Si–OH Nest and Al Distribution of Silicalite-1 Core/Al-ZSM-5 Shell Zeolites for Methane Dehydroaromatization Reaction

Silicalite-1 core/Al-ZSM-5 shell zeolite crystals were prepared in various sizes for use as catalysts in methane dehydroaromatization (MDA), and the growth kinetics and corresponding physicochemical properties of this core–shell zeolite were investigated. Al-ZSM-5 was grown on silicalite-1 seeds at various Si/Al ratios. Core–shell catalysts of all size variations exhibited similar deactivation trends in the MDA reaction, with minor changes in aromatic yields despite clear differences in reaction channel lengths and acid-site properties. This outcome was shown to originate from the unique growth kinetics of the Al-ZSM-5 layer on silicalite-1 seeds, in which the Al species in the sol used in the synthesis were consumed quickly during the early aggregative growth period. This led to an interesting spatial distribution of Al in the Al-ZSM-5 layer, in that the inner layer was relatively Al-rich. This distribution is advantageous because it can inhibit coke deactivation, which often occurs at the catalyst surface during MDA. However, a substantial quantity of Si–OH nests, which inhibit the effective loading of Mo species at the acid sites of the crystals, were detected in the microstructural analysis of large crystals. Therefore, this study shows that silicalite-1 core/Al-ZSM-5 shell zeolites can be prepared for use as coke-resistant catalysts for the MDA reaction. Further work is required, however, to design a synthesis method which reduces the number of Si–OH nests formed.

Heterogeneous Nucleation and Growth of CaCO3 on Calcite (104) and Aragonite (110) Surfaces: Implications for the Formation of Abiogenic Carbonate Cements in the Ocean

Although near-surface seawater is supersaturated with CaCO3, only a minor part of it is abiogenic (e.g., carbonate cements). The possible reason for such a phenomenon has attracted much attention in the past decades. Substrate effects on the heterogeneous nucleation and growth of CaCO3 at various Mg2+/Ca2+ ratios may contribute to the understanding of the origin of abiogenic CaCO3 cements. Here, we used in situ atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy to study the heterogeneous nucleation and growth of CaCO3 on both calcite (104) and aragonite (110) surfaces. The results show that (1) calcite spiral growth occurs on calcite (104) surfaces by monomer-by-monomer addition; (2) the aggregative growth of aragonite appears on aragonite (110) surfaces through a substrate-controlled oriented attachment (OA) along the [001] direction, followed by the formation of elongated columnar aragonite; and (3) Mg2+ inhibits the crystallization of both calcite and aragonite without impacting on crystallization pathways. These findings disclose that calcite and aragonite substrates determine the crystallization pathways, while the Mg2+/Ca2+ ratios control the growth rate of CaCO3, indicating that both types of CaCO3 substrate in shallow sediments and aqueous Mg2+/Ca2+ ratios constrain the deposition of abiogenic CaCO3 cements in the ocean.

The Autotransporter IcsA PromotesShigella flexneriBiofilm Formation in the Presence of Bile Salts

ABSTRACTShigella flexneriis an intracellular bacterial pathogen that invades epithelial cells in the colonic mucosa, leading to bloody diarrhea. A previous study showed thatS. flexneriforms biofilms in the presence of bile salts, through an unknown mechanism. Here, we investigated the potential role of adhesin-like autotransporter proteins inS. flexneribiofilm formation. BLAST search analysis revealed that theS. flexneri2457T genome harbors 4 genes,S1242,S1289,S2406, andicsA, encoding adhesin-like autotransporter proteins. Deletion mutants of theS1242,S1289,S2406andicsAgenes were generated and tested for biofilm formation. Phenotypic analysis of the mutant strains revealed that disruption oficsAabolished bile salt-induced biofilm formation. IcsA is an outer membrane protein secreted at the bacterial pole that is required forS. flexneriactin-based motility during intracellular infection. In extracellular biofilms, IcsA was also secreted at the bacterial pole and mediated bacterial cell-cell contacts and aggregative growth in the presence of bile salts. Dissecting individual roles of bile salts showed that deoxycholate is a robust biofilm inducer compared to cholate. The release of the extracellular domain of IcsA through IcsP-mediated cleavage was greater in the presence of cholate, suggesting that the robustness of biofilm formation was inversely correlated with IcsA processing. Accordingly, deletion oficsPabrogated IcsA processing in biofilms and enhanced biofilm formation.

Role of Annexin A2 isoform 2 on the aggregative growth of dermal papillae cells

The dermal papilla is a major component of hair, which signals the follicular epithelial cells to prolong the hair growth process. Human Annexin A2 was preliminarily identified by two-dimensional gel electrophoresis (2-DE), MALDI-TOF-MS and database searching. The aim of the present study was to explore the role of Annexin A2 in the aggregative growth of dermal papillae cells (DPC). Reverse transcription-polymerase chain reaction (RT-PCR) and Western blot were adopted to detect the expression of Annexin A2. And siRNA technique was used to suppress the expression of Annexin A2. Construction of over-expression vector was used to up-regulate the expression of Annexin A2. Cell Counting Kit 8 (CCK-8) and proliferating cell nuclear antigen (PCNA) were taken to detect the proliferation of DPC. The expression of Annexin A2 mRNA was up-regulated in passage 3 DPC compared with passage 10 DPC by RT-PCR. In line with the results at the mRNA level, Western blot analysis revealed that Annexin A2 isoform 2 was up-regulated significantly in passage 3 DPC compared with passage 10 DPC. The Annexin A2 isoform 2 siRNA was synthesized and transfected into passage 3 DPC. RT-PCR data showed the mRNA expression of Annexin A2 isoform 2 was suppressed in passage 3 DPC. Western blot results showed the expression level of Annexin A2 isoform 2 and PCNA were suppressed in passage 3 DPC. CCK-8 results showed that the proliferation of passage 3 DPC was suppressed (P < 0.05). Recombinant plasmid PLJM-Annexin A2 isoform 2-expression vector were constructed and were transfected into passage 10 DPC. RT-PCR data showed the mRNA expression of Annexin A2 isoform 2 was up-regulated in passage 10 DPC. Western blot results showed the expression level of annexin A2 isoform 2 and PCNA were up-regulated in passage 10 DPC. CCK-8 assay showed the proliferation of DPC was stimulated compared with control group (*P < 0.05). Our study proved that Annexin A2 isoform 2 may participate in regulating the proliferation of DPC and may be related to aggregative growth of dermal papilla cells. Therefore, our study suggests that Annexin A2 may be linked to hair follicle growth cycle.

Numerical insights into the early stages of nanoscale electrodeposition: nanocluster surface diffusion and aggregative growth

Fundamental understanding of the early stages of electrodeposition at the nanoscale is key to address the challenges in a wide range of applications. In this work, we introduce a novel modelling approach that couples a finite element method (FEM) with a random walk algorithm, to study the early stages of nanocluster formation, aggregation and growth, during electrochemical deposition.