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Asparaginase (Asp) is one of the most important drugs for treating acute lymphoblastic leukemia (ALL). However, off-protocol Asp administration (OPAA) or hypersensitivity may disturb its pharmacokinetic profile. In this retrospective study, we sought to determine whether OPAA and hypersensitivity to Escherichia coli asparaginase (E coli Asp) impaired extramedullary relapse prevention in a pediatric ALL cohort treated according to SCMC-ALL-2005 protocol from 2005 to 2014 at the Shanghai Children's Medical Center (SCMC). In total, 676 patients were enrolled in this study, including 369 with OPAA and 60 exhibiting hypersensitivity to E coli Asp. At the end of the most recent follow-up, 58 patients had extramedullary relapse. The 5-year cumulative extramedullary relapse incidence in patients with OPAA was 11.01%, whereas that in patients without OPAA was 5.28% (P = .0036). Moreover, the 5-year cumulative extramedullary relapse incidence in patients that exhibited hypersensitivity to E coli Asp was 16.48%, whereas that in patients without hypersensitivity was 7.59% (P = .0195). Concerning the relapse site, OPAA not only increased central nervous system (CNS) relapse but testicular relapse as well. Based on Fine and Gray multivariate analysis, OPAA and hypersensitivity to Asp were independent risk factors for extramedullary relapse. In conclusion, to prevent extramedullary relapse of ALL, adequate duration to administrate Asp was more important than the total dosage, and more attention should be paid to Asp inadequate due to hypersensitivity.

Diabetic nephropathy (DN) is one of the major microvascular complications of diabetes. Nuclear factor erythroid 2-related factor 2 (Nrf2) is a crucial cellular defense factor to cope with oxidative stress. Silent information regulator T1 (Sirt1) is a deacetylase with antioxidative stress activity. Fucoxanthin is a marine-derived carotenoid. This study was conducted to investigate whether fucoxanthin could alleviate oxidative stress by activating Sirt1/Nrf2 signaling to alleviate DN. In streptozotocin-induced diabetic rats, fucoxanthin treatment effectively improved renal function, alleviated glomerulosclerosis. Fucoxanthin reversed the decreased protein levels of Sirt1 and Nrf2 in the kidney of diabetic rats and glomerular mesangial cells cultured in high glucose. Conversely, EX527, a Sirt1 inhibitor, counteracted the effect of fucoxanthin on the expression of Nrf2. Furthermore, in vivo and vitro results showed that fucoxanthin treatment reversed the low expression and activity of superoxide dismutase and heme oxygenase 1, depending on Sirt1 activation. Our results suggest that fucoxanthin improves diabetic kidney function and renal fibrosis by activating Sirt1/Nrf2 signaling to reduce oxidative stress.

Chemical looping processes present great potentials to achieve carbon capture and fuel conversion with high thermodynamic efficiencies. Well-known applications of chemical looping include combustion and methane reforming, where phase interactions in oxygen carriers play important roles in determining the process performance. In this study, we systematically investigate the interactions between various phases in Ni-Cu-Al2O3 mixed oxides oxygen carriers, which were prepared from layered double hydroxides precursors, synthesized hydrothermally using urea and metal nitrates. It appears that the addition of 32–45 wt% Al2O3 was sufficient to prevent sintering effects over 100 redox cycles at 800 °C, 1 atm, using methane as the fuel. The oxide phases and their compositions were determined using a set of complementary analytical techniques, allowing us to establish relationships between (i) the compositions of the mixed oxides, (ii) the chemical activity of the various types of lattice oxygen present and (iii) the distributions of gaseous products of chemical looping methane oxidation. We found that the mutual doping between NiO and CuO leads to enhanced lattice oxygen activities, whilst the solid solution of NiAl2O4 and CuAl2O4 leads to reduced lattice oxygen activity in the spinel phase, which also turns out to be particularly resistant to carbon deposition. The generality of the composition – activity - performance relationship is demonstrated by the successful prediction of the product distributions of methane oxidation based on solely the elemental compositions of the oxygen carriers. These findings enable the rational formulation of Ni-Cu-Al2O3 oxygen carriers for methane conversion with precise control of product selectivity. National Research Foundation (NRF) This work is funded by the National Research Foundation (NRF), Prime Minister’s Office, Singapore under its Campus for Research Excellence and Technological Enterprise (CREATE) programme. The synchrotron experiments were performed on beamline ID22 at the European Synchrotron Radiation Facility (ESRF), Grenoble, France. The authors are grateful to Catherine Dejoie at the ESRF for providing assistance in using beamline ID22.

