Silver Nanocluster-Tagged Electrochemiluminescence Immunoassay with a Sole and Narrow Triggering Potential Window.

The commercialized electrochemiluminescence (ECL) immunoassay is carried out by holding luminophore Ru(bpy)32+ at a given potential. Designing an electrochemiluminophore with a narrow triggering potential window is strongly anticipated to decrease the electrochemical cross-talk and improve the flux of the commercialized ECL immunoassay in a potential-resolved way. Herein, L-penicillamine-capped silver nanoclusters (LPA-AgNCs) are facilely synthesized and utilized as tags to perform the ECL immunoassay with a sole and narrow triggering potential window of 0.24 V by employing hydrazine (N2H4) as a coreactant. The maximum ECL emission of the LPA-AgNCs/N2H4 system is located ca. +1.27 V. Upon immobilizing LPA-AgNCs onto the electrode surface via forming a sandwich immunocomplex, the ECL of LPA-AgNCs/N2H4 can be utilized to sensitively and selectively determine human carcinoembryonic antigen from 0.5 to 1000 pg/mL with a low limit of detection of 0.1 pg/mL (S/N = 3). This work might open a way to screen electrochemiluminophores for the multiple ECL immunoassay in a potential-resolved way.

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.

Solid-State Synthesis of Aluminophosphate Zeotypes by Calcination of Amorphous Precursors.

Because of the growing interest in the applications of zeolitic materials and the various challenges associated with traditional synthesis methods, the development of novel synthesis approaches remains of fundamental importance. Herein, we report a general route for the synthesis of aluminophosphate (AlPO) zeotypes by simple calcination of amorphous precursors at moderate temperatures (250-450 °C) for short reaction times (3-60 min). Accordingly, highly crystalline AlPO zeotypes with various topologies of AST, SOD, LTA, AEL, AFI, and -CLO, ranging from ultra-small to extra-large pores, have been successfully synthesized. Multinuclear multidimensional solid-state NMR techniques combined with complementary operando mass spectrometry (MS), powder X-ray diffraction, high-resolution transmission electron microscopy, and Raman characterizations reveal that covalently bonded fluoride in the intermediates catalyze the bond breaking and remaking processes. The confined organic structure-directing agents with high thermal stability direct the ordered rearrangement. This novel synthesis strategy not only shows excellent synthesis efficiency in terms of a simple synthesis procedure, a fast crystallization rate, and a high product yield, but also sheds new light on the crystallization mechanism of zeolitic materials.

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.

Facile Synthesis of Hierarchical Nanosized Single-Crystal Aluminophosphate Molecular Sieves from Highly Homogeneous and Concentrated Precursors.

The synthesis of hierarchical nanosized zeolite materials without growth modifiers and mesoporogens remains a substantial challenge. Herein, we report a general synthetic approach to produce hierarchical nanosized single-crystal aluminophosphate molecular sieves by preparing highly homogeneous and concentrated precursors and heating at elevated temperatures. Accordingly, aluminophosphate zeotypes of LTA (8-rings), AEL (10-rings), AFI (12-rings), and -CLO (20-rings) topologies, ranging from small to extra-large pores, were synthesized. These materials show exceptional properties, including small crystallites (30-150 nm), good monodispersity, abundant mesopores, and excellent thermal stability. A time-dependent study revealed a non-classical crystallization pathway by particle attachment. This work opens a new avenue for the development of hierarchical nanosized zeolite materials and understanding their crystallization mechanism.

SEQdata-BEACON: a comprehensive database of sequencing performance and statistical tools for performance evaluation and yield simulation in BGISEQ-500.

BACKGROUND: The sequencing platform BGISEQ-500 is based on DNBSEQ technology and provides high throughput with low costs. This sequencer has been widely used in various areas of scientific and clinical research. A better understanding of the sequencing process and performance of this system is essential for stabilizing the sequencing process, accurately interpreting sequencing results and efficiently solving sequencing problems. To address these concerns, a comprehensive database, SEQdata-BEACON, was constructed to accumulate the run performance data in BGISEQ-500. RESULTS: A total of 60 BGISEQ-500 instruments in the BGI-Wuhan lab were used to collect sequencing performance data. Lanes in paired-end 100 (PE100) sequencing using 10 bp barcode were chosen, and each lane was assigned a unique entry number as its identification number (ID). From November 2018 to April 2019, 2236 entries were recorded in the database containing 65 metrics about sample, yield, quality, machine state and supplies information. Using a correlation matrix, 52 numerical metrics were clustered into three groups signifying yield-quality, machine state and sequencing calibration. The distributions of the metrics also delivered information about patterns and rendered clues for further explanation or analysis of the sequencing process. Using the data of a total of 200 cycles, a linear regression model well simulated the final outputs. Moreover, the predicted final yield could be provided in the 15th cycle of the early stage of sequencing, and the corresponding R2 of the 200th and 15th cycle models were 0.97 and 0.81, respectively. The model was run with the test sets obtained from May 2019 to predict the yield, which resulted in an R2 of 0.96. These results indicate that our simulation model was reliable and effective. CONCLUSIONS: Data sources, statistical findings and application tools provide a constantly updated reference for BGISEQ-500 users to comprehensively understand DNBSEQ technology, solve sequencing problems and optimize run performance. These resources are available on our website http://seqBEACON.genomics.cn:443/home.html.

