Revealing the effect of substitutional cation doping in the A-site of nanoscale APbI3 perovskite layers for enhanced retention and endurance in optoelectronic resistive switching for non-volatile bipolar memory devices.

The effect of substitutional cation doping in the A-site of the nanoscale APbI3 perovskite layer has been systematically investigated to achieve improvements in the charge-carrier dynamics and endurance of non-volatile bipolar (NVB) memory devices. We successfully adopted an energy-efficient, ultra-fast microwave-assisted solvothermal (MW-ST) synthesis route to prepare a sequence of APbI3 (A = MA+, FA+, MAFA+, CsMA+ and CsMAFA+) perovskite powders with morphological transitions from cube-like polyhedrons to mixed polyhedrons and rods within 10 minutes at 120 °C without requiring any inert-gas atmosphere under high-humid ambient conditions. As-prepared APbI3 powders were dissolved in DMSO:DMF, followed by the fabrication of a thin film via spin-coating. Upon annealing at 120 °C, the nanoscale self-assembled thin-film layer was formed. We observed that devices with the inorganic Cs+ cation with organic cations, (CsMAPI and CsMAFAPI) device showed improved endurance (3500 and 5000 cycles, respectively) and outstanding retention (60 000 s) owing to effective charge-carrier dynamics, compared to organic cation-based MAPI, FAPI and MAFAPI (1800, 1200 and 1300 cycles, respectively). Significantly, various cation-doped APbI3-powders obtained via the MW-ST method remained to be stable for up to 5-months under high-humid conditions. Thus, enhanced optoelectronic-memory performance studies could provide an opportunity for next-generation nanoscale ORSNVB-memory devices for artificial intelligence (AI) and Internet of Things (IoT) applications.

Microwave-Enhanced Chemistry at Solid-Liquid Interfaces: Synthesis of All-Inorganic CsPbX3 Nanocrystals and Unveiling the Anion-Induced Evolution of Structural and Optical Properties.

We demonstrate how microwaves could enhance the chemistry at interfaces of heterogeneous reactions involved in the microwave-solvothermal (MW-ST) synthesis of all-inorganic CsPbX3 (X = Cl, Br, I) perovskite nanocrystals (PNCs) within 6 min, unlike a conventional hot-injection method that requires 3 h. The enhanced MW-ST reaction rate was quantitatively analyzed by the Eyring equation, and it has been observed that the decreased activation free energy (ΔG⧧) and increased activation entropy (ΔS⧧) are caused by changes in the relative energies of reactants at their solid-liquid interfaces, leading to the formation of "hot spots", where microwave energy absorption is at its maximum. This rapid and homogeneous microwave heating could facilitate the self-assembly of uniformly distributed CsPbX3 nanocubes with precise control over the stoichiometric ratio, as confirmed by high-resolution transmission electron microscopy and energy-dispersive X-ray analyses. X-ray diffraction and Raman results indicate that lattice contraction and expansion in CsPbBr3-yXy have occurred because of an increase in the metal-halide bond length upon moving down the groups Cl → Br → I, as further ascertained by the Rietveld refinement studies. These anion-induced structural variations accordingly affected the electronic properties of MW-ST-synthesized CsPbX3 PNCs, which is apparent from the shifts in their conduction-band (CB) and valence-band (VB) positions. Consequently, the optical properties were also altered, resulting in a color-tuned emission from blue to red, with excellent photoluminescence quantum yields (up to 92%) and narrow emission line widths, as is evident from UV-vis and photoluminescence spectroscopy. The MW-ST-synthesized CsPbX3 PNCs were used as color-conversion layers for the fabrication of light-emitting diodes (LEDs) with commercial 456 nm UV-LED chips.

Human Umbilical Cord Wharton's Jelly-Derived Mesenchymal Stem Cells Labeled with Mn2+ and Gd3+ Co-Doped CuInS2-ZnS Nanocrystals for Multimodality Imaging in a Tumor Mice Model.

