Engineering ZrO2-Ru interface to boost Fischer-Tropsch synthesis to olefins.

Understanding the structures and reaction mechanisms of interfacial active sites in the Fisher-Tropsch synthesis reaction is highly desirable but challenging. Herein, we show that the ZrO2-Ru interface could be engineered by loading the ZrO2 promoter onto silica-supported Ru nanoparticles (ZrRu/SiO2), achieving 7.6 times higher intrinsic activity and ~45% reduction in the apparent activation energy compared with the unpromoted Ru/SiO2 catalyst. Various characterizations and theoretical calculations reveal that the highly dispersed ZrO2 promoter strongly binds the Ru nanoparticles to form the Zr-O-Ru interfacial structure, which strengthens the hydrogen spillover effect and serves as a reservoir for active H species by forming Zr-OH* species. In particular, the formation of the Zr-O-Ru interface and presence of the hydroxyl species alter the H-assisted CO dissociation route from the formyl (HCO*) pathway to the hydroxy-methylidyne (COH*) pathway, significantly lowering the energy barrier of rate-limiting CO dissociation step and greatly increasing the reactivity. This investigation deepens our understanding of the metal-promoter interaction, and provides an effective strategy to design efficient industrial Fisher-Tropsch synthesis catalysts.

Biodegradable MXene Quantum Dots with High Near-Infrared Photothermal Performance for Cancer Treatment.

Photothermal therapy (PTT) offers significant potential in cancer treatment due to its short, simple, and less harmful nature. However, obtaining a photothermal agent (PTA) with good photothermal performance and biocompatibility remains a challenge. MXenes, which are PTAs, have shown promising results in cancer treatment. This study presents the preparation of Ti3C2 MXene quantum dots (MXene QDs) using a simple hydrothermal and ultrasonic method and their use as a PTA for cancer treatment. Compared to conventional MXene QDs synthesized using only the hydrothermal method, the ultrasonic process increased the degree of oxidation on the surface of the MXene QDs. This resulted in the presence of more hydrophilic groups such as hydroxyl groups on the MXene QD surfaces, leading to excellent dispersion in the aqueous system and biocompatibility of the prepared MXene QDs without the need for surface modification. The MXene QDs showed great photothermal performance with a photothermal conversion efficiency of 62.5%, resulting in the highest photothermal conversion efficiency among similar materials reported thus far. Both in vitro and in vivo experiments have proved the potent tumor inhibitory effect of the MXene QD-mediated PTT, with minimal harm to mice. Therefore, these MXene QDs hold a significant promise for clinical applications.

Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO2.

The covalent organic frameworks (COFs) possessing high crystallinity and capability to capture low-concentration CO2 (400 ppm) from air are still underdeveloped. The challenge lies in simultaneously incorporating high-density active sites for CO2 insertion and maintaining the ordered structure. Herein, a structure engineering approach is developed to afford an ionic pair-functionalized crystalline and stable fluorinated COF (F-COF) skeleton. The ordered structure of the F-COF is well maintained after the integration of abundant basic fluorinated alcoholate anions, as revealed by synchrotron X-ray scattering experiments. The breakthrough test demonstrates its attractive performance in capturing (400 ppm) CO2 from gas mixtures via O─C bond formation, as indicated by the in situ spectroscopy and operando nuclear magnetic resonance spectroscopy using 13C-labeled CO2 sources. Both theoretical and experimental thermodynamic studies reveal the reaction enthalpy of ≈-40 kJ mol-1 between CO2 and the COF scaffolds. This implies weaker interaction strength compared with state-of-the-art amine-derived sorbents, thus allowing complete CO2 release with less energy input. The structure evolution study from synchrotron X-ray scattering and small-angle neutron scattering confirms the well-maintained crystalline patterns after CO2 insertion. The as-developed proof-of-concept approach provides guidance on anchoring binding sites for direct air capture (DAC) of CO2 in crystalline scaffolds.

Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO2 to ethylene and CO.

