Search Results (103)

A reflective plasmonic humidity sensor based on an Au–PVA–Au nanohole sandwich structure is investigated. The device consists of a periodic gold nanohole array, a poly(vinyl alcohol) (PVA) spacer, and a continuous gold film. A humidity-dependent model considering both the refractive-index decrease and thickness swelling of PVA is established to analyze the optical response and resonance-modulation mechanism. Within the relative humidity range of 20–98%RH, the reflection resonance dip exhibits a continuous blueshift with a total wavelength shift of approximately 135 nm. Piecewise linear fitting shows sensitivities of 1.3857 nm/%RH in the 20–74%RH range and 2.5000 nm/%RH in the 74–98%RH range. At approximately 74%RH, the resonance wavelength, full width at half maximum, and quality factor are about 830 nm, 19 nm, and 43.7, respectively. Decoupling analysis confirms that both PVA refractive-index reduction and thickness swelling contribute to the blueshift, while their combined effect produces the largest response. These results demonstrate that the proposed structure converts humidity-induced optical and geometric variations in PVA into a pronounced wavelength response, providing a mechanism-guided design route for reflective nanoplasmonic humidity sensors based on polymer-assisted cavity modulation. Full article

Background/Objectives: We aimed to identify eating habits associated with hepatic fat fraction (HFF) and assess effect modification by an established genetic variant for fatty liver disease, PNPLA3 rs738409, among 381 general-risk adolescents. Methods: Dietary intake was assessed using the Block Kids Food Frequency Questionnaire and HFF was measured via magnetic resonance imaging (MRI) at age ~16 years. We first characterized naturally occurring dietary patterns using principal component analysis followed by reduced-rank regression with HFF as the response variable to identify a dietary pattern that is both relevant to the population and associated with HFF. Next, we investigated associations of the dietary pattern with HFF using linear regression models that accounted for maternal gestational diabetes, education, and prenatal smoking and child sex, age, Tanner stage, and BMI. Finally, we tested for a dietary pattern and PNPLA3 rs738409 interaction and stratified by genotype if P-interaction < 0.05. Results: The participants were 16.7 ± 1.2 years (range: 12.6–19.6 years). Half were female (50.4%) and 52.0% identified as non-Hispanic White. The dietary pattern of interest was composed of vegetables, fruit, nuts and seeds, oatmeal, sports bars, crackers and sandwiches, and beef, and was inversely associated with HFF (−0.48 [95% CI: −0.81, −0.16]). Stratified analyses revealed the strongest inverse association observed between the diet pattern score and HFF in the high-risk-variant (GG) group (−2.19 [−4.35, −0.03]), followed by the intermediate-risk (CG) group (−0.43 [−0.77, −0.10]), but not the low-risk (CC) group (−0.32 [−0.77, 0.13]). Conclusions: A diet high in vegetables, fruit, nuts and seeds, oatmeal, sports bars, crackers and sandwiches, and beef—potentially capturing an active, on-the-go lifestyle—is associated with lower HFF during adolescence, especially among individuals at genetic risk. Full article

