Robust excitonic light emission in 2D tin halide perovskites by weak excited state polaronic effect.

2D perovskites hold immense promise in optoelectronics due to their strongly bound electron-hole pairs (i.e., excitons). While exciton polaron from interplay between exciton and lattice has been established in 2D lead-based perovskites, the exciton nature and behavior in the emerging 2D tin-based perovskites remains unclear. By combining spin-resolved ultrafast spectroscopy and sophisticated theoretical calculations, we reveal 2D tin-based perovskites as genuine excitonic semiconductors with weak polaronic screening effect and persistent Coulomb interaction, thanks to weak exciton-phonon coupling. We determine an excited state exciton binding energy of ~0.18 eV in n = 2 tin iodide perovskites, nearly twice of that in lead counterpart, despite of same large value of ~0.2 eV from steady state measurement. This finding emphasizes the pivotal role of excited state polaronic effect in these materials. The robust excitons in 2D tin-based perovskites exhibit excitation power-insensitive, high-efficiency and color-purity emission, rendering them superior for light-emitting applications.

Simulation and Experimental Investigation on Additive Manufacturing of Highly Dense Pure Tungsten by Laser Powder Bed Fusion.

Tungsten and its alloys have a high atomic number, high melting temperature, and high thermal conductivity, which make them fairly appropriate for use in nuclear applications in an extremely harsh radioactive environment. In recent years, there has been growing research interest in using additive manufacturing techniques to produce tungsten components with complex structures. However, the critical bottleneck for tungsten engineering manufacturing is the high melting temperature and high ductile-to-brittle transition temperature. In this study, laser powder bed fusion has been studied to produce bulk pure tungsten. And finite element analysis was used to simulate the temperature and stress field during laser irradiation. The as-printed surface as well as transverse sections were observed by optical microscopy and scanning electron microscopy to quantitatively study processing defects. The simulated temperature field suggests small-sized powder is beneficial for homogenous melting and provides guidelines for the selection of laser energy density. The experimental results show that ultra-dense tungsten bulk has been successfully obtained within a volumetric energy density of 200-391 J/mm3. The obtained relative density can be as high as 99.98%. By quantitative analysis of the pores and surface cracks, the relationships of cracks and pores with laser volumetric energy density have been phenomenologically established. The results are beneficial for controlling defects and surface quality in future engineering applications of tungsten components by additive manufacturing.

Helicity-Resolved Vibrational Coupling in Twist WS2/WSe2 Heterostructures.

Helicity-resolved Raman spectra can provide an intricate view into lattice structural details. Through the analysis of peak positions, intensities, and circular polarized Raman signals, a wealth of information about chiral structure arrangement within the moiré superlattice, interlayer interaction strength, polarizability change in chemical bond, and beyond can be unveiled. However, the relationship between the circular polarization of high-frequency Raman and twist angle is still not clear. Here, we utilize helicity-resolved Raman spectroscopy to explore the interlayer interactions and the effect of the moiré superlattice in WS2/WSe2 heterostructures. For the out-of-plane Raman mode A1g of WS2 (A1g and 1E2g of WSe2), its intensity is significantly enhanced (suppressed) in WS2/WSe2 heterostructures when θ is less than 10° or greater than 50°. This observation could be attributed to the large polarizability changes in both W-S and W-Se covalent bonds. The circular polarization of 2LA(M) in WSe2 of the WS2/WSe2 heterostructure (θ < 10° or θ > 50°) is significantly enhanced compared to that of 2LA(M) in the monolayer WSe2. We deduce that the circular polarization of the Raman mode correlates with the proportion of high-symmetry area within a supercell of the moiré lattice. Our findings improve the understanding of twist-angle-modulated Raman modes in TMD heterostructures.

Revealing the Optical Transition Properties of Interlayer Excitons in Defective WS2/WSe2 Heterobilayers.