Developing atomically synergistic bifunctional catalysts relies on the creation of colocalized active atoms to facilitate distinct elementary steps in catalytic cycles. Herein, we show that the atomically-synergistic binuclear-site catalyst (ABC) consisting of [Formula: see text]-O-Cr6+ on zeolite SSZ-13 displays unique catalytic properties for iso-stoichiometric co-conversion of ethane and CO2. Ethylene selectivity and utilization of converted CO2 can reach 100 % and 99.0% under 500 °C at ethane conversion of 9.6%, respectively. In-situ/ex-situ spectroscopic studies and DFT calculations reveal atomic synergies between acidic Zn and redox Cr sites. [Formula: see text] ([Formula: see text]) sites facilitate ß-C-H bond cleavage in ethane and the formation of Zn-Hδ- hydride, thereby the enhanced basicity promotes CO2 adsorption/activation and prevents ethane C-C bond scission. The redox Cr site accelerates CO2 dissociation by replenishing lattice oxygen and facilitates H2O formation/desorption. This study presents the advantages of the ABC concept, paving the way for the rational design of novel advanced catalysts.

Respiration-Responsive Colorful Room-Temperature Phosphorescent Materials and Assembly-Induced Phosphorescence Enhancement Strategies.

It is still very challenging to obtain colorful and long-afterglow room-temperature phosphorescent (RTP) materials from pure organic polymers. Herein, it is found that chitosan (CS), a natural polymer, not only has its own RTP, but also reacts with different phosphorescent molecules to obtain a multicolor, long-afterglow RTP material. CS can emit RTP with a lifetime of 48 ms. In addition, CS is rich in amino groups, and grafting different phosphorescent molecules onto CS by an amidation reaction can modulate it to emit different colors of phosphorescence and obtain a series of colorful CS derivatives. The obtained polymer films also have ultra-long RTP due to the good film-forming ability. In addition, one of the CS derivatives selected with α-cyclodextrin is used to construct RTP materials with lifetimes of up to seconds. The host-guest interactions are used to suppress nonradiative relaxation and build crystalline domains, thus synergistically enhancing the RTP. Interestingly, the RTP properties of the CS derivative films are extremely sensitive to water and heat stimuli, because water broke the hydrogen bonds between adjacent CS molecules and thus altered the rigid environment in the material. Finally, they can be used as a stimuli-responsive ink and for monitoring environmental humidity.

Crystalline micro-nanoparticles enhance cross-linked hydrogels via a confined assembly of chitosan and γ-cyclodextrin.

Hydrogels constructed by traditional polymer networks usually have poor mechanical properties limiting their applications. Here, we proposed a new strategy for ionic interaction modulation of crystalline micro-nanoparticles (CMNPs) to enhance the mechanical properties of polyacrylamide hydrogels. CMNPs were formed via confinement assembly under an aggregated state based on host-guest interactions between chitosan-grafted polyethylene glycol (CS-PEG) and γ-cyclodextrin (γ-CD). Furthermore, the aggregation behavior of the CMNPs was achieved based on the ionic interaction of CS with citrate (Cit3-). These Cit3--regulated CMNPs were introduced into PAM hydrogels. The modulus (618.44 kPa, 67.6 times), fracture stress (1054.59 kPa, 25.3 times), and toughness (6.23 MJ m-3, 41.7 times) of the composite hydrogels were greatly improved without affecting the tensile properties (fracture strain, ~1000 %). Finally, we further designed a strain sensor that could monitor human motion, and we verified its potential application in the field of wearable flexible electronics.

Direct production of olefins from syngas with ultrahigh carbon efficiency.

Syngas conversion serves as a competitive strategy to produce olefins chemicals from nonpetroleum resources. However, the goal to achieve desirable olefins selectivity with limited undesired C1 by-products remains a grand challenge. Herein, we present a non-classical Fischer-Tropsch to olefins process featuring high carbon efficiency that realizes 80.1% olefins selectivity with ultralow total selectivity of CH4 and CO2 (<5%) at CO conversion of 45.8%. This is enabled by sodium-promoted metallic ruthenium (Ru) nanoparticles with negligible water-gas-shift reactivity. Change in the local electronic structure and the decreased reactivity of chemisorbed H species on Ru surfaces tailor the reaction pathway to favor olefins production. No obvious deactivation is observed within 550 hours and the pellet catalyst also exhibits excellent catalytic performance in a pilot-scale reactor, suggesting promising practical applications.

