Air and Thermally Stable Fluoride Bridged Rare-Earth Clusters Showing Intense Photoluminescence and Potential LED Application.

Fluoride based lattice is attractive for reducing phonon-induced quenching in rare-earth (RE) based luminescent materials. However, due to the strong affinity between RE and oxygen, the synthesis of fluoride-based complexes has to be protected under anhydrous conditions, and many known fluoride bridged RE clusters are unstable in air. Here, by using the "mixed-ligand" strategy a family of fluoride bridged RE clusters is synthesized, namely RE16(µ4-F)6(µ3-F)12(tBuCOO)18[N(CH2CH2O)3]4 (RE = Eu, EuFC-16; RE = Tb, TbFC-16), which are highly stable in air and decomposed thermally only when heating above 435 °C. Moreover, both clusters exhibit high photoluminescence quantum yields (PLQYEuFC-16 = 87.7%, PLQYTbFC-16 = 99.0%). Upon warming, EuFC-16 and TbFC-16 display excellent structural, thermal, and chroma stability. Thus, EuFC-16 and TbFC-16 have the potential to be used in light-emitting diode (LED) devices, offering many advantages over commercial phosphors. First, both clusters are soluble in UV-curable resin at any mixing rate, and the emission colors can be tuned from magenta, turquoise, willow green, and ivory to pure white if mixing blue phosphor BAM:Eu2+. Second, the clusters are hydrophobic, and the LEDs work well after soaking in water, indicating a good quality for outdoor lighting.

Triple-negative breast cancer treatment with core-shell Magnetic@Platinium-Metal organic framework/epirubicin nano-platforms for chemo-photodynamic based combinational therapy: A review.

The combination of chemotherapy and photodynamic therapy (PDT), enabled by core-shell nano-platforms, is a promising method to improve cancer therapy by overcoming hypoxia and boosting drug penetration in breast tumor. Core-shell magnetic (iron oxide: Fe3O4)@platinum-metal organic framework/epirubicin (abbreviated as M@Pt-MOF/EPI) nano-platform is considered an effective cancer therapeutic agent. Relatively small particle size, round shape, and specific response to pH, are the key features of these nanomaterials to be used as promising therapeutic agents. Chemotherapy and photodynamic therapy, when applied in addition to the anticancer effects of nanomaterials, further enhance the therapeutic efficacy. The extensive use, utilization, and efficacy of Core-Shell Magnetic@Platinium-Metal Organic Framework/epirubicin Nano-Platforms for chemo-photodynamic combination therapy in the treatment of several cancers, including triple-negative breast cancer, are examined in this in-depth investigation.

The anomalous effect of electric field on friction for microscale structural superlubric graphite/Au contact.

The current-carrying friction characteristics are crucial for the performance of a sliding electrical contact, which plays critical roles in numerous electrical machines and devices. However, these characteristics are influenced by multiple factors such as material surface quality, chemical reactions, and atmospheric environment, leading to a challenge for researchers to comprehensively consider these impacts. Structural superlubricity (SSL), a state of nearly zero friction and no wear between contact solid surfaces, provides an ideal experimental system for these studies. Here, with microscale graphite flakes on atomic-flattened Au surface under applied voltages, we observed two opposite friction phenomena, depending only on whether the edge of graphite flake was in contact with the Au substrate. When in contact the friction force would increase with an increasing voltage, otherwise, the friction force would decrease. Notably, when the voltage was turned off, the friction force quickly recovered to its original level, indicating the absence of wear. Through atmosphere control and molecular dynamics simulations, we revealed the mechanism to be the different roles played by the water molecules confined at the interface or adsorbed near the edges. Our experimental results demonstrate the remarkable tunable and robust frictional properties of SSL under an electrical field, providing an ideal system for the fundamental research of not only sliding electrical contacts, but also novel devices which demand tunable frictions.

High-efficiency dysprosium-ion extraction enabled by a biomimetic nanofluidic channel.