The thermal and chemical expansivity of La1-xSrxFeO3-δ (x ​= ​0.4) was measured using in situ powder neutron and synchrotron X-ray diffraction at temperatures between 932 ​K and 1170 ​K and oxygen partial pressures, PO2, between 10−19 ​bar and 0.1 ​bar, giving a wide range of oxygen non-stoichiometry from δ = 0.05 to 0.22. Changes in δ were measured independently using gas analysis. This PO2 and temperature range covers the material's use as a chemical looping oxygen carrier, a sensor material and in solid oxide fuel cells. Thermal and chemical expansivities were found to be dependent on the oxygen non-stoichiometry, δ. For δ ​< ​0.2 and T ​= ​932–1050 ​K, the linear thermal expansivity was 5.72(4) ​× ​10−5 ​Å/K and the linear chemical expansivity was 0.144(9) Å per unit change in δ. For δ ​> ​0.2 and T ​= ​973–1173 ​K, the linear thermal expansivity increases to 6.18(8) ​× ​10−5 ​Å/K. For δ ​> ​0.2, the linear chemical expansivity varies with both δ and temperature.

Aims Atherosclerosis is the dominant pathologic basis of many cardiovascular diseases. Large genome-wide association studies have identified that single-nucleotide polymorphisms proximal to Krüppel-like factor 14 (KLF14), a member of the zinc finger family of transcription factors, are associated with higher cardiovascular risks. Macrophage dysfunction contributes to atherosclerosis development and has been recognized as a potential therapeutic target for treating many cardiovascular diseases. Herein, we address the biologic function of KLF14 in macrophages and its role during the development of atherosclerosis. Methods and results KLF14 expression was markedly decreased in cholesterol loaded foam cells, and overexpression of KLF14 significantly increased cholesterol efflux and inhibited the inflammatory response in macrophages. We generated myeloid cell-selective Klf14 knockout (Klf14LysM) mice in the ApoE-/- background for the atherosclerosis study. Klf14LysMApoE-/- and litter-mate control mice (Klf14fl/flApoE-/-) were placed on the Western Diet for 12 weeks to induce atherosclerosis. Macrophage Klf14 deficiency resulted in increased atherosclerosis development without affecting the plasma lipid profiles. Klf14-deficient peritoneal macrophages showed significantly reduced cholesterol efflux resulting in increased lipid accumulation and exacerbated inflammatory response. Mechanistically, KLF14 upregulates the expression of a key cholesterol efflux transporter, ABCA1 (ATP-binding cassette transporter A1), while it suppresses the expression of several critical components of the inflammatory cascade. In macrophages, activation of KLF14 by its activator, perhexiline, a drug clinically used to treat angina, significantly inhibited the inflammatory response and increased cholesterol efflux in a KLF14-dependent manner in macrophages without triggering hepatic lipogenesis. Conclusions This study provides insights into the anti-atherosclerotic effects of myeloid KLF14 through promoting cholesterol efflux and suppressing the inflammatory response. Activation of KLF14 may represent a potential new therapeutic approach to prevent or treat atherosclerosis.

Membranes for CO2 capture should offer high permeant fluxes to keep membrane surface area small and material requirements low. Ag-supported, dual-phase, molten-carbonate membranes routinely demonstrate the highest CO2 fluxes in this class of membrane. However, using Ag as a support incurs high cost. Here, the non-equilibrium conditions of permeation were exploited to stimulate the self-assembly of a percolating, dendritic network of Ag from the molten carbonate. Multiple membrane support geometries and Ag incorporation methods were employed, demonstrating the generality of the approach, while X-ray micro-computed tomography confirmed that CO2 and O2 permeation stimulated self-assembly. We report the highest flux of Ag-supported molten-salt membranes to date (1.25 ml min−1 cm−2 at 650 °C) and ultrahigh permeability (9.4 × 10−11 mol m−1 s−1 Pa−1), surpassing the permeability requirement for economically-competitive post-combustion CO2 capture, all whilst reducing the membrane-volume-normalised demand for Ag by one order of magnitude.

