Methane-H2S Reforming Catalyzed by Carbon and Metal Sulfide Stabilized Sulfur Dimers.

H2S reforming of methane (HRM) provides a potential strategy to directly utilize sour natural gas for the production of COx-free H2 and sulfur chemicals. Several carbon allotropes were found to be active and selective for HRM, while the additional presence of transition metals led to further rate enhancements and outstanding stability (e.g., Ru supported on carbon black). Most metals are transformed to sulfides, but the carbon supports prevent sintering under the harsh reaction conditions. Supported by theoretical calculations, kinetic and isotopic investigations with representative catalysts showed that H2S decomposition and the recombination of surface H atoms are quasi-equilibrated, while the first C-H bond scission is the kinetically relevant step. Theory and experiments jointly establish that dynamically formed surface sulfur dimers are responsible for methane activation and catalytic turnovers on sulfide and carbon surfaces that are otherwise inert without reaction-derived active sites.

Cu-OFF/ERI Zeolite: Intergrowth Structure Synergistically Boosting Selective Catalytic Reduction of NOx with NH3.

Cu-SSZ-13 has been commercialized for selective catalytic reduction with ammonia (NH3-SCR) to remove NOx from diesel exhaust. As its synthesis usually requires toxic and costly organic templates, the discovery of alternative Cu-based zeolite catalysts with organotemplate-free synthesis and comparable or even superior NH3-SCR activity to that of Cu-SSZ-13 is of great academic and industrial significance. Herein, we demonstrated that Cu-T with an intergrowth structure of offretite (OFF) and erionite (ERI) synthesized by an organotemplate-free method showed better catalytic performance than Cu-ERI and Cu-OFF as well as Cu-SSZ-13. Structure characterizations and density functional theory calculations indicated that the intergrowth structure promoted more isolated Cu2+ located at the 6MR of the intergrowth interface, resulting in a better hydrothermal stability of Cu-T than Cu-ERI and Cu-OFF. Strikingly, the low-temperature activity of Cu-T significantly increased after hydrothermal aging, while that of Cu-ERI and Cu-OFF substantially decreased. Based on in situ diffuse reflectance infrared Fourier transform spectra analysis and density functional theory calculations, the reason can be attributed to the fact that NH4NO3 formed on the CuxOy species within ERI polymorph of Cu-T underwent a fast SCR reaction pathway with the assistance of Brønsted acid sites at the intergrowth interfaces under standard SCR reaction conditions. Significantly, Cu-T exhibited a wider temperature window at a catalytic activity of over 90% than Cu-SSZ-13 (175-550 vs 175-500 °C for fresh and 225-500 vs 250-400 °C for hydrothermal treatment). This work provides a new direction for the design of high-performance NH3-SCR catalysts in terms of the interplay of the intergrowth structure of zeolites.

Complete Metal Recycling from Lithium-Ion Batteries Enabled by Hydrogen Evolution Catalyst Reconstruction.

Mass adoption of electric vehicles and the depletion of finite metal resources make it imperative to recycle lithium-ion batteries (LIBs). However, current recycling routes of pyrometallurgy and hydrometallurgy are mainly developed for LiCoO2 and suffer from great energy inputs and extensive processing; thus, alternative versatile and green approaches are in urgent demand. Here, we report an ingenious and versatile strategy for recycling LIBs via catalyst reconstruction, using hydrogen evolution reaction as a proof of concept. Layered, spinel, and polyanion oxide cathode materials, as catalysts, are structurally transformed into hydroxides assisted by protons or hydroxide ions, facilitating complete metal extraction (e.g., Li, Co, Ni, Mn, Fe) with high leaching efficiencies approaching 100%. This recycling method is generally applicable to almost all commercial cathode systems and extended to actual spent pouch cells. Such a green hydrogen coupling approach provides a versatile and sustainable alternative to conventional approaches and has a broad impact beyond battery recycling.

