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High-performance metabolic analysis is emerging in the diagnosis and prognosis of breast cancer (BrCa). Still, advanced tools are in demand to deliver the application potentials of metabolic analysis. Here, we used fast nanoparticle-enhanced laser desorption/ionization mass spectrometry (NPELDI-MS) to record serum metabolic fingerprints (SMFs) of BrCa in seconds, achieving high reproducibility and low consumption of direct serum detection without treatment. Subsequently, machine learning of SMFs generated by NPELDI-MS functioned as an efficient readout to distinguish BrCa from non-BrCa with an area under the curve of 0.948. Furthermore, a metabolic prognosis scoring system was constructed using SMFs with effective prediction performance toward BrCa (P < 0.005). Finally, we identified a biomarker panel of seven metabolites that were differentially enriched in BrCa serum and their related pathways. Together, our findings provide an efficient serum metabolic tool to characterize BrCa and highlight certain metabolic signatures as potential diagnostic and prognostic factors of diseases including but not limited to BrCa.
Assuntos
Neoplasias da Mama , Biomarcadores Tumorais/metabolismo , Neoplasias da Mama/diagnóstico , Neoplasias da Mama/metabolismo , Feminino , Humanos , Espectrometria de Massas/métodos , Prognóstico , Reprodutibilidade dos TestesRESUMO
The vinylene-linked covalent organic frameworks (viCOFs) have been generally synthesized in the presence of homogeneous catalysts such as KOH or trifluoroacetic acid. However, highly ordered viCOFs cannot always be obtained due to the uncommitted growth of viCOF layers in the homogeneous system with ubiquitous catalysts. Here, we propose a scalable protocol to restrict the growth of viCOFs along the two-dimensional (2D) plane by introducing a heterogeneous catalyst, polyoxometalates (POMs). With the unique Brønsted alkalinity and catalytic surface, POMs induce the growth of 2D viCOF layers along the surface of the catalytic substrate and restrain the generation of out-of-plane branches. Based on this protocol, six typical 2D viCOFs with high crystallinity and porosity were synthesized within a shorter reaction time as compared with the reported works using the common homogeneous catalysts for viCOF synthesis. On the basis of the density functional theory calculations and experimental results, a bottom intercalation growth pattern of viCOFs was revealed during the heterogeneous reaction. The unique growth pattern greatly promotes the orderly assembly of monomers, thus shortening the reaction time and improving the crystallinity of viCOFs. Furthermore, this heterogeneous catalysis strategy is suitable for the gram-scale preparation of 2D viCOFs. These results provide a novel avenue for the synthesis of high-quality viCOFs and may bring new insights into the synthetic methodology of COFs.
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The synthesis of highly efficient visible-light-responsive photocatalysts is fundamental to solving the problems of low efficiency and poor selectivity in photocatalytic organic synthesis reactions. We synthesized a crystalline polyoxometalate @metal-organic framework material {Zn4 (H2 O)8 [Ir(ppy)2 (dcbpy)]4 [SiW12 O40 ]} â 4H2 O (Ir-SiW) by self-assembly of Ir metalloligands with POMs. The introduction of Ir metalloligands extends the light absorbing range to visible light, improving the efficient utilization of solar energy. The transfer of photogenerated electrons from Ir metalloligands to SiW12 was observed under visible light irradiation, which boosted the carrier separation efficiency. The synergistic effect of the two components increased the photocatalytic thioether oxidation activity, and the product methyl phenyl sulfoxide for 2.5â h under visible light irradiation (λ >400â nm) reached 99.5 %, which was higher than those of other POM-based photocatalysts. Meanwhile, the yield of methyl phenyl sulfoxide was still higher than 97 % after three cycles, demonstrating the high stability and reusability of Ir-SiW.
