Crystalline Phase Regulates Microbial Methylation Potential of Mercury Bound to MoS2 Nanosheets: Implications for Safe Design of Mercury Removal Materials.

Transition-metal dichalcogenides (TMDs) have shown great promise as selective and high-capacity sorbents for Hg(II) removal from water. Yet, their design should consider safe disposal of spent materials, particularly the subsequent formation of methylmercury (MeHg), a highly potent and bioaccumulative neurotoxin. Here, we show that microbial methylation of mercury bound to MoS2 nanosheets (a representative TMD material) is significant under anoxic conditions commonly encountered in landfills. Notably, the methylation potential is highly dependent on the phase compositions of MoS2. MeHg production was higher for 1T MoS2, as mercury bound to this phase primarily exists as surface complexes that are available for ligand exchange. In comparison, mercury on 2H MoS2 occurs largely in the form of precipitates, particularly monovalent mercury minerals (e.g., Hg2MoO4 and Hg2SO4) that are minimally bioavailable. Thus, even though 1T MoS2 is more effective in Hg(II) removal from aqueous solution due to its higher adsorption affinity and reductive ability, it poses a higher risk of MeHg formation after landfill disposal. These findings highlight the critical role of nanoscale surfaces in enriching heavy metals and subsequently regulating their bioavailability and risks and shed light on the safe design of heavy metal sorbent materials through surface structural modulation.

Flexible terahertz phase shifter for optically controlled polydimethylsiloxane-vanadium dioxide composite film.

In the terahertz (THz) band, modulation research has become a focal point, with precise control of the phase shift of THz waves playing a pivotal role. In this study, we investigate the optical control of THz phase shift modulation in a polydimethylsiloxane (PDMS)-vanadium dioxide (VO2) flexible material using THz time-domain spectroscopy. Under the influence of an 808-nm continuous wave (CW) laser with power densities ranging from 0 to 2.74 W/cm2, the PDMS-VO2 flexible material exhibits significant phase shift modulation in the frequency range of 0.2 to 1.0 THz. The maximum optical-pumping phase shift reaches 0.27π rad at 1.0 THz in a composite material with a VO2 mass fraction of 5% and a thickness of 360 µm, and the amplitude transmittance from 0.2 THz to 1.0 THz exceeds 70%. Furthermore, the composite material exhibits good stability under at least 640 switching cycle times, as confirmed through repeatability tests. The proposed composite devices offer a new approach for more flexible phase shift modulation owing to the flexibility of the composite material and the non-contact and precise modulation of light control. Additionally, the stress-adjustable characteristics of flexible materials make them highly suitable for use in wearable THz modulators, highlighting their significant application potential.

Terahertz polarization and chirality modulation induced by asymmetry inversion combining chiral metasurface and liquid crystal anisotropy.

We experimentally demonstrate a dynamic terahertz (THz) chiral device based on a composite structure of anisotropic liquid crystals (LCs) sandwiched between a bilayer metasurface. The device supports the symmetric mode and antisymmetric mode under the incidence of left- and right-circular polarized waves, respectively. The different coupling strengths of the two modes reflect the chirality of the device, and the anisotropy of the LCs can change the coupling strength of the modes, which brings tunability to the chirality of the device. The experimental results show that the circular dichroism of the device can be dynamically controlled from 28 dB to -32 dB (i.e., inversion regulation) at approximately 0.47 THz and from -32 dB to 1 dB (i.e., switching regulation) at approximately 0.97 THz. Moreover, the polarization state of the output wave is also tunable. Such flexible and dynamic manipulation of THz chirality and polarization might build an alternative pathway for complex THz chirality control, high-sensitivity THz chirality detection, and THz chiral sensing.

Active terahertz beam deflection based on a phase gradient metasurface with liquid crystal-enhanced cavity mode conversion.

Active manipulation of terahertz (THz) beam deflection and intensity is highly desired for possible applications in wireless communication, radar, and remote sensing. Here, by integrating the phase-gradient metasurfaces and tunable liquid crystal materials, we demonstrate an active THz beam deflection device based on polarization mode conversion. The resonant modes in the photonic cavity formed by the double-layer metasurface and the tunable anisotropic liquid crystal material in the cavity not only improve the polarization conversion efficiency of the device, but also actively regulate the resonance matching conditions. As a consequence, a beam deflection of 47.5° with 50% diffraction intensity at 0.69 THz is achieved in the x-to-y polarization conversion mode, and this beam can be actively modulated with an ultrahigh modulation depth of 99.6% by rotating the anisotropic optical axis of liquid crystals. Moreover, the proposed device can also work as the deflection of 32.5° in the y-to-x polarization conversion mode at 0.94 THz with a maximum diffraction intensity of 38% and an intensity modulation depth of 97.8%. This work provides a new approach based on liquid crystal photonic devices for wavefront manipulation and active modulation for THz waves.