Biomass-Derived Graphene-like Carbon: Efficient Metal-Free Carbocatalysts for Epoxidation.

N-doped graphene-like layered carbon (NG) could be synthesized via a metal-free pyrolysis route from glucose, fructose, and 5-hydroxymethylfurfural (5-HMF), which are cheap and widely available biomass or biomass derivatives. A well-developed thin-layer structure with large lateral dimensions could be obtained when 5-HMF was used as the precursor. More importantly, the 5-HMF-derived NG gave superior performance in epoxidation reactions compared with the conventional carbon catalysts and the performance of 5-HMF derived NG was even similar to that of a cobalt catalyst. Characterizations by TEM and XPS accompanied by EPR analysis revealed that the enhanced catalytic properties for NG arise from its high activation ability for both alkenes and O2 , which are attributed to the graphitic layered structure and graphitic N species, respectively.

Design and preparation of efficient hydroisomerization catalysts by the formation of stable SAPO-11 molecular sieve nanosheets with 10-20 nm thickness and partially blocked acidic sites.

SAPO-11 nanosheets with partially filled micropores (N-SAPO-11) and a thickness of 10-20 nm were synthesized using polyhexamethylene biguanide hydrochloride (PHMB) as a mesoporogen and di-n-propylamine (DPA) as a microporous template. After Pt loading (0.5 wt%), the Pt/N-SAPO-11 catalyst exhibits higher selectivity for the isomers and lower selectivity for cracking products than conventional Pt/SAPO-11 catalysts in the hydroisomerization of n-dodecane.

Hydrothermal Carbon Enriched with Oxygenated Groups from Biomass Glucose as an Efficient Carbocatalyst.

Metal-free carbocatalysts enriched with specific oxygenated groups with different morphology and size were synthesized from glucose by hydrothermal carbonization, in which cheap and widely available biomass could be converted into functionalized carbon using an environmentally benign process. The hydroxy- and carbonyl-enriched hydrothermal carbon (HTC) could be used in nitrobenzene reduction, and higher conversion was obtained on the sphere morphology with smaller size. In the Beckmann rearrangement of cyclohexanone oxime, carboxyl-enriched HTC exhibited superior performance compared with conventional solid acid (such as HY and HZSM-5), on which the strong acid sites and weak Lewis acid sites lead to high selectivity for the side product. Although the intrinsic acidity of carbon is weak, the carboxyl-enriched carbon was used in weak Brønsted acid-catalyzed reactions, such as the Beckmann rearrangement.

Occurrence, structure, and evolution of nitric oxide synthase-like proteins in the plant kingdom.

Nitric oxide (NO) signaling regulates various physiological processes in both animals and plants. In animals, NO synthesis is mainly catalyzed by NO synthase (NOS) enzymes. Although NOS-like activities that are sensitive to mammalian NOS inhibitors have been detected in plant extracts, few bona fide plant NOS enzymes have been identified. We searched the data set produced by the 1000 Plants (1KP) international consortium for the presence of transcripts encoding NOS-like proteins in over 1000 species of land plants and algae. We also searched for genes encoding NOS-like enzymes in 24 publicly available algal genomes. We identified no typical NOS sequences in 1087 sequenced transcriptomes of land plants. In contrast, we identified NOS-like sequences in 15 of the 265 algal species analyzed. Even if the presence of NOS enzymes assembled from multipolypeptides in plants cannot be conclusively discarded, the emerging data suggest that, instead of generating NO with evolutionarily conserved NOS enzymes, land plants have evolved finely regulated nitrate assimilation and reduction processes to synthesize NO through a mechanism different than that in animals.

Synthesis of polymorph A-enriched beta zeolites in a HF-concentrated system.