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An unclassical structure of {Ru(C6 H6 )}-based polyoxometalate, Cs6 H4 [Te2 Mo12 O46 {Ru(C6 H6 )}] â 16.5H2 O (1), has been successfully constructed from {Te2 Mo12 O46 }-type heteropolymolybdate and {Ru(C6 H6 )} group, which structure type was discovered for the first time. Compound 1 not only possesses strong light-harvesting ability, but also exhibits high carrier separation efficiency and lower charge transfer resistance. Under visible light irradiation, compound 1 displayed excellent catalytic activity and circularity in the conversion of benzyl alcohol to benzaldehyde (yield=94 %; turnover number=500; turnover frequency=20.8â h-1 ). Finally, the electron paramagnetic resonance measurement and energy level matching analysis provide theoretical basis for the derivation of the reaction mechanism.
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Exploring a novel photocatalyst for catalytic oxidation of toluene is a sustainable strategy for energy conversion in times of an energy crisis. However, designing an effective photocatalyst for the conversion of toluene remains challenging. Herein, a novel organic monophosphonate-modified high nucleus Cu-incorporated polyoxotungstate, K8H33[{Cu0.5(H2O)4}{Cu2(O3PCH2COO)(1,4,9-α-P2W15O56)}]4·Cl·60H2O (1), has been intentionally synthesized by a self-assembly process utilizing conventional aqueous method. It reveals that 1 contains a polyanion of [{Cu0.5(H2O)}4{Cu2(O3PCH2COO)(1,4,9-α-P2W15O56)}]440- composed of four Dawson-type {1,4,9-α-P2W15} subunits, forming an oval-shaped structure and further connecting into a three-dimensional (3D) framework by lateral {Cu(H2O)4}2+. Interestingly, the trivacant {1,4,9-α-P2W15} subunits were observed in the organophosphonate acid-functionalized polyoxometalates for the first time. Notably, 1 exhibits a wonderful performance in catalytic oxidation of the recalcitrant C(sp3)-H bond of toluene to benzoic acid with a conversion as high as 97% under visible light utilizing O2 as an oxidant.
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Three unique dl-malic acid covalently modified tetra-Ln3+-implanted tellurotungstates [H2(CH3)2]9NaH9[Ln4(H2O)14W6O13(OH)5(Mal)2(B-α-TeW9O33)4]·48H2O [Ln = La3+ (1), Ce3+ (2), Pr3+ (3); H3Mal = dl-malic acid] were fabricated by reacting Na2TeO3, Na2WO4·2H2O, Mal, and LnCl3·6H2O with dimethylamine hydrochloride in an aqueous solution. The most prominent architectural feature of these compounds is the covalent connection mode of an organic ligand and a polyoxometallate backbone, which is relatively rare in the realm of polyoxotungstates. The tetrameric polyanion can be deemed as four [TeW9O33]8- fragments fused together via an intriguing hexanuclearity [W6O13(OH)5(Mal)2Ln4(H2O)14]13+ cluster. Impedance measurements manifest that all three complexes display splendid proton conduction properties, with an exceptional conductivity for 2 up to 2.48 × 10-2 S·cm-1 under 85 °C and 95% relative humidity. Moreover, compounds 1 and 3 exhibited fast reversible photochromic properties with allochroic half-life periods t1/2 of 1.046 and 0.544 min, respectively.
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With the excellent properties of POM in the field of proton conductivity, the preparation of POM-based proton-conductive materials has burst into life. Herein, an unprecedented Sb-templated all-inorganic trimer Na8H18.64[(SbW14O52)3(Sb2W6.12Ru5.88O18)]·85H2O (1), which is based on tetravacant Dawson-like [SbW14O52]17- blocks and exhibits a trefoil type with D3 symmetry, has been successfully designed and synthesized by the assembly of simple materials with a one-pot hydrothermal method under acidic conditions. Also, compound 1 is systematically characterized by single-crystal X-ray diffraction, PXRD, ESI-MS, IR spectroscopy, UV-vis, elemental analysis, and TGA. Crystal structure data analysis demonstrates that compound 1 is constructed by a hexagonal prismatic heterometallic {Sb2W6.12Ru5.88O18} core and three equivalent {SbW14} units bridged through µ2-O atoms in periphery. Subsequently, further property experiments show that compound 1 exhibits high proton conductivity with a conductivity value (σ) of 3.07 × 10-2 S cm-1 at 75 °C and 80% relative humidity (RH). The activation energy of compound 1 evaluated by the Arrhenius plots is 0.22 eV, which indicates that the Grotthuss mechanism is dominant during the process of proton transfer.