Targeting at enhancing reverse cholesterol transport (RCT) is apromising strategy for treating atherosclerosis via infusion of reconstitute high density lipoprotein (HDL) as cholesterol acceptors or increase of cholesterol efflux by activation of macrophage liver X receptors (LXRs). However, systemic activation of LXRs triggers excessive lipogenesis in the liver and infusion of HDL downregulates cholesterol efflux from macrophages. Here we describe an enlightened strategy using phospholipid reconstituted apoA-I peptide (22A)-derived synthetic HDL (sHDL) to deliver LXR agonists to the atheroma and examine their effect on atherosclerosis regression in vivo. A synthetic LXR agonist, T0901317 (T1317) was encapsulated in sHDL nanoparticles (sHDL-T1317). Similar to the T1317 compound, the sHDL-T1317 nanoparticles upregulated the expression of ATP-binding cassette transporters and increased cholesterol efflux in macrophages in vitro and in vivo. The sHDL nanoparticles accumulated in the atherosclerotic plaques of ApoE-deficient mice. Moreover, a 6-week low-dose LXR agonist-sHDL treatment induced atherosclerosis regression while avoiding lipid accumulation in the liver. These findings identify LXR agonist loaded sHDL nanoparticles as a promising therapeutic approach to treat atherosclerosis by targeting RCT in a multifaceted manner: sHDL itself serving as both a drug carrier and cholesterol acceptor and the LXR agonist mediating upregulation of ABC transporters in the aorta., Highlights • Macrophage liver X receptors (LXRs) have been established as potential therapeutic targets for treatment of atherosclerosis. • Synthetic high-density lipoprotein nanoparticles deliver LXR agonists to the atheroma and promote atherosclerosis regression. • Systemic administration of LXR ligands (LXR-L) has stalled because of their side effects, especially increased hepatic lipogenesis. Macrophage LXRs have been established as potential therapeutic targets for treatment of atherosclerosis based on the beneficial effects on enhance of reverse cholesterol transport (RCT). However, systemic activation of LXRs triggers excessive lipogenesis in the liver. Synthetic high-density lipoprotein (sHDL) nanoparticles can deliver LXR agonists to the atheroma and promote atherosclerosis regression by targeting RCT in a multifaceted manner: sHDL itself serving as both a drug carrier and cholesterol acceptor and the LXR agonist enhancing cholesterol efflux in the macrophages in the atherosclerotic plaques.

Detection and identification of metal ions by fluorescent turn-on sensors are challenging due to the quenching effect of most of the tested metal ions. In the present work, three ferrocene-modified pyrene-based probes 2-4 were synthesized to act as turn-on fluorescent sensors for Cu2+. The measurements of fluorescence quantum yield and fluorescence lifetime reveal that ferrocenyl unit can efficiently reduce the fluorescence emission of pyrene moiety. Steady-state fluorescence measurements find that the three ferrocene-modified fluorophores exhibit selective turn-on responses to Cu2+. Moreover, this turn-on effect to Cu2+ is highly influenced by the type of the counter ion. It is found that the presence of Cl- or NO3- could realize the turn-on response to Cu2+, whereas, the presence of SO42- or Ac- could not induce any fluorescence enhancement to Cu2+. Control experiments with ferrocene-free pyrene-based probe 1 reveal that the ferrocenyl unit plays the key role in the turn-on response to Cu2+. The possible mechanism for the turn-on responses is attributed to the oxidation behavior of Cu2+ to the ferrocene unit, which is confirmed by the control experiments with sodium ascorbate. Cyclic voltammetry measurements show that Cu2+ can influence the redox behaviors of ferrocenyl derivatives, which is also highly dependent on the anion of the copper salts. The influence of anion on the turn-on responses to Cu2+ was further used for anion detection and fluorescent logic gate.

Two fuels were burned in electrically heated beds of alumina sand, fluidised by air. The fuels were: (i) paraffin wax, which is a solid containing 100% volatile matter and (ii) glycerol, a liquid, whose potential as a fuel needs assessing. The bubbling fluidised beds were held in the range 400–900 °C. Pieces of paraffin wax burned like a plastic, so when fed on top of a bed, the wax floated and generated clouds of soot. Soon, it then sank into the bed. When the sand was below ∼800 °C, combustion occurred noisily in exploding bubbles leaving the bed. In beds hotter than ∼800 °C, combustion proceeded in bubbles fairly low in the bed and was controlled by the mixing of hydrocarbon vapours (from the wax) with the fluidising air. If wax were fed half way up a bed, bubbles of hydrocarbon vapours were quickly produced; they ascended and mixed with the fluidising air. In a bed below 800 °C, combustion mainly occurred noisily in bubbles just after leaving the bed, but in a hotter bed, there was quieter burning in smaller bubbles, before they reached the top of the bed. Glycerol behaved similarly, when fed into the middle of a bed. Thus bubbles of glycerol vapour were formed; they mixed with air ascending the bed as either bubbles or percolating between particles. Again bubbles exploded noisily at the top of a bed below 800 °C. With the bed above 800 °C, glycerol burned inside smaller bubbles below the bed’s upper surface. No soot was observed when burning glycerol in such a hot bed, yielding CO and CO 2 as the only products of combustion. It appears that burning glycerol cleanly in a hot fluidised bed is a feasible proposition.