[Development of Self Training Device for Lung Function Compliance Guided by Meridians].

OBJECTIVE: To develop a self deep breathing training device which can improve lung function compliance and blood oxygen saturation. METHODS: The device consists of four parts:flow tube, measuring cylinder, mobile phone holder and meridian guidance audio-visual synthesis training software. The flow tube measures the flow rate of inhaled gas, the metering cylinder measures the total amount of inhaled gas, and the mobile phone rack is equipped with a mobile phone storing the meridian guidance audio-visual synthesis training software. RESULTS: The device is reasonable in structure and flexible in operation, which can meet the requirements of self deep inspiration training under the guidance of training module. CONCLUSIONS: Deep inspiration training under the guidance of guidance training module can form "deep and slow" abdominal breathing, and then improve lung function.

Synthesis of gold Nanoshells through Improved Seed-Mediated Growth Approach: Brust-like, in Situ Seed Formation.

Gold nanoshells have shown great potentials in various fields. However, the widely used seed-mediated growth method based on a silica template for gold nanoshells is a complex and time-consuming procedure. In this work, mercaptosilica was first used as a template to synthesize gold nanoshells through improved seed-mediated growth method. It is verified that gold seeds were formed and attached onto the mercaptosilica nanospheres through Brust-like, in situ process, which makes this method extremely time-saving and easy to manipulate. Importantly, the key factors affecting the in situ process were demonstrated, allowing fine control on the synthesis in a highly reproducible manner. The as-synthesized nanoshells are monodisperse with well-defined morphology and tunable near-IR plasmon resonance. Furthermore, other metal nanoparticles such as Pt and Pd could be grafted onto the surface of mercaptosilica nanospheres through the same Brust-like, in situ process. These provide new insights into seed attachment, and the improved seed-mediated growth approach based on Brust-like, in situ seed formation will take an important step forward toward the widespread application of gold nanoshells.

[Study on the Characteristics of EMG Signal of the Masticatory Muscles in Different Materials].

Objective: To investigate the activities of different soft and hard materials during right chewing masticatory muscles, describing the masticatory muscles of time domain and frequency domain features. Methods: 11 experimental subjects who conform to the standards of measurement chew two materials of different soft and hard texture. Then record surface EMG of each bilateral temporalis anterior bundle, masseter, two bilateral anterior abdominal muscles, analysis to 5 kinds of characteristics of the study of EMG. Results: When subjects chewing different soft and hard materials, al the EMG features in the bilateral anterior temporalis and masseter values had significant difference (P < 0.05). The results in bilateral digastric anterior abdominal except zero crossing rate have significant difference; median frequency on the right side of the masticatory muscle has decreased trend. Conclusion: The anterior temporalis and masseter EMG active more intense when chewing hard objects; the right side of the masticatory muscles have obvious fatigue trend after chewing hard masticatory 30 cycles.

Controlled synthesis of multilayered gold nanoshells for enhanced photothermal therapy and SERS detection.

It can be streamlined: A facile and controllable approach for the fabrication of core/shell-structured multilayer gold nanoshells with uniform nanosize, monodispersity, and tunable plasmonic properties has been successfully developed by utilizing an organosilica layer as the dielectric spacer layer.

[Design of Rehabilitation Training System with Electromyography Feedback for Stroke Patients].

This paper proposed a rehabilitation training system with electromyography (sEMG) feedback for stroke patients based on ARM embedded system and LabVIEW. The system can achieve real-time acquisition, processing and dualview of multi-channel sEMGs and compute related sEMG parameters including iEMG, RMS, MPF and co-contraction ratio. The system was detected by clinical experiments and related inspection department. The result showed that the system is functional, interactive and in accordance with the relevant standards for medical devices so that it can fully satisfy the clinical demands. In addition, the system can help doctors to master the training state of the patient more effectively in a real-time and quantitative way that is direct to improve the training programs of stroke patients.

