The synergistic interplay of hierarchy, crystal size, and Ga-promotion in the methanol-to-aromatics process over ZSM-5 zeolites.

In the context of advancing social modernization, the projected shortfall in the demand for renewable aromatic hydrocarbons is expected to widen, influenced by industries like high-end materials, pharmaceuticals, and consumer goods. Sustainable methods for aromatic production from alternative sources, particularly the methanol-to-aromatics (MTA) process using zeolite ZSM-5 and associated with the "methanol economy", have garnered widespread attention. To facilitate this transition, our project consolidates conventional strategies that impact aromatics selectivity-such as using hierarchical zeolites, metallic promoters, or altering zeolite physicochemical properties-into a unified study. Our findings demonstrate the beneficial impact of elongated crystal size and heightened zeolite hierarchy on preferential aromatics selectivity, albeit through distinct mechanisms involving the consumption of shorter olefins. While metallic promoters enhance MTA performance, crystal size, and hierarchy remain pivotal in achieving the maximized aromatics selectivity. This study contributes to a deeper understanding of achieving superior aromatics selectivity through physicochemical modifications in zeolite ZSM-5 during MTA catalysis, thereby advancing the field's comprehension of structure-reactivity relationships.

Transitioning from Methanol to Olefins (MTO) toward a Tandem CO2 Hydrogenation Process: On the Role and Fate of Heteroatoms (Mg, Si) in MAPO-18 Zeotypes.

The tandem CO2 hydrogenation to hydrocarbons over mixed metal oxide/zeolite catalysts (OXZEO) is an efficient way of producing value-added hydrocarbons (platform chemicals and fuels) directly from CO2via methanol intermediate in a single reactor. In this contribution, two MAPO-18 zeotypes (M = Mg, Si) were tested and their performance was compared under methanol-to-olefins (MTO) conditions (350 °C, PCH3OH = 0.04 bar, 6.5 gCH3OH h-1 g-1), methanol/CO/H2 cofeed conditions (350 °C, PCH3OH/PCO/PH2 = 1:7.3:21.7 bar, 2.5 gCH3OH h-1 g-1), and tandem CO2 hydrogenation-to-olefin conditions (350 °C, PCO2/PH2 = 7.5:22.5 bar, 1.4-12.0 gMAPO-18 h molCO2-1). In the latter case, the zeotypes were mixed with a fixed amount of ZnO:ZrO2 catalyst, well-known for the conversion of CO2/H2 to methanol. Focus was set on the methanol conversion activity, product selectivity, and performance stability with time-on-stream. In situ and ex situ Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), solid-state nuclear magnetic resonance (NMR), sorption experiments, and ab initio molecular dynamics (AIMD) calculations were performed to correlate material performance with material characteristics. The catalytic tests demonstrated the better performance of MgAPO-18 versus SAPO-18 at MTO conditions, the much superior performance of MgAPO-18 under methanol/CO/H2 cofeeds, and yet the increasingly similar performance of the two materials under tandem conditions upon increasing the zeotype-to-oxide ratio in the tandem catalyst bed. In situ FT-IR measurements coupled with AIMD calculations revealed differences in the MTO initiation mechanism between the two materials. SAPO-18 promoted initial CO2 formation, indicative of a formaldehyde-based decarboxylation mechanism, while CO and ketene were the main constituents of the initiation pool in MgAPO-18, suggesting a decarbonylation mechanism. Under tandem CO2 hydrogenation conditions, the presence of high water concentrations and low methanol partial pressure in the reaction medium led to lower, and increasingly similar, methanol turnover frequencies for the zeotypes. Despite both MAPO-18 zeotypes showing signs of activity loss upon storage due to the interaction of the sites with ambient humidity, they presented a remarkable stability after reaching steady state under tandem reaction conditions and after steaming and regeneration cycles at high temperatures. Water adsorption experiments at room temperature confirmed this observation. The faster activity loss observed in the Mg version is assigned to its harder Mg2+-ion character and the higher concentration of CHA defects in the AEI structure, identified by solid-state NMR and XRD. The low stability of a MgAPO-34 zeotype (CHA structure) upon storage corroborated the relationship between CHA defects and instability.

Structure-sensitive epoxidation of dicyclopentadiene over TiO2 catalysts.