Dispersive liquid–liquid microextraction (DLLME) based on Fe3O4 magnetic nanoparticle-assisted in situ ionic liquid was developed as a novel method for the pretreatment of pyrethroid pesticides (flumethrin, bifenthrin and silafluofen) in urine samples. [N4,4,4,4]Cl and Na[N(CN)2] formed a ionic liquid ([N4,4,4,4][N(CN)2]), which provides an alternative to highly toxic solvents; moreover, high extraction recoveries and enrichment factors were achieved. The extraction parameters affecting the extraction recoveries were investigated. Under optimum conditions, the analytical method showed a good linear response, with correlation coefficient (R2) values ranging from 0.9994 to 0.9996. The enrichment factor, limit of detection and recovery were 108–125, 2.7–5.0 μg L−1 and 88.0–101.1%, respectively. Therefore, this green and simple method is suitable for the microextraction of pyrethroid pesticides in urine samples. It is valuable to establish a sensitive method for monitoring trace levels of pyrethroids, which could contribute to the use of rapid and green sample preparation procedures in urine samples.

The synthesized sheet-like polypyrrole (ppy) nanowires were used as solid phase extraction materials, followed by gas chromatography-mass spectrometry (GC–MS) for the detection of traces residues of pyrethroid pesticides in human plasma. A multiresidue method was developed and verified for the determination of trace pyrethroid residues (transfluthrin, allethrin, resmethrin, fenpropathrin, etofenprox, fenvalerate) in human plasma. In this study, using the cationic surfactant cetyltrimethylammonium bromide (CTAB) as a soft template, ppy nanowires with regular morphology were prepared by oxidative polymerization. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and other techniques were employed for characterization. Molecular dynamics analyses were used to simulate the adsorption mechanism of each pyrethroid and ppy nanowires. Based on density analysis, molecular recognition analysis, and binding energy, the van der Waals force was considered as an important driving force for the adsorption of pyrethroids and ppy nanowires. The limits of detection (LOD) of six pyrethroids were 0.008–0051 ng mL−1, and the limits of quantification (LOQ) were 0.028–0.162 ng mL−1. The relative standard deviations of ppy nanowires were 2.12–5.09%, and the recoveries of six pyrethroids ranged from 76.9 to 110.4%. The enrichment factors were within the range of 47.09–51.30. The experimental results showed that the method could be an efficient detection method for trace residue analysis of pyrethroid pesticides in complex biological samples. It would be advantageous for clinical monitoring and toxicological studies of pyrethroids.

The reversible decomposition of CuO into Cu2O and oxygen at high temperature, typically between 850 and 1000 °C, provides a means of separating pure oxygen from air. In such a process, the oxide generally has to be supported on a refractory oxide, e.g. alumina, to maintain its capacity when cycled many times between CuO and Cu2O. One problem is that if the CuO reacts with the alumina to form CuAl2O4, the latter releases oxygen too slowly to be of practical use so that the capacity for oxygen release of such a carrier falls progressively as more aluminate is formed. However, the reported temperatures at which CuAl2O4 forms are inconsistent so far. This work sets out to investigate the interaction between CuO and different aluminas (and precursors), which are commonly used as support materials, at temperatures between 700 and 1000 °C, as well as some chemical properties of the resulting copper aluminates. It was found that the formation of CuAl2O4 occurred at around 700 °C, 800 °C and 950 °C, when amorphous aluminium hydroxide, γ-alumina, and α-alumina were used as the source of alumina support, respectively. The decomposition of CuAl2O4 in an oxygen-lean environment can lead to the formation of α-alumina as well as γ-alumina, depending on the partial pressure of oxygen. Given that the α-form does not react with CuO around 900 °C, the typical operating temperature for the CuO/Cu2O couple, this observation can be used to partially regenerate CuO from CuAl2O4, for oxygen storage and production at this temperature by decomposing the spinel in a controlled atmosphere to form only α-alumina. However, during the decomposition of CuAl2O4, delafossite CuAlO2 is also formed, limiting the amount of Cu that could be recovered as CuO in a single process cycle.

