Constructing layer-by-layer self-assembly MoS2/C nanomaterials by a one-step hydrothermal method for catalytic hydrogenation of phenanthrene.

Layer-by-layer self-assembly MoS2/C nanomaterials are constructed through the electrostatic adsorption between MoS2 nuclei with positive charge and C nuclei with negative charge using a facile one-step hydrothermal method. The layer-by-layer self-assembly MoS2/C catalysts with high exposure of catalytic hydrogenation active sites exhibit enhanced catalytic performance in phenanthrene hydrogenation.

Slurry-Phase Hydrogenation of Different Asphaltenes to Liquid Fuels on Dispersed MoS2 Nanocatalysts.

Asphaltene, the most complex and recalcitrant fraction of heavy oil, was investigated in this study to gain new insights into its structure and reactivity. Two types of asphaltenes, ECT-As and COB-As, were extracted from ethylene cracking tar (ECT) and Canada's oil sands bitumen (COB), respectively, and used as reactants for slurry-phase hydrogenation. Characterization of ECT-As and COB-As was carried out by a combination of techniques, including XRD, elemental analysis, simulated distillation, SEM, TEM, NMR, and FT-IR, to gain insights into their composition and structure. A dispersed MoS2 nanocatalyst was used to study the reactivity of ECT-As and COB-As under hydrogenation conditions. The results showed that under optimal catalytic conditions, the vacuum residue content of hydrogenation products could be reduced to less than 20%, and the products contained over 50% light components (gasoline and diesel oil), indicating that ECT-As and COB-As were effectively upgraded. The characterization results indicated that ECT-As contained a higher aromatic carbon content, shorter alkyl side chains, fewer heteroatoms, and less highly condensed aromatics than COB-As. The light components (gasoline and diesel oil) of ECT-As hydrogenation products mainly consisted of aromatic compounds with 1-4 rings, with the alkyl chains mainly composed of C1-C2, while light components of COB-As hydrogenation products were mainly composed of aromatic compounds with 1-2 rings and C11-C22 paraffins. The characterization of ECT-As and COB-As and their hydrogenation products revealed that ECT-As was an "archipelago type" asphaltene, composed of multiple small aromatic nuclei interconnected through short alkyl chains, while COB-As was an "island type" asphaltene, with long alkyl chains connected to aromatic nuclei. It is suggested that the structure of asphaltene has a significant impact on both its reactivity and product distribution.

Development and validation of a mutation-based model to predict immunotherapeutic efficacy in NSCLC.

Background: Immunotherapy has become increasingly important in the perioperative period of non-small-cell lung cancer (NSCLC). In this study, we intended to develop a mutation-based model to predict the therapeutic effificacy of immune checkpoint inhibitors (ICIs) in patients with NSCLC. Methods: Random Forest (RF) classifiers were generated to identify tumor gene mutated features associated with immunotherapy outcomes. Then the best classifier with the highest accuracy served for the development of the predictive model. The correlations of some reported biomarkers with the model were analyzed, such as TMB, PD-(L)1, KEAP1-driven co-mutations, and immune subtypes. The training cohort and validation cohorts performed survival analyses to estimate the predictive efficiency independently. Results: An 18-gene set was selected using random forest (RF) classififiers. A predictive model was developed based on the number of mutant genes among the candidate genes, and patients were divided into the MT group (mutant gene ≥ 2) and WT group (mutant gene < 2). The MT group (N = 54) had better overall survival (OS) compared to the WT group (N = 290); the median OS was not reached vs. nine months (P < 0.0001, AUC = 0.73). The robust predictive performance was confifirmed in three validation cohorts, with an AUC of 0.70, 0.57, and 0.64 (P < 0.05). The MT group was characterized by high tumor neoantigen burden (TNB), increased immune infifiltration cells such as CD8 T and macrophage cells, and upregulated immune checkpoint molecules, suggesting potential biological advantages in ICIs therapy. Conclusions: The predictive model could precisely predict the immunotherapeutic efficacy in NSCLC based on the mutant genes within the model. Furthermore, some immune-related features and cell expression could support robust efficiency.

Interleukin-1α, interleukin-1ß and interleukin-1 receptor antagonist share a common U-shaped recognition epitope on interleukin-1 receptor surface.

