Defective UiO-66-NH2 (Zr) for Simultaneous Adsorption of Phosphate and Pb2+ for Hydrogen Peroxide Purification.

Removal of hetero ions from the hydrogen peroxide solution is a crucial step in purifying electronic-grade H2O2. Conventional adsorption materials are challenged to meet the need for the simultaneous adsorption of both anions and cations in solvents. UiO-66 (Zr) modified by acetic acid and amino group for simultaneous adsorption of phosphate and Pb2+ in H2O2 purification was fabricated in this work. The as-prepared defective UiO-66-NH2 (Zr) demonstrated a significant increase in specific surface area and porosity, along with more exposed sites for phosphate and Pb2+ adsorption. The adsorption capacity of De-UiO-66-NH2 for phosphate and Pb2+ in H2O2 solution was 52.28 mg g-1 and 35.4 mg g-1, which is 1.19 times and 1.88 times that of unmodified UiO-66 (Zr), respectively. The trace simultaneous adsorption with both 100 ppb phosphate and Pb2+ showed removal rates of 94.0% and 88.7%, respectively, confirming the practicality of MOF materials in the purification of electronic chemicals. This work highlights the potential of Zr-based MOFs as anionic and cationic simultaneous adsorbents for highly efficient purification of electronic-grade solvents.

Precise Regulation in Chain-Edge Structural Microenvironments of 1D Covalent Organic Frameworks for Photocatalysis.

Covalent organic frameworks (COFs) constitute a promising research topic for photocatalytic reactions, but the rules and conformational relationships of 1D COFs are poorly defined. Herein, the chain edge structure is designed by precise modulation at the atomic level, and the 1D COFs bonded by C, O, and S elements is directionally prepared for oxygen-tolerant photoinduced electron transfer-atom transfer radical polymerization (PET-ATRP) reactions. It is demonstrated that heteroatom-type chain edge structures (─O─, ─S─) lead to a decrease in intra-plane conjugation, which restricts the effective transport of photogenerated electrons along the direction of the 1D strip. In contrast, the all-carbon type chain edge structure (─C─) with higher intra-plane conjugation not only reduces the energy loss of photoexcited electrons but also enhances the carrier density, which exhibits the optimal photopolymerization performance. This work offers valuable guidance in the exploitation of 1D COFs for high photocatalytic performance. This work offers valuable guidance in the exploitation of 1D COFs for high photocatalytic performance.

Construction of Hierarchical Porous UiO-66-Br2@PS/DVB-Packed Columns by High Internal Phase Emulsion Strategy for Enhanced Separation of CF4/N2 and SF6/N2.

Recovery and separation of anthropogenic emissions of electronic specialty gases (F-gases, such as CF4 and SF6) from the semiconductor sector are of critical importance. In this work, the hierarchical porous UiO-66-Br2@PS/DVB-packed column was constructed by a high internal phase emulsions strategy. UiO-66-Br2@PS/DVB exhibits a superior selectivity of CF4/N2 (2.67) and SF6/N2 (3.34) predicted by the IAST due to the diffusion limitation in the micropore and the gas-framework affinity. Especially, UiO-66-Br2@PS/DVB showed significant CF4 and SF6 retention and enabled the successful separation of CF4/N2 and SF6/N2 with a resolution of 2.37 and 8.89, respectively, when used as a packed column in gas chromatography. Compared with the Porapak Q column, the HETP of the UiO-66-Br2@PS/DVB-packed column decreased and showed good reproducibility. This research not only offers a convenient method for fabricating a hierarchical porous MOF-packed column but also showcases the prospective utilization of MOFs for the separation of the F-gas/N2 mixture.

Spatially Amplified and Rigid Junction in Diblock Copolymers: Reduced Microphase Separation Size via Interface Expansion.

We introduce an approach in diblock copolymer design, where modifying the junction point with rigid bulky monomer expands the cross-sectional area of the interface and leads to a decrease in the repeat period. Using living anionic polymerization, we synthesized a series of dialkynyl midfunctionalized poly(styrene-b-methyl methacrylate) (PSM-DA) and functionalized them using the thiol-alkyne click reaction with specifically selected rigid bulky monomers: PSS-(3-mercapto)propyl-heptaisobutyl substituted (PSS) and 1-adamantanethiol (ADA). This modification, though involving only a single monomer unit within the diblock copolymer structure, brought about a significant reduction in domain size, with PSS and ADA reducing it by 18% and 15%, respectively. The results indicate a method for reducing the domain sizes of block copolymers, which could lead to advancements in lithography and various nanotechnological applications.