Target-Binding Accelerated Response for Sensitive Detection of Basal H2O2 in Tumor Cells and Tissues via a Dual-Functional Fluorescence Probe.

Aberrant production of H2O2 is involved in cancer. The levels of H2O2 are significantly higher in tumor cells than in normal cells. It is important to develop fluorescent probes to image basal H2O2 selectively in tumor cells. So far, a cancer cell-targeting probe to image basal H2O2 has not been reported. Thus, we developed a fluorescent probe, BBHP, which contains benzil as a H2O2-recognition site and biotin as a target binding motif for the selective and sufficient detection of H2O2 in tumor cells. BBHP enables a selective fluorescence turn-on response to H2O2. The binding of the probe with biotin receptors can greatly accelerate the fluorescence response to H2O2. As a result, BBHP can sufficiently image basal H2O2 in biotin receptor-positive cancer cells and tumor tissues. Finally, BBHP was successfully applied to discriminate between cancerous and normal tissues.

Cationic Peptidopolysaccharide with an Intrinsic AIE Effect for Combating Bacteria and Multicolor Imaging.

An antibacterial polymer peptidopolysaccharide (COS-AMP) that integrates antibacterial and detection functions is constructed with a simple synthetic method. The COS-AMP is constructed by simulating the structure of peptidoglycan of the bacterial cell wall with chitooligosaccharide with intrinsic aggregation-induced emission (AIE) effect as the main chain, as well as a peptide polymer grafted onto its amino group. Based on the AIE effect and excitation-dependent fluorescence of COS-AMP, it is tentatively applied to multicolor imaging and quantification of bacteria. This multicolor imaging helps to match different excitation sources of fluorescent instrument for straightforward imaging and detection. The structural similarity with the bacterial cell wall component facilitates the passage of COS-AMP across the cell wall and destroys the bacterial structure, thus it has a good broad-spectrum antibacterial activity. In addition, aromatic fluorophores are not needed, and excellent biocompatibility will make it have broad application prospects.

Biocompatible AIE material from natural resources: Chitosan and its multifunctional applications.

New sources of AIE materials with good water solubility, biocompatibility, degradability, and mass production are urgently needed. Here, we found that chitosan, a very abundant polysaccharide in nature, has fluorescence emission in both solid and solution states with AIE effect, and explored its multifunctional applications. Chitosan can emit a variety of colors from blue to red at different excitation wavelengths with excellent multicolor imaging capabilities at the cellular level. Utilizing the cationic and antibacterial properties of chitosan, the quantification of bacteria can be achieved through the AIE effect. Concurrently, it can be used as fluorescent probes for multi-channel bacterial imaging via lighting-up bacteria. Furthermore, the chitosan solution exhibits a sensitive quenching response to Fe3+, which can be used as a biosensor for detecting the concentration of Fe3+. These interesting results indicate that chitosan will have broad application prospects as a new class of AIE material.

AIE Supramolecular Assembly with FRET Effect for Visualizing Drug Delivery.

Here, we constructed a nanostructured pH/redox dual-responsive supramolecular drug carrier with both aggregation-induced emission (AIE) and Forster resonance energy transfer (FRET) effects, which enabled selective drug release and monitoring drug delivery and release processes. Taking the hyperbranched polyamide amine (H-PAMAM) with intrinsic AIE effects as the core, poly(ethylene glycol) (PEG) was bridged on its periphery by dithiodipropionic acid. Then, through the host-guest interaction of PEG and α-cyclodextrin, the supramolecular nanoparticles with AIE effects were constructed to load the anticancer drug doxorubicin (DOX). The supramolecular assembly has sufficiently large DOX loading due to the abundant cavities formed by branched structures. The hyperbranched core H-PAMAM has strong fluorescence, and the dynamic track of drug carriers and the dynamic drug release process can be monitored by the AIE and FRET effects between H-PAMAM and DOX, respectively. Furthermore, the introduction of disulfide bonds and the pH sensitivity of H-PAMAM enable the achievement of rapid selective release of loaded DOX at the tumor while remaining stable under normal physiological conditions. In vitro cytotoxicity indicates that the drug-loaded supramolecular assembly has a good therapeutic effect on cancer. In addition, the H-PAMAM core is different from the traditional AIE functional group, which has no conjugated structure, such as a benzene ring, thereby providing better biocompatibility. This technology will have broad applications as a new drug delivery system.