Coaxial dual-beam wavefront shaping using nonlocal diffractive metasurfaces in terahertz frequencies.

Metasurfaces for wavefront shaping rely on local phase modulation in subwavelength unit cells, which show limited degree of freedom in dealing with complex and multiple beam transformation. Here, we assign multiple beams into different diffraction orders coaxially located along the same direction, whose wavefronts are tailored by optimizing the diffraction coefficients in two orders and two polarization states of a supercell. By evenly splitting the energy into two orders and adjusting the zeroth-order diffraction phase, a Bessel beam and a vortex beam are simultaneously generated in the near field and far field along a coaxial direction. The effectiveness of the method is validated by the excellent agreement between the simulation and experimental characterization of the two beams.

Terahertz Spin-Conjugate Symmetry Breaking for Nonreciprocal Chirality and One-Way Transmission Based on Magneto-Optical Moiré Metasurface.

In this work, the gyrotropic semiconductor InSb into the twisted bilayer metasurface to form a magneto-optical moiré metasurface is introduced. Through the theoretical analysis, the "moiré angle" is developed in which case the nonreciprocity and chirality with the spin-conjugate asymmetric transmission are obtained due to the simultaneous breaking of both time-reversal symmetry and spatial mirror symmetry. The experiments confirm that the chirality can be actively manipulated by rotating the twisted angle and the external magnetic field, realizing spin-conjugate asymmetric transmission. Meanwhile, the two spin states also realize the nonreciprocal one-way transmission, and their isolation spectra are also spin-conjugate asymmetric: one is enhanced up to 48 dB, and the other's bandwidth is widened to over 730 GHz. This spin-conjugate symmetry-breaking effect in the MOMM brings a combination of time-space asymmetric transmission, and it also provides a new scheme for the implementation of high-performance THz chirality controllers and isolators.

Partial Oxidation of FeS Nanoparticles Enhances Cr(VI) Sequestration.

Iron sulfide nanoparticles (nano-FeS) have shown great potential for in situ remediation of Cr(VI) pollution by reducing Cr(VI) to the less soluble and toxic Cr(III). However, material oxidation that inevitably occurs during storage and application alters its reactivity. Herein, we show that partial oxidation of nanoparticulate mackinawite (FeS) significantly enhances its capability in sequestering Cr(VI). Oxidation of nano-FeS increases its binding affinity to Cr(VI), likely due to preferential inner-sphere complexation of Cr(VI) oxyanions to ferric over ferrous iron in mackinawite/lepidocrocite (FeS/γ-FeOOH) nanocomposites. A trade-off is that oxidation mitigates Cr(VI) reduction by lowering the electron-donating potential of the material and the electron transfer at a solution-material interface and consequently hinders the transformation of adsorbed Cr(VI) to Cr(III). Notably, the rate-limiting step of Cr(VI) sequestration transitions from adsorption to reduction during oxidation, as demonstrated with batch experiments coupled with kinetic modeling. Thus, an optimum oxidation degree exists, wherein the gain in the overall performance from enhanced adsorption overcompensates the loss from inhibited reduction, resulting in maximum sequestration of aqueous Cr(VI) as solid-phase Cr(III). Our findings inform better assessment and design of nanomaterials for Cr(VI) remediation and may be extended to interactions of other oxyanions with natural and engineered nanoparticles during oxidative aging.

Synthesis of AC1903 analogs as potent transient receptor potential canonical channel 4/5 inhibitors and biological evaluation.

Transient receptor potential canonical (TRPC) channels are a class of non-selective cation channels expressed in a variety of tissues and organ systems where they functionally regulate physiological and pathological processes. TRPC5 has been shown to be a promising target for focal segmental glomerulosclerosis treatment. In this study, we report the synthesis and biological evaluation of a novel series of benzimidazole-based TRPC5 inhibitors. One compound, 8b, is 100-fold more potent than the parent compound, AC1903, in the suppression of TRPC5 channel activity. Interestingly, both AC1903 and 8b also suppressed TRPC4 channel activity with similar potency. Compound 8b also significantly blunts protamine sulfate-induced reorganization of podocyte cytoskeleton, interleukin (IL)-17-induced cell proliferation, and the expression of proinflammatory mediators in human keratinocyte HaCaT cells.