Biological ion channels exhibit high selectivity and permeability of ions because of their asymmetrical pore structures and surface chemistries. Here, we demonstrate a biomimetic nanofluidic channel (BNC) with an asymmetrical structure and glycyl-L-proline (GLP) -functionalization for ultrafast, selective, and unidirectional Dy3+ extraction over other lanthanide (Ln3+) ions with very similar electronic configurations. The selective extraction mainly depends on the amplified chemical affinity differences between the Ln3+ ions and GLPs in nanoconfinement. In particular, the conductivities of Ln3+ ions across the BNC even reach up to two orders of magnitude higher than in a bulk solution, and a high Dy3+/Nd3+ selectivity of approximately 60 could be achieved. The designed BNC can effectively extract Dy3+ ions with ultralow concentrations and thereby purify Nd3+ ions to an ultimate content of 99.8 wt.%, which contribute to the recycling of rare earth resources and environmental protection. Theoretical simulations reveal that the BNC preferentially binds to Dy3+ ion due to its highest affinity among Ln3+ ions in nanoconfinement, which attributes to the coupling of ion radius and coordination matching. These findings suggest that BNC-based ion selectivity system provides alternative routes to achieving highly efficient lanthanide separation.

TRPM4-Inspired Polymeric Nanochannels with Preferential Cation Transport for High-Efficiency Salinity-Gradient Energy Conversion.

Biological ion channels exhibit switchable cation transport with ultrahigh selectivity for efficient energy conversion, such as Ca2+-activated TRPM4 channels tuned by cation-π interactions, but achieving an analogous highly selective function is challenging in artificial nanochannels. Here, we design a TRPM4-inspired cation-selective nanochannel (CN) assembled by two poly(ether sulfone)s, respectively, with sulfonate acid and indole moieties, which act as cation-selective activators to manage Na+/Cl- selectivity via ionic and cation-π interactions. The cation selectivity of CNs can be activated by Na+, and thereby the Na+ transference number significantly improves from 0.720 to 0.982 (Na+/Cl- selectivity ratio from 2.6 to 54.6) under a 50-fold salinity gradient, surpassing the K+ transference number (0.886) and Li+ transference number (0.900). The TRPM4-inspired nanochannel membrane enabled a maximum output power density of 5.7 W m-2 for salinity-gradient power harvesting. Moreover, a record energy conversion efficiency of up to 46.5% is provided, superior to most nanochannel membranes (below 30%). This work proposes a novel strategy to biomimetic nanochannels for highly selective cation transport and high-efficiency salinity-gradient energy conversion.

Effect of Mn2+ Doping on the Photoluminescence of Hybrid One-Dimensional Lead Halide Post-Perovskites.

Although organic-inorganic hybrid one-dimensional (1D) lead halide postperovskites (LHPPs) have been reported to show white luminescence and tunable photoluminescence quantum yield (PLQY), their structure-property relationships are not fully understood. Here, we used Mn2+ to test the doping effect on the luminescence of two 1D-LHPPs compounds, namely, {TETA[Pb2Br6]}n 1 and {TETA[Pb2Cl6]}n 2, where TETA = triethylenetetrammonium. We found the pristine compounds show yellowish (551 nm) and bluish (447 nm) emission for 1 and 2, respectively, nanosecond excitation lifetimes (4.17 ns for 1 and 2.29 ns for 2) and low PLQYs (4.65 and 3.57% for 1 and 2, respectively). By fine-doping the Mn2+ ions to ca. 8% the PLQYs for 1 and 2 are maximized to 24 and 25% for 1 and 2, respectively. Upon the increasing Mn2+ dopant, the emission wavelengths can also vary gradually from 551 to 615 nm and from 447 to 660 nm for 1 and 2, respectively, covering almost the whole visible-light range, and the excitation lifetimes are enhanced to microseconds (0.77 µs for 1 and 0.39 µs for 2), owing to the more spin-forbidden d-d transition (4T1-6A1) component from the Mn2+ ions present in the photoluminescence spectra. Moreover, these Mn2+-doped 1D-LHPPs demonstrate high structural and optical stability in humid and high-temperature environments. Hence, such doped materials can be fabricated into a UV-pumped white light-emitting diode, rendering the potential application for solid-state lighting and display systems.