Revealing the contradiction between DLVO/XDLVO theory and membrane fouling propensity for oil-in-water emulsion separation.

Oil fouling is the crucial issue for the separation of oil-in-water emulsion by membrane technology. The latest research found that the membrane fouling rate was opposite to the widely used theoretical prediction by Derjaguin-Landau-Verwey-Overbeek (DLVO) or extended DLVO (XDLVO) theory. To interpret the contradiction, the molecular dynamics was adopted to explore the molecular behavior of oil and emulsifier (Tween 80) at membrane interface with the assistance of DLVO/XDLVO theory and membrane fouling models. The decreased flux attenuation and fitting of fouling models proved that the existence of Tween 80 effectively alleviated membrane fouling. Conversely, DLVO/XDLVO theory predicted that the membrane fouling should be exacerbated with the increase of Tween 80 concentration in O/W emulsion. This contradiction originated from the different interaction energy between oil/Tween 80 molecules and polyether sulfone (PES) membrane. The favorable free energy of Tween 80 was resulted from the sulfuryl groups in PES and hydrogen bonds (O-H…O) formation further strengthened the interaction. Therefore, Tween 80 could preferentially adsorb on membrane surface and form an isolation layer by demulsification and steric hindrance and resist the aggregation of oil, which effectively alleviated membrane fouling. This study provided a new insight in the interpretation of interaction in O/W emulsion.

Targeting Nanomotor with Near-Infrared/Ultrasound Triggered-Transformation for Polystage-Propelled Cascade Thrombolysis and Multimodal Imaging Diagnosis.

Nowadays, cardiovascular and cerebrovascular diseases caused by venous thromboembolism become main causes of mortality around the world. The current thrombolytic strategies in clinics are confined primarily due to poor penetration of nanoplatforms, limited thrombolytic efficiency, and extremely-low imaging accuracy. Herein, a novel nanomotor (NM) is engineered by combining iron oxide/perfluorohexane (PFH)/urokinase (UK) into liposome nanovesicle, which exhibits near-infrared/ultrasound (NIR/US) triggered transformation, achieves non-invasive vein thrombolysis, and realizes multimodal imaging diagnosis altogether. Interestingly, a three-step propelled cascade thrombolytic therapy is revealed from such intelligent NM. First, the NM is effectively herded at the thrombus site under guidance of a magnetic field. Afterwards, stimulations of NIR/US propel phase transition of PFH, which intensifies penetration of the NM toward deep thrombus dependent on cavitation effect. Ultimately, UK is released from the collapsed NM and achieves pharmaceutical thrombolysis in a synergistic way. After an intravenous injection of NM in vivo, the whole thrombolytic process is monitored in real-time through multimodal photoacoustic, ultrasonic, and color Doppler ultrasonic imagings. Overall, such advanced nanoplatform provides a brand-new strategy for time-critical vein thrombolytic therapy through efficient thrombolysis and multimodal imaging diagnosis.

Designing a Dimension Reduced Hybrid Perovskite with Robust Large Birefringence by Expanding Cationic π-Delocation.

It is in great demand to discover new materials with large birefringence for the miniaturization of optical communication devices. In this work, a new one-dimensional hybrid halide perovskite, (C6 N10 H8 )Pb2 Br6 , is obtained successfully through structural design of dimension reduction from the notable three-dimensional halide perovskite CsPbBr3 . Remarkably, (C6 N10 H8 )Pb2 Br6 exhibits a significantly enhanced birefringence of ∆n = 0.42@550 nm, which is the largest among halide perovskites so far. Furthermore, its birefringence performance is robust in a wide temperature range of 300-440 K. Theoretical calculations reveal that this outstanding birefringence results from the synergistic effect of [PbBr6 ]4- octahedra and [C6 N10 H8 ]2+ cations with expanding π-delocation. According to further structural analyses, the structural dimension reduction cooperating with the increase of [PbBr6 ]4- octahedral distortion leads to the enhanced birefringence. This work uncovers the great promise of hybrid halide perovskites as robust birefringent crystals in future optical communication and would shed useful insights on the design and synthesis of new birefringent crystals.