1550 nm near-infrared (NIR) light excited lanthanide ion (Ln3+) doped up-conversion (UC) materials with tunable emission color have great application potential in optical anti-counterfeiting and it is essential to explore new stable phosphors and expand the emission color gamut for multicolor security printing. Herein, a new type of double perovskite tungstate UC phosphors LiYMgWO6: Er3+ with green and red double color emissions under 1550 nm excitation were synthesized by high temperature solid-state method. The emission color output of LiYMgWO6: Er3+ was adjusted from yellow-green to red by introducing Ho3+ ion to enhance the red emission and suppress the green emission. Fluorescent lifetime measurements were carried out to illustrate the color modulation mechanism. As a proof of concept, the fluorescent printing inks based on as-prepared phosphors were synthesized and fluorescent labels with special patterns were designed to demonstrate the anti-counterfeiting application.

Novel strategies of developing fluorescent sensors for proteins are highly demanded. In this work, we particularly synthesized a cholesterol-derivatized pyrene probe. Its fluorescence emission is effectively tuned by the aggregation state of a cationic surfactant dodecyltrimethylammonium bromide (DTAB). The used probe/DTAB assemblies exhibit highly sensitive ratiometric responses to pepsin and ovalbumin egg (o-egg) with detection limits of 4.8 and 18.9 nM, respectively. The fluorescence changes indicate the protein-surfactant interaction leads to further aggregation of DTAB assemblies. The results from Tyndall effect and dynamic light scattering verify this assumption. The responses to pepsin and o-egg are due to their strong electrostatic or hydrophobic interaction with DTAB assemblies at pH 7.4. The present noncovalent supramolecular sensor represents a novel and simple strategy for sensing proteins, which is based on the encapsulated fluorophore probing the aggregation variation of the surfactant assemblies.

A new cationic dansyl derivative-based (DIlSD) fluorescence probe was designed and synthesized. Its combination with anionic surfactant SDS assemblies shows enhanced fluorescence intensity and blue-shifted maximum wavelength. Its fluorescence can be slightly quenched by Cu2+; however, the fluorescence quenching efficiency by Cu2+ is highly increased upon titration of arginine (Arg). As a result, the ternary system containing the cationic fluorophore, anionic surfactant, and Cu2+ functions as a highly sensitive and selective sensor to Arg. The optimized sensor system displays a detection limit of 170 nM, representing the highest sensitivity to Arg in total aqueous solution by a fluorescent sensor. Control experiments reveal that the imidazolium groups in the fluorophore, the anionic surfactant, and Cu2+ all play important roles in the process of sensing Arg. The electrostatic interaction between the cationic fluorophore and anionic surfactants facilitates the binding of imidazolium rings with Cu2+, the sur...

Chemical looping combustion (CLC) has been proposed as an efficient carbon capture process for power generation. Oxygen stored within a solid metal oxide is used to combust the fuel, either by releasing the oxygen into the gas phase, or by direct contact with the fuel; this oxyfuel combustion produces flue gases which are not diluted by N₂. These materials can also be used to perform air-separation to produce a stream of oxygen mixed with CO₂, which can subsequently be used in the conventional oxyfuel combustion process to produce sequesterable CO₂. The temperature and oxygen partial pressures under which various oxide materials will react in this way are controlled by their thermodynamic equilibria with respect to reduction and oxidation. While many materials have been proposed for use in chemical looping, many suffer from poor kinetics or irreversible capacity loss due to carbonation, and therefore applying large scale in silico screening methods to this process is a promising way to obtain new candidate materials. In this study we report the first such large scale screening of oxide materials for oxyfuel combustion, utilising the Materials Project database of theoretically determined structures and ground state energies. From this screening several promising candidates were selected due to their predicted thermodynamic properties and subjected to initial experimental thermodynamic testing, with SrFeO$_{3-\delta}$ emerging as a promising material for use in CLC. SrFeO$_{3-\delta}$ was further shown to have excellent cycling stability and resistance to carbonation over the temperatures of operation. This work further advances how in silico screening methods can be implemented as an efficient way to sample a large compositional space in order to find novel functional materials.