Histamine Sensitization of the Voltage-Gated Sodium Channel Nav1.7 Contributes to Histaminergic Itch in Mice.

Itch, a common clinical symptom of many skin diseases, severely impairs the life quality of patients. Nav1.7, a subtype of voltage-gated sodium channels mainly expressed in primary sensory neurons, is responsible for the amplification of threshold currents that trigger action potential (AP) generation. Gain-of-function mutation of Nav1.7 leads to paroxysmal itch, while pharmacological inhibition of Nav1.7 alleviates histamine-dependent itch. However, the crosstalk between histamine and Nav1.7 that leads to itch is unclear. In the present study, we demonstrated that in the dorsal root ganglion (DRG) neurons from histamine-dependent itch model mice induced by compound 48/80, tetrodotoxin-sensitive (TTX-S) but not TTX-resistant Na+ currents were activated at more hyperpolarized membrane potentials compared to those on DRG neurons from vehicle-treated mice. Meanwhile, bath application of histamine shifted the activation voltages of TTX-S Na+ currents to the hyperpolarized direction, increased the AP frequency, and reduced the current threshold required to elicit APs. Further mechanistic studies demonstrated that selective activation of H1 but not H2 and H4 receptors mimicked histamine effect on TTX-S Na+ channels in DRG neurons. The protein kinase C (PKC) inhibitor GO 8963, but not the PKA inhibitor H89, normalized histamine-sensitized TTX-S Na+ channels. We also demonstrated that histamine shifted the activation voltages of Na+ currents to the hyperpolarized direction in Chinese hamster ovary (CHO) cells expressing Nav1.7. Importantly, selective inhibition of Nav1.7 by PF-05089771 significantly relieved the scratching frequency in a histamine-dependent itch model induced by compound 48/80. Taken together, these data suggest that activation of H1 receptors by histamine sensitizes Nav1.7 channels through the PKC pathway in DRG neurons that contributes to histamine-dependent itch.

Multi-band terahertz linear polarization converter based on carbon nanotube integrated metamaterial.

Herein, we fabricated and investigated the carbon nanotube (CNT) integrated metamaterial for orthogonal polarization control in the THz regime, which is composed of a sandwiched CNT layer with the adjacent metal gratings in the sub-wavelength integration. Under the mechanism of multilayer polarization selection and multiple reflections in CNT constructed micro-cavity, the perfect orthogonal polarization conversion is achieved and the transmittance spectrum presents multi-band peaks and valleys, which coincide with the theoretical Fabry-Perot resonance. Besides, by controlling the layer number and orientations of the middle CNT, the active modulation of the amplitude and phase in compound metamaterials are realized. Based on the simulation of CNT in the grating model, it obtains a good agreement with the experimental results, and the simulated electric field distribution also confirmed the inner polarization conversion mechanism. This work combines nanomaterials with optical microstructures and successfully applies them to the THz polarization control, which will bring new ideas for design novel THz devices.

Temperature-dependent chirality of cholesteric liquid crystal for terahertz waves.

Recently, the terahertz (THz) chiral field control opens a new window to THz devices and their applications. In this Letter, the active manipulation for THz chiral states based on the cholesteric liquid crystal (CLC) has been demonstrated by THz time domain cross-polarization spectroscopy. The results show that the CLC has strong THz optical activity and circular dichroism (CD) effect, and the strongest THz CD of 22 dB and a polarization rotation angle of 88.4° occur around the phase transition temperature TS-N=250K. Rising to a room temperature of 300 K, the CLC turns from a chiral state to an isotropic state for THz waves with the phase transition processes of CLC molecules. Therefore, this CLC device can be performed as a thermally active THz circular polarizer, which brings potential applications in THz polarization imaging, broadband communication, and spectroscopy.

Terahertz birefringence anisotropy and relaxation effects in polymer-dispersed liquid crystal doped with gold nanoparticles.

Terahertz (THz) birefringence anisotropy of the polymer-dispersed liquid crystal (PDLC) doped with gold nanoparticles (Au NPs) is investigated by using terahertz time domain polarization spectroscopy. Controlled by the electric field, the change rate of refractive index for PDLC doped with Au NPs is 0.91% V-1 as the voltage increases, smaller than the pure PDLC, which indicates that the response of the PDLC doped with Au NPs to electric field is more uniform than that of pure PDLC. Therefore, the PDLC doped with Au NPs is more suitable for tunable phase shifters. Furthermore, we found that under the high-frequency alternating electric field, the anisotropic polarization effect of PDLC will disappear to this electric field, namely polarization relaxation phenomenon. However, the results show that the PDLC doped with Au NPs can respond to an electric field with higher alternating frequencies, and the relaxation frequency of PDLC with an Au NPs concentration of 0.2 wt% was improved over two times compared with the pure PDLC and four times higher than that of the precursor mixture without ultraviolet radiation. This work has the significance for the potential applications of tunable THz liquid crystal phase and polarization devices, providing a more uniform and faster relaxation response to the operating electric field.