Epoxidation of dicyclopentadiene (DCPD) is studied on a series of TiO2 catalysts using hydrogen peroxide as an oxidant. DCPD derivatives have applications in several areas including polymer, pharmaceutical and pesticide products. The control of selectivity leading to the desired product is important for many of these applications. Using experimental and computational studies, we show that the surface crystalline phases of TiO2 play crucial roles not only in the formation of peroxo species but also in the selective epoxidation of two different CC double bonds in DCPD.

The Importance of Thermal Treatment on Wet-Kneaded Silica-Magnesia Catalyst and Lebedev Ethanol-to-Butadiene Process.

The Lebedev process, in which ethanol is catalytically converted into 1,3-butadiene, is an alternative process for the production of this commodity chemical. Silica-magnesia (SiO2-MgO) is a benchmark catalyst for the Lebedev process. Among the different preparation methods, the SiO2-MgO catalysts prepared by wet-kneading typically perform best owing to the surface magnesium silicates formed during wet-kneading. Although the thermal treatment is of pivotal importance as a last step in the catalyst preparation, the effect of the calcination temperature of the wet-kneaded SiO2-MgO on the Lebedev process has not been clarified yet. Here, we prepared and characterized in detail a series of wet-kneaded SiO2-MgO catalysts using varying calcination temperatures. We find that the thermal treatment largely influences the type of magnesium silicates, which have different catalytic properties. Our results suggest that the structurally ill-defined amorphous magnesium silicates and lizardite are responsible for the production of ethylene. Further, we argue that forsterite, which has been conventionally considered detrimental for the formation of ethylene, favors the formation of butadiene, especially when combined with stevensite.

Genesis of MgCl2 -based Ziegler-Natta Catalysts as Probed with Operando Spectroscopy.

Ziegler-Natta catalysts for olefin polymerization are intrinsically complex multi-component systems. The genesis of the active sites involves several simultaneous and sequential steps, making the individual steps and interconnections difficult to be unraveled in an unambiguous manner. In this work, we combine X-ray diffraction and spectroscopy to probe each step of the birth and life of a MgCl2 -based Ziegler-Natta catalyst, namely the formation of high surface area MgCl2 by dealcoholation of an alcoholate precursor, the TiCl4 grafting, and the subsequent activation by triethylaluminum as co-catalyst. The so-prepared catalyst was tested towards ethylene polymerization, leading to the production of mainly crystalline high-density polyethylene. The use of operando characterization techniques allowed probing the transient details that are difficult to be dissected in the aftermath, but can radically affect the overall catalytic process.

Streptomyces panaciradicis sp. nov., a ß-glucosidase-producing bacterium isolated from ginseng rhizoplane.

A Gram-staining-positive actinobacterium, designated strain 1MR-8(T), was isolated from the rhizoplane of ginseng and its taxonomic status was determined using a polyphasic approach. The isolate formed long chains of spores that were straight, cylindrical and smooth-surfaced. Strain 1MR-8(T) grew at 10-37 °C (optimum 28 °C), whilst no growth was observed at 45 °C. The pH range for growth was 4.0-11.0 (optimum pH 6.0-8.0) and the NaCl range for growth was 0-7% (w/v) with optimum growth at 1% (w/v). Strain 1MR-8(T) had cell-wall peptidoglycans based on ll-diaminopimelic acid. Glucose, mannose and ribose were the whole-cell sugars. The predominant isoprenoid quinones were MK-9 (H4), MK-9 (H6) and MK-9 (H8) and the major fatty acids were anteiso-C(15:0), iso-C(15:0), anteiso-C(17:0) and iso-C(16:0). 16S rRNA gene sequencing studies showed that the novel strain was closely related to the type strains of Streptomyces caeruleatus GIMN4(T), Streptomyces curacoi NRRL B-2901(T), Streptomyces capoamus JCM 4734(T) and Streptomyces coeruleorubidus NBRC 12761(T) with similarities of 98.8%. However, DNA-DNA relatedness, as well as physiological and biochemical analyses, showed that strain 1MR-8(T) could be differentiated from its closest phylogenetic relatives. It is proposed that this strain should be classified as a representative of a novel species of the genus Streptomyces, with the suggested name Streptomyces panaciradicis sp. nov. The type strain is 1MR-8(T) ( = KACC 17632(T) = NBRC 109811(T)).