Upconversion luminescent NaYF4:Yb3+, Er3+/Tm3+ nanocrystals were successfully synthesized via a facile and one-pot solvothermal method using oleic acid/oleylamine (OA/OM) as surfactants. The effects of synthetic parameters including rare earth ion doping concentrations and temperatures on the crystal phase structure, size and shape of NaYF4:Yb3+, Er3+/Tm3+ nanocrystals were systematically investigated. By modulating the synthetic parameters, the shape of NaYF4:Yb3+, Er3+/Tm3+ nanocrystals were controlled in forms of nanorods and nanowires. The reaction temperature has large effects on the phase structure of NaYF4:Yb3+, Er+/Tm3+ nanorods, exhibiting a phase transformation from cubic phase (alpha-) in low temperatures to hexagonal phase (beta-) in high temperatures. Moreover, the upconversion luminescence of NaYF4:Yb3+, Er3+/Tm3+ nanocrystals was found to be dependent on the rare earth ion doping concentrations and temperatures.

Pattern recognition has been widely used to detect and identify multiple analytes. The strategies for realizing pattern recognition of a single sensor are in significant demand. In the present work, a particular bispyrene-based fluorophore containing a hydrophilic spacer, Py-TOA-Py, was synthesized, and it was observed that its mixture with anionic surfactant assemblies realizes multiple fluorescence responses to different metal ions. The combination of fluorescence variation at four emission wavelengths enables the fluorophore/surfactant sensor system to provide specific recognition patterns to different metal ions. Principle component analysis shows that the present single sensor system could discriminate 6 metal ions, namely Fe3+, Co2+, Ni2+, Cu2+, Pb2+, and Hg2+, 5 of which are heavy metal ions. Results from UV-vis measurements rule out the possibility of the bispyrene fluorophore binding with metal ions. Fluorescence titration of metal ions with two other bispyrene fluorophores reveals that the ones with similar hydrophilic spacer, Py-EOA-Py, exhibit similar multiple fluorescence responses, whereas, the ones with hydrophobic spacer, Py-DDA-Py, display no cross-reactive responses. Time-resolved emission spectra measurements reveal that the spacer polarity plays an important role in determining the location of bispyrene in surfactant assemblies, which further influences its cross-reactive responses to metal ions. The present work provides a new strategy for developing fluorescent sensors with pattern recognition abilities.

A dansyl-functionalized fluorescent film sensor was specially designed and prepared by assembling dansyl on a glass plate surface via a long flexible spacer containing oligo(oxyethylene) and amine units. The chemical attachment of dansyl moieties on the surface was verified by contact angle, XPS, and fluorescence measurements. Solvent effect examination revealed that the polarity-sensitivity was retained for the surface-confined dansyl moieties. Fluorescence quenching studies in water declared that the dansyl-functionalized SAM possesses a higher sensitivity towards Hg(2+) and Cu(2+) than the other tested divalent metal ions including Zn(2+), Cd(2+), Co(2+), and Pb(2+). Further measurements of the fluorescence responses of the film towards Cu(2+) and Hg(2+) in three solvents including water, acetonitrile, and THF evidenced that the present film exhibits cross-reactive responses to these two metal ions. The combined signals from the three solvents provide a recognition pattern for both metal ions at a certain concentration and realize the identification between Hg(2+) and Cu(2+). Moreover, using principle component analysis, this method can be extended to identify metal ions that are hard to detect by the film sensor in water such as Co(2+) and Ni(2+).

Three-dimensionally ordered macro- and meso-porous (3DOM) M/CeO2 (M = Pt, Au and Pt–Au) catalysts supported with different noble metal nanoparticles of Pt, Au and Pt–Au alloy were synthesized by thermal decomposition of cerium nitrate precursor using the close packed structures of PS colloidal crystals as templates. The obtained 3DOM M/CeO2 catalysts possess well-defined 3DOM skeletons composed of ultrafine CeO2 nanoparticles. The macroporous CeO2 skeletons contain the mesoporous walls possessing the nanopores of ∼3–4 nm and the noble metal nanoparticles of Pt, Au, and Pt–Au alloy with the grain sizes of ∼5.0 nm homogenously dispersed. The catalytic performance of CO preferential oxidation (PROX) in H2-rich gases on 3DOM Pt/CeO2, Au/CeO2, and Pt–Au/CeO2 catalysts were systematically studied. The superior catalytic performance with 90% CO conversion and 83% CO2 selectivity are realized on 3DOM 1 wt.% Pt1Au1/CeO2 catalyst at 80 °C under the weight hourly space velocity of 30,000 mL g−1 h−1. Moreover, the 3DOM 1 wt.% Pt1Au1/CeO2 catalyst exhibits excellent catalytic stability maintaining 90% CO conversion and 56% CO2 selectivity even after the test period of 260 h under the same flow rate. The three-dimensionally ordered macro- and meso-porous skeletons, the synergistic effect due to the formation of Pt–Au alloy, and the strong interaction of Pt–Au alloy nanoparticles with CeO2 supports are identified to be beneficial to the improvement of catalytic activity and stability of CO PROX. The obtained 3DOM Pt–Au/CeO2 catalysts may be potential candidates with the improved catalytic performance of CO PROX reaction in H2-rich gases for polymer electrolyte membrane fuel cells (PEMFCs) applications.