Manipulation of physical properties in multidimensional tunable moiré superlattice systems is a key focus in nanophotonics, especially for interlayer excitons (IXs) in two-dimensional materials. However, the impact of defects on IXs remains unclear. Here, we thoroughly study the optical properties of WS2/WSe2 heterobilayers with varying defect densities. Low-temperature photoluminescence (PL) characterizations reveal that the low-energy IXs are more susceptible to defects compared to the high-energy IXs. The low-energy IXs also show much faster PL quenching rate with temperature, faster peak width broadening rate with laser power, shorter lifetime, and lower circular polarization compared to the low-energy IXs in the region with fewer defects. These effects are attributed to the combined effects of increased electron scattering, exciton-phonon interactions, and nonradiative channels introduced by the defects. Our findings aid in optimizing moiré superlattice structures.

Robust and Efficient Out-of-Plane Exciton Transport in Two-Dimensional Perovskites via Ultrafast Förster Energy Transfer.

Two-dimensional (2D) perovskites, comprising inorganic semiconductor layers separated by organic spacers, hold promise for light harvesting and optoelectronic applications. Exciton transport in these materials is pivotal for device performance, often necessitating deliberate alignment of the inorganic layers with respect to the contacting layers to facilitate exciton transport. While much attention has focused on in-plane exciton transport, little has been paid to out-of-plane interlayer transport, which presumably is sluggish and unfavorable. Herein, by time-resolved photoluminescence, we unveil surprisingly efficient out-of-plane exciton transport in 2D perovskites, with diffusion coefficients (up to ∼0.1 cm2 s-1) and lengths (∼100 nm) merely a few times smaller or comparable to their in-plane counterparts. We unambiguously confirm that the out-of-plane exciton diffusion coefficient corresponds to a subpicosecond interlayer exciton transfer, governed by the Förster resonance energy transfer (FRET) mechanism. Intriguingly, in contrast to temperature-sensitive intralayer band-like transport, the interlayer exciton transport exhibits negligible temperature dependence, implying a lowest-lying bright exciton state in 2D perovskites, irrespective of spacer molecules. The robust and ultrafast interlayer exciton transport alleviates the constraints on crystal orientation that are crucial for the design of 2D perovskite-based light harvesting and optoelectronic devices.

ALPL regulates pro-angiogenic capacity of mesenchymal stem cells through ATP-P2X7 axis controlled exosomes secretion.

BACKGROUND: Early-onset bone dysplasia is a common manifestation of hypophosphatasia (HPP), an autosomal inherited disease caused by ALPL mutation. ALPL ablation induces prototypical premature bone ageing characteristics, resulting in impaired osteogenic differentiation capacity of human bone marrow mesenchymal stem cells (hBMMSCs). As angiogenesis is tightly coupled with osteogenesis, it also plays a necessary role in sustaining bone homeostasis. We have previously observed a decrease in expression of angiogenesis marker gene CD31 in the metaphysis of long bone in Alpl+/- mice. However, the role of ALPL in regulation of angiogenesis in bone has remained largely unknown. METHODS: Exosomes derived from Normal and HPP hBMMSCs were isolated and identified by ultracentrifugation, transmission electron microscopy, and nanoparticle size measurement. The effects of ALPL on the angiogenic capacity of hBMMSCs from HPP patients were assessed by immunofluorescence, tube formation, wound healing and migration assay. exo-ELISA and Western Blot were used to evaluate the exosomes secretion of hBMMSCs from HPP, and the protein expression of VEGF, PDGFBB, Angiostatin and Endostatin in exosomes respectively. RESULTS: We verified that ALPL ablation resulted in impaired pro-angiogenic capacity of hBMMSCs, accounting for reduced migration and tube formation of human umbilical vein endothelial cells, as the quantities and proteins composition of exosomes varied with ALPL expression. Mechanistically, loss of function of ALPL enhanced ATP release. Additional ATP, in turn, led to markedly elevated level of ATP receptor P2X7, which consequently promoted exosomes secretion, resulting in a decreased capacity to promote angiogenesis. Conversely, inhibition of P2X7 increased the angiogenic induction capacity by preventing excessive release of anti-angiogenic exosomes in ALPL deficient-hBMMSCs. CONCLUSION: The ALPL-ATP axis regulates the pro-angiogenic ability of hBMMSCs by controlling exosomes secretion through the P2X7 receptor. Thus, P2X7 may be proved as an effective therapeutic target for accelerating neovascularization in ALPL-deficient bone defects.