Tumor-repopulating cells evade ferroptosis via PCK2-dependent phospholipid remodeling.

Whether stem-cell-like cancer cells avert ferroptosis to mediate therapy resistance remains unclear. In this study, using a soft fibrin gel culture system, we found that tumor-repopulating cells (TRCs) with stem-cell-like cancer cell characteristics resist chemotherapy and radiotherapy by decreasing ferroptosis sensitivity. Mechanistically, through quantitative mass spectrometry and lipidomic analysis, we determined that mitochondria metabolic kinase PCK2 phosphorylates and activates ACSL4 to drive ferroptosis-associated phospholipid remodeling. TRCs downregulate the PCK2 expression to confer themselves on a structural ferroptosis-resistant state. Notably, in addition to confirming the role of PCK2-pACSL4(T679) in multiple preclinical models, we discovered that higher PCK2 and pACSL4(T679) levels are correlated with better response to chemotherapy and radiotherapy as well as lower distant metastasis in nasopharyngeal carcinoma cohorts.

Quasi-distributed quartz enhanced photoacoustic spectroscopy sensing based on hollow waveguide micropores.

In this Letter, a quasi-distributed quartz enhanced photoacoustic spectroscopy (QEPAS) gas sensing system based on hollow waveguide micropores (HWGMP) was reported for the first time, to the best of our knowledge. Three micropores were developed on the HWG to achieve distributed detection units. Three self-designed quartz tuning forks (QTFs) with low resonant frequency of 8.7 kHz were selected as the acoustic wave transducer to improve the detection performance. Compared with micro-nano fiber evanescent wave (FEW) QEPAS, the HWGMP-QEPAS sensor has advantages such as strong anti-interference ability, low loss, and low cost. Acetylene (C2H2) was selected as the target gas to verify the characteristics of the reported sensor. The experimental results showed that the three QTFs almost had the same sensing ability and possessed an excellent linear concentration response to C2H2. The minimum detection limits (MDLs) for the three QTFs were determined as 68.90, 68.31, and 66.62 ppm, respectively. Allan deviation analysis indicated that the system had good long-term stability, and the MDL can be improved below 3 ppm in an average time of 1000 s.

Quantum-Geometry-Induced Anomalous Hall Effect in Nonunitary Superconductors and Application to Sr_{2}RuO_{4}.

The polar Kerr effect and the closely related anomalous charge Hall effect are among the most distinguishing signatures of the superconducting state in Sr_{2}RuO_{4}, as well as in several other compounds. These effects are often thought to be derived from chiral superconducting pairing, and different mechanisms have been invoked for the explanation. However, the intrinsic mechanisms proposed previously often involve unrealistically strong interband Cooper pairing. We show in this Letter that, even without interband pairing, nonunitary superconducting states can support the intrinsic anomalous charge Hall effect, thanks to the quantum geometric properties of the Bloch electrons. The key here is to have a normal-state spin Hall effect, for which a nonzero spin-orbit coupling is essential. A finite charge Hall effect then naturally arises at the onset of a spin-polarized nonunitary superconducting pairing. It depends on both the spin polarization and the normal-state electron Berry curvature, the latter of which is the imaginary part of the quantum geometric tensor of the Bloch states. Applying our results to the weakly paired Sr_{2}RuO_{4} we conclude that, if the reported Kerr effect is of intrinsic origin, the superconducting state is most likely nonunitary and has odd parity. Our theory may be generalized to other superconductors that exhibit the polar Kerr effect.

Ion-Concentration-Hopping Heterolayer Gel for Ultrahigh Gradient Energy Conversion.