Improving the hydrothermal stability of Al-rich Cu-SSZ-13 zeolite via Pr-ion modification.

Al-rich (Si/Al = 4-6) Cu-SSZ-13 has been recognized as one of the potential catalysts to replace the commercial Cu-SSZ-13 (Si/Al = 10-12) towards ammonia-assisted selective catalytic reduction (NH3-SCR). However, poor hydrothermal stability is a great obstacle for Al-rich zeolites to meet the catalytic applications containing water vapor. Herein, we demonstrate that the hydrothermal stability of Al-rich Cu-SSZ-13 can be dramatically enhanced via Pr-ion modification. Particularly, after high-temperature hydrothermal aging (HTA), CuPr1.2-SSZ-13-HTA with an optimal Pr content of 1.2 wt% exhibits a T80 (temperature window of NO conversion above 80%) window of 225-550 °C and a T90 window of 250-350 °C. These values are superior to those of Cu-SSZ-13-HTA (225-450 °C for T80 and no T90 window). The results of X-ray diffraction Rietveld refinement, electron paramagnetic resonance (EPR) and spectral characterization reveal that Pr ions mainly located in the eight-membered rings (8MRs) in SSZ-13 zeolite can inhibit the generation of inactive CuOx during hydrothermal aging. This finding is further supported by density functional theory (DFT) calculations, which suggest that the presence of Pr ions restrains the transformation from Cu2+ ions in 6MRs into CuOx, resulting in enhanced hydrothermal stability. It is also noted that an excessive amount of Pr ions in Cu-SSZ-13 would result in the production of CuOx that causes the decline of catalytic performance. The present work provides a promising strategy for creating a hydrothermally stable Cu-SSZ-13 zeolite catalyst by adding secondary metal ions.

A simple route to prepare monodisperse Au NP-decorated, dye-doped, superparamagnetic nanocomposites for optical, MR, and CT trimodal imaging.

Monodisperse and uniform AuNP-decorated, dye-doped, superparamagnetic nanocomposites (Fe3 O4 @dye-hybrid@Au) are fabricated by using a simple method in which the Au NP formation and their attachment onto the core surface via S-Au covalent bonds proceeds almost simultaneously in a one-pot synthesis. The as-synthesized nanocomposites can simultaneously enhance the contrast effects for MR, CT, and cellular-sensitive optical imaging.

One-pot synthesis of mesoporous silica nanocarriers with tunable particle sizes and pendent carboxylic groups for cisplatin delivery.

Mesoporous silica nanocarriers with tunable particle sizes and different loadings of pendent carboxylic groups were successfully prepared by a straightforward and reproducible strategy, in which carboxyethylsilanetriol sodium salt was co-condensed with tetraethoxyorthosilicate to introduce the carboxylic groups. The key in this strategy was to separate the synthesis process into two steps of the nuclei formation and particle growth. The uniform particle size and ordered structure of the synthesized nanocarriers were manifested by several techniques such as XRD, TEM, SEM, and BET. DLS measurement illustrated that nanocarriers could be well suspended in aqueous solution. The integration and content tunability of the carboxylic groups within mesoporous silica nanoparticles (MSNs) were verified by FT-IR and (29)Si NMR. The inherent carboxylic units on the obtained carboxylic group modified MSNs (MSNs-C) effectively enhanced the capture and tailored the release properties of the anticancer drug of cisplatin. The accumulation of drug in the HeLa cells was greatly enhanced due to the highly efficient platinum uptake efficiency transported by the synthesized nanocarriers. The drug encapsulated in the MSNs-C exhibited a higher antitumor activity than free cisplatin against both MCF-7 and HeLa cells.

Designing virtual reality based 3D modeling and interaction technologies for museums.