Ultrafast Interlayer Charge Transfer Outcompeting Intralayer Valley Relaxation in Few-Layer 2D Heterostructures.

While 2D transition metal dichalcogenides (TMDs) feature interesting layer-tunable multivalley band structures, their preeminent role in determining the photoexcitation charge transfer dynamics in 2D heterostructures (HSs) is yet to be unraveled, as previous charge transfer studies on TMD HSs have been mostly focused on monolayers with a direct bandgap at the K valley. By ultrafast transient absorption spectroscopy and deliberately designed few-layer WSe2/WS2 HSs, we have observed an ultrafast interlayer electron transfer from photoexcited few-layer WSe2 to WS2, prior to intralayer relaxation to lower lying dark valleys. More interestingly, we have identified an unconventional ∼0.5 ps electron back-transfer process after the initial interlayer electron transfer in HSs with WSe2 layers ≥ 3, regenerating indirect intralayer excitons. The result reveals an ielectron and valley relaxation pathway mediated by interlayer charge transfer in 2D HSs, faster than intralayer relaxation. It also sheds light on the origin of generally observed robust ultrafast interlayer charge transfer in TMD HSs and provides guidance toward optoelectronic and valleytronic devices using few-layer TMDs.

Umbilical cord mesenchymal stem cell-derived apoptotic extracellular vesicles ameliorate cutaneous wound healing in type 2 diabetic mice via macrophage pyroptosis inhibition.

BACKGROUND: Delayed healing of diabetic cutaneous wounds is one of the most common complications of type 2 diabetes mellitus (T2DM), which can bring great distress to patients. In diabetic patients, macrophages accumulate around skin wounds and produce NLRP3 (NOD-, LRR-, and pyrin domain-containing protein 3) inflammasomes, which in turn undergo pyroptosis and produce inflammatory factors such as interleukin-1ß that affect wound healing. Although our previous study revealed that apoptotic extracellular vesicles (ApoEVs) produced from mesenchymal stem cells (MSCs) improve cutaneous wound healing in normal C57BL/6 mice, whether ApoEVs can also improve diabetic wound healing remains unclear. METHODS: Umbilical cord mesenchymal stem cells (UCMSCs) were cultured in vitro and apoptosis was induced. ApoEVs were extracted and identified and used in a T2DM mouse cutaneous wound model to evaluate the efficacy. The inhibitory effect of ApoEVs on macrophage pyroptosis was verified in vivo and in vitro, and the level of oxidative stress in macrophages was assessed to explore the mechanism by which ApoEVs play a role. RESULTS: UCMSC-derived ApoEVs improved skin defect healing in T2DM mice. Moreover, UCMSC-derived ApoEVs inhibited macrophage pyroptosis in T2DM mice in vivo as well as in vitro under high-glucose culture conditions. In addition, we demonstrated that ApoEVs reduce oxidative stress levels, which is a possible mechanism by which they inhibit macrophage pyroptosis. CONCLUSIONS: Our study confirmed that local application of UCMSC-derived ApoEVs improved cutaneous wound healing in T2DM mice. ApoEVs, as products of MSC apoptosis, can inhibit macrophage pyroptosis and regulate the death process by decreasing the level of oxidative stress.

ErbB4 processing is involved in OGD/R induced neuron injury.

