Engineering topological interface states in metal-wire waveguides for broadband terahertz signal processing.

Innovative terahertz waveguides are in high demand to serve as a versatile platform for transporting and manipulating terahertz signals for the full deployment of future six-generation (6G) communication systems. Metal-wire waveguides have emerged as promising candidates, offering the crucial advantage of sustaining low-loss and low-dispersion propagation of broadband terahertz pulses. Recent advances have opened up new avenues for implementing signal-processing functionalities within metal-wire waveguides by directly engraving grooves along the wire surfaces. However, the challenge remains to design novel groove structures to unlock unprecedented signal-processing functionalities. In this study, we report a plasmonic signal processor by engineering topological interface states within a terahertz two-wire waveguide. We construct the interface by connecting two multiscale groove structures with distinct topological invariants, i.e., featuring a π-shift difference in the Zak phases. The existence of this topological interface within the waveguide is experimentally validated by investigating the transmission spectrum, revealing a prominent transmission peak in the center of the topological bandgap. Remarkably, we show that this resonance is highly robust against structural disorders, and its quality factor can be flexibly controlled. This unique feature not only facilitates essential functions such as band filtering and isolating but also promises to serve as a linear differential equation solver. Our approach paves the way for the development of new-generation all-optical analog signal processors tailored for future terahertz networks, featuring remarkable structural simplicity, ultrafast processing speeds, as well as highly reliable performance.

Single-shot ultrafast terahertz photography.

Multidimensional imaging of transient events has proven pivotal in unveiling many fundamental mechanisms in physics, chemistry, and biology. In particular, real-time imaging modalities with ultrahigh temporal resolutions are required for capturing ultrashort events on picosecond timescales. Despite recent approaches witnessing a dramatic boost in high-speed photography, current single-shot ultrafast imaging schemes operate only at conventional optical wavelengths, being suitable solely within an optically-transparent framework. Here, leveraging on the unique penetration capability of terahertz radiation, we demonstrate a single-shot ultrafast terahertz photography system that can capture multiple frames of a complex ultrafast scene in non-transparent media with sub-picosecond temporal resolution. By multiplexing an optical probe beam in both the time and spatial-frequency domains, we encode the terahertz-captured three-dimensional dynamics into distinct spatial-frequency regions of a superimposed optical image, which is then computationally decoded and reconstructed. Our approach opens up the investigation of non-repeatable or destructive events that occur in optically-opaque scenarios.

Core-shell metal-organic frameworks with pH/GSH dual-responsiveness for combined chemo-chemodynamic therapy.

A novel core-shell metal organic framework (MOF), Cu-MOF@SMON/DOX-HA, was fabricated using 3-amino-1,2,4-triazole (3-AT) and organosilicon for combined chemo-chemodynamic therapy with high drug-loading capacity, pH/GSH dual-responsiveness, and good biocompatibility. The Cu-MOF@SMON/DOX-HA could not only generate reactive oxygen species, but also effectively consume glutathione (GSH) to induce cell ferroptosis. This work involves the modification of organosilicon on the surface of MOFs, which possess good performance in high drug-loading ability and pH/GSH dual-responsive degradation for combined chemo-chemodynamic therapy.

pH-responsive Mannose-modified ferrocene Metal-Organic frameworks with rare earth for Tumor-targeted synchronous Chemo/Chemodynamic therapy.

The combination of chemodynamic therapy (CDT) and chemotherapy is a promising strategy to achieve enhanced anticancer effects. Metal-organic frameworks (MOFs), as multifunctional drug delivery vehicles, have received extensive attention in the biomedical field. Carbohydrate has excellent biocompatibility and targeting ability, which can be used as a targeting ligand due to a specific recognition with glycoprotein receptors that overexpress on cancer cell membranes. Herein, the pH-responsive mannose-modified ferrocene MOFs with rare earth metal were synthesized via coordination-driven self-assembly of 1,1'-Ferrocenedicarboxylic acid and ytterbium chloride. Subsequently, DOX@Fc-MOFs-Mann nanoparticles (NPs) were obtained by loading doxorubicin (DOX) and modifying mannose (Mann), where DOX@Fc-MOFs-Mann NPs were able to precisely target HepG2 cells via mannose receptor and slowly decompose in the acidic environment of tumor to release ferrocene, DOX, and Yb3+. Fe2+ in ferrocene effectively activated Fenton reaction to produce high levels of reactive oxygen species (ROS) for irreversible induction of cell apoptosis or necroptosis. Combined with the chemotherapy (CT) ability of DOX, Yb3+ further induced cell death through its own toxicity to successfully achieved the rare earth metal synergistic CDT and CT combination therapy. This synergistic CDT and CT strategy not only opens up new horizons for rare earth metals in biomedical applications but also provides new inspiration into the construction of glycosyl-modified MOFs.