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The synthesis of visible light-responsive and efficient photocatalysts toward green Baeyer-Villiger oxidation organic synthesis is of extraordinary significance. In this work, we have synthesized two examples of visible light responsive crystalline polyoxometalate@metal-organic framework materials Ru-NiMo and Ru-CoMo by introducing Ru metalloligands and {CdM3O12} bimetallic units (M = Ni or Co). This is the first report of metalloligand-modified polyoxometalate@metal-organic framework materials with bimetallic nodes, and the materials form a three-dimensional framework directly through coordination bonds between {CdM3O12} bimetallic units and metalloligands. In particular, Ru-NiMo can achieve efficient photocatalytic conversion of cyclohexanone to ε-caprolactone in yields as high as 95.5% under visible light excitation in the range of λ > 400 nm, achieving a turnover number and turnover frequency of 955 and 440 h-1, respectively, which are the best known photocatalysts for Baeyer-Villiger oxidation, while apparent quantum yield measured at 485 nm is 4.4%. Moreover, Ru-NiMo exhibited excellent structural stability and recyclability, producing a 90.8% yield after five cycles of recycling.
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In this paper, we have successfully synthesized a structurally novel heteropolytungstate via coordination of four {Ru(C6H6)} and trivacant {TeW9O33} clusters, formulated as Cs4Na2H2[Te2W20O72(H2O){(C6H6)Ru}4]·12H2O (1). Compound 1 inherited the strong absorption of [Ru(C6H6)Cl2]2 in the visible region and {TeW9O33} in the UV region, providing a good basis for photocatalysis. As expected, compound 1 showed good photocatalytic activity in the visible-light-driven reduction of nitrobenzene using N2H4·H2O as a reductant with a yield of 99.8%, a high turnover number (TON = 330), and a high turnover frequency (TOF = 24 h-1). The cyclic experiment of nitrobenzene reduction indicated that compound 1 was an effective and stable heterogeneous catalyst. Finally, the nitrobenzene reduction pathway was affirmed using condensation with azobenzene as a reaction intermediate based on control experiments.
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A 6-Ti-substituted polyoxometalate, (NH4)5Cs7Na3H2[Cs@(Ti2GeMo10O39)3]·34H2O (1), was synthesized by reacting (NH4)6Mo7O24·4H2O, GeO2, and TiOSO4 through the conventional aqueous method. Polyanion 1a is composed of three {Ti2GeMo10} segments linked by Ti-O-Ti linkages and shows a trefoil-shaped structure. Furthermore, one Cs+ cation is encapsulated in the cavity of 1a. Notably, it possesses the highest number of Ti centers among the reported polyoxomolybdates. In addition, serving as a high-efficiency heterogeneous catalyst, 1 enables the conversion of methyl phenyl sulfide within 20 min, yielding 96.4% of the corresponding sulfoxide with good recyclability.
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A novel Ru(III)-containing tungstoantimonate Na16H22[(B-ß-SbW9O33)6(W3RuO7)2(W4O11)]·118H2O (1) hexamer was successfully synthesized using the hydrothermal synthesis method. Analysis by single-crystal X-ray diffraction revealed that the polyanion comprises six trivacant Keggin-type [B-ß-SbW9O33]9- units interconnected by six {WO6} and six Ru/W disorder octahedra, resulting in an intriguing cyclohexane boat-like conformation. Compound 1 exhibits favorable proton conductivity, with a measured conductivity (σ) of 5.41 × 10-3 S cm-1 at 333 K and 55% relative humidity (RH). The activation energy (Ea) of compound 1 was determined to be 0.40 eV, providing evidence that its proton conductivity conforms to the Grotthus mechanism.