OBJECTIVE: Our previous study found that ErbB4 gene expression was changed after oxygen-glucose deprivation/reperfusion (OGD/R). However, the exact role and mechanism of ErbB4 in brain ischemia are largely unknown. In this study, we explored the protective effects of ErbB4 and its possible mechanism after OGD/R. METHODS: Cerebral ischemia/reperfusion (I/R) injury model was established in vitro and in vivo. Cell viability, apoptosis, and ROS production were measured by MTT, TUNEL, and fluorescent probe 2', 7'-dichlorofluorescein diacetate (DCFH-DA). Infarct size was evaluated by TTC. We performed bioinformatics analyses to screen for novel key genes involved in ErbB4 changes. RNA-Seq was used to transcriptome analysis. RNA and protein expression were detected by quantitative RT‒PCR and western bloting. RESULTS: The expression of 80-kDa ErbB4 decreased after cerebral I/R injury in vitro and in vivo. Co-expression network analysis revealed that ErbB4 expression was correlated with the changes in Adrb1, Adrb2, Ldlr, and Dab2. Quantitative RT‒PCR revealed that the mRNA expression levels of Adrb1, Adrb2, and Dab2 were upregulated, and that of Ldlr was decreased after OGD/R. Activation of ErbB4 expression by neuregulin 1 (NRG1) significantly promoted cell survival, attenuated hippocampal apoptosis, and decreased ROS production after OGD/R. Furthermore, the elimination of ErbB4 using a specific siRNA reversed these beneficial effects. CONCLUSION: Our data revealed the neuroprotective effects of ErbB4 against OGD/R injury, and the action could be related to changes in the ErbB4 membrane-associated fragment and the expression of Adrb1, Adrb2, Ldlr, and Dab2.

Phase-pure 2D tin halide perovskite thin flakes for stable lasing.

Ruddlesden-Popper tin halide perovskites are a class of two-dimensional (2D) semiconductors with exceptional optoelectronic properties, high carrier mobility, and low toxicity. However, the synthesis of phase-pure 2D tin perovskites is still challenging, and the fundamental understanding of their optoelectronic properties is deficient compared to their lead counterparts. Here, we report the synthesis of a series of 2D tin perovskite bulk crystals with high phase purity via a mixed-solvent strategy. By engineering the quantum-well thickness (related to n value) and organic ligands, the optoelectronic properties, including photoluminescence emission, exciton-phonon coupling strength, and exciton binding energy, exhibit a wide tunability. In addition, these 2D tin perovskites exhibited excellent lasing performance. Both high-n value tin perovskite (n > 1) and n = 1 tin perovskite thin flakes were successfully optically pumped to lase. Furthermore, the lasing from 2D tin perovskites could be maintained up to room temperature. Our findings highlight the tremendous potential of 2D tin perovskites as promising candidates for high-performance lasers.

Traumatic temporomandibular joint bony ankylosis in growing rats.

BACKGROUND: The pathogenesis of traumatic temporomandibular joint (TMJ) bony ankylosis remains unknown. This study aimed to explore the pathogenesis of traumatic TMJ bony ankylosis in a rat model. METHODS: Twenty-four 3-week-old male Sprague-Dawley rats were used in this study. Excision of the whole disc, the fibrocartilage damage of the condyle and glenoid fossa, and narrowed joint space were performed in the left TMJ of the operation group to induce TMJ bony ankylosis (experimental side). The right TMJ underwent a sham operation (sham side). The control group did not undergo any operations. At 1, 4, and 8 weeks postoperatively, rats of the operation group were sacrificed and TMJ complexes were evaluated by gross observation, Micro-CT, histological examinations, and immunofluorescence microscopy. Total RNA of TMJ complexes in the operation group were analyzed using RNA-seq. RESULTS: Gross observations revealed TMJ bony ankylosis on the experimental side. Micro-CT analysis demonstrated that compared to the sham side, the experimental side showed a larger volume of growth, and a considerable calcified bone callus formation in the narrowed joint space and on the rougher articular surfaces. Histological examinations indicated that endochondral ossification was observed on the experimental side, but not on the sham side. RNA-seq analysis and immunofluorescence revealed that Matrix metallopeptidase 13 (MMP13) and Runt-related transcription factor 2 (RUNX2) genes of endochondral ossification were significantly more downregulated on the experimental side than on the sham side. The primary pathways related to endochondral ossification were Parathyroid hormone synthesis, secretion and action, Relaxin signaling pathway, and IL-17 signaling pathway. CONCLUSIONS: The present study provided an innovative and reliable rat model of TMJ bony ankylosis by compound trauma and narrowed joint space. Furthermore, we demonstrated the downregulation of MMP13 and RUNX2 in the process of endochondral ossification in TMJ bony ankylosis.