Revealing inscriptions obscured by time on an early-modern lead funerary cross using terahertz multispectral imaging.

The presence of a corrosion layer on lead art and archæological objects can severely impede the interpretation of inscriptions, thus hampering our overall understanding of the object and its context. While the oxidation of lead that dominates corrosion may be chemically reversible via reduction, potentially providing some access to inscriptions otherwise obscured by time, corrosion damage is overall neither entirely reversible nor is the reduction process in all cases easy or feasible to carry out. In this study, by taking advantage of the unique penetration ability of terahertz radiation and the abundant frequency bands covered by a single-cycle terahertz pulse, we perform nondestructive terahertz multispectral imaging to look under the corrosion on a sixteenth century lead funerary cross (croix d'absolution) from Remiremont in Lorraine, France. The multispectral images obtained from various terahertz frequency bands are fed into a judiciously designed post-processing chain for image restoration and enhancement, thus allowing us for the first time to read obscured inscriptions that might have otherwise been lost. Our approach, which brings together in a new way the THz properties of the constituent materials and advanced signal- and image-processing techniques, opens up new perspectives for multi-resolution analysis at terahertz frequencies as a technique in archæometry and will ultimately provide unprecedented information for digital acquisition and documentation, character extraction, classification, and recognition in archæological studies.

Versatile metal-wire waveguides for broadband terahertz signal processing and multiplexing.

Waveguides play a pivotal role in the full deployment of terahertz communication systems. Besides signal transporting, innovative terahertz waveguides are required to provide versatile signal-processing functionalities. Despite fundamental components, such as Bragg gratings, have been recently realized, they typically rely on complex hybridization, in turn making it extremely challenging to go beyond the most elementary functions. Here, we propose a universal approach, in which multiscale-structured Bragg gratings can be directly etched on metal-wires. Such an approach, in combination with diverse waveguide designs, allows for the realization of a unique platform with remarkable structural simplicity, yet featuring unprecedented signal-processing capabilities. As an example, we introduce a four-wire waveguide geometry, amenable to support the low-loss and low-dispersion propagation of polarization-division multiplexed terahertz signals. Furthermore, by engraving on the wires judiciously designed Bragg gratings based on multiscale structures, it is possible to independently manipulate two polarization-division multiplexed terahertz signals. This platform opens up new exciting perspectives for exploiting the polarization degree of freedom and ultimately boosting the capacity and spectral efficiency of future terahertz networks.

pH-responsive aminotriazole doped metal organic frameworks nanoplatform enables self-boosting reactive oxygen species generation through regulating the activity of catalase for targeted chemo/chemodynamic combination therapy.

The rational integration of chemotherapy and hydroxyl radical (·OH)-mediated chemodynamic therapy (CDT) via functional metal-organic frameworks (MOF) carriers has great potential in cancer therapy. In this work, aminotriazole (3-AT) doped polyhedral metal organic frameworks (denoted as MAF) were prepared by template ligand replacement, where CDT was initiated by Cu2+/Cu+ modulated Fenton reaction and enhanced by effectively regulating the catalase activity with 3-AT. However, a rod-like Cu-MOF with 3-AT served as a ligand was obtained by the hydrothermal method without using template. In contrast to Cu-MOF, pH-responsive MAF was chosen as the carrier for targeted drug delivery due to its higher drug load of 17.6% and relatively uniform size, where doxorubicin (DOX) as a model drug was loaded in its cavity and hyaluronic acid (HA) was coated on its surface via electrostatic interactions (denoted as HA-MAF@DOX). In vitro experiments demonstrated that HA-MAF@DOX had high transport efficiency of DOX, effective regulation of catalase (CAT) activity and enhanced cytotoxicity to HepG2 cells. This work is the first use of enzyme inhibitors as ligands to construct functional MOFs via template ligand replacement for effective regulating enzyme activity, mediating intracellular redox homeostasis and enhancing CDT efficacy, which provides a feasible strategy for the construction the functional MOFs in cancer therapy.

Terahertz three-dimensional monitoring of nanoparticle-assisted laser tissue soldering.

In view of minimally-invasive clinical interventions, laser tissue soldering assisted by plasmonic nanoparticles is emerging as an appealing concept in surgical medicine, holding the promise of surgeries without sutures. Rigorous monitoring of the plasmonically-heated solder and the underlying tissue is crucial for optimizing the soldering bonding strength and minimizing the photothermal damage. To this end, we propose a non-invasive, non-contact, and non-ionizing modality for monitoring nanoparticle-assisted laser-tissue interaction and visualizing the localized photothermal damage, by taking advantage of the unique sensitivity of terahertz radiation to the hydration level of biological tissue. We demonstrate that terahertz radiation can be employed as a versatile tool to reveal the thermally-affected evolution in tissue, and to quantitatively characterize the photothermal damage induced by nanoparticle-assisted laser tissue soldering in three dimensions. Our approach can be easily extended and applied across a broad range of clinical applications involving laser-tissue interaction, such as laser ablation and photothermal therapies.