Terriglobus tenax sp. nov., an exopolysaccharide-producing acidobacterium isolated from rhizosphere soil of a medicinal plant.

An exopolysaccharide-producing bacterium, designated strain DRP 35(T), was isolated from the rhizosphere soil of a medicinal herb, Angelica sinensis, at Geumsan in Korea. Cells were Gram-staining-negative, non-motile, catalase-positive and oxidase-negative short rods. The isolate grew aerobically from 15 to 45 °C (optimum 30 °C), pH 3.5-7.0 (optimum pH 5.0) and in the presence of 0-1.0% (w/v) NaCl. Phylogenetic analyses based on 16S rRNA gene sequences indicated that strain DRP 35(T) belongs to the genus Terriglobus in the phylum Acidobacteria with a sequence similarity of 97.2% and 97.0% to Terriglobus saanensis SP1PR4(T) and Terriglobus roseus KBS63(T), respectively. The genomic DNA G+C content was 62.1 mol%. DNA-DNA relatedness between strain DRP 35(T) and the type strains of the other species of the genus Terriglobus, T. saanensis SP1PR4(T) and T. roseus KBS63(T), were 24.6 and 17.2%, respectively. The predominant menaquinone was MK-8. Major fatty acids were iso-C(15 : 0), C(16 : 1)ω7c and C(16 : 0). The polar lipids were phosphatidylethanolamine, unidentified aminophospholipid and unknown phospholipids. On the basis of polyphasic analysis from this study, strain DRP 35(T) represents a novel species of the genus Terriglobus for which the name Terriglobus tenax sp. nov. is proposed. The type strain is DRP 35(T) ( = KACC 16474(T) = NBRC 109677(T)).

Highly dispersed ruthenium nanoparticle-embedded mesoporous silica as a catalyst for the production of gamma-butyrolactone from succinic anhydride.

In this study, a novel, strategic method was developed for the synthesis of a mesoporous silica catalyst embedded with ruthenium nanoparticles (RuNPs/SiO2) by combining the polyol and modified sol-gel methods. By applying this new procedure, uniformly synthesized ruthenium nanoparticles with an average size of 3.8 nm and 95% spherical shape were highly dispersed in the mesoporous silica support material. Coordinated carbonyl groups of PVP remaining from the synthesis of the RuNPs were effectively removed by the thermal treatment (calcined at 573 K for 4 h) and the sythesized RuNPs/SiO2 catalysts were reduced under hydrogen at 20 bar for 2 h. These catalysts were analyzed using transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), N2 adsorption-desorption, and X-ray diffraction (XRD). After the thermal treatment and the reduction procedure, the size and shape of the embedded RuNPs were nearly unchanged, and the catalyst was active in the liquid-phase hydrogenation of succinic anhydride (SAN) to selectively form y-butyrolactone (GBL) with a maximum yield of 90.1%. This novel catalyst preparation is a potentially useful method for the synthesis of metal nanoparticles as heterogeneous catalysts.

Oxidation of ammonia to nitrogen over Pt/Fe/ZSM5 catalyst: influence of catalyst support on the low temperature activity.

In this study, Pt/Fe/ZSM5 catalysts were applied to oxidation of ammonia, where the catalysts showed good low-temperature activity (≤ 200°C) for converting ammonia into nitrogen. With 1.5% Pt/0.5% Fe/ZSM5 catalyst, we could obtain 81% NH(3) conversion and 93% N(2) selectivity at 175°C at the short contact-time of w/f=0.00012 g min/mL. Through the characterization studies using high-resolution transmission electron microscopy (HRTEM) and X-ray spectroscopies (XRD, XPS), we could find that the active species was collaborating Pt/Fe species, which structure and activity were largely influenced by support material - in a positive way by ZSM5, rather than by Al(2)O(3) and SiO(2). When using ZSM5 as the support material, Pt was highly dispersed exclusively on the Fe oxide, and the valence state and dispersion of Pt changed according to Fe loading amount.

Features of a unique intronless cluster of class I small heat shock protein genes in tandem with box C/D snoRNA genes on chromosome 6 in tomato (Solanum lycopersicum).