A multifunctional drug consisting of tetracycline conjugated with odanacatib for efficient periodontitis therapy.

The treatment of periodontitis can be very challenging due to its complex etiologies. A new pharmacologic strategy entitled "host-modulation therapy," has been introduced to improve periodontal treatment outcomes. Supposedly, a multifunctional drug with the potential for bacterial infection prevention, host-response modulation and bone healing promotion would be a promising option for periodontitis therapy, but related studies remain substantially lacking. In this study, we successfully conjugated tetracycline with odanacatib (a selective inhibitor of cathepsin K) to construct a multifunctional drug (TC-ODN). We discovered that TC-ODN could promote macrophages polarizing toward anti-inflammatory phenotype and promote osteogenesis of PDLSCs under inflammatory microenvironment. In vivo, TC-ODN could be absorbed and distributed specifically to the bone after systemic administration, and accumulation of TC-ODN increased bone mineral density in ovariectomized rats. Importantly, periodontal administration of TC-ODN could successfully promote bone healing in periodontitis rats with alveolar bone loss. The findings in our study uncovered the excellent biocompatibility and multifunction of TC-ODN, including bone-targeted accumulation, immunoregulation, anti-inflammatory activity and promotion of bone healing, which might contribute to the clinical treatment of periodontitis.

Platelet count and clinical outcomes among ischemic stroke patients with endovascular thrombectomy in DIRECT-MT.

OBJECTIVES: The prognostic role of baseline platelet count (PLT) in acute ischemic stroke patients with large vessel occlusion undergoing endovascular thrombectomy is unclear. Whether PLT modifies alteplase treatment effect on clinical outcome in those patients is also uncertain. METHODS: We derived data from a multicenter randomized clinical trial (DIRECT-MT) comparing intravenous alteplase before endovascular treatment vs. endovascular treatment only. The 654 patients with available PLT data were included. Primary outcome was the ordinal modified Rankin Scale (mRS) score evaluated at 90 days. We also assessed various secondary and safety outcomes. RESULTS: After adjusting for confounding factors, patients in the top tertile of PLT had a significantly lower risk of a worse shift in the distribution of mRS score (Odds Ratio: 0.671, 95% Confidence Interval: 0.473-0.953, p for trend=0.025), major disability and death (Odds Ratio: 0.617, 95% Confidence Interval: 0.393-0.97, p for trend=0.037) as well as death (Odds Ratio: 0.544, 95% Confidence Interval: 0.313-0.947, p for trend=0.031), respectively, compared with the bottom one. Among patients in the bottom tertile of PLT, combination therapy was associated with a better imaging outcome of eTICI score of 2b, 2c or 3 on final angiogram (Odds Ratio: 3.23, 95% Confidence Interval: 1.49-7.002) with a marginally significant interaction effect. CONCLUSIONS: Participants with higher baseline PLT had a decreased risk of poor functional outcomes. Low baseline PLT modified alteplase treatment effect on the eTICI score on final angiogram. Combination therapy was beneficial for patients with low baseline PLT to have a better reperfusion status.

Effect on implant drills and postoperative reactions for pre-extraction interradicular implant bed preparation during the COVID-19 pandemic and beyond.

The aim of the present study was to observe the abrasion of implant drills and postoperative reactions for the preparation of the interradicular immediate implant bed during the COVID-19 pandemic and beyond. Thirty-two implant drills were included in four groups: blank, improved surgery, traditional surgery, and control. In the improved surgery group, a dental handpiece with a surgical bur was used to decoronate the first molar and create a hole in the middle of the retained root complex, followed by the pilot drilling protocol through the hole. The remaining root complex was separated using a surgical bur and then extracted. Subsequently, the implant bed was prepared. Implant drills were used in the traditional surgery group to complete the decoronation, hole creation, and implant-drilling processes. The tooth remained intact until the implant bed was prepared. The surface roughness of the pilot drill was observed and measured. Surgery time, postoperative reactions (swelling, pain, and trismus), and fear of coronavirus disease 2019 scale (FCV-19S) were measured and recorded, respectively. Statistical analysis revealed significant difference with surface roughness among blank group (0.41 ± 0.05 µm), improved surgery group (0.37 ± 0.06 µm), traditional surgery group (0.16 ± 0.06 µm), and control group (0.26 ± 0.04 µm) (P < .001). Significant differences were revealed with surgery time between improved surgery group (5.63 ± 1.77 min) and traditional surgery group (33.63 ± 2.13 min) (P < .001). Swelling, pain, and trismus (improved group: r ≥ 0.864, P ≤ .006; traditional group: r ≥ 0.741, P ≤ .035) were positively correlated with the FCV-19S. This study proved that a new pilot drill could only be used once in traditional surgery but could be used regularly in improved surgery. Improved surgery was more effective, efficient, and economical than the traditional surgery. The higher FCV-19S, the more severe swelling, pain, and trismus.