Conventional solid ion channel systems relying on single one- or two-dimensional confined nanochannels enabled selective and ultrafast convective ion transport. However, due to intrinsic solid channel stacking, these systems often face pore-pore polarization and ion concentration blockage, thereby restricting their efficiency in macroscale ion transport. Here, we constructed a soft heterolayer-gel system that integrated an ion-selective hydrogel layer with a water-barrier organogel layer, achieving ultrahigh cation selectivity and flux and effectively providing high-efficiency gradient energy conversion on a macroscale order of magnitude. Specifically, the hydrogel layer featured an unconfined 3D network, where the fluctuations of highly hydrated polyelectrolyte chains driven by thermal dynamics enhanced cation selectivity and mitigated transfer energy barriers. Such chain fluctuation mechanisms facilitated ion-cluster internal transmission, thereby enhancing ion concentration hopping for more efficient ion-selective transport. Compared to the existing rigid nanochannel-based gradient energy conversion systems, such a heterogel-based power generator exhibited a record power density of 192.90 and 1.07 W/m2 at the square micrometer scale and square centimeter scale, respectively (under a 500-fold artificial solution). We anticipate that such heterolayer gels would be a promising candidate for energy separation and storage applications.

Ultrahigh Critical Current Density across Sliding Electrical Contacts in Structural Superlubric State.

In conventional sliding electrical contacts (SECs), large critical current density (CCD) requires a high ratio between actual and apparent contact area, while low friction and wear require the opposites. Structural superlubricity (SSL) has the characteristics of zero wear, near zero friction, and all-atoms in real contact between the contacting surfaces. Here, we show a measured current density up to 17.5 GA/m^{2} between microscale graphite contact surfaces while sliding under ambient conditions. This value is nearly 146 times higher than the maximum CCD of other SECs reported in literatures (0.12 GA/m^{2}). Meanwhile, the coefficient of friction for the graphite contact is less than 0.01 and the sliding interface is wear-free according to the Raman characterization, indicating the presence of the SSL state. Furthermore, we estimate the intrinsic CCD of single crystalline graphite to be 6.69 GA/m^{2} by measuring the scaling relation of CCD. Theoretical analysis reveals that the CCD is limited by thermal effect due to the Joule heat. Our results show the great potential of the SSL contacts to be used as SECs, such as micro- or nanocontact switches, conductive slip rings, or pantographs.

Mid-infrared all-fiber light-induced thermoelastic spectroscopy sensor based on hollow-core anti-resonant fiber.

In this article, a mid-infrared all-fiber light-induced thermoelastic spectroscopy (LITES) sensor based on a hollow-core anti-resonant fiber (HC-ARF) was reported for the first time. The HC-ARF was applied as a light transmission medium and gas chamber. The constructed all-fiber structure has merits of low loss, easy optical alignment, good system stability, reduced sensor size and cost. The mid-infrared transmission structure can be utilized to target the strongest gas absorption lines. The reversely-tapered SM1950 fiber and the HC-ARF were spatially butt-coupled with a V-shaped groove between the two fibers to facilitate gas entry. Carbon monoxide (CO) with an absorption line at 4291.50 cm-1 (2.33 µm) was chosen as the target gas to verify the sensing performance. The experimental results showed that the all-fiber LITES sensor based on HC-ARF had an excellent linear response to CO concentration. Allan deviation analysis indicated that the system had excellent long-term stability. A minimum detection limit (MDL) of 3.85 ppm can be obtained when the average time was 100 s.

Fine Tuning Ag(I)-Sb(III) Hybrid Iodides for Light Detection.

Lead-free hybrid double perovskite iodides (HDPIs) have piqued increasing research interest due to their environmental friendliness and high stability. However, such antimony-based HDPIs with strong photocurrent response are currently very limited. Here, we successfully design and construct five Ag(I)-Sb(III)-based HDPIs using two types of cyclic aliphatic amines as A-site templates. Interestingly, these Ag(I)-Sb(III) HDPIs exhibit relatively narrow band gaps, preferred orientation, and high stability after being processed into thin films on the indium tin oxide (ITO) substrate. Notably, under illuminations of a xenon lamp, all HDPIs exhibit considerable photocurrent responses, reaching a maximum difference of 17 µA·cm-2 for ASI 1, which is the highest among lead-free halogen-based organic-inorganic hybrid compounds to date. Combining the considerable photocurrents and the high stability, the optoelectronic applications of two-dimensional Ag(I)-Sb(III) HDPIs can be expected.