Mesenchymal stem cell (MSCs) therapy has recently received profound interest as a targeting platform in cancer theranostics because of inherent tumor-homing abilities. However, the terminal tracking of MSCs engraftment by fluorescent in situ hybridization, immuno-histochemistry, and flow-cytometry techniques to translate into clinics is still challenging because of a dearth of inherent MSCs-specific markers and FDA approval for genetic modifications of MSCs. To address this challenge, a cost-effective noninvasive imaging technology based on multifunctional nanocrystals (NCs) with enhanced detection sensitivity, spatial-temporal resolution, and deep-tissue diagnosis is needed to be developed to track the transplanted stem cells. A hassle-free labeling of human umbilical cord Wharton's Jelly (WJ)-derived MSCs with Mn2+ and Gd3+ co-doped CuInS2-ZnS (CIS-ZMGS) NCs has been demonstrated in 2 h without requiring an electroporation process or transfection agents. It has been found that WJ-MSCs labeling did not affect their multilineage differentiation (adipocyte, osteocyte, chondrocyte), immuno-phenotypes (CD44+, CD105+, CD90+), protein (ß-actin, vimentin, CD73, α-SMCA), and gene expressions. Interestingly, CIS-ZMGS-NCs-labeled WJ-MSCs exhibit near-infrared (NIR) fluorescence with a quantum yield of 84%, radiant intensity of ∼3.999 × 1011 (p/s/cm2/sr)/(µW/cm2), magnetic relaxivity (longitudinal r1 = 2.26 mM-1 s-1, transverse r2 = 16.47 mM-1 s-1), and X-ray attenuation (78 HU) potential for early noninvasive multimodality imaging of a subcutaneous melanoma in B16F10-tumor-bearing C57BL/6 mice in 6 h. The ex vivo imaging and inductively coupled plasma mass-spectroscopy analyses of excised organs along with confocal microscopy and immunofluorescence of tumor results also significantly confirmed the positive tropism of CIS-ZMGS-NCs-labeled WJ-MSCs in the tumor environment. Hence, we propose the magnetofluorescent CIS-ZMGS-NCs-labeled WJ-MSCs as a next-generation nanobioprobe of three commonly used imaging modalities for stem cell-assisted anticancer therapy and tracking tissue/organ regenerations.

Noninvasive Tracking and Regenerative Capabilities of Transplanted Human Umbilical Cord-Derived Mesenchymal Stem Cells Labeled with I-III-IV Semiconducting Nanocrystals in Liver-Injured Living Mice.

Acute liver injury is a critical syndrome ascribed to prevalent death of hepatocytes and imperatively requires liver transplantation. Such a methodology is certainly hampered due to the deficit of healthy donors. In this regard, stem cell-based regenerative therapies are attractive in repairing injured tissues and organs for medical applications. However, it is crucial to understand the migration, engraftment, and regeneration capabilities of transplanted stem cells in the living animal models. For the first time, we demonstrate rapid labeling of umbilical cord-derived mesenchymal stem cells (MSCs) with near-infrared (NIR)-fluorescent CuInS2-ZnS nanocrystals (CIZS-NCs) to develop innovative nanobioconjugates (MSCs-CIZS-NBCs) that exhibit 98% labeling efficiency. Before nanobioconjugate synthesis, the pristine CIZS-NCs were prepared via a two-step, hot-injection, rapid and low-cost domestic-microwave-refluxing (MW-R) method within 6 min. The as-synthesized CIZS-NCs display high photoluminescence quantum yield (∼88%) and long-lived lifetime (23.4 µs). In contrast to unlabeled MSCs, the MSCs-CIZS nanobioconjugates show excellent biocompatibility without affecting the stemness, as confirmed by cell viability, immunophenotyping (CD44+, CD105+, CD90+), multi-lineage-specific gene expressions, and differentiation into adipocytes, osteocytes, and chondrocytes. The in vivo fluorescence tracking analyses revealed that the MSCs-CIZS-NBCs after tail-vein injection were initially trapped in the lungs and gradually engrafted in the injured liver within 2 h. The regeneration potential of MSCs-CIZS-NBCs was confirmed via renewal of the portal tract composed of portal veins, bile ducts, and hepatic arteries around the hepatocytes. Consequently, no apparent inflammations, necrosis, or apoptosis was observed in the acetaminophen (APAP)-induced liver-injured BALB/c mice model over 3 days after transplantation, as corroborated using laser-scanning confocal microscopy and histopathological and hematological analyses. Hence, our innovative NIR-fluorescent MSCs-CIZS-NBCs offer an off-the-self technology for noninvasive tracking of transplanted MSCs in an acute-liver-injured animal model for future image-guided cell-therapies.