Influence laws of air gap structure manipulation of covalent organic frameworks on dielectric properties and exciton effects for photopolymerization.

Boosting the dissociation of excitons is essential to enhance the photocatalytic efficiency. However, the relationship between the structure of the catalyst and the exciton effect on the photocatalytic activity is still unclear as the main problem. Here, it is proposed that as a descriptive factor, an experimentally measurable dielectric constant (εr) is available to quantitatively describe its relationship with exciton binding energy (Eb) and photocatalytic activity. With tuning the linker of covalent organic frameworks (COFs), the "air gap" structure is oriented to shrink, leading to an increased εr of COFs and a lower Eb to facilitate exciton dissociation. Meanwhile, taking "water-/oxygen-fueled" photo-induced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization as a demonstration platform, it can be seen that COFs with a small "air gap" structure have relatively superior photocatalytic activity. This provides important implications for the evolution of efficient photocatalysts.

Identifying And Unveiling the Role of Multivalent Metal States for Bidirectional UOR and HER Over Ni, Mo-Trithiocyanuric Based Coordination Polymer.

Urea oxidation reaction (UOR), an ideal alternative to oxygen evolution reaction (OER), has received increasing attention for realizing energy-saving H2 production and relieving pollutant degradation. Normally, most studied Ni-based UOR catalysts pre-oxidate to NiOOH and then act as active sites. However, the unpredictable transformation of the catalyst's structure and its dissolution and leaching, may complicate the accuracy of mechanism studies and limit its further applications. Herein, a novel self-supported bimetallic Mo-Ni-C3 N3 S3 coordination polymers (Mo-NT@NF) with strong metal-ligand interactions and different H2 O/urea adsorption energy are prepared, which realize a bidirectional UOR/hydrogen evolution reaction (HER) reaction pathway. A series of Mo-NT@NF is prepared through a one-step mild solvothermal method and their multivalent metal states and HER/UOR performance relationship is evaluated. Combining catalytic kinetics, in situ electrochemical spectroscopic characterization, and density-functional theory (DFT) calculations, a bidirectional catalytic pathway is proposed by N, S-anchored Mo5+ and reconstruction-free Ni3+ sites for catalytic active center of HER and UOR, respectively. The effective anchoring of the metal sites and the fast transfer of the intermediate H* by N and S in the ligand C3 N3 S3 H3 further contribute to the fast kinetic catalysis. Ultimately, the coupled HER||UOR system with Mo-NT@NF as the electrodes can achieve energy-efficient overall-urea electrolysis for H2 production.

POSS-based polyionic liquids for efficient CO2 cycloaddition reactions under solvent- and cocatalyst-free conditions at ambient pressure.

The conversion of CO2 into value-added chemicals has become an imminent research topic and the cycloaddition of CO2 with a C1 resource to produce cyclic carbonates is a promising pathway for CO2 utilization. Herein, a series of POSS-based polyionic liquids (PILs) were synthesized by the copolymerization of octavinyl polyhedral oligomeric silsesquioxane (POSS) with an imidazolium ion linker. The prepared PILs have the characteristics of hydrogen bond donors, halogen atom sites, stable pore structures, and thermal stability, and are used as heterogeneous catalysts for the cycloaddition of epoxides with carbon dioxide. The effect of linkers on the cycloaddition is investigated by tuning the ratio of POSS units to imidazolium ions. Under the optimized conditions, the conversion of epichlorohydrin can reach 99.18% at atmospheric pressure with neither co-catalysts nor solvents. It is concluded that the reaction of the cycloaddition of epoxides with carbon dioxide follows pseudo-first-order kinetics. Moreover, the presence of the catalysis of PILs leads to a significant decrease in the activation energy barrier for cycloaddition. The catalyst can be facilely recovered due to its high stability, and only a slight decrease in conversion was observed after five successive runs. In addition, the mechanism of PILs catalyzing the cycloaddition reaction of epoxides with CO2 is proposed. This work not only provides a sustainable and green process for CO2 cycloaddition, but also highlights the potential of using PILs for CO2 utilization.

Facilely Control Grafting Density and Side Chain Composition of Bottlebrush Polymer.