Immediate, non-submerged, three-dimensionally printed, one-piece mandibular molar porous root-analogue titanium implants: A 2-year prospective study involving 18 patients.

This study prospectively evaluated non-submerged, three-dimensionally printed, one-piece molar porous root-analogue titanium implants. A total of 18 non-restorable multiple-rooted teeth in 18 patients, aged 22-64 years, were included in this study. A series of computed tomography images of the mandible were selected and rendered into a digital model. The non-restorable mandibular molars were digitally separated from the surrounding alveolar bone, and served as the template on which the porous root-analogue titanium implants (RAIs) were designed with computer-aided design (CAD) software. The porous molar RAIs were fabricated with the selective laser melting technique (average particle size 20 µm) and inserted into the alveolar sockets after extraction of the non-restorable molars. Definitive restorations were placed after 3 months of uninterrupted healing. Peri-implant clinical and radiographic measurements were obtained 2 years later. All patients functioned well following 2 years of functional loading, and peri-implant clinical and radiographic measurements demonstrated implant stability. No implants were lost at the 2-year follow-up, and the survival rate was 100%. Three-dimensionally printed one-piece molar porous RAIs may be a promising option for the replacement of non-restorable molars that are planned for extraction. Additional studies are required to evaluate the long-term survival of implants fabricated using this technique.

Spatiotemporally Coupled Electron-Hole Dynamics in Two Dimensional Heterostructures.

Coulomb interactions play a crucial role in low-dimensional semiconductor materials, e.g., 2D layered semiconductors, dictating their electronic and optical properties. However, fundamental questions remain as to whether and how Coulomb interactions affect the charge or energy flow in 2D heterostructures, which is essential for their light-electricity conversions. Herein, using ultrafast spectroscopy, we report real space coupled electron-hole dynamics in 2D heterostructures. We show in (WSe2/)WS2/MoTe2 with a controlled energy gradient for the hole and a near flat band for electron transfer, the fate of the electron is controlled by the hole in coupled dynamics. The interfacial electron transfer from WS2 to MoTe2 follows the hole closely and can be facilitated or suppressed by dynamic Coulomb interaction. In parallel to the band alignment, this study reveals the critical role of Coulomb interactions on the fate of photogenerated charges in 2D heterostructures, providing experimental evidence for coupled electron-hole dynamics and a new knob for steering nanoscale charge or energy transfer process.

Selectively Tracking Nanoparticles in Aquatic Plant Using Core-Shell Nanoparticle-Enhanced Raman Spectroscopy Imaging.

Nanoparticles contribute to enormous environmental processes, but, due to analytical challenges, the understanding of nanoparticle fate remains elusive in complex environmental matrices. To address the challenge, a core-shell nanoparticle-enhanced Raman spectroscopy (CSNERS) imaging method was developed to selectively track prevalent SiO2 nanoparticles in an aquatic plant, Lemna minor. By encapsulating gold nanoparticles and Raman reporters inside, the resonance Raman signature was enhanced, thus enabling the sensitive and selective detection of SiO2 nanoparticles at an environmentally relevant concentration. The panoramic visualization of the translocation pathway of nanoparticles shows an unexpected, fast (in hours) and a preferential accumulation of nanoparticles on the node, leaf edge, root cap, etc., implying the ability of CSNERS to spectroscopically determine nanotoxicity. The core-shell design in CSNERS was capable of multiplex labeling two differently charged nanoparticles and distinguishing their biobehavior simultaneously. Meanwhile, the CSNERS method can be further applied for a variety of nanoparticles, implying its promising applications for nanotoxicity research and biogeochemical study.

