This study introduces hollow sponge Haliclona sp. spicules (oSHS) as an innovative microneedle technology for enhancing the skin delivery of biomacromolecules. oSHS were developed by etching SHS in 2 mol/L NaOH for 48 h, optimizing hollow channel formation while preserving structural integrity. In vitro experiments demonstrated that oSHS significantly enhanced drug absorption efficiency compared to SHS, microneedles, roller microneedles, and iontophoresis alone. Combining oSHS with iontophoresis yielded a synergistic effect, increasing biomacromolecule delivery by up to 35.09% (p <0.05). In vivo skin delivery of ovalbumin (OVA) via oSHS elicited immune responses comparable to subcutaneous injection, with elevated OVA-specific IgE and IL-4 levels. A mathematical model was developed to describe oSHS-mediated permeation, revealing dose-dependent delivery and uniform distribution of biomacromolecules in deep skin layers, contrasting with localized accumulation from injections. Safety assessments confirmed minimal and reversible skin irritation, resolving within 72 h. These findings highlight oSHS as a safe, efficient, and scalable strategy for skin delivery of proteins, nucleic acids, and other macromolecules, offering significant potential for non-invasive therapeutic applications.

The sluggish kinetics of the oxygen evolution reaction (OER) impede efficient water electrolysis, motivating the development of robust, non-precious-metal electrocatalysts. Here, we construct a self-supported bimetallic metal-organic framework precatalyst (PAx-NiCo-BDC) through a two-step strategy using phytic acid (PA) for mild etching and multidentate coordination. This treatment introduces oxygen-vacancy-related coordination defects and regulates the precursor morphology. The optimized PA3-NiCo-BDC requires only 212 mV to reach 10 mA cm[-] [2], exhibits a Tafel slope of 20.2 mV dec[-] [1], and shows excellent durability, outperforming commercial RuO2. An anion-exchange-membrane water electrolyzer employing PA3-NiCo-BDC delivers 1 A cm[-] [2] at 1.72 V and operates stably for 300 h. In situ Raman spectroscopy reveals that PA-induced defects enable the lower-potential formation of Ni[3+]-O-containing NiOOH-like surface species. Differential electrochemical mass spectrometry identifies the adsorbate evolution mechanism as the dominant OER pathway. Density functional theory calculations further show that defect-induced d-band-center modulation optimizes the adsorption and desorption of OER intermediates at Ni sites and lowers the OER energy barrier. This green coordination-engineering strategy provides a versatile route to efficient and durable MOF-based electrodes for practical water electrolysis.

The discovery of in-plane ordered MAX (i-MAX) phases containing lanthanides provides a promising route to novel MXenes. Most MXenes have transition elements occupying the M site. However, the distinctive optical and magnetic properties of lanthanides could yield multifunctional MAX phases and MXenes with applications in aeronautics, radiation shielding, and space technology. Previously, lanthanide-containing i-MAX phases were etched to produce ordered vacancy MXenes via lanthanide removal. Here, we report the first synthesis of (Mo2/3Nd1/3)2CTx i-MXene retaining Nd and compare wet chemical etching, fluorine-free molten salt etching, and hydrothermal etching routes. A key challenge is removing Al without also removing Nd. Etching with concentrated hydrofluoric acid (HF) yielded i-MXene along with neodymium fluoride. Etching using lithium fluoride (LiF) and hydrochloric acid (HCl) produced an accordion-like morphology typical of MXenes. Mixed acids (HF and HCl) yielded more uniform etching compared to other etchants. Both molten salt etching and alkali etching proved less effective. We discuss the potential and challenges of each etching method. Based on the similar chemical behavior of lanthanides, we expect results for the Nd-containing i-MAX phase to be representative. This comparative study reveals significant morphological and structural differences, paving the way for the synthesis of a new family of lanthanide-containing i-MXenes.