A fluorescent film sensor for Cu(II) and Hg(II) ions was designed and prepared by chemical attaching pyrene moieties on an epoxy-terminated surface via a long flexible and hydrophilic spacer. The chemical attachment of pyrene moieties on the surface was verified by contact angle, XPS, and fluorescence characterization. The fluorescence responses of the present film to a series of metal ions in aqueous solution indicate that this film sensor is sensitive to both copper and mercury ions. Presence of other metal ions, including Ni(II), Fe(III), Pb(II), Mg(II), Ba(II), Zn(II), La(II) and Eu(II), has little effect upon the fluorescence emission of the film. The sensitivity of the present film sensor is quite high toward both Cu(II) and Hg(II) ions in the form of inorganic salts as revealed by the large KSV values. Moreover, the presence of organic anions produces little influence on the sensitivity of the film sensor toward metal ions, suggesting the introduction of the hydrophilic spacer weakens the spacer layer screening effect in aqueous solution. The novel fluorescent film sensor may have potentials as Cu(II) and Hg(II) sensors to probe natural environments.

Protein glycosylation drives many biological processes and serves as markers for disease; therefore, the development of tools to study glycosylation is an essential and growing area of research. Mass spectrometry can be used to identify both the glycans of interest and the glycosylation sites to which those glycans are attached, when proteins are proteolytically digested and their glycopeptides are analyzed by a combination of high-resolution mass spectrometry (MS) and tandem mass spectrometry (MS/MS) methods. One major challenge in these experiments is collecting the requisite MS/MS data. The digested glycopeptides are often present in complex mixtures and in low abundance, and the most commonly used approach to collect MS/MS data on these species is data-dependent acquisition (DDA), where only the most intense precursor ions trigger MS/MS. DDA results in limited glycopeptide coverage. Semi-targeted data acquisition is an alternative experimental approach that can alleviate this difficulty. However, due to the massive heterogeneity of glycopeptides, it is not obvious how to expediently generate inclusion lists for these types of analyses. To solve this problem, we developed the software tool GlycoPep MassList, which can be used to generate inclusion lists for liquid chromatography tandem-mass spectrometry (LC-MS/MS) experiments. The utility of the software was tested by conducting comparisons between semi-targeted and untargeted data-dependent analysis experiments on a variety of proteins, including IgG, a protein whose glycosylation must be characterized during its production as a biotherapeutic. When the GlycoPep MassList software was used to generate inclusion lists for LC-MS/MS experiments, more unique glycopeptides were selected for fragmentation. Generally, ∼30 % more unique glycopeptides can be analyzed per protein, in the simplest cases, with low background. In cases where background ions from proteins or other interferents are high, usage of an inclusion list is even more advantageous. The software is freely publically accessible. Graphical abstract Software increases the number of glycopeptides that get selected for MS/MS analysis.

Three-dimensionally ordered macroporous (3DOM) Au/CeO 2 -Co 3 O 4 catalysts were created via a precursor thermal decomposition-assisted colloidal crystal templating method. The 3DOM Au/CeO 2 -Co 3 O 4 catalysts possessed well-defined 3DOM structures with adjustable pore sizes, and their compositions, phase structures, and surface elemental valence states can be well controlled by solely adjusting the Ce/Co molar ratio. Moreover, the nanoporous walls with pore sizes around ∼3–4 nm were created in 3DOM Au/CeO 2 -Co 3 O 4 catalysts through the thermal decomposition of Co and Ce oxalate precursors during the preparation. The 3DOM Au/CeO 2 -Co 3 O 4 catalysts exhibited superior catalytic activity for formaldehyde (HCHO) catalytic oxidation into CO 2 and H 2 O with a 100% conversion rate at temperatures as low as ∼39 °C. A catalytic mechanism of the synergistic effect between CeO 2 and Co 3 O 4 supports, which greatly accelerates the surface active oxygen migration and activates the Au species, was proposed for explaining the enhanced HCHO catalytic oxidation over 3DOM Au/CeO 2 -Co 3 O 4 catalysts. The well-controlled method for creation of 3DOM Au/CeO 2 -Co 3 O 4 catalysts with nanoporous walls could be adopted for generation of other catalytic materials with mixed macroporous and mesoporous structures. The superior catalytic activity of 3DOM Au/CeO 2 -Co 3 O 4 catalysts makes them potentially applicable to indoor HCHO decontamination and industrial catalysis.