Alkali and Phosphorus Resistant Zeolite-like Catalysts for NOx Reduction by NH3.

At present, the deactivation of selective catalytic reduction (SCR) catalysts caused by the coexistence of alkali metal and phosphorus (P) remains an urgent problem and lacks corresponding strategies against catalyst poisoning. Herein, a novel zeolite-like Ce-Si5Al2Ox catalyst derived from an ultrasmall nanozeolite EMT precursor was synthesized without organic templates at ambient temperature. This catalyst was able to maintain above 95% NOx conversion in the 270-540 °C temperature range. Moreover, 1 wt % potassium (K) and 5 wt % P loading had no influence on the SCR performance of the Ce-Si5Al2Ox catalyst at 300-480 °C. It was demonstrated that cerium (Ce) was highly dispersed in the amorphous aluminum (Al) silicate derived from EMT zeolites and expressed high catalytic performance. Besides, a large number of acid sites were reserved to absorb ammonia allowing effective participation in the SCR reaction and capturing alkali metals, thus improving the SCR performance and K resistance. Additionally, the strong interaction between Ce and aluminosilicate decreased cerium phosphate production, preventing deactivation of the catalysts. Thus, this novel low-cost zeolite-like Ce-Si5Al2Ox catalyst with a highly active ion-exchanged metal phase and abundant surface acid sites paves a way for designing new efficient and poisoning-resistant SCR catalysts for practical applications.

Effects of Extracellular Polymeric Substances on the Formation and Methylation of Mercury Sulfide Nanoparticles.

Growing evidence has suggested that microbial biofilms are potential environmental "hotspots" for the production and accumulation of a bioaccumulative neurotoxin, methylmercury. Here, we demonstrate that extracellular polymeric substances (EPS), the main components of biofilm matrices, significantly interfere with mercury sulfide precipitation and lead to the formation of nanoparticulate metacinnabar available for microbial methylation, a natural process predominantly responsible for the environmental occurrence of methylmercury. EPS derived from mercury methylating bacteria, particularly Desulfovibrio desulfuricans ND132, substantially increase the methylation potential of nanoparticulate mercury. This is likely due to the abundant aromatic biomolecules in EPS that strongly interact with mercury sulfide via inner-sphere complexation and consequently enhance the short-range structural disorder while mitigating the aggregation of nanoparticulate mercury. The EPS-elevated bioavailability of nanoparticulate mercury to D. desulfuricans ND132 is not induced by dissolution of these nanoparticles in aqueous phase, and may be dictated by cell-nanoparticle interfacial reactions. Our discovery is the first step of mechanistically understanding methylmercury production in biofilms. These new mechanistic insights will help incorporate microbial EPS and particulate-phase mercury into mercury methylation models, and may facilitate the assessment of biogeochemical cycling of other nutrient or toxic elements driven by EPS-producing microorganisms that are prevalent in nature.

The Effect of rTMS over the Different Targets on Language Recovery in Stroke Patients with Global Aphasia: A Randomized Sham-Controlled Study.

OBJECTIVE: To evaluate and compare the effects of repetitive transcranial magnetic stimulation (rTMS) over the right pars triangularis of the posterior inferior frontal gyrus (pIFG) and the right posterior superior temporal gyrus (pSMG) in global aphasia following subacute stroke. METHODS: Fifty-four patients with subacute poststroke global aphasia were randomized to 15-day protocols of 20-minute inhibitory 1 Hz rTMS over either the right triangular part of the pIFG (the rTMS-b group) or the right pSTG (the rTMS-w group) or to sham stimulation, followed by 30 minutes of speech and language therapy. Language outcomes were assessed by aphasia quotient (AQ) scores obtained from the Chinese version of the Western Aphasia Battery (WAB) at baseline and immediately after 3 weeks (15 days) of experimental treatment. RESULTS: Forty-five patients completed the entire study. The primary outcome measures include the changes in WAB-AQ score, spontaneous speech, auditory comprehension, and repetition. These measures indicated significant main effect between the baseline of the rTMS-w, rTMS-b, and sham groups and immediately after stimulation (P<0.05). Compared with the sham group, the increases were significant for auditory comprehension, repetition, and AQ in the rTMS-w group (P<0.05), whereas the changes in repetition, spontaneous speech, and AQ tended to be higher in the rTMS-b group (P<0.05). CONCLUSIONS: Inhibitory rTMS targeting the right pIFG and pSTG can be an effective treatment for subacute stroke patients with global aphasia. The effect of rTMS may depend on the stimulation site. Low-frequency rTMS inhibited the right pSTG and significantly improved language recovery in terms of auditory comprehension and repetition, whereas LF-rTMS inhibited the right pIFG, leading to apparent changes in spontaneous speech and repetition.