The conversion of CO2 to CO using electrochemistry requires the use of earth abundant catalysts with high selectivity, rapid reaction rate, and durability. In this work, hierarchically porous Co-N-C catalysts were synthesized via co-pyrolysis of a bimetallic zeolitic imidazolate framework (Zn/Co) and the dicyandiamide (DCD) followed by acid etching. By systematically adjusting the pyrolysis temperature (800 °C-1,000 °C) and the Co feed ratio (5-20 mol%), volcano-type activity relationships are found, which are controlled by the interplay of the three factors graphitization, nitrogen retention, and the density of Co-Nx sites. The optimized catalyst CoNC-900 achieves a Faradaic efficiency of CO of 94.9% ± 1.0% at -0.75 V vs. RHE in CO2-saturated 0.5 M KHCO3 with a CO partial current density of 16.0 mA cm[-2], a lower bound turnover frequency of ≥0.33 s[-1] and ≈11% current decay FE_CO retained above 92% over 24 h. The observed selectivity can be rationalized, as the density functional theory calculations indicate that the barrier of the rate-determining step, namely the formation of COOH is lowered on the Co-N4 moiety (0.42 eV, whereas ≥1.79 eV on the metal-free nitrogen sites). A transferable design rule is developed for CO2 electrolysis that relates bimetallic MOF precursor chemistry, hierarchical porosity, and M-Nx site engineering.

Light naphtha is a critical feedstock whose full value relies on molecular-level fractionation into value-specific streams. Achieving such precise separation remains difficult because its components exhibit extremely similar physicochemical properties. Here, we address this challenge by developing a graded membrane cascade based on metal-organic framework CuBTC whose pore size and surface chemistry are continuously tuned through mild tannic acid treatment. Membranes with distinct sieving characteristics were created to sequentially co-separate linear and mono-branched alkanes and then selectively permeate aromatics. The integrated cascade fractionated a 15-component C5-C7 mixture into three high-purity streams, ethylene feedstock, chemical intermediates, and gasoline fuel, with recoveries of 85%-90% and an estimated 91% reduction in energy consumption compared to conventional distillation. This strategy establishes an energy-efficient route toward molecular refining.

We demonstrate a tunable organic/inorganic metal-organic framework (MOF) structure, constructed on in-plane MBene (i-MBene) to serve as electrodes for supercapacitors. Bimetallic Zn/Cu MOF was synthesized and hybridized in situ over in-plane Mo4/3Y2/3B2 (ZC-MYB), whereas i-MBene was produced by etching aluminum layers using hydrofluoric acid. The ZC-MYB composite demonstrated a 46% increase in specific capacitance compared to ZC MOF and a 5.6-fold increase over i-MBene at 1 A/g in hybrid (asymmetric) supercapacitors. The ZC-MYB composite exhibited an 81% cyclic durability over 9000 cycles. The apparent diffusion coefficient of ZC and ZC-MYB obtained from the Warburg element decreased, while electrochemical impedance analysis exhibited a much lower polarization resistance and a CPE response closer to the ideal capacitive behavior in 6 M KOH. The ZC-MYB/AC device, operating as an asymmetric supercapacitor, demonstrated a specific capacitance of 73.4 F/g at a scan rate of 2 mV/s and maintained a voltage window of 1.6 V. A Random Forest model trained on 200 experimental observations from 35 independently synthesized samples showed a moderate within-domain prediction (R[2] = 0.522), under a leave-one-sample-out validation. However, very low prediction of the high specific capacitance data illustrated the role of the model as an exploratory, rather than a universal predictor.

Pulsed electric field gene electrotransfer addresses the need for safe, directed "vector-free" delivery of DNA/mRNA therapeutics in deep tissue targets. We report the development of a disposable needle-type "electro-lens" probe for precision delivery of DNA/mRNA to tissues via translocation of nucleic acids into cells using focused single-pulse electric fields. We developed and manufactured a novel ganged linear bionic electrode array enhanced by incorporating integrated microfluidics to deliver naked DNA expression cassettes in a low-conductivity carrier ("conductivity-clamping," CC). This system was packaged in a disposable wireless probe for single capacitive discharge conductivity-clamped gene electrotransfer (SCD-CC-GET), powered by an integrated capacitor with automated discharge mechanism. The electrode array was achieved by laser-etching parylene-insulated concentric stainless steel needles, with the lensing effect of the electric field tuned by varying the separation between elongated conductive elements. Our novel SCD-CC-GET probe is fully wireless and standalone, featuring integrated fluidics with minimal dead space, and an automated discharge mechanism. The probe was validated in vitro through HEK293 cell transfection of green fluorescent protein reporter plasmid DNA, where CC significantly expanded the transfection zone by up to 3×. In vivo proof of concept for deep tissue gene delivery by SCD-CC-GET was achieved in the mouse gastrocnemius muscle with long-term expression of mCherry reporter DNA. Our technology for GET is compact, low-cost, and fully wireless, with only a single point of insertion, and produces maximal electric fields at the target zone, allowing for more efficient gene therapies with minimal charge transfer, in a fine needle profile.