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Two novel arsenotungstate species, [As4W48O168]36- (1a) and [As2W21O77(H2O)3]22- (2a), have been successfully isolated under a one-pot synthetic method. 1a is the second largest arsenotungstate cluster and is constructed from four {AsW12} clusters combined together. 2a can be described as lacunary sites of {As2W19} filled by {W2O8} units. Compounds 1 and 2 exhibit proton conductivity properties, and the conductivity value of 1 is 5.0 × 10-3 S cm-1 at 98% relative humidity and 75 °C. This work proves that the lattice water molecules and polyoxoanions can participate in the formation of a hydrogen bond, acting as effective pathway for intermolecular proton conduction.
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A high-nuclearity carboxylic-modified heteropolyoxovanadate, Na2K10H15[P8VIV24(tart)15(H2O)15(OH)O51]·58H2O [1, tart = C4H2O6], has been successfully synthesized by a conventional aqueous method under mild conditions. The crystallographic study reveals that compound 1 crystallizes in the tetragonal I41/a space group and is composed by a trilayer saddle-like polyoxoanion {P8V24}. Two {V3(tart)(H2O)O11} as linking units bridge the top {P4VIV9(tart)7(H2O)4(OH)O23} and the bottom {P4VIV9(tart)6(H2O)9O22} layers via tartrate ligands and {PO4} tetrahedra, resulting in a 24-nuclearity POV skeleton structure. More interestingly, compound 1 serves as a heterogeneous catalyst for the selective oxidation of diphenylmethanes with 96.2% conversion and 93.6% selectivity under the optimized conditions.
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Converting solar energy into storable hydrogen energy by employing green photocatalytic technology offers a reliable alternative for meeting the energy crisis. The polyoxometalates are a promising candidate for hydrogen production photocatalysts because of their unique electronic and structural properties and controllable design at the molecular level. Introducing noble metals was proven to be an effective method to greatly enhance the photocatalytic efficiency of polyoxometalates. Herein, two unprecedented compounds of hexameric Ru-POMs, Na4H10[As2RuIV2W11O18(OH)4(H2O)6{AsW8RuIVO31(OH)Cl}2(B-ß-AsW9O33)4]·93H2O (1) and Na2H19[AsRuIII2W11O20(OH)2(H2O)6(RuIIICl3)(B-ß-AsW9O33)6]·90H2O (2), were successfully self-assembled. The H2 evolution rates of 1 and 2 under optimal conditions were 3578.75 and 3027.69 µmol h-1 g-1 with TONs of 255 and 205, respectively. The stability of 1 was demonstrated by a series of characterizations. Besides, a possible photocatalytic mechanism was proposed.
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Two 48-nuclei silver nanocages with similar structures and compositions were synthesized by using Keggin-type polyoxometalates (POMs) BW12 and SiW11Ni as anionic templates. However, their photoluminescence and photocurrent properties showed obvious differences. These results suggest that POMs not only serve as anion templates in constructing silver clusters but also influence their properties.
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Two two-dimensional Ln-substituted prazine dicarboxylic acid-functionalized selenotungstates Na3H9[(H2N(CH3)2]2{(Se4W27O100)[Ln4(H2O)8(Hpzdc)2(pzdc)]}·26H2O [Ln = Nd (1) and Ce (2)]; H2pzdc = 2,3-pyrazine dicarboxylic acid) have been synthesized by one-pot self-assembly strategy, in which the basic polyanion [Se4W27O100]22-was composed of two [SeW8O31]10- fragments, a [SeW9O33]8- segment and an intriguing {SeO} group, simultaneously tetra-nuclear Ln3+ ions with H2pzdc pendants were embedded. Compounds 1 and 2 showed excellent catalytic oxidation of thioether properties within a short time (20 min) with high 100% conversion and 98.9% selectivity. In addition, the pioneering Ln-substituted selenotungstates were used as catalysts to degrade sulfur mustard simulant 2-chloroethyl ethyl sulfide at room temperature with 99% conversion and 100% selectivity. The chemical kinetic experiment studies revealed that the catalytic reaction was in compliance with the first-order reaction, and the kinetic half-life (t1/2) values were 3.814 and 3.849 min, respectively.