Background/Objectives: The neonatal Fc receptor (FcRn) plays a crucial role in extending the systemic half-life of monoclonal antibodies (mAbs), but its influence on ocular distribution remains incompletely understood. This study investigated the impact of FcRn on the ocular disposition of mAbs following systemic administration in rabbits. Methods: New Zealand White rabbits received a single intravenous dose (1 mg/kg) of either wild-type trastuzumab (TS-WT) or its FcRn non-binding variant (IHH). Plasma and ocular tissues (retina, iris–ciliary body, vitreous humor, aqueous humor, cornea, conjunctiva, and tears) were collected at terminal time points up to 336 h for TS-WT and 168 h for IHH. Antibody concentrations were quantified using a validated sandwich ELISA. Pharmacokinetic parameters and antibody biodistribution coefficients (ABC) were calculated to assess the FcRn-mediated effects on ocular distribution. Results: TS-WT demonstrated 2-fold higher systemic exposure compared to IHH. The iris–ciliary body exhibited the highest absolute exposure for both antibodies, with TS-WT showing significantly higher accumulation (ABC_0–168h: 14.95% vs. 8.89%). Retinal distribution remained comparable between antibodies (5.96% vs. 5.51%). Both antibodies were detectable in tears, with ABC value of ~4% reported for TS-WT. TS-WT also demonstrated markedly increased distribution in vitreous humor and tear fluid (3.5- and 5.5-fold higher ABC values, respectively) compared to IHH. The cornea (5.76% vs. 5.57%) and conjunctiva (7.71% vs. 7.21%) showed comparable relative distribution between TS-WT and IHH, while aqueous humor showed minimal differences (0.44% vs. 0.52%). Conclusions: This investigation reveals distinct tissue-specific patterns of FcRn-mediated mAb distribution within the eye. FcRn binding significantly enhanced antibody distribution in ocular tissues, such as the iris–ciliary body, and tears, with less pronounced effects on the retina, cornea, conjunctiva and aqueous humor. These findings provide mechanistic insights for optimizing mAb-based therapeutics for ocular disease and understanding the ocular toxicity of mAb-based therapeutics, such as antibody–drug conjugates. Full article

The integration of mechanics-based analysis and materials design procedures has become central to the development of multi-material structures with tailored mechanical and dynamic performance. In this study, the dynamic and flexural behaviour of multi-material FDM sandwich beams composed of PETG face sheets and an ABS core is experimentally investigated. Seven different infill patterns Grid, Line, Wavy, Honeycomb, Gyroid, Cubic, and Triangle were implemented in the core layer to assess their influence on damping and natural frequency behaviour. Experimental modal analysis was performed using impact testing to identify the first three vibration modes. Natural frequencies were extracted from Frequency Response Functions (FRFs), and modal damping ratios were determined using the half-power bandwidth method. The reliability of the damping results was evaluated through statistical analysis. Additionally, quasi-static three-point bending tests were conducted to assess flexural strength and load-carrying capacity. The results demonstrate that infill topology has a significant impact on both dynamic and mechanical responses. In particular, geometrically complex infill patterns exhibit enhanced stiffness, higher natural frequencies, and improved damping performance. Among the investigated designs, the Triangle infill exhibited the highest natural frequency values across the first three vibration modes (f₁ ≈ 24.910 Hz, f₂ ≈ 162.609 Hz, f ≈ 466.595 Hz), indicating its superior stiffness characteristics. In terms of damping behaviour, the Cubic infill showed the highest loss factor in the first vibration mode (0.0426), while the Line and Gyroid patterns exhibited the highest damping in the second (0.0439) and third modes (0.0354), respectively. Moreover, the force–displacement results revealed that the Triangle infill exhibited the highest load-bearing capacity, further confirming its superior structural stiffness among the investigated designs (SEA = 110.83 J/kg). These findings highlight the potential of multi-material FDM for designing polymer-based sandwich structures with tailored vibration and energy dissipation characteristics. Full article

Density functional theory (DFT) calculations elucidate the mechanism of diastereoselective cyclization of 2-picoline with 1,5-hexadiene catalyzed by a cationic half-sandwich scandium complex. The catalytic cycle proceeds through four key stages: formation of active species, initial alkene insertion, cis-selective cyclization, and protonation. Central to the mechanism is the dual role of 2-picoline, which initially coordinates as a supporting ligand to facilitate C–H activation and regioselective 1,2-insertion but must dissociate to enable stereocontrol. The mono(2-picoline)-coordinated complex C3 is identified as the thermodynamically favored active species. C–H activation reactivity follows the trend: ortho-C(sp²)–H (2-picoline-free) > ortho-C(sp²)–H (2-picoline-coordinated) > benzylic C(sp³)–H (2-picoline-free) > benzylic C(sp³)–H (2-picoline-coordinated), a preference governed by a wider C_α–Sc–C_α′ angle and shorter Sc···X (X = C_α, C_α′, H) distances that enhance scandium–substrate interaction. Subsequent 1,5-hexadiene insertion proceeds with high 1,2-regioselectivity through a picoline-assisted pathway. The stereoselectivity-determining step reveals a mechanistic dichotomy: while picoline coordination is essential for initial activation, its dissociation is required for intramolecular cyclization. This ligand displacement avoids prohibitive steric repulsion in the transition state, directing the reaction exclusively toward the cis-cyclized product. The cycle concludes with a sterically accessible mono-coordinated protonation. This work establishes a “ligand-enabled then ligand-displaced” mechanism, highlighting dynamic substrate coordination as a critical design principle for achieving high selectivity in rare-earth-catalyzed C–H functionalization. Full article

