, the metastatic cancer cells studied here are observed to die-glucose coating appears to slow that process; (iv) cells that accumulate mNPs are much more susceptible to killing by laser illumination than cells that do not accumulate mNPs; and (v) non-metastatic VM-NM1 cancer cells also studied in this work do not ingest the mNPs, and remain unaffected after receiving identical optical energy levels and doses. Results of this study could lead to the development of a therapy for control of metastatic stages of cancer.

Corrosion Resistance of Aluminum against Acid Activation: Impact of Benzothiazole-Substituted Gallium Phthalocyanine.

This study describes the adsorption behavior of organic inhibitors at the aluminum-HCl solution interface and their corrosion inhibition performance. The organic inhibitors employed are: 4-(benzo [d]thiazol-2ylthio)phthalonitrile (BTThio) and tetrakis[(benzo[d]thiazol-2-yl-thio)phthalo- cyaninato]gallium(III) chloride (ClGaBTThioPc). The corrosion behavior of these inhibitors is investigated using electrochemical and computational techniques. Open circuit potential results reveal predominant cathodic character for the mechanism of aluminum corrosion inhibition by the inhibitors. Inhibition efficiency values from potentiodynamic polarization measurements increase from 46.9 to 70.8% for BTThio and 59.7 to 81.0% for ClGaBTThioPc within the concentration range of 2 to 10 µM. Scanning electron microscopy (SEM) measurements reveal protection of the metal surface from acid attack, in the presence of the inhibitors and energy dispersive X-ray (EDX) measurements show that the most probable way by which the inhibitors protect the metal surface would be by shielding it from the corrosion attacks of Cl- from the acid. Quantum chemical parameters corroborate well with experimental findings.

Photophysical and enhanced nonlinear optical response in asymmetric benzothiazole substituted phthalocyanine covalently linked to semiconductor quantum dots.

The synthesis of asymmetric benzothiazole substituted phthalocyanines (complexes 3 to 5) and their covalent attachment to glutathione (GSH) functionalized quantum dots (QDs) are reported in this work. Additionally, their photophysical and nonlinear optical properties were investigated. A decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield was observed when the complexes were covalently linked to glutathione (GSH) functionalized cadmium telluride (CdTe) quantum dots. Reverse saturable absorption was found to be predominantly dominated by excited state absorption. The observed limiting threshold values range from 0.29-0.75 J/cm2.

Glycosylated zinc phthalocyanine-gold nanoparticle conjugates for photodynamic therapy: Effect of nanoparticle shape.

In this work, we report on the synthesis of tris-[(2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-5-yl)methoxy)-2-(4-benzo[d]thiazol-2-ylphenoxyphthalocyaninato] zinc(II) (complex 3) and its linkage to gold nanoparticles (AuNPs) of different shapes through S-Au/N-Au self-assembly. The conjugates of complex 3 (with both gold nanorods (AuNR) and nanospheres (AuNS)), displayed decreased fluorescence quantum yield with corresponding improved triplet and singlet quantum yields compared to complex 3 alone, however 3-AuNR showed improved properties than 3-AuNS. Complex 3 showed relatively low in vitro dark cytotoxicity against the epithelial breast cancer cells with cell survival ≥ 85% at concentration ≤ 160 µg/mL but afforded reduced photodynamic therapy activity which may be due to aggregation. 3-AuNR afforded superior PDT activity with <50% viable cells at concentration ≥ 40 µg/mL in comparison to 3-AuNS with <50% viable cells at concentration ≥ 80 µg/mL. The superior activity of 3-AuNR is attributed to the photothermal therapy effect since nanorods absorb more light at 680 nm than nanospheres.