Controlling Photocarrier Lifetime in Graphene for Enhanced Photocurrent Generation via Cascade Hot Electron Transfer.

Because of its broad absorption and high carrier mobility, graphene has been regarded as a promising photoactive material for optoelectronics. However, its ultrashort photoexcited carrier lifetime greatly restricts the device performance. Herein, we show that by constructing a graphene/WS2/MoS2 vertical heterostructure with a cascade electron-transfer pathway, the hot electrons in graphene under low-energy photoexcitation can efficiently transfer through WS2 to MoS2 in 180 fs, thus effectively photogating the graphene layer. Because of the spatial separation and energy barrier imposed by the WS2 intermediate layer which retards back electron transfer, the photocarrier lifetime in graphene is significantly prolonged to ∼382.7 ps, more than 2 orders of magnitude longer than in isolated graphene and graphene/WS2 binary heterostructure. The prolonged photocarrier lifetime in graphene leads to dramatically enhanced photocurrent generation and photoresponsivity. This study offers an exciting approach to control photocarrier lifetime in graphene for hot carrier devices with simultaneous broadband and high responsivity.

Scalable synthesis of multicomponent multifunctional inorganic core@mesoporous silica shell nanocomposites.

Integrating multiple materials with different functionalities in a single nanostructure enables advances in many scientific and technological applications. However, such highly sophisticated nanomaterials usually require complex synthesis processes that complicate their preparation in a sustainable and industrially feasible manner. Herein, we designed a simple general method to grow a mesoporous silica shell onto any combination of hydrophilic nanoparticle cores. The synthetic strategy, based on the adjustment of the key parameters of the sol-gel process for the silica shell formation, allows for the embedment of single, double, and triple inorganic nanoparticles within the same shell, as well as the size-control of the obtained nanocomposites. No additional interfacial adhesive layer is required on the nanoparticle surfaces for the embedding process. Adopting this approach, electrostatically stabilized, small-sized (from 4 to 15 nm) CeO2, Fe3O4, Gd2O3, NaYF4, Au, and Ag cores were used to test the methodology. The mean diameter of the resulting nanocomposites could be as low as 55 nm, with high monodispersity. These are very feasible sizes for biological intervention, and we further observed increased nanoparticle stability in physiological environments. As a demonstration of their increased activity as a result of this, the antioxidant activity of CeO2 cores was enhanced when in core-shell form. Remarkably, the method is conducted entirely at room temperature, atmospheric conditions, and in aqueous solvent with the use of ethanol as co-solvent. These facile and even "green" synthesis conditions favor scalability and easy preparation of multicomponent nanocomposite libraries with standard laboratory glassware and simple benchtop chemistry, through this sustainable and cost-effective fabrication process.

Deciphering asymmetric charge transfer at transition metal dichalcogenide-graphene interface by helicity-resolved ultrafast spectroscopy.

Transition metal dichalcogenide (TMD)/graphene (Gr) heterostructures constitute a key component for two-dimensional devices. The operation of TMD/Gr devices relies on interfacial charge/energy transfer processes, which remains unclear and challenging to unravel. Fortunately, the coupled spin and valley index in TMDs adds a new degree of freedom to the charges and, thus, another dimension to spectroscopy. Here, by helicity-resolved ultrafast spectroscopy, we find that photoexcitation in TMDs transfers to graphene by asynchronous charge transfer, with one type of charge transferring in the order of femtoseconds and the other in picoseconds. The rate correlates well with energy offset between TMD and graphene, regardless of compositions and charge species. Spin-polarized hole injection or long-lived polarized hole can be achieved with deliberately designed heterostructures. This study shows helicity-resolved ultrafast spectroscopy as a powerful and facile approach to reveal the fundamental and complex charge/spin dynamics in TMD-based heterostructures, paving the way toward valleytronic and optoelectronic applications.