Current tumor diagnostics rely on fluorodeoxyglucose (FDG)-PET imaging, but FDG’s short half-life and high cost limit its widespread use. Infrared (IR) probes are emerging as non-radioactive alternatives to conventional tracers for tissue section and other in vitro imaging applications. Because cells and tissues are relatively free of absorption peaks between 1800 and 2200 cm⁻¹, metal-carbonyl complexes, especially cyclopentadienylrhenium(I) tricarbonyl (Cp[Re(CO)₃]) derivatives, absorb strongly in this window and provide robust platforms for bioconjugation. Furthermore, Cp[Re(CO)₃] fragments can be introduced into organic substrates via an elegant three-component reaction that simultaneously forges the cyclopentadienyl-metal and cyclopentadienyl-substituent bonds. As a result, the functionalized half-sandwich complex is obtained in a single step without any special handling issues. We have therefore properly modified a glucose molecule with that complex and developed a novel glucoconjugated Cp[Re(CO)₃] probe that enables IR-based visualization of diseased cells at 2100 cm⁻¹, offering a non-invasive, non-radioactive histological tool and a promising basis for future medical imaging devices. Full article

The number of structurally investigated cyclopentadienyl (Cp⁻) complexes of technetium is limited in contrast to the situation with its heavier homolog, rhenium. Although this could be attributed to the radioactivity of all isotopes of the radioelement, there are also clear chemical differences to analogous compounds of the other group seven elements, manganese and rhenium. Technetium Cp⁻ compounds are known with the metal in the oxidation states “+1” to “+7”, with a clear dominance of Tc(I) carbonyls and nitrosyls. Corresponding carbonyl complexes also play a significant role in the development of ^99mTc-based radiopharmaceuticals with the aromatic ring as an ideal position for the attachment of biomarkers. In this paper, the present status of the synthetic and structural chemistry of technetium with Cp⁻ ligands is discussed, together with recent developments in the corresponding ^99mTc labeling chemistry. Full article

This study describes a series of water-soluble half-sandwich ruthenium(II), rhodium(III), and iridium(III) complexes with α-diimine ligands containing substituted aromatic groups. These ligands were derived from glyoxal and 2-aminophenol (a), 4-methyl-2-aminophenol (b), 4-aminophenol (c), phenyl hydrazine (d), and 1-aminonaphthalene (e). The ruthenium(II) (1b–1e), rhodium(III) (2a–2c, 2e), and iridium(III) complexes (3a–3e) were obtained by reacting the ligands (a–e) with the corresponding dimeric precursor [(η⁶-p-cym)RuCl₂]₂ (p-cym = p-cymene) or [(η⁵-Cp*)MCl₂]₂ (Cp* = pentamethylcyclopentadienyl, M = Rh, Ir) in air and under nonanhydro conditions. The air-stable and water-soluble ruthenium(II), rhodium(III), and iridium(III) complexes were characterized via nuclear magnetic resonance spectroscopy and electrospray ionization–mass spectrometry. The structures of complexes [(η⁶-p-cym)Ru(d)Cl]Cl, 1d; [(η⁵-Cp*)Ir(a)Cl]Cl, 3a; and [(η⁵-Cp*)Ir(c)Cl]Cl, 3c were determined via single-crystal X-ray diffraction. Additionally, the complexes exhibited catalytic activity as precatalysts in formic acid decomposition. Complex [(η⁵-Cp*)Ir(d)Cl]Cl, 3d achieved turnover number (TON) and turnover frequency (TOF) values of up to 2150 and 3861 h⁻¹, respectively, at short reaction times. In the hydrogenation of carbon dioxide, [(η⁶-p-cym)Ru(e)Cl]Cl, 1e attained TON and TOF values of up to 1385 and 69.25 h⁻¹, respectively. Full article