Interleukin-1 (IL-1) plays a central role in the regulation of immune and inflammatory responses. There are two forms of IL-1 agonists (IL-1α and IL-1ß) and one form of IL-1 antagonist (IL-1Ra); they share a similar binding mode to the IL-1 receptor (IL-1R) but exhibit opposite biological functions on the receptor. In this study, the intermolecular interactions of IL-1R receptors with IL-1α, IL-1ß and IL-1Ra ligands were systematically investigated at structural, energetic and dynamic levels. It was found that the receptor primarily adopts a U-shaped, double-stranded and linear/conformational-hybrid epitope to commonly interact with the three ligands. The epitope covers a common protein segment (residues 107-127), which is fully located within the C2T2 subdomain of the IL-1R extracellular domain and contributes ~40% to the total binding energy of IL-1R/ligand association. The epitope is natively folded into an ordered conformation in the IL-1R protein context but would become largely disordered out of the context. Here, we adopted a disulfide bridge to staple U-shaped epitope-derived peptides, which can be effectively constrained into a native-like conformation and thus exhibit an improved affinity to ligands as compared to their unstapled counterpart, with affinity increase by up to ~15-fold. These disulfide bridges were designed to point out of ligand/peptide complex interface and thus would not disrupt the direct complex interaction. Energetic decomposition imparted that the stapling has only a modest influence on the interaction enthalpy and desolvation effect of ligand/peptide binding, but can substantially reduce entropy penalty upon the binding. For a peptide, the stapling-addressed entropic reduction can be roughly regarded as a constant, which only improves peptide affinity to these ligands, but does not change peptide selectivity over different ligands.

Interleukin-25 recognition by its unique receptor IL-17Rb via two discrete linear and cyclic epitopes.

Interleukin-17 (IL-17) is a family of pro-inflammatory cytokines and has been involved in the pathogenesis of chronic inflammatory and autoimmune diseases. The IL-17E, also known as IL-25, is a distinct member of this family that binds to its unique receptor IL-17Rb to induce the activation of nuclear factor kappa-light-chain enhancer of activated B cells. Here, we systematically examined the intermolecular recognition and association of IL-25 with IL-17Rb and demonstrated that the IL-25 primarily adopts two discrete linear and cyclic epitopes to interact with IL-17Rb. The two epitopes are separately located in the monomers 1 and 2 of IL-25 homodimer and cover sequences 125 DPRGNSELLYHN136 and 77 ELDRDLNRLPQDLY90 . They totally contribute 71.6% binding energy to the full-length IL-25. The linear epitope targets a site spanning over the extracellular fnIIID1 and fnIIID2 domains of IL-17Rb, while the cyclic epitope primarily binds at the fnIIID1 domain. In addition, we also found that the linear and cyclic epitopes are natively folded into ordered single-stranded and double-stranded conformations in IL-25 protein context, respectively, but would become largely disordered when splitting from the context to be free peptides, which, however, cannot bind effectively to IL-17Rb as them in the native state. In this respect, we extended the cyclic epitope to cover the whole IL-25 double-stranded region and added a disulfide bridge across its two strands at three selected anchor residue pairs. It is revealed that the disulfide-stapled peptides can be constrained into a native-like conformation and thus exhibit an improved binding potency to IL-17Rb as compared to their unstapled counterpart.

Highly Effective Pd/MgO/γ-Al2O3 Catalysts for CO Oxidative Coupling to Dimethyl Oxalate: The Effect of MgO Coating on γ-Al2O3.

The support of MgO/γ-Al2O3 was initially prepared by a multiple impregnation method and Pd was placed on the surface of the MgO/γ-Al2O3 support via incipient wetness impregnation. Pd/MgO/γ-Al2O3 (Pd/MAO) catalysts were systematically characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), CO2-temperature-programmed desorption (TPD), transmission electron microscopy (TEM), CO-Fourier transform infrared (CO-FTIR), and X-ray photoelectron spectroscopy (XPS) and tested in the CO oxidative coupling to dimethyl oxalate (DMO) reaction. Compared to Pd/γ-Al2O3, the catalytic activities of the Pd/MAO catalysts improved significantly. The Pd/MAO catalyst with a 30% mass ratio of Mg to γ-Al2O3 delivers 3 times higher STY of DMO than that of Pd/γ-Al2O3. It has been demonstrated that MgO covered γ-Al2O3 layer-by-layer forming MAO supports, which can increase surface basicity and the interaction between Pd particles and the MAO supports. Moreover, the relationship between metal and support interaction and catalytic performance was discussed.

Direct synthesis of shaped MgAPO-11 molecular sieves and the catalytic performance in n-dodecane hydroisomerization.