Transition Metal Ion (Mn2+, Fe2+, Co2+, and Ni2+)-Doped Carbon Dots Synthesized via Microwave-Assisted Pyrolysis: A Potential Nanoprobe for Magneto-fluorescent Dual-Modality Bioimaging.

Heteroatom-doped carbon dots (C-dots) have captured widespread research interest owing to high fluorescence and biocompatibility for multimodal bioimaging applications. Here, we exemplify a rapid, facile synthesis of ethylenediamine (EDA)-functionalized transition metal ion (Mn2+, Fe2+, Co2+, and Ni2+)-doped C-dots via one-pot microwave (MW)-assisted pyrolysis at 800 W within 6 min using Citrus limon (lemon) extract as a carbon source. During MW pyrolysis, the precursor extract undergoes simultaneous carbonization and doping of metal ions onto C-dot surfaces in the presence of EDA. The EDA-functionalized transition metal ion-doped C-dots (i.e., Mn/C, Fe/C, Co/C, and Ni/C-dots) are collectively termed as TMCDs. The water-soluble TMCDs exhibited a size of 3.2 ± 0.485 nm and were enriched with amino and oxo functionalities and corresponding metal-oxide traces on the surfaces, as revealed from Fourier transfer infrared and X-ray photoelectron spectroscopy analyses. Interestingly, TMCDs demonstrated excitation-wavelength-dependent emission with brighter photoluminescence (PL) at 460 nm. Compared to pristine C-dots with a PL quantum yield (QY) of 48.31% and a fluorescence lifetime of 3.6 ns, the synthesized Mn/C, Fe/C, Co/C, and Ni/C-dots exhibited PL QY values of 35.71, 41.72, 75.07, and 50.84% as well as enhanced fluorescence lifetimes (τav) of 9.4, 8.6, 9.2, and 8.9 ns, respectively. The TMCDs significantly exhibited enhanced biocompatibility in human colon cancer cells (SW480) for fluorescence bioimaging and showed ferromagnetic and superparamagnetic behavior with vibrant T1-contrast ability. Interestingly, the maximum longitudinal (r1) relaxivity of 0.341 mM-1 s-1 was observed for Mn/C-dots in comparison to that of 3.1-3.5 mM-1 s-1 of clinically used Gd-DTPA magnetic resonance (MR)-contrast agent in vitro (1.5 T). Similarly, the maximum longitudinal relaxivity (r1) of 0.356 mM-1 s-1 was observed for Ni/C-dots (1.5 T) with respect to 4.16 ± 0.02 mM-1 s-1 attained for Gd-DTPA in vivo (8.45 T). Thus, the rapid, energy-efficient MW-assisted pyrolysis presents lemon extract derived, EDA-functionalized TMCDs with enhanced PL and efficient T1 contrast as potential magneto-fluorescent nanoprobes for dual-modality bioimaging applications.

Facile synthesis of carbon-decorated single-crystalline Fe3O4 nanowires and their application as high performance anode in lithium ion batteries.

A facile microwave-hydrothermal approach has been used to synthesize single-crystalline Fe(3)O(4) nanowires within 15 min at 150 degrees C. The Fe(3)O(4) nanowires, after decorating with carbon, exhibit excellent cyclability and rate performance when employed as an anode in lithium ion batteries.