Control over polymer architecture and composition is essential for disclosing structure-property relationships and developing high-performance materials. Herein, a new method is successfully developed to synthesize bottlebrush polymer (BP) with controllable graft density and side chain composition by "grafting-from" strategy using in situ halogen exchange and reversible chain transfer catalyzed polymerization (RTCP). The main chain of the BP is first synthesized by the polymerization of methacrylates containing alkyl bromide as a side group. Then, the alkyl bromine is quantitatively converted to alkyl iodide with sodium iodide (NaI) via in situ halogen exchange to efficiently initiate the RTCP of methacrylates. By adjusting the input amount of NaI and monomers in sequence, BP named PBPEMA-g-PMMA/PBzMA/PPEGMEMA which contains three different kinds of polymer side chains including hydrophilic PPEGMEMA, hydrophobic PMMA, and PBzMA is synthesized with narrow molecular weight distribution (Mw /Mn  ≤ 1.36). The grafting density and the chain length of each polymer side chain are well controlled by the addition of NaI in batches and following RTCP. Moreover, the obtained BP self-assembled into spherical vesicles in aqueous with hydrophilic coronal structure, core region, and the hydrophobic wall between the former two, which enables to wrap hydrophobic pyrene and hydrophilic Rhodamine 6G separately or simultaneously.

Thermo-Responsive Poly(N-isopropylacrylamide)/Hydroxypropylmethyl Cellulose Hydrogel with High Luminous Transmittance and Solar Modulation for Smart Windows.

Thermochromic smart windows are considered to be promising energy-saving devices for reducing energy consumption in buildings. The ideal materials for thermochromic smart windows should have high transmittance, high solar modulation, low phase-transition temperature, and excellent high-temperature thermal stability, which are difficult to achieve simultaneously. This work reports a simple one-step low-temperature polymerization method to prepare a thermo-responsive poly(N-isopropylacrylamide)/hydroxypropylmethyl cellulose (PNIPAM/HPMC) hydrogel achieving the above performances simultaneously. The low-temperature polymerization environment endowed the hydrogel with a high luminous transmittance (Tlum) of 90.82%. HPMC as a functional material effectively enhanced the mechanical properties and thermal stability of the hydrogel. Meanwhile, the PNIPAM/HPMC hydrogel showed a low phase-transition temperature (∼32 °C) and high solar modulation (ΔTsol = 81.52%), which proved that it is an ideal material for thermochromic smart windows. Moreover, a PNIPAM/HPMC smart window exhibited high light transmittance (T380-760 = 86.27%), excellent light modulation (ΔT365 = 74.27%, ΔT380-760 = 86.17%, and ΔT940 = 63.93%), good indoor temperature regulation ability and stability, which indicated that it was an attractive candidate for application in reducing energy consumption in buildings. This work also provides an option and direction for modifying PNIPAM-based thermochromic smart windows.

Skeleton-coated CoCu-Based bimetal hollow nanoprisms as High-Performance electrocatalysts for oxygen evolution reaction.

CoSx materials with high catalytic activity are considered as promising HER electrocatalysts, but their inherent low electrical conductivity and easy loss of active sites have greatly limited their applications in OER electrocatalysis. Herein, we present a convenient method to synthesize Co-Cu hollow nanoprisms after wrapping and calcining with trithiocyanuric acid (C3H3N3S3) (denoted N-Co-Cu-S-x HNs). The results showed that Cu doping modified the charge density of Co center, leading to the enhancement of the intrinsic activity of the Co3S4 active center, meanwhile wrapping trithiocyanuric acid on the surfaces and calcinating to form N-containing C skeleton as a flexible substrate to encapsulate the catalysts, which effectively protected the active sites inside the catalysts. Notably, the OER catalyst that was optimized by adjusting the metal ratio and controlling the trithiocyanuric acid incorporation exhibited a low overpotential of 306 mV under a current density of 10 mA cm-2 and showed a superior durability of more than 27 h. This work may provide some insights into the preparation of oxygen evolution reaction catalysts with excellent performance through doping transition metals and protecting the internal active sites strategies.

Ionic Conjugated Polymers as Heterogeneous Catalysts for the Cycloaddition of Carbon Dioxide to Epoxides to Form Carbonates under Solvent- and Cocatalyst-Free Conditions.