Gradient Quasi-Solid Electrolyte Enables Selective and Fast Ion Transport for Robust Aqueous Zinc-Ion Batteries.

The quasi-solid electrolytes (QSEs) attract extensive attention due to their improved ion transport properties and high stability, which is synergistically based on tunable functional groups and confined solvent molecules among the polymetric networks. However, the trade-off effect between the polymer content and ionic conductivity exists in QSEs, limiting their rate performance. In this work, the epitaxial polymerization strategy is used to build the gradient hydrogel networks (GHNs) covalently fixed on zinc anode. Then, it is revealed that the asymmetric distribution of negative charges benefits GHNs with fast and selective ionic transport properties, realizing a higher Zn2+ transference number of 0.65 than that (0.52) for homogeneous hydrogel networks (HHNs) with the same polymer content. Meanwhile, the high-density networks formed at Zn/GHNs interface can efficiently immobilize free water molecules and homogenize the Zn2+ flux, greatly inhibiting the water-involved parasitic reactions and dendrite growth. Thus, the GHNs enable dendrite-free stripping/plating over 1000 h at 8 mA cm-2 and 1 mAh cm-2 in a Zn||Zn symmetric cell, as well as the evidently prolonged cycles in various full cells. This work will shed light on asymmetric engineering of ion transport channels in advanced quasi-solid battery systems to achieve high energy and safety.

Filtering Robust Graphite without Incommensurate Interfaces by Electrical Technique.

Two-dimensional (2D) van der Waals (vdW) layered materials have attracted considerable attention due to their potential applications in various fields. Among these materials, graphite is widely employed to achieve structural superlubricity (SSL), where the interfacial friction between two solids is almost negligible and the wear is zero. However, the development of integrated SSL systems using graphite flakes still faces a major obstacle stemming from the inherent delamination-induced instability in vdW layered materials. To address this issue, we propose a nondestructive filtering technique that utilizes electrical measurement to identify robust graphite flakes without delamination. Our experimental results confirm that all the filtered graphite flakes exhibit delamination-free behavior after more than 7000 cycles of sliding on a series of 2D and 3D substrates. Besides, we employ three types of characterizing methods to confirm that the filtering process does not impair the graphite flakes. Moreover, with focused ion beam (FIB) assisted slicing characterization and statistical analysis, we have discovered that all of the filtered flakes possess a graphite layer thickness below 100 nm. This is consistent with the thickness of the single crystalline graphite layer of our samples reported in the literature, suggesting the absence of incommensurate interfaces in the filtered graphite flakes. Our work contributes to a deeper understanding of the relationship between graphite conductance and incommensurate interfaces. In addition, we present a possible solution to address the delamination problem in layered materials, and this technique shows the potential to characterize the internal microstructure of grains and the distribution of grain boundaries in vdW materials on a large scale.

Cascade-heterogated biphasic gel iontronics for electronic-to-multi-ionic signal transmission.

Currently, electronics and iontronics in abiotic-biotic systems can only use electrons and single-species ions as unitary signal carriers. Thus, a mechanism of gating transmission for multiple biosignals in such devices is needed to match and modulate complex aqueous-phase biological systems. Here we report the use of cascade-heterogated biphasic gel iontronics to achieve diverse electronic-to-multi-ionic signal transmission. The cascade-heterogated property determined the transfer free energy barriers experienced by ions and ionic hydration-dehydration states under an electric potential field, fundamentally enhancing the distinction of cross-interface transmission between different ions by several orders of magnitude. Such heterogated or chemical-heterogated iontronics with programmable features can be coupled with multi-ion cross-interface mobilities for hierarchical and selective cross-stage signal transmission. We expect that such iontronics would be ideal candidates for a variety of biotechnology applications.