In China, museums are of great historical significance, which can greatly improve the country's cultural standards. With the advent of new media and economic times, people's behavior and way of thinking have changed, so they are less and less interested in traditional museum displays. How to create a museum moving image that meets the aesthetic and experiential requirements of the general audience has become critical. The purpose of this paper was to study the design of moving image displays using virtual reality (VR) in museums. This paper proposed a VR-based 3D modeling technology and human-computer interaction algorithm. Both of these technologies were an important part of VR technology. It can manage museums digitally and display objects clearly in two-dimensional and three-dimensional spaces. According to the experimental results of this paper, among the 80 participants, 40% were very satisfied with the exhibition hall experience of Chengde Mountain Resort Museum, and 35% were only moderately satisfied. It can be seen that most people find it very attractive to integrate VR technology into the showroom experience. Therefore, it is very important to integrate VR technology into the dynamic image display of the museum.

Interplay between copper redox and transfer and support acidity and topology in low temperature NH3-SCR.

Low-temperature standard NH3-SCR over copper-exchanged zeolite catalysts occurs on NH3-solvated Cu-ion active sites in a quasi-homogeneous manner. As key kinetically relevant reaction steps, the reaction intermediate CuII(NH3)4 ion hydrolyzes to CuII(OH)(NH3)3 ion to gain redox activity. The CuII(OH)(NH3)3 ion also transfers between neighboring zeolite cages to form highly reactive reaction intermediates. Via operando electron paramagnetic resonance spectroscopy and SCR kinetic measurements and density functional theory calculations, we demonstrate here that such kinetically relevant steps become energetically more difficult with lower support Brønsted acid strength and density. Consequently, Cu/LTA displays lower Cu atomic efficiency than Cu/CHA and Cu/AEI, which can also be rationalized by considering differences in their support topology. By carrying out hydrothermal aging to eliminate support Brønsted acid sites, both CuII(NH3)4 ion hydrolysis and CuII(OH)(NH3)3 ion migration are hindered, leading to a marked decrease in Cu atomic efficiency for all catalysts.

A simple route to synthesize mesoporous ZSM-5 templated by ammonium-modified chitosan.

Uniform mesoporous zeolite ZSM-5 crystals have been successfully fabricated through a simple hydrothermal synthetic method by utilizing ammonium-modified chitosan and tetrapropylammonium hydroxide (TPAOH) as the meso- and microscale template, respectively. It was revealed that mesopores with diameters of 5-20 nm coexisted with microporous network within mesoporous ZSM-5 crystals. Ammonium-modified chitosan was demonstrated to serve as a mesoporogen, self-assembling with the zeolite precursor through strong static interactions. As expected, the prepared mesoporous ZSM-5 exhibited greatly enhanced catalytic activities compared with conventional ZSM-5 and Al-MCM-41 in reactions involving bulky molecules, such as the Claisen-Schmidt condensation of 2-hydroxyacetophenone with benzaldehyde and the esterification reaction of dodecanoic acid and 2-ethylhexanol.

In Situ 3D-to-2D Transformation of Manganese-Based Layered Silicates for Tumor-Specific T1-Weighted Magnetic Resonance Imaging with High Signal-to-Noise and Excretability.