A colloidal crystal template method coupled with a precursor complexion process was developed to create three-dimensionally ordered macroporous (3DOM) Au/CeO 2 catalyst. The resultant Au/CeO 2 catalyst possesses well-defined 3DOM structure, and shows enhanced catalytic performance for formaldehyde (HCHO) oxidation with 100% HCHO conversion at ∼75 °C. The catalytic mechanism of HCHO catalytic oxidation over 3DOM Au/CeO 2 catalyst was systematically investigated by means of gas chromatograph (GC), H 2 -temperature programmed reduction (H 2 -TPR), temperature programmed surface reaction (TPSR), CO 2 -temperature programmed desorption (TPD), and Fourier transform infra-red (FT-IR) spectroscopy. GC results indicate that HCOOH intermediate is generated during HCHO catalytic oxidation. TPD and TPSR tests show that the weak absorption ability of CO 2 over 3DOM Au/CeO 2 catalyst and the existence of Au active species in ionic and metallic states in 3DOM Au/CeO 2 catalyst largely improve the catalytic activity, favoring the enhanced HCHO catalytic oxidation. FT-IR tests prove that the carbonate and hydrocarbonate formed on the surface of 3DOM Au/CeO 2 catalyst during HCHO catalytic oxidation may account for its deactivation. Based on the above investigation, a new catalytic mechanism of enhanced HCHO catalytic oxidation over 3DOM Au/CeO 2 catalyst is proposed. The mechanism may afford the scientific guidance for preparing high efficiency oxide supported noble metal catalysts and present a solution for solving their deactivation problem.

Three dimensionally ordered macroporous (3DOM) Au/CeO2 catalysts were synthesized via a thermal decomposition-assisted colloidal crystal templating method following different synthetic procedures using citric acid and oxalic acid as chelating ligands and CeCl3 and Ce(NO3)3 as cerium salt precursors. All 3DOM Au/CeO2 catalysts possess well-defined 3DOM skeletons composed of well-crystallized CeO2 nanoparticles, based on the different synthetic procedures, the 3DOM Au/CeO2 catalysts show variations in surface elemental compositions, particle sizes of CeO2, macroporous and mesoporous structures, and valence states of Au. The mesoporous walls with nanopores ∼3–4 nm on 3DOM Au/CeO2 skeletons can be created when using Ce(NO3)3 as precursor. The catalytic performance of 3DOM Au/CeO2 catalysts for CO preferential oxidation in H2-rich gases was systematically investigated. The catalytic performance is closely correlated to surface elemental compositions, particle sizes of CeO2, macroporous and mesoporous structures, and valence states of Au due to the different synthetic procedures. The 3DOM Au/CeO2 catalysts prepared using oxalic acid as chelating ligand and Ce(NO3)3 as cerium salt precursor show the highest catalytic activity for CO preferential oxidation in H2-rich gases with 90.1% CO conversion and 59.9% CO2 selectivity at 50 °C, and 88.3% CO conversion and 59.3% CO2 selectivity at 80 °C, respectively. The obtained 3DOM Au/CeO2 catalysts may be of importance for guiding the design of efficient catalysts with desired porous structures that are potentially applicable in polymer electrolyte membrane fuel cells.

We report the design and realization of double shelled @CeO2/M@M/TiO2 (M = Au and/or Pd) nanospheres with dual noble metal nanoparticles encapsulated in metal oxide shells via a layer-by-layer deposition process followed by an alkali etching method. The resulting nanospheres possess uniform sizes, variable shell components and thicknesses, adjustable noble metal nanoparticles encapsulated, regulable chamber spaces between the two shells, and good structural stability, which can be used as unique microreactors with extremely high catalytic activity and stability in the Suzuki-Miyaura coupling reaction, benzyl aerobic alcohol oxidation, and 4-nitrophenol reduction reaction due to their structural features with multiple interactions and strong synergistic effects between the noble metal nanoparticles and metal oxide shells, and less depletion of catalytic active species. The designed double shelled hollow @CeO2/M@M/TiO2 nanocatalysts can be used as novel catalyst systems with highly efficient catalytic performance for various catalytic reactions depending on their shell components and noble metal nanoparticles encapsulated. The synthetic strategy provides a new methodology to design high-performance and multifunctional nanocatalysts.