CT Findings of Undifferentiated Pancreatic Cancer With Osteoclast-Like Giant Cells: A Case Series from a Single Center's Experience With 10 Cases.

Little is known about the imaging features of undifferentiated carcinoma with osteoclast-like giant cells of the pancreas (UCOGCP) because of its extremely low incidence. To improve the diagnostic accuracy of this tumor, 10 UCOGCP cases with confirmed histopathology were collected and their clinical and image data features were analyzed. We found that the median age of our study was 61 years (50-76 years in range) and the main clinical manifestations were nonspecific abdominal pain. There were some differences in the degree of enhancement and computed tomography (CT) features between the tumor located at the head and body or tail of the pancreas. Perhaps these subtle imaging findings can provide valuable diagnostic information.

Hollow-waveguide-based light-induced thermoelastic spectroscopy sensing.

In this Letter, a hollow waveguide (HWG)-based light-induced thermoelastic spectroscopy (LITES) gas sensing is proposed. An HWG with a length of 65 cm and inner diameter of 4 mm was used as the light transmission medium and gas chamber. The inner wall of the HWG was coated with a silver (Ag) film to improve reflectivity. Compared with the usually used multi-pass cell (MPC), the HWG has many advantages, such as small size, simple structure and fast filling. Compared with a hollow-core anti-resonant fiber (HC-ARF), the HWG has the merits of easy optical coupling, high system stability, and wide transmission range. A diode laser with output wavelength of 1.53 µm and a quantum cascade laser (QCL) with output wavelength of 4.58 µm were selected as the sources of excitation to target acetylene (C2H2) and carbon monoxide (CO), respectively, to verify the performance of the HWG-based LITES sensor in the near-infrared and mid-infrared regions. The experimental results showed that the HWG-based LITES sensor had a great linear responsiveness to the target gas concentration. The minimum detection limit (MDL) for C2H2 and CO was 6.07 ppm and 98.66 ppb, respectively.

Neuron-Inspired Nanofluidic Biosensors for Highly Sensitive and Selective Imidacloprid Detection.

Pesticides have caused concerns about food safety due to their residual effects in vegetables and fruits. Imidacloprid, as the frequently used neonicotinoid pesticide, could harm cardiovascular and respiratory function and cause reproductive toxicity in humans. Therefore, reliable methods for portable, selective, and rapid detection are desirable to develop. Herein, we report a neuron-inspired nanofluidic biosensor based on a tyrosine-modified artificial nanochannel for sensitively detecting imidacloprid. The functional tyrosine is modified on the outer surface of porous anodic aluminum oxide to rapidly capture imidacloprid through π-π interactions and hydrogen bonds. The integrated nanofluidic biosensor has a wide concentration range from 10-8 to 10-4 g/mL with an ultralow detection limit of 6.28 × 10-9 g/mL, which outperforms the state-of-the-art sensors. This work provides a new perspective on detecting imidacloprid residues as well as other hazardous pesticide residues in environmental and food samples.

Recent Advances of Fe(III)/Fe(II)-MPNs in Biomedical Applications.

Metal-phenolic networks (MPNs) are a new type of nanomaterial self-assembled by metal ions and polyphenols that have been developed rapidly in recent decades. They have been widely investigated, in the biomedical field, for their environmental friendliness, high quality, good bio-adhesiveness, and bio-compatibility, playing a crucial role in tumor treatment. As the most common subclass of the MPNs family, Fe-based MPNs are most frequently used in chemodynamic therapy (CDT) and phototherapy (PTT), where they are often used as nanocoatings to encapsulate drugs, as well as good Fenton reagents and photosensitizers to improve tumor therapeutic efficiency substantially. In this review, strategies for preparing various types of Fe-based MPNs are first summarized. We highlight the advantages of Fe-based MPNs under the different species of polyphenol ligands for their application in tumor treatments. Finally, some current problems and challenges of Fe-based MPNs, along with a future perspective on biomedical applications, are discussed.