Metal-polyphenol-network coated CaCO3 as pH-responsive nanocarriers to enable effective intratumoral penetration and reversal of multidrug resistance for augmented cancer treatments

Construction of multifunctional stimuli-responsive nanotherapeutics enabling improved intratumoral penetration of therapeutics and reversal of multiple-drug resistance (MDR) is potent to achieve effective cancer treatment. Herein, we report a general method to synthesize pH-dissociable calcium carbonate (CaCO₃) hollow nanoparticles with amorphous CaCO₃ as the template, gallic acid (GA) as the organic ligand, and ferrous ions as the metallic center via a one-pot coordination reaction. The obtained GA–Fe@CaCO₃ exhibits high loading efficiencies to both oxidized cisplatin prodrug and doxorubicin, yielding drug loaded GA–Fe@CaCO₃ nanotherapeutics featured in pH-responsive size shrinkage, drug release, and Fenton catalytic activity. Compared to nonresponsive GA–Fe@silica nanoparticles prepared with silica nanoparticles as the template, such GA–Fe@CaCO₃ confers significantly improved intratumoral penetration capacity. Moreover, both types of drug-loaded GA–Fe@CaCO₃ nanotherapeutics exhibit synergistic therapeutic efficacies to corresponding MDR cancer cells because of the GA–Fe mediated intracellular oxidative stress amplification that could reduce the efflux of engulfed drugs by impairing the mitochondrial-mediated production of adenosine triphosphate (ATP). As a result, it is found that the doxorubicin loaded GA–Fe@CaCO₃ exhibits superior therapeutic effect towards doxorubicin-resistant 4T1 breast tumors via combined chemodynamic and chemo-therapies. This work highlights the preparation of pH-dissociable CaCO₃-based nanotherapeutics to enable effective tumor penetration for enhanced treatment of drug-resistant tumors.

     

Interlayer Engineering of Molybdenum Trioxide toward High‐Capacity and Stable Sodium Ion Half/Full Batteries

Orthorhombic molybdenum trioxide (MoO₃) is one of the most promising anode materials for sodium‐ion batteries because of its rich chemistry associated with multiple valence states and intriguing layered structure. However, MoO₃ still suffers from the low rate capability and poor cycle induced by pulverization during de/sodiation. An ingenious two‐step synthesis strategy to fine tune the layer structure of MoO₃ targeting stable and fast sodium ionic diffusion channels is reported here. By integrating partially reduction and organic molecule intercalation methodologies, the interlayer spacing of MoO₃ is remarkably enlarged to 10.40 Å and the layer structural integration are reinforced by dimercapto groups of bismuththiol molecules. Comprehensive characterizations and density functional theory calculations prove that the intercalated bismuththiol (DMcT) molecules substantially enhanced electronic conductivity and effectively shield the electrostatic interaction between Na⁺ and the MoO₃ host by conjugated double bond, resulting in improved Na⁺ insertion/extraction kinetics. Benefiting from these features, the newly devised layered MoO₃ electrode achieves excellent long‐term cycling stability and outstanding rate performance. These achievements are of vital significance for the preparation of sodium‐ion battery anode materials with high‐rate capability and long cycling life using intercalation chemistry.     

Broad-Spectral-Range Sustainability and Controllable Excitation of Hyperbolic Phonon Polaritons in α-MoO3

Hyperbolic phonon polaritons (HPhPs) in orthorhombic-phase molybdenum trioxide (α-MoO₃) show in-plane hyperbolicity, great wavelength compression, and ultralong lifetime, therefore holding great potential in nanophotonic applications. However, its polaritonic response in the far-infrared (FIR) range remains unexplored due to challenges in experimental characterization. Here, monochromated electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) is used to probe HPhPs in α-MoO₃ in both mid-infrared (MIR) and FIR frequencies and correlate their behaviors with microstructures and orientations. It is found that low structural symmetry leads to various phonon modes and multiple Reststrahlen bands (RBs) over a broad spectral range (over 70 meV) and in different directions (55–63 meV and 119–125 meV along the b-axis, 68–106 meV along the c-axis, and 101–121 meV along the a-axis). These HPhPs can be selectively excited by controlling the direction of swift electrons. These findings provide new opportunities in nanophotonic and optoelectronic applications, such as directed light propagation, hyperlenses, and heat transfer.     