Direct Production of Higher Oxygenates by Syngas Conversion over a Multifunctional Catalyst.

Selective synthesis of higher oxygenates (linear α-alcohols and α-aldehydes, C 2 + OH) from syngas is highly attractive but remains challenging owing to the low C 2 + OH selectivity and low catalytic stability. Herein we introduce a multifunctional catalyst composed of CoMn and CuZnAlZr oxides that dramatically increased the oxygenates selectivity to 58.1 wt %, where more than 92.0 wt % of the produced oxygenates are C 2 + OH. Notably, the total selectivity to value-added chemicals including oxygenates and olefins reached 80.6 wt % at CO conversion of 29.0 % with high stability. The appropriate component proximity can effectively suppress the formation of the undesired C1 products, and the selectively propulsion of reaction network by synergetic effect of different components contributes to the enhanced selectivity to higher oxygenates. This work provides an alternative strategy for the rational design of new catalysts for direct conversion of syngas into higher oxygenates with co-production of olefins.

The design strategy of intelligent biomedical magnesium with controlled-release platform.

Magnesium has a very promising adhibition in biomedical field for its excellent mechanical and biodegradable properties, however, the intelligent applications of biomedical magnesium developed difficultly due to its characteristic degradation. A intelligent biomedical magnesium was constructed on magnesium (Mg) surface by incorporating polydopamine (PD) and mechanized hollow mesoporous silica nanoparticles (HMSs) as smart delivery platform nanocontainers. The supramolecular nanovalves of mechanized HMSs consisted of alginate/chitosan multilayers by self-assembly, which are capable of entrapping rhodamine 6G in the mesopores and can release the cargo under the chemical environment of alkali or Mg iron stimuli that correspond to the degradation of biomedical Mg. The alkali/Mg2+ dual stimuli-responsive release property of the HMSs endows the biodegradable Mg with controlled release potential. The well-designed smart delivery nanocontainers were combined with polydopamine deposited on Mg for excellent adhesion properties and positively charged amino group of PD. Furthermore, when the biomedical Mg with these mechanized HMSs was degraded in the simulated body environment, the alkali/Mg2+-triggered release of cargos from this smart delivery platform could bring a more functional application.

Nanoengineered Peptide-Grafted Hyperbranched Polymers for Killing of Bacteria Monitored in Real Time via Intrinsic Aggregation-Induced Emission.

Facing the global health crisis caused by drug-resistant bacteria, antimicrobial peptides and their analogues offer exciting solutions to this widespread problem. Without additionally introducing a fluorescent probe, novel nanoengineered peptide-grafted hyperbranched polymers (NPGHPs) are constructed for their combined outstanding antimicrobial activity and sensitive bacterial detection in real time. Hyperbranched polyamide amine (H-PAMAM) that exhibits aggregation-induced emission (AIE) effects is synthesized. Then, NPGHPs are prepared by ring-opening polymerization of α-amino acid N-carboxyanhydrides on the periphery of the H-PAMAM. The NPGHPs exhibit high-efficiency antibacterial properties against a wide spectrum of bacteria, especially against Gram-negative bacteria. On the basis of the AIE effect of NPGHPs, the interaction between NPGHPs and Escherichia coli is explored and the fluorescence intensity of NPGHPs is dependent on the number of E. coli present. Thus, a method for monitoring E. coli concentration is developed, and the detection limit is 1 × 104 CFU mL-1. Furthermore, NPGHPs are used as fluorescent probes to visualize antibacterial process via lighting-up bacteria. NPGHPs can penetrate the membrane of bacteria and cause cell rupture and apoptosis. In addition, the excellent selectivity of NPGHPs toward bacteria over mammalian cells makes them bright prospects for clinical applications.

pH and redox-operated nanovalve for size-selective cargo delivery on hollow mesoporous silica spheres.