Polymorph A-enriched beta zeolites were synthesized by employing high HF concentrations in the synthesis medium. The polymorphic compositions of the synthesized beta zeolites were determined by the complementary characterization methods (19)F NMR analysis and PXRD simulation. With a variety of SDAs, a high HF concentration (HF/SDA > 1.0) in the synthesis medium results in the A-rich feature (55-65% A) of beta zeolites, while a moderate HF concentration only results in typical beta zeolites. A systematic study on the synthesis conditions reveals the existence of a buffered system of H(+) and F(-) formed in the highly HF-concentrated medium. This buffer results in a small but continuous supply of F(-) during zeolite crystallization, in contrast to the conventional fluoride route where all F(-) are discharged all-at-once at the initial stage.

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.

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.

Metagenomic analysis of microbiome in colon tissue from subjects with inflammatory bowel diseases reveals interplay of viruses and bacteria.

Inflammatory bowel diseases (IBD), Crohn's disease and ulcerative colitis, are poorly understood disorders affecting the intestinal tract. The current model for disease suggests that genetically susceptible patients develop intolerance to gut microflora, and chronic inflammation develops as a result of environmental insults. Although interest has mainly focused on studying genetic variants and gut bacterial flora, little is known about the potential of viral infection to contribute to disease. Accordingly, we conducted a metagenomic analysis to document the baseline virome in colonic biopsy samples from patients with IBD in order to assess the contribution of viral infection to IBD. Libraries were generated from colon RNA to create approximately 2 GB sequence data per library. Using a bioinformatic pipeline designed to detect viral sequences, more than 1000 viral reads were derived directly from tissue without any coculture or isolation procedure. Herein, we describe the complexity and abundance of viruses, bacteria/bacteriophage, and human endogenous retroviral sequences from 10 patients with IBD and 5 healthy subjects undergoing surveillance colonoscopy. Differences in gut microflora and the abundance of mammalian viruses and human endogenous retroviruses were readily detected in the metagenomic analyses. Specifically, patients with herpesviridae sequences in their colon demonstrated increased expression of human endogenous viral sequences and differences in the diversity of their microbiome. This study provides a promising metagenomic approach to describe the colonic microbiome that can be used to better understand virus-host and phage-bacteria interactions in IBD.

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.

Phylotranscriptomic analysis of the origin and early diversification of land plants.

Reconstructing the origin and evolution of land plants and their algal relatives is a fundamental problem in plant phylogenetics, and is essential for understanding how critical adaptations arose, including the embryo, vascular tissue, seeds, and flowers. Despite advances in molecular systematics, some hypotheses of relationships remain weakly resolved. Inferring deep phylogenies with bouts of rapid diversification can be problematic; however, genome-scale data should significantly increase the number of informative characters for analyses. Recent phylogenomic reconstructions focused on the major divergences of plants have resulted in promising but inconsistent results. One limitation is sparse taxon sampling, likely resulting from the difficulty and cost of data generation. To address this limitation, transcriptome data for 92 streptophyte taxa were generated and analyzed along with 11 published plant genome sequences. Phylogenetic reconstructions were conducted using up to 852 nuclear genes and 1,701,170 aligned sites. Sixty-nine analyses were performed to test the robustness of phylogenetic inferences to permutations of the data matrix or to phylogenetic method, including supermatrix, supertree, and coalescent-based approaches, maximum-likelihood and Bayesian methods, partitioned and unpartitioned analyses, and amino acid versus DNA alignments. Among other results, we find robust support for a sister-group relationship between land plants and one group of streptophyte green algae, the Zygnematophyceae. Strong and robust support for a clade comprising liverworts and mosses is inconsistent with a widely accepted view of early land plant evolution, and suggests that phylogenetic hypotheses used to understand the evolution of fundamental plant traits should be reevaluated.

Horizontal transfer of an adaptive chimeric photoreceptor from bryophytes to ferns.

Ferns are well known for their shade-dwelling habits. Their ability to thrive under low-light conditions has been linked to the evolution of a novel chimeric photoreceptor--neochrome--that fuses red-sensing phytochrome and blue-sensing phototropin modules into a single gene, thereby optimizing phototropic responses. Despite being implicated in facilitating the diversification of modern ferns, the origin of neochrome has remained a mystery. We present evidence for neochrome in hornworts (a bryophyte lineage) and demonstrate that ferns acquired neochrome from hornworts via horizontal gene transfer (HGT). Fern neochromes are nested within hornwort neochromes in our large-scale phylogenetic reconstructions of phototropin and phytochrome gene families. Divergence date estimates further support the HGT hypothesis, with fern and hornwort neochromes diverging 179 Mya, long after the split between the two plant lineages (at least 400 Mya). By analyzing the draft genome of the hornwort Anthoceros punctatus, we also discovered a previously unidentified phototropin gene that likely represents the ancestral lineage of the neochrome phototropin module. Thus, a neochrome originating in hornworts was transferred horizontally to ferns, where it may have played a significant role in the diversification of modern ferns.