The generation of cyclic carbonates by the cycloaddition of CO2 with epoxides is attractive in the industry, by which CO2 is efficiently used as C1 source. Herein, a series of catalysts were developed to efficient mediate the cycloaddition of CO2 with epoxides to generate carbonates. The catalysts were easily synthesized via the amine-formaldehyde condensation of ethidium bromide with a variety of linkers. The newly prepared heterogeneous catalysts have high thermal stability and degradation temperatures. The surface of the catalysts is smooth and spherical in shape. The effect of temperature, pressure, reaction time and catalyst dosage on the cycloaddition of CO2 with epoxide were investigated. The results show that the catalyst with 1,3,5-tris(4-formylphenyl)benzene as the linker can achieve 97.4 % conversion efficiency at the conditions of 100 °C, reaction time of 12 h, and the reaction pressure of 1.2 MPa in a solvent-free environment. Notably, the polymers serve as homogeneous catalysts during the reaction (reaction temperature above Tg ) and can be separated and recovered easily as homogeneous catalysts at room temperature. In addition, the catalyst is not only suitable for a wide range of epoxide substrates, but also can be recycled many times. Furthermore, DFT calculations show that the coordination between the electrophilic center of the catalyst and the epoxide reduces the energy barrier, and the reaction mechanism is proposed based on the reaction kinetic studies and DFT calculations.

Highly tough and ionic conductive starch/poly(vinyl alcohol) hydrogels based on a universal soaking strategy.

High-performance hydrogels with favorable mechanical strength, high modulus, sufficient ionic conductivity and freezing resistance have far-ranging applications in flexible electronic equipment. Nevertheless, it is challenging to combine admirable mechanical properties and high ionic conductivity into one hydrogel. Herein, a facile strategy was developed for the preparation of the hydrogel with excellent strength (1.45 MPa), super Young's modulus (8.85 MPa) and high conductivity (1.47 S/m) using starch and poly(vinyl alcohol) (PVA) as raw materials. The starch/PVA/Gly/Na3Cit (SPGN) gel was firstly cross-linked by crystalline regions of PVA upon freezing-thawing cycles. It was further immersed in the saturated Na3Cit solution to enhance the interaction between the substrates through the salting-out effect. The effect of soaking time on the crystallinity, intermolecular interactions, mechanical and electrical properties of SPGN gel was demonstrated by X-ray diffraction, Fourier transform infrared spectroscopy, tensile and impedance testing measurements. The introduction of glycerol and Na3Cit also endowed SPGN gels with favorable anti-freezing properties. The SPGN gel could maintain high mechanical flexibility and ionic conductivity at -15 °C.

Influence of the Building Unit on Covalent Organic Frameworks in Mediating Photo-induced Energy-Transfer Reversible Complexation-Mediated Radical Polymerization (PET-RCMP).

Two imine-based covalent organic framework photocatalysts with different building units, TPB-DMTA-COF and TAT-DMTA-COF, for photo-induced energy transfer reversible complexation-mediated radical polymerization (PET-RCMP) were developed and investigated, producing ideal polymers with accurate molecular weight and moderate dispersity under visible light irradiation. The chain extension and spatiotemporal control experiments revealed the high chain-end fidelity of polymers and the compatibility of RCMP processes in both bulk and aqueous system. Moreover, density functional theory (DFT) calculations verified that heteroatom-doped TAT-DMTA-COF exhibits higher activities for weakening C-I bond energy barrier, which promotes PET-RCMP polymerization performance. This work demonstrates that rational adjustment of building block for constructing COF heterogeneous photocatalyst can enhance the catalytic performance of PET-RCMP, providing a design methodology for the development of polymeric organic photoelectric semiconductor catalysts to mediate RCMP.

Osteoimmunity-Regulating Biomimetically Hierarchical Scaffold for Augmented Bone Regeneration.