A pH and redox dual-responsive nanovalve with a long stalk was introduced on the surface of hollow mesoporous silica nanoparticles (HMSs-S1) to achieve cargo size selectivity delivery. The responsive nanovalve was designed by constructing of a stalk/ß-cyclodextrins (CDs) supramolecular complex, which is based on an acid-labile acetal group and the host-guest interactions between ß-cyclodextrins and ferrocenyl moiety (Fc). With stimulation by different pH and H2O2, Rhodamine 6G showed well-responsive behavior. On account of the long stalks of nanovalve, doxorubicin hydrochloride and 5-fluorouracil with different sized cargos are encapsulated in HMSs-S1 to test its behavior of cargo size-selective delivery. Moreover the HMSs-S2 with a short stalk based on ß-CDs/Fc inclusion complex is synthesized to load small sized 5-FU drug as contrast experiment. Compared with HMSs-S2, HMSs-S1 is compatible with larger drug molecules such as Rhodamine 6G (R6G) and doxorubicin hydrochloride (DOX), while small sized 5-fluorouracil (5-FU) is unable to be sealed by the nanovalve. Dual responsiveness and drug size selectivity make mechanized HMSs possess potential applications in drug delivery system.

Oxidation and pH responsive nanoparticles based on ferrocene-modified chitosan oligosaccharide for 5-fluorouracil delivery.

Stimuli-responsive nanoparticles based on biodegradable and biocompatible saccharides are potentially superior carriers under different physical conditions. In this study, we present a detailed investigation on the oxidation and pH responses of ferrocene-modified chitosan oligosaccharide (FcCOS) nanoparticles for 5-Fluorouracil (5-FU) Delivery. The dispersion of FcCOS nanoparticles depends strongly on pH change. NaClO, H2O2 and oxygen, as oxidant models, in a weak acid solution displayed varying accelerations as the disassembly progressed. 5-FU, as a drug model, is efficiently uploaded in FcCOS nanoparticle (approximately 238 nm). The in vitro release of 5-FU from FcCOS nanoparticles studies show that the accumulative release increased with the decrease of pH under bubbled N2. Interestingly, the sample under bubbled air has a higher accumulative release up to 59.64% at pH 3.8, compared with samples under bubbled N2 just 49.02%. The results suggested that FcCOS nanoparticles disassembled faster and the release of drug molecules was accelerated because of the synergistic effect of oxidative agent and low pH. Thus, FcCOS can be developed as an effective pH and oxidation dual-responsive carrier to enhance drug efficacy for cancer treatment.

Multi-morphological self-assembled structures in water of a biodegradable ß-cyclodextrin-based copolymer.

A rigid-coil ß-cyclodextrin-poly (ɛ-caprolactone) (CD-PCL) copolymer was synthesized in which biodegradable flexible multi PCL arms were selectively connected onto the wide side of the rigid torus-shaped ß-CD through ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and protection/deprotection technique of ß-cyclodextrin (ß-CD) via trimethylsilyl groups. (1)H NMR, FT-IR, and GPC analysis confirmed the "jellyfish-like" branched architecture of CD-PCL copolymers. The self-assembled structures in water of the amphiphilic CD-PCL copolymer were investigated by transmission electron microscopy (TEM), dynamic light scattering (DLC) and viscometry. The results showed that CD-PCL could self-assemble into multi-morphological aggregates such as spheres, rods, vesicles, vesicular clusters and vesicular network in water. Interestingly, hierarchical stripe structure was observed in the formed vesicular network, which was driven by the crystallization of PCL segment in micelles. Moreover, the inclusion ability of copolymer micelles with ferrocenecarboxylic acid was investigated by UV.

Multiple morphologies from amphiphilic graft copolymers based on chitooligosaccharides as backbones and polycaprolactones as branches.

A new route to form multiple morphologies was outlined using amphiphilic graft copolymers with interesting biological and pharmacological properties by proper adjustment of backbone and graft chain length.

Study on lyotropic liquid-crystalline properties of trimethylsilyl hydroxypropylcellulose.

The lyotropic liquid-crystalline behavior of trimethylsilyl hydroxypropylcellulose (TMS-HPC) is reported in this paper. The introduction of the trimethylsilyl (TMS) group in the parent HPC increases the solubility in organic solvents, and the lyotropic mesophase can be formed in concentrated acetone solution. The critical concentration (C*) in acetone is approximately 36%. The liquid crystalline nature of TMS-HPC/acetone solution was confirmed by PLM, and the mechanism of liquid crystallization was studied by FTIR and WAXD methods.