Plasmonic metasurfaces that convert hydrogen-induced dielectric changes into optical signals hold promise for next-generation hydrogen sensors. Here, we employ simulations and theoretical analysis to systematically assess single-layer, bilayer, and trilayer nanodisk arrays comprising magnesium, palladium, and noble metals. Although monolithic Mg nanodisks show strong optical contrast after hydrogenation, the corresponding surface plasmon resonance disappears completely, preventing quantitative spectral tracking. In contrast, bilayer heterostructures, particularly those combining Mg and Au, achieve a resonance red-shift of Δλ = 62 nm, a narrowed full width at half maximum (FWHM) of 207 nm, and a figure of merit (FoM) of 0.30. Notably, the FoM is boosted by up to 15-fold when tuning both material choice and stacking sequence (from Mg-Ag to Au-Mg), underscoring the critical role of interface engineering. Trilayer “sandwich” architectures further amplify performance, achieving a max 10-fold and 13-fold enhancement in Δλ and FoM, respectively, relative to its bilayer counterpart. Particularly, the trilayer Mg-Au-Mg reaches Δλ = 120 nm and FoM = 0.41, outperforming most previous plasmonic hydrogen sensors. These enhancements arise from maximized electric-field overlap with dynamically changing dielectric regions at noble-metal–hydride interfaces, as confirmed by first-order perturbation theory. These results indicate that multilayer designs combining Mg and noble metals can simultaneously maximize hydrogen-induced spectral shifts and signal quality, providing a practical pathway toward high-performance all-optical hydrogen sensors. Full article

Polybutadiene (PB) and polyisoprene (PI) rubbers are indispensable synthetic elastomeric materials widely used in tires, footwear, hose, belts, sealants, electricity, construction, and other applications. Nowadays, PB and PI elastomers are produced from butadiene (BD) and isoprene (IP) monomers via transition-metal-mediated coordination polymerization. Transition metal catalytic systems consist of a precise characteristic structural unit at the molecular level: well known as “single-site catalysts” (SSCs). These have experienced a revolutionary advance in the recently developed conjugated dienes synthetic rubber method. Among the SSCs, a class of rare-earth, metal-centered half-sandwich molecule has been identified as a high-performance catalytic system for conjugated dienes polymerization. These novel half-sandwich rare-earth (HSRE) catalytic systems exhibit several irreplaceable advantages compared with the conventional Ziegler–Natta-type catalytic systems. These HSRE catalytic systems can create novel conjugated diene rubbers (CDRs) with high catalytic reactivity, high stereoselectivity, an adjustable polymer chain microstructure, and high molecular weights and are considered to be the next generation of ecofriendly and economic catalytic systems for industrial applications. This paper delivers a concise review of some important synthetic methods for representative HSRE complexes with characteristic structures and of the utilization of some HSRE catalytic systems for the preparation of high-performance CDRs, especially highly stereoregular PI and PB materials. Full article