Syntheses, structures, and magnetic properties of mixed-ligand complexes based on 3,6-bis(benzimidazol-1-yl)pyridazine.

Six new metal-organic coordination polymers (CPs) [Ni(L)(2,5-TDC)(H2O)] n (1), [Ni(L)(1,3-BDC)(H2O)] n (2), [Ni(L)(1,4-BDC)(H2O)] n (3), [Mn(L)(2,5-TDC)(H2O)] n (4), [Mn(L)(2,6-PYDC)(H2O)] n (5) and [Mn(L)(1,4-NDC)] n (6) were achieved by reactions of the corresponding metal salt with mixed organic ligands (L = 3,6-bis(benzimidazol-1-yl)pyridazine, 2,5-H2TDC = thiophene-2,5-dicarboxylic acid, 1,3-H2BDC = isophthalic acid, 1,4-H2BDC = terephthalic acid, 2,6-H2PYDC = pyridine-2,6-dicarboxylic acid, 1,4-H2NDC = naphthalene-1,4-dicarboxylic acid) under solvothermal condition. CPs 1-6 were characterized by single-crystal X-ray diffraction, IR, TG, XRD and elemental analyses. Their structures range from the intricate 3D CPs 1, 3, 4 and 6 to the 2D coordination polymer 2 and the infinite 1D chain 5. The CPs 1-4 and 6 underlying networks were classified from the topological viewpoint, disclosing the distinct sql (in 1), pcu (in 3 and 6), new topology (in 2), and dia (in 4) topological nets. Moreover, analysis of thermal stability shows that they had good thermal stability. Finally, magnetic properties of CPs 1-6 have been studied, the results showed that complex 2 had ferromagnetic coupling and complexes 1, 3-6 were antiferromagnetic.

Global mapping of stratigraphy of an old-master painting using sparsity-based terahertz reflectometry.

The process by which art paintings are produced typically involves the successive applications of preparatory and paint layers to a canvas or other support; however, there is an absence of nondestructive modalities to provide a global mapping of the stratigraphy, information that is crucial for evaluation of its authenticity and attribution, for insights into historical or artist-specific techniques, as well as for conservation. We demonstrate sparsity-based terahertz reflectometry can be applied to extract a detailed 3D mapping of the layer structure of the 17th century easel painting Madonna in Preghiera by the workshop of Giovanni Battista Salvi da Sassoferrato, in which the structure of the canvas support, the ground, imprimatura, underpainting, pictorial, and varnish layers are identified quantitatively. In addition, a hitherto unidentified restoration of the varnish has been found. Our approach unlocks the full promise of terahertz reflectometry to provide a global and detailed account of an easel painting's stratigraphy by exploiting the sparse deconvolution, without which terahertz reflectometry in the past has only provided a meager tool for the characterization of paintings with paint-layer thicknesses smaller than 50 µm. The proposed modality can also be employed across a broad range of applications in nondestructive testing and biomedical imaging.

Depth resolution enhancement of terahertz deconvolution by autoregressive spectral extrapolation.

This Letter presents a method for enhancing the depth resolution of terahertz deconvolution based on autoregressive (AR) spectral extrapolation. The terahertz frequency components with a high signal-to-noise ratio (SNR) are modeled with an AR process, and the missing frequency components in the regions with low SNRs are extrapolated based on the AR model. In this way, the entire terahertz frequency spectrum of the impulse response function, corresponding to the material structure, is recovered. This method, which is verified numerically and experimentally, is able to provide a "quasi-ideal" impulse response function and, therefore, greatly enhances the depth resolution for characterizing optically thin layers in the terahertz regime.

Terahertz frequency-wavelet domain deconvolution for stratigraphic and subsurface investigation of art painting.

Terahertz frequency-wavelet deconvolution is utilized specifically for the stratigraphic and subsurface investigation of art paintings with terahertz reflective imaging. In order to resolve the optically thin paint layers, a deconvolution technique is enhanced by the combination of frequency-domain filtering and stationary wavelet shrinkage, and applied to investigate a mid-20th century Italian oil painting on paperboard, After Fishing, by Ausonio Tanda. Based on the deconvolved terahertz data, the stratigraphy of the painting including the paint layers is reconstructed and subsurface features are clearly revealed, demonstrating that terahertz frequency-wavelet deconvolution can be an effective tool to characterize stratified systems with optically thin layers.