In industrial application, molecular sieves are usually used in a certain shape. This requires the addition of binder and causes the reduction of both the molecular sieve content and catalytic performance. Herein, pseudo-boemite was mixed with deionized water at room temperature, followed by the drop-wise addition of phosphoric acid, magnesium acetate solution, hydrofluoric acid, di-n-propylamine and 1-ethyl-3-methyl imidazolium bromide with vigorous stirring. The molar ratio of Al2O3 : P2O5 : MgO : HF : DPA : [EMIm]Br : H2O in the gel was 1 : 1 : 0.03 : 0.18 : 0.4 : 1 : 45. Then the gel was dried, extruded and directly crystallized to form a shaped MgAPO-11 molecular sieve. X-ray diffraction, scanning electron microscopy, N2 adsorption, ammonia temperature programmed desorption, pyridine adsorption infrared spectroscopy and nuclear magnetic resonance spectroscopy were used to investigate the physicochemical properties of the samples. X-ray diffraction, scanning electron microscopy and N2 adsorption tests show that the shaped MgAPO-11 molecular sieve is fully crystallized and possesses hierarchical porosity. Mg is incorporated into the molecular sieve framework and the Pt catalyst supported by the obtained shaped MgAPO-11 exhibits excellent catalytic performance with n-dodecane conversion of 94% and isomer selectivity of 95% at 280 °C. Such a method for the direct synthesis of shaped molecular sieves shows potential for the green synthesis of molecular sieves in industry.

Ionothermal Synthesis of MnAPO-SOD Molecular Sieve without the Aid of Organic Structure-Directing Agents.

An SOD-type metalloaluminophosphate molecular sieve (denoted as SOD-Mn) was ionothermally synthesized by introducing manganese(II) cations into the reaction mixture via MnO-acid or MnO2-reductant reactions. Composition and structure analyses results show that two kinds of manganese(II) cations exist in the SOD-Mn structure. Part of the manganese(II) cations isomorphously substitute the framework aluminum(III) with a substitution degree of ∼30%. The rest of the manganese(II) cations occupy a fraction of the sod cages in their hydrated forms. A comprehensive investigation of the synthesis parameters, crystal sizes, and crystallization kinetics indicates that the in situ released hydrated manganese(II) cations direct the formation of SOD-Mn. Such structure-directing effect may be inhibited by both the fluorination of manganese(II) cations and the water accumulation during crystallization. In the fluoride anion-containing reaction mixture with a low ionic liquid content, the crystallization process is strongly suppressed, and large SOD-Mn single crystals of over 200 µm in size are yielded. SOD-Mn is free from organics and shows improved thermal stability compared with metalloaluminophosphates synthesized by using organic structure-directing agents.

One-step synthesis of honeycomb-like AlPO4-11 macrostructures based on epitaxial growth and phase transformation mechanisms.

Honeycomb-like AlPO4-11 macrostructures built of hollow tubular arrays have been directly achieved in a eutectic mixture. A time-dependent study reveals that the formation process obeys in situ epitaxial growth and phase transformation mechanisms.

Synthesis of discrete aluminophosphate -CLO nanocrystals in a eutectic mixture.

Extra-large-pore aluminophosphate -CLO (i.e., DNL-1) nanocrystals were synthesized in a eutectic mixture composed of diethylamine hydrochloride (DEAC) and ethylene glycol (EG) with 1-methylimidazole (1-MIm) as an additional amine using both conventional and microwave heating. The effects of the synthesis parameters, such as the amount of 1-MIm and the P/Al ratio, on the formation of DNL-1 nanocrystals were studied. The products were characterized using a variety of techniques. XRD, DLS, SEM and TEM results indicate that the as-synthesized DNL-1 nanocrystals have good crystallinity and narrow particle size distributions, and their average particle size was controlled in the 100-220nm range by simply adjusting the amount of 1-MIm. TG-DSC and N2 adsorption analyses reveal that the as-synthesized DNL-1 nanocrystals exhibit good thermal stability and the calcined samples possess high BET surface areas and large pore volumes. In addition, the cooperative structure-directing effects of 1-MIm and the eutectic mixture cation (DEA(+)) in the formation of DNL-1 nanocrystals were discussed.

One-step hydrotreatment of vegetable oil to produce high quality diesel-range alkanes.