Precise Extraction of Charge Carrier Mobility for Organic Transistors

Unreliable mobility values, and particularly greatly overestimated values and severely distorted temperature dependences, have recently hampered the development of the organic transistor field. Given that organic field‐effect transistors (OFETs) have been routinely used to evaluate mobility, precise parameter extraction using the electrical properties of OFETs is thus of primary importance. This review examines the origins of the various mobilities that must be determined for OFET applications, the relevant extraction methods, and the data selection limitations, which help in avoiding conceptual errors during mobility extraction. For increased precision, the review also discusses device fabrication considerations, calibration of both the specific gate‐dielectric capacitance and the threshold voltage, the contact effects, and the bias and temperature dependences, which must actually be handled with great care but have mostly been overlooked to date. This review serves as a systematic overview of the OFET mobility extraction process to ensure high precision and will also aid in improving future research.     

Assembly of a DNA Origami Chinese Knot by Only 15% of the Staple Strands

As a giant leap in DNA self-assembly, DNA origami has exhibited an unprecedented ability to construct nanostructures with arbitrary shapes and sizes. In typical DNA origami, hundreds of short DNA staple strands fold a long, single-stranded (ss) DNA scaffold cooperatively into designed nanostructures. However, large numbers of DNA strands are expensive and would hinder applications such as pharmaceutical investigations because of the complicated components. Therefore, one challenge is how to reduce the number of staple strands needed to construct DNA origami. For a DNA origami structure, the scale-free folding pattern of the scaffold strand is determined by staple strands at the branching vertexes. Simple duplex regions help to define the size-related features of the origami geometry. In this study, we hypothesized that a scaffold strand can be correctly folded into a designed topology by using only staple strands involved in branching vertexes. After assembly, any remaining, flexible, single-stranded regions of the scaffold could be converted into rigid duplexes by DNA polymerase to achieve the designed geometric structures. To demonstrate the concept, we used only 18 staple strands (covering 15 % of the scaffold strand) to assemble a porous DNA nanostructure, which was visualized by atomic force microscopy (AFM). This study helps understanding of the role of cooperativity in origami folding, and provides a cost-effective approach for small-scale prototyping DNA origami.     

Flotation Behavior,Collector Adsorption Mechanism of Quartz and Feldspar-Quartz Systems Using PEA as a Novel Green Collector

Silicon - A novel green cationic surfactant Poly (propylene glycol) bis (2-aminopropyl ether) (PEA) with multiple amine groups was utilized as a collector for flotation separation of quartz from...     

Cerebral microbleeds and cognitive decline in a hemodialysis patient: Case report and review of literature

Cerebral microbleeds (CMBs) are small hemosiderin deposits indicative of prior cerebral microscopic hemorrhage and previously thought to be clinically silent. Recent population‐based cross‐sectional studies and prospective longitudinal cohort studies have revealed association between CMB and cognitive dysfunction. In the general population, CMBs are associated with age, hypertension, and cerebral amyloid angiopathy. In the chronic kidney disease (CKD) population, diminished estimated glomerular filtration rate has been found to be an independent risk factor for CMB, raising the possibility that a uremic milieu may predispose to microbleeds. In the end‐stage renal disease (ESRD) population on hemodialysis, the incidence of microbleeds is significantly higher compared with a control group without history of CKD or stroke. We present an ESRD patient on chronic hemodialysis with a history of gradual cognitive decline and progressive CMBs. Through this case and literature review, we illustrate the need to develop detection and prediction models to treat this frequent development in ESRD patients.     

Two-step pyrolytic engineering to form porous nitrogen-rich carbons with a 3D network structure for Zn-air battery oxygen reduction electrocatalysis

It is of great urgency to design inexpensive and high-performance oxygen reduction reaction (ORR) electrocatalysts derived from biowastes as substitutes for Pt-based materials in electrochemical energy-conversion devices. Here we propose a strategy to synthesize three-dimensional (3D) porous nitrogen-doped network carbons to catalyze the ORR from two-step pyrolysis engineering of biowaste scale combined with the use of a ZnCl₂ activator and a FeCl₂ promotor. Electrochemical tests show that the synthesized network carbons have exhibited comparable ORR catalytic activity with a half-wave potential (~0.85 V vs. RHE) and outstanding cyclical stability in comparison to the Pt/C catalyst. Beyond that, a high electron transfer number (~3.8) and a low peroxide yield (<7.6%) can be obtained, indicating a four-electron reaction pathway. The maximum power density is ~68 mW cm^?2, but continuous discharge curves (at a constant potential of ~1.30 V) for 12 h are not obviously declined in Zn-air battery tests using synthesized network carbons as the cathodic catalyst. The formation of 3D porous structures with high BET surface area can effectively expose the surface catalytic sites and promote mass transportation to boost the ORR activity. This work may open a new idea to prepare porous carbon-based catalysts for some important reactions in new energy devices.