Recently, Mn(II)-based T1-weighted magnetic resonance imaging (MRI) contrast agents (CAs) have been explored widely for cancer diagnosis. However, the "always-on" properties and poor excretability of the conventional Mn(II)-based CAs leads to high background signals and unsatisfactory clearance from the body. Here, we report an "in situ three-dimensional to two-dimensional (3D-to-2D) transformation" method to prepare novel excretable 2D manganese-based layered silicates (Mn-LSNs) with extremely high signal-to-noise for tumor-specific MR imaging for the first time. Our observations combined with density functional theory (DFT) calculations reveal that 3D metal (Mn, Fe, Co) oxide nanoparticles are initially formed from the molecular precursor solution and then in situ transform into 2D metal (Mn, Fe, Co)-based layered silicates triggered by the addition of tetraethyl orthosilicate, which provides a time-saving and versatile way to prepare novel 2D silicate nanomaterials. The unique ion-exchangeable capacity and high host layer charge density endow Mn-LSNs with an "ON/OFF" pH/GSH stimuli-activatable T1 relaxivity with superb high signal-to-noise (640-, 1200-fold for slightly acidic and reductive changes, respectively). Further in vivo MR imaging reveals that Mn-LSNs exhibit a continuously rapid T1-MRI signal enhancement in tumor tissue and no visible signal enhancement in normal tissue, indicating an excellent tumor-specific imaging. In addition, Mn-LSNs exhibit a rapid excretion from the mouse body in 24 h and invisible organ toxicity, which could help to solve the critical intractable degradation issue of conventional inorganic CAs. Moreover, the tumor microenvironment (pH/GSH/H2O2) specific degradability of Mn-LSNs could help to improve the penetration depth of particles into the tumor parenchyma. Developing this novel Mn-LSNs contrast agent, together with the already demonstrated capacity of layered silicates for drug and gene delivery, provides opportunities for future cancer theranostics.

Biodegradable organosilica magnetic micelles for magnetically targeted MRI and GSH-triggered tumor chemotherapy.

Recently, block copolymer micelles have attracted widespread attention due to their controlled biodegradability and excellent loading capability. Unfortunately, the poor in vivo stability and low delivery efficiency of drug-loaded micelles greatly hampered their biomedical applications. Herein, we develop a new kind of biodegradable magnetite/doxorubicin (Fe3O4/DOX) co-loaded PEGylated organosilica micelles (designated as FDPOMs) with both high circulating stability and smart GSH-triggered biodegradability for magnetically targeted magnetic resonance imaging (MRI) and tumor chemotherapy. The FDPOMs are prepared by the self-assembly of biodegradable polycaprolactone-block-poly(glutamic acid) (PCL-b-PGA), a chemotherapeutic DOX drug and Fe3O4 nanoparticles in an oil/water system, subsequent organosilica cross-linking with 3-mercaptopropyltrimethoxysilane (MPTMS) molecules and surface PEGylation. The resultant FDPOMs exhibit excellent dispersity and stability in biological media, remarkable T2-weighted MR imaging capability, unique GSH-responsive release behavior and selective toxicity to tumor cells. The in vivo experiments show that the FDPOMs not only have improved MR tumor imaging capability, but also exhibit high anti-tumor efficacy due to the strong magnetic targeting ability under an external magnetic field. Consequently, the FDPOMs are promising candidates for magnetically targeted MR imaging and imaging-guided tumor chemotherapy.

Facile synthesis of organosilica-capped mesoporous silica nanocarriers with selective redox-triggered drug release properties for safe tumor chemotherapy.

As drug-delivery carriers for cancer chemotherapy, gatekeeper-capped mesoporous silica nanoparticles (MSNs) have been widely studied due to their high drug-loading capability, controlled drug release property and good biocompatibility. However, the currently reported gatekeeper-capped MSNs suffer from complex synthetic procedures, potential toxicity of gatekeepers, unsatisfactory control on drug stimuli-release, etc. In this work, we develop a simple but efficient approach to fabricate PEGylated organosilica-capped mesoporous silica nanoparticles (POMSNs) by employing a disulfide-doped organosilica coating as the gatekeeper formed by the hydrolysis and condensation of a silane coupling agent 3-(mercaptopropyl)trimethoxysilane (MPTMS) to block the mesopores of MSNs. Owing to the glutathione (GSH)-responsive biodegradation behavior of the disulfide-doped organosilica gatekeeper, the DOX-loaded POMSNs exhibit only 20% cell viability towards SMMC-7721 tumor cells, and almost no toxicity towards L-02 cells at a DOX concentration of 50 µg mL-1 was measured, demonstrating their selective cytotoxicity in vitro. More importantly, it is demonstrated that the DOX-loaded POMSNs exhibit a tumor inhibition rate of 71.3% and negligible systematic toxicity. Consequently, the resultant POMSNs show great potential as drug nanocarriers for redox-responsive drug release and passive-targeting tumor chemotherapy.