A one-step hydrotreatment of vegetable oil combining deoxygenation and isomerization to directly produce low cloud point, high quality diesel is devised. The Pt/zeolite bifunctional catalysts prepared by using SAPO-11 and ZSM-22 zeolites as supports are used in this process. Catalytic reactions are conducted in a fixed-bed reactor under a hydrogen atmosphere. Over the bifunctional catalyst, 100 % conversion of soybean oil is obtained at 357 °C, 4 MPa, and 1 h(-1), and 80 % organic liquid yield is achieved, which is close to the maximum theoretical liquid yield. In the organic products, the alkanes selectivity is 100 % with an i-alkanes selectivity above 63 %. NH(3)-temperature programmed desorption (TPD), pyridine IR spectroscopy, and other characterization techniques are used to study the effect of the support acidity on the reaction pathway. Over the Pt/zeolite bifunctional catalyst with less strong Lewis acid sites, the reaction proceeds via the decarboxylation plus decarbonylation pathway. This one-step method provides a new strategy to produce low cloud point, high quality diesel from biomass feedstock in a more economic and attractive way.

Mixed template effect adjusted by amine concentration in ionothermal synthesis of molecular sieves.

Cationic templating of imidazolium adjusted by the amine concentration in an ionothermal system results in products with larger channels or cage-like structures by reassembling the inorganic hosts around the changed organic guests.

New insights into the role of amines in the synthesis of molecular sieves in ionic liquids.

A combination of state-of-the art in situ one- and two-dimensional NMR spectroscopy and density functional theory (DFT) calculations have been employed for the first time to investigate the role of amines in the synthesis of aluminophosphate molecular sieves in ionic liquids (ILs). In situ rotating-frame nuclear Overhauser effect spectroscopy (ROESY) was used to demonstrate that the hybrid of imidazolium ionic liquids with organic amines, such as morpholine, connected through a hydrogen bond can be formed in the gel during the crystallization of molecular sieves. By combining the characterizations of the final solid products obtained by using XRD analyses, solid-state NMR spectroscopy, thermogravimetric analysis, and DFT calculation results, it was verified that the hybrid between morpholine and the imidazolium cation in the initial preparation stage can act as the structure-directing agent (SDA) for the synthesis of AFI-structured aluminophosphate molecular sieves. Our findings may suggest a synthesis mechanism of molecular sieves in ionic liquids in which the IL-organic amine hybrid is required in the nucleation step, whereas the crystal growth occurs through the occlusion of ionic liquids in the zeolite channels.

Selective enrichment of endogenous peptides by chemically modified porous nanoparticles for peptidome analysis.

We report the development of a combined strategy for high capacity, comprehensive enrichment of endogenous peptide from complex biological samples at natural pH condition. MCM-41 nanoparticles with highly ordered nanoscale pores (i.e. 4.8nm) and high-surface area (i.e. 751m(2)/g) were synthesized and modified with strong cation-exchange (SCX-MCM-41) and strong anion-exchange (SAX-MCM-41) groups. The modified nanoparticles demonstrated good size-exclusion effect for the adsorption of standard protein lysozyme with molecular weight (MW) of ca. 15kDa; and the peptides with MW lower than this value can be well adsorbed. Step elution of the enriched peptides with five salt concentrations presented that both modified nanoparticles have high capacity and complementarity for peptides enrichment, and the SAX-MCM-41 nanoparticles has obviously high selectivity for acidic peptides with pI (isoelectric point) lower than 4. Large-scale enrichment of endogenous peptides in 2mg mouse liver extract was achieved by further combination of SCX-MCM-41 and SAX-MCM-41 with unmodified MCM-41 nanoparticles. On-line 2D nano-LC/MS/MS was applied to analyze the enriched samples, and 2721 unique peptides were identified in total. Two-dimensional analysis of MW versus pI distribution combined with abundance of the identified peptides demonstrated that the three types of nanoparticles have comprehensive complementarity for peptidome enrichment.

Effect of water on the ionothermal synthesis of molecular sieves.

AlPO4-11 and AlPO4-5 molecular sieves are ionothermally prepared without addition of water by using anhydrous starting materials, such as NH4H2PO4, pseudoboehmite (AlOOH), and NH4F. The synthesis appears to be an autocatalytic process. Water has a remarkable effect on the synthesis process. Addition of reagent quantities of water (H2O/Al = 1, molar ratio) can enhance the crystallization kinetics greatly.

Structure-directing role of amines in the ionothermal synthesis.

The structure-directing effect of amine has been observed in the ionothermal synthesis of aluminophosphate molecular sieves in 1-butyl-3-methylimidazolium bromide ionic liquid. The seven different amines we tested have an influence on the crystallization dynamics and the final product, leading to the formation of pure AFI and ATV structures.