Towards the efforts to expand the bioactivity and to reduce toxic and adverse properties of known metal-based drugs, various multinuclear complexes have recently been studied. They have shown enhancement of target specificity and selectivity. Different from small organic compounds and traditional metal-based complexes with anticancer activity, iridium(III) multinuclear or heteronuclear metallodrugs have confirmed potential advantages due to their unique biological and chemical diversities, better activity and different anticancer mechanisms. Ir(III) coordination compounds, similar to most Pt group compounds, are of excessive interest because of their potential cytotoxic activity, effective cellular uptake and tolerance by healthy cells. Although mononuclear Ir(III) complex compounds have been extensively studied as promising candidates for antitumor application, the research on the antineoplastic potential of homo- or hetero-multinuclear iridium(III) complexes is not as abundant; nevertheless, intensive investigations have been conducted in the recent years towards developing complexes that are anticipated to have improved therapeutic potential and biotarget selectivity. Multimetallic iridium(III) frameworks have offered interesting possibilities for designing new antitumor agents by exploiting the action of different metal cations at the same time. This method was very successful in the design of homo- and hetero-multinuclear cyclometalated and half-sandwich organometallic Ir(III) compounds. In the described background, many homonuclear and heteronuclear Ir(III) complexes have been estimated and have exposed promising advantages in cancer therapy. This review intends to summarize newly reported innovative and promising multinuclear Ir(III)-based complexes and to afford a wide-ranging overview of current development and perspectives for the practical impact of these complexes in the tumor therapy field. It is anticipated that this analysis will provide significant direction for the further progress of active homonuclear and heteronuclear iridium-based anticancer agents. Full article

This paper presents the development of two solutions for sandwich panels composed of a thin-layer alkali-activated composite (AAc) layer and a thicker insulation layer, formed by extruded polystyrene foam or expanded cork agglomerate (panels named AP_XPS or AP_ICB, respectively). The AAc combined ceramic waste from clay bricks and roof tiles (75%) with ladle furnace slag (25%), activated with sodium silicate. The AAc layer was further reinforced with polyacrylonitrile (PAN) fibers (1% content). The mechanical behavior was assessed by measuring the uniaxial compressive strength of cubic AAc specimens, shear bond strength, pull-off strength between the AAc layer and the insulation material, and the flexural behavior of the sandwich panels. The thermal performance was characterized by heat flux, inner surface temperatures, the thermal transmission coefficient, thermal resistance, and thermal conductivity. Mechanical test results indicated clear differences between the two proposed solutions. Although AP_XPS panels exhibited higher tensile bond strength values, the AP_ICB panels demonstrated superior interlayer bond performance. Similar findings were observed for the shear bond strength, where the irregular surface of the ICB positively influenced the adhesion to the AAc layer. In terms of flexural behavior, after the initial peak load, the AP_XPS exhibited a deflection-hardening response, achieving greater load-bearing capacity and energy absorption capacity compared to the AP_ICB. Finally, thermal resistance values of 1.02 m² °C/W and 1.14 m² °C/W for AP_ICB and AP_XPS were estimated, respectively, showing promising results in comparison to currently available building materials. Full article

Globally, an estimated 254 million people are living with chronic hepatitis B virus (HBV) infection, yet only 10.5% have been diagnosed, underscoring the urgent need to expand testing to meet the World Health Organization’s HBV elimination targets by 2030. Many HBV diagnostic tests remain expensive and inaccessible in resource-limited settings. In this study, we demonstrate how individually sourced, commercially available reagents can be used to develop cost-effective in-house assays for total DNA isolation, HBV viral load quantification by (q)PCR, and qHBsAg and qHBeAg measurement using sandwich ELISA. These assays were validated using known HBV-positive and HBV-negative plasma samples (genotypes A–F) and HepAD38 cells treated with tenofovir disoproxil fumarate (TDF). DNA isolation using a commercial column-based kit was compared to a high-throughput, column-free method, allowing for HBV quantification from 50 µL of plasma with lower limits of detection (LLOD) of 1.8 × 10³ and 1.8 × 10⁴ HBV DNA copies IU/mL, respectively. Both commercial and in-house DNA isolation methods yielded comparable half-maximal effective concentration (EC₅₀) values in TDF-treated HepAD38 cells. Additionally, in-house sandwich ELISA assays were developed for quantitative HBsAg and HBeAg detection, with LLOD values of 0.78 IU/mL and 0.38 PEI U/mL (Paul Ehrlich Institute), respectively. The in-house reagents for DNA isolation, molecular testing, and serological detection of HBV were estimated to be at least 10 times more cost-effective than commercially available kits, highlighting their potential for broader application in resource-limited regions. Full article