Engineering a proper immune response following biomaterial implantation is essential to bone tissue regeneration. Herein, a biomimetically hierarchical scaffold composed of deferoxamine@poly(ε-caprolactone) nanoparticles (DFO@PCL NPs), manganese carbonyl (MnCO) nanosheets, gelatin methacryloyl hydrogel, and a polylactide/hydroxyapatite (HA) matrix is fabricated to augment bone repair by facilitating the balance of the immune system and bone metabolism. First, a 3D printed stiff scaffold with a well-organized gradient structure mimics the cortical and cancellous bone tissues; meanwhile, an inside infusion of a soft hydrogel further endows the scaffold with characteristics of the extracellular matrix. A Fenton-like reaction between MnCO and endogenous hydrogen peroxide generated at the implant-tissue site triggers continuous release of carbon monoxide and Mn2+ , thus significantly lessening inflammatory response by upregulating the M2 phenotype of macrophages, which also secretes vascular endothelial growth factor to induce vascular formation. Through activating the hypoxia-inducible factor-1α pathway, Mn2+ and DFO@PCL NP further promote angiogenesis. Moreover, DFO inhibits osteoclast differentiation and synergistically collaborates with the osteoinductive activity of HA. Based on amounts of data in vitro and in vivo, strong immunomodulatory, intensive angiogenic, weak osteoclastogenic, and superior osteogenic abilities of such an osteoimmunity-regulating scaffold present a profound effect on improving bone regeneration, which puts forward a worthy base and positive enlightenment for large-scale bone defect repair.

Micropore-Forming Gelatin Methacryloyl (GelMA) Bioink Toolbox 2.0: Designable Tunability and Adaptability for 3D Bioprinting Applications.

It is well-known that tissue engineering scaffolds that feature highly interconnected and size-adjustable micropores are oftentimes desired to promote cellular viability, motility, and functions. Unfortunately, the ability of precise control over the microporous structures within bioinks in a cytocompatible manner for applications in 3D bioprinting is generally lacking, until a method of micropore-forming bioink based on gelatin methacryloyl (GelMA) was reported recently. This bioink took advantage of the unique aqueous two-phase emulsion (ATPE) system, where poly(ethylene oxide) (PEO) droplets are utilized as the porogen. Considering the limitations associated with this very initial demonstration, this article has furthered the understanding of the micropore-forming GelMA bioinks by conducting a systematic investigation into the additional GelMA types (porcine and fish, different methacryloyl-modification degrees) and porogen types (PEO, poly(vinyl alcohol), and dextran), as well as the effects of the porogen concentrations and molecular weights on the properties of the GelMA-based ATPE bioink system. This article exemplifies not only the significantly wider range of micropore sizes achievable and better emulsion stability, but also the improved suitability for both extrusion and digital light processing bioprinting with favorable cellular responses.

Stimuli-Responsive Nanoparticles for Controlled Drug Delivery in Synergistic Cancer Immunotherapy.

Cancer immunotherapy has achieved promising clinical progress over the recent years for its potential to treat metastatic tumors and inhibit their recurrences effectively. However, low patient response rates and dose-limiting toxicity remain as major dilemmas for immunotherapy. Stimuli-responsive nanoparticles (srNPs) combined with immunotherapy offer the possibility to amplify anti-tumor immune responses, where the weak acidity, high concentration of glutathione, overexpressions of enzymes, and reactive oxygen species, and external stimuli in tumors act as triggers for controlled drug release. This review highlights the design of srNPs based on tumor microenvironment and/or external stimuli to combine with different anti-tumor drugs, especially the immunoregulatory agents, which eventually realize synergistic immunotherapy of malignant primary or metastatic tumors and acquire a long-term immune memory to prevent tumor recurrence. The authors hope that this review can provide theoretical guidance for the construction and clinical transformation of smart srNPs for controlled drug delivery in synergistic cancer immunotherapy.

Efficient Persistent Luminescence Tuning Using a Cyclodextrin Inclusion Complex as Efficient Light Conversion Materials.

Developing an appropriate method to broaden the color of long persistent luminescence materials has important scientific significance and practical value but remains a great challenge. Herein, we have developed a unique strategy to fine-tune the persistent luminescence using the inclusion complex of rhodamine 6G with (2-hydroxypropyl)-ß-cyclodextrin as efficient light conversion materials. The emitting color of the novel persistent luminescence material could be tuned from green to orange by changing the concentration of the light conversion agent. Furthermore, afterglow decay measurements showed that the initial afterglow brightness is 9.65 cd/m2, and the initial afterglow brightness gradually decreased as the cyclodextrin inclusion compound coating increased. This design concept introduces a new perspective for broadening the luminescence color of afterglow phosphors, which may open up new opportunities for persistent luminescence materials toward many emerging applications.