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The development of visible-light-responsive, environmentally friendly, and reusable photocatalysts for organic oxidation reactions is of vital significance. Herein, four polyoxometalate-based metal-organic frameworks (POMOFs) were synthesized and systematically characterized by assembling the paddlewheel complex Rh2(OAc)4 and various polyoxometalates (POMs). Single-crystal X-ray diffraction analysis revealed that the four POMOFs were isomorphic and possessed rare structural features among the POMOFs, with POMs as nodes and Rh2(OAc)4 as linkers. As expected, the activities of the four POMOFs for the photocatalytic oxidative coupling of benzylamine were better than that of Rh2(OAc)4 or POMs individually, which was ascribed to the synergistic effect between them, and the intrinsic reasons for the difference in the activity were explained via electrochemical measurements. In particular, the product imine yield reached 96.1% with NaRh-SiW12 as the catalyst and a turnover number and a turnover frequency of 480.5 and 120.5 h-1, respectively, while the product yield remained as high as 92% after three repetitions, evidencing its high stability. Moreover, the higher activities of the four POMOFs for the selective epoxidation of various alkenes reaffirm the synergistic effect between Rh2(OAc)4 and POMs.
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A d-methionine-bonded nanosized arsenotungstate, Ba9K10H6[{As2W19O67(H2O)}2{AsW9O33}2{W3O6(H2O)(d-Met)}2{W2O4(OH)(d-Met)}]·60H2O [1; d-Met = d-methionine (C5H11NO2S)], is constructed without the use of lanthanide ions. The polyanion of 1 contains two {As2W19O67(H2O)}14- building blocks and two {B-ß-AsW9O33}9- subunits, integrated together with a {W2O4(OH)(d-Met)}2+ and two {W3O6(H2O)(d-Met)}5+ subclusters. Interestingly, 1 displays a highly reversible photocoloration property with a half-life (t1/2) time measured as about 0.793 min.
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A synchronous crystal- and microstructure-dependent strategy was implemented to synthesize the organic hybrid antimoniotungstate layered ionic crystal Na5.5H6.5[(SbW9O33)2{WO2(OH)}2{WO2}RuC7H3NO4]·36H2O, and the layered structure was constructed through the Na+ bridged sheet and the hydrogen-bonded layers. It displayed an effective proton conductivity of 2.97 × 10-2 S cm-1 at 348 K and 75% RH, owing to the complete interlayer confined hydrogen-bond network formed by the hydrogens of interlayer crystal waters, organic ligands ({RuC7H3NO4}2+, {C7H3NO4} is formed by the hydrolysis of pyridine 2,5-dicarboxylic acid (C7H5NO4)), and acidic protons (H+), along with the interlayer domain as a transport channel. Furthermore, the hydrogen-bond network originating from interlayer organic ligands and acidic protons was more stable at a higher temperature of 423 K, preserving a high conductivity of 1.99 × 10-2 S cm-1.
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BACKGROUND: Metabolomics is a primary omics topic, which occupies an important position in both clinical applications and basic researches for metabolic signatures and biomarkers. Unfortunately, the relevant studies are challenged by the batch effect caused by many external factors. In last decade, the technique of deep learning has become a dominant tool in data science, such that one may train a diagnosis network from a known batch and then generalize it to a new batch. However, the batch effect inevitably hinders such efforts, as the two batches under consideration can be highly mismatched. RESULTS: We propose an end-to-end deep learning framework, for joint batch effect removal and then classification upon metabolomics data. We firstly validate the proposed deep learning framework on a public CyTOF dataset as a simulated experiment. We also visually compare the t-SNE distribution and demonstrate that our method effectively removes the batch effects in latent space. Then, for a private MALDI MS dataset, we have achieved the highest diagnostic accuracy, with about 5.1 ~ 7.9% increase on average over state-of-the-art methods. CONCLUSIONS: Both experiments conclude that our method performs significantly better in classification than conventional methods benefitting from the effective removal of batch effect.