The conversion of abandoned butted well salt cavities into underground storage facilities holds immense significance for safeguarding energy security and improving the ecological environment. A significant barrier to the reconstruction of these old cavities is the limited comprehension of their complete morphology, caused by residue coverage. The three-dimensional seismic techniques excel in identifying complex geological structures but have a limited understanding of underground old salt cavity morphology, thus the seismic forward simulation method is utilized to study their seismic response patterns. Based on 3D seismic data, well logging data, and measured cavity shape parameters from the Yexian salt mine region in Henan Province, China, a geological model and observation system were established. The seismic response characteristics of the butted well salt cavern model, encompassing five distinct morphological attributes such as cavity spacing, cavity diameter, cavity height, sediment height, and horizontal connection channel height, were thoroughly investigated. The findings show that the cavity roof exhibits a distinctive “two peaks sandwiching a strong valley” feature, with the positions of the valley and roof remaining aligned and serving as a reliable indicator for identifying the cavity’s top surface. The width of the roof waveform exhibits an exponential amplification effect relative to the cavern width. The residue’s top surface presents an “upward-opening arc” wave peak with a downward shift that diminishes as the residue’s height increases. This peak forms a circular feature with the cavity roof reflection waveform, and the residue’s top surface is always located in the upper half of this circular waveform. The horizontal connection channel’s top and bottom surfaces exhibit contrasting reflection patterns, with the top position aligning with the reflection trough and the bottom reflection waveform shifting downward as the channel height increases. The brine cavern, residue, and bottom of the salt cavern mainly exhibit chaotic reflections. There are distinct identification characteristics on the cavity top, residue top, and connecting channel top in forward simulation. The research findings provide valuable guidance for identifying the morphology of the underground real butted well salt cavity based on 3D seismic data and accelerating the construction of underground energy storage facilities. Full article

Heterobimetallic complexes of an ambidentate deferiprone derivative, 3-hydroxy-2-methyl-1-(3-((pyridin-2-ylmethyl)amino)propyl)pyridin-4(1H)-one (PyPropHpH), incorporating an octahedral [Co(4N)]³⁺ (4N = tris(2-aminoethyl)amine (tren) or tris(2-pyridylmethyl)amine (tpa)) and a half-sandwich type [(η⁶-p-cym)Ru]²⁺ (p-cym = p-cymene) entity have been synthesized and characterized by various analytical techniques. The reaction between PyPropHpH and [Co(4N)Cl]Cl₂ resulted in the exclusive (O,O) coordination of the ligand to Co(III) yielding [Co(tren)PyPropHp](PF₆)₂ (1) and [Co(tpa)PyPropHp](PF₆)₂ (2). This binding mode was further supported by the molecular structure of [Co(tpa)PyPropHp]₂(ClO₄)₃(OH)·6H₂O (5) and [Co(tren)PyPropHpH]Cl(PF₆)₂·2H₂O·C₂H₅OH (6), respectively, obtained via the slow evaporation of the appropriate reaction mixtures and analyzed using X-ray crystallography. Subsequent treatment of 1 or 2 with [Ru(η⁶-p-cym)Cl₂]₂ in a one-pot reaction afforded the corresponding heterobimetallic complexes, [Co(tren)PyPropHp(η⁶-p-cym)RuCl](PF₆)₃ (3) and [Co(tpa)PyPropHp(η⁶-p-cym)RuCl](PF₆)₃ (4), in which the piano-stool Ru core is coordinated by the (N,N) chelating set of the ligand. Cyclic voltammetric measurements revealed that the tpa complexes can be reduced at less negative potentials, suggesting their capability to be bioreductively activated under hypoxia (1% O₂). Hypoxia activation of 2 and 4 was demonstrated by cytotoxicity studies on the MCF-7 human breast cancer cell line. PyPropHpH was shown to be a typical iron-chelating anticancer agent, raising the mRNA levels of TfR1, Ndrg1 and p21. Further qRT-PCR studies provided unambiguous evidence for the bioreduction of 2 after 72 h incubation under hypoxia, in which the characteristic gene induction profile caused by the liberated iron-sequestering PyPropHpH was observed. Full article