Confined growth of multiple gold nanorices in dual-mesoporous silica nanospheres for improved computed tomography imaging and photothermal therapy.

INTRODUCTION: In this work, we have developed a novel "confined-growth" strategy to synthesize PEGylated multiple gold nanorices-encapsulated dual-mesoporous silica nanospheres (designated as PEGylated MGNRs@DMSSs) containing both small mesopores (2.5 nm) in the shell and large mesopores (21.7 nm) in the core based on a well-established, seed-mediated growth method. The photothermal effect and CT imaging ability were also studied. METHODS: The nanoparticles were characterized by Fourier transform infrared (FT-IR) spectra, N2 absorption isotherms, Field-emission scanning electron microscopy (FE-SEM), Transmission electron microscopy (TEM), Inductively coupled plasma atomic emission spectroscopy (ICP-AES) and Confocal microscopy. RESULTS: The longitudinally-localized surface (LSPR) absorption properties of MGNRs@DMSSs can be easily tuned by altering the amount of HAuCl4 in the gold growth solution. Additionally, the resultant PEGylated MGNRs@DMSSs have monodispersed, spherical morphology and good colloidal stability in an aqueous solution. More importantly, when exposed to NIR irradiation, the PEGylated MGNRs@DMSSs exhibit both higher temperature increments and better photothermal effects than that of single PEGylated gold nanorods at nearly an equivalent LSPR absorption. In addition, as CT contrast agents, the PEGylated MGNRs@DMSSs display a better CT imaging performance, in comparison with single PEGylated gold nanorods at the same Au concentration. CONCLUSION: Taken together, results indicate the potential for MGNRs@DMSSs used in CT imaging-guided photothermal therapy. Such a simple "confined-growth" strategy within a porous matrix offers a promising platform to design and prepare novel metal(s) oxide@silica nanocomposites for use in further cancer bio-imaging and therapy.

Extraction-Induced Fabrication of Yolk-Shell-Structured Nanoparticles with Deformable Micellar Cores and Mesoporous Silica Shells for Multidrug Delivery.

Yolk-shell-structured nanoparticles (YSNs) provide useful carriers for applications in biomedicine and catalysis due to the excellent loading capability and versatile functionality of the flexible core and porous shell. Unfortunately, the reported YSNs always require complex multistep synthesis processes and a harsh hard-template etching strategy. Herein, a facile "selective extraction" strategy is developed to synthesize yolk-shell-structured polymer@void@mSiO2 nanoparticles (designated as YSPNs) comprising deformable and soft polystyrene-b-poly(acrylic acid) (PS-b-PAA) micellar cores and mesoporous silica shells. The YSPNs are formed by a morphological change and volume shrinkage of the PS-b-PAA aggregates from large compound vesicles to large compound micelles during the extraction process. As a multidrug vehicle, both hydrophobic curcumin (Cur, 6.4 wt %) and hydrophilic doxorubicin hydrochloride (Dox, 19.4 wt %) can be coloaded onto YSPNs through a successive impregnation method. Moreover, the resulting Cur/Dox@YSPNs possess intelligent pH-responsive capability, time-sequenced release behavior, and high in vivo antitumor efficiency, demonstrating excellent potential as safe and efficient multidrug nanocarriers for tumor chemotherapy. We envision that such a facile "selective extraction" strategy will enable pathways to construct organic-inorganic hybrid nanoparticles with yolk-shell structures for various applications.

A facile approach to fabricate functionalized superparamagnetic copolymer-silica nanocomposite spheres.

Novel amino- or thiol-functionalized superparamagnetic copolymer-silica nanospheres (NH2-SMCSNs/SH-SMCSNs), which consist of a magnetic core and a silica cross-linked block copolymer shell, have been fabricated.