Terahertz resonance switch induced by the polarization conversion of liquid crystal in compound metasurface.

We experimentally demonstrate an active terahertz (THz) resonance switch induced by the polarization conversion in a compound metasurface, which is a LC layer sandwiched by a metallic wire grating and resonance metamaterial (LCGM). Here, the liquid crystal (LC) plays the role of polarization conversion, which can induce the TE resonance. Moreover, there exists a localized resonance between metallic grating and metamaterial layers, and then the excited resonance will be greatly enhanced. The results show that the high extinction ratio of the resonance switch exceeds 30 dB at 0.82 THz. This work will bring new ideas for the research in developing THz phase, polarization, and switch devices with LC and metasurface.

Manipulation enhancement of terahertz liquid crystal phase shifter magnetically induced by ferromagnetic nanoparticles.

Ferromagnetic liquid crystals (FLCs), the suspensions of magnetic nanoparticles dispersed at different concentrations in liquid crystals (LCs), and their special magnetically induced birefringence characteristics have been investigated in the terahertz regime, mainly focusing on the interaction between magnetic cluster chains and LC molecules. We experimentally demonstrated the surface anchoring effect of the magnetic cluster chains on LC molecules in a mm-thick LC cell under an extremely weak external magnetic field (EMF), leading to a uniform anchoring arrangement of the LC molecules over the entire LC cell. Unlike pure 5CB LCs, the phase shift range of the FLCs at 1.45 THz up to π (no to ne or ne to no) can be achieved over the whole tunable range by simply changing the magnitude of the EMF without changing its direction, and the optical axis of LC molecules can be controlled to rotate by 90°, thereby realizing a tunable THz wave plate. This work provides a new way in the development of THz magneto-optic devices and phase devices.

Broadband controllable terahertz quarter-wave plate based on graphene gratings with liquid crystals.

Developing the broadband controllable or tunable terahertz (THz) polarization and phase devices are in an urgent need. In this paper, we demonstrate a broadband controllable THz quarter-wave plate (QWP) with double layers of graphene grating and a layer of liquid crystals. The double layer graphene gratings can achieve a switchable QWP to switch between linear-to-linear and linear-to-circular polarization states with over 0.35THz bandwidth in the ON or OFF state by applying biased electric field on the graphene grating or not. Moreover, this QWP based on the structure of periodic gradient grating can significantly enhance the phase difference between two orthogonally polarized components compared to that based on equal-periodic grating structure because of the additional phase distribution of the gradient structures. Furthermore, we incorporate liquid crystals into the graphene grating to form a tunable QWP, of which operating frequency can be continuously tuned in a wide frequency range by electrically controlling the molecular director of the liquid crystals. The results show that the graphene periodic gradient grating with LCs not only broadens the operating bandwidth, but also reduces the external electric field. This device offers a further step in the development of THz polarization and phase devices for potential applications in THz polarized imaging, spectroscopy, and communication.

Terahertz artificial birefringence and tunable phase shifter based on dielectric metasurface with compound lattice.

A dielectric metasurface with line-square compound lattice structure has been fabricated and demonstrated in the terahertz (THz) regime by the THz time-domain spectroscopy and numerical simulation. A polarization dependent electromagnetically induced transparency (EIT) effect is achieved in this metasurface due to the mode coupling and interference between the resonance modes in line and square subunits of the metasurface. Accompany with the EIT effect, a large artificial birefringence effect between two orthogonal polarization states is also observed in this compound metasurface, of which birefringence is over 0.6. Furthermore, the liquid crystals are filled on the surface of this dielectric metasurface to fabricate an electrically tunable THz LC phase shifter. The experimental results show that its tunable phase shift under the biased electric field reaches 0.33π, 1.8 times higher than the bare silicon, which confirms the enhancement role of THz microstructure on the LC phase shift in the THz regime. The large birefringence phase shift of this compound metasurface and its LC tunable phase shifter will be of great significance for potential applications in THz polarization and phase devices.