Physical clustering of genes has been shown in plants; however, little is known about gene clusters that have different functions, particularly those expressed in the tomato fruit. A class I 17.6 small heat shock protein (Sl17.6 shsp) gene was cloned and used as a probe to screen a tomato (Solanum lycopersicum) genomic library. An 8.3-kb genomic fragment was isolated and its DNA sequence determined. Analysis of the genomic fragment identified intronless open reading frames of three class I shsp genes (Sl17.6, Sl20.0, and Sl20.1), the Sl17.6 gene flanked by Sl20.1 and Sl20.0, with complete 5' and 3' UTRs. Upstream of the Sl20.0 shsp, and within the shsp gene cluster, resides a box C/D snoRNA cluster made of SlsnoR12.1 and SlU24a. Characteristic C and D, and C' and D', boxes are conserved in SlsnoR12.1 and SlU24a while the upstream flanking region of SlsnoR12.1 carries TATA box 1, homol-E and homol-D box-like cis sequences, TM6 promoter, and an uncharacterized tomato EST. Molecular phylogenetic analysis revealed that this particular arrangement of shsps is conserved in tomato genome but is distinct from other species. The intronless genomic sequence is decorated with cis elements previously shown to be responsive to cues from plant hormones, dehydration, cold, heat, and MYC/MYB and WRKY71 transcription factors. Chromosomal mapping localized the tomato genomic sequence on the short arm of chromosome 6 in the introgression line (IL) 6-3. Quantitative polymerase chain reaction analysis of gene cluster members revealed differential expression during ripening of tomato fruit, and relatively different abundances in other plant parts.

Brace compression for treatment of pectus carinatum.

BACKGROUND: Surgery has been the classical treatment of pectus carinatum (PC), though compressive orthotic braces have shown successful results in recent years. We propose a non-operative approach using a lightweight, patient-controlled dynamic chest-bracing device. MATERIALS AND METHODS: Eighteen patients with PC were treated between July 2008 and June 2009. The treatment involved fitting of the brace, which was worn for at least 20 hours per day for 6 months. Their degree of satisfaction (1, no correction; 4, remarkable correction) was measured at 12 months after the initiation of the treatment. RESULTS: Thirteen (72.2%) patients completed the treatment (mean time, 4.9±1.4 months). In patients who completed the treatment, the mean overall satisfaction score was 3.73±0.39. The mean satisfaction score was 4, and there was no recurrence of pectus carinatum in patients who underwent the treatment for at least 6 months. Minimal recurrence of pectus carinatum after removal of the compressive brace occurred in 5 (38.5%) patients who stopped wearing the compressive brace at 4 months. CONCLUSION: Compressive bracing results in a significant improvement in PC appearance in patients with an immature skeleton. However, patient compliance and diligent follow-up appear to be paramount for the success of this method of treatment. We currently offer this approach as a first-line treatment for PC.

The synthesis of silica and silica-ceria, core-shell nanoparticles in a water-in-oil (W/O) microemulsion composed of heptane and water with the binary surfactants AOT and NP-5.

In this study, a strategy was developed for the synthesis of nano-sized, silica-ceria, core-shell composites in a water-oil (W/O) microemulsion consisting of water, heptane and the binary surfactants AOT (sulfosuccinic acid bis (2-ethylhexyl) ester sodium salt) and NP-5 (polyoxyethylene (5) nonylphenyl ether). The core-shell, silica-ceria particles were prepared in a stepwise procedure: (1) the precipitation of the core-silica particles in a W/O microemulsion and (2) the surface precipitation of ceria on the core silica dispersed over the microemulsion. The composition of the binary surfactant greatly influenced the growth rate of the core-silica particles. The virial coefficient of diffusion was utilized to estimate the effect of the surfactant composition on the degree of intermicellar interaction that is important for the growth rate of the silica along with the flexibility of the micellar interface and the structure of the water domain. The deposition of the ceria on the core silica was not straightforward because the bulk and surface precipitation competed with each other. The promotion of surface precipitation was attempted by: (1) chemically modifying the silica surface with an organoamine group and (2) slowing down the precipitation rate of the ceria in a semi-batch operation. These attempts successfully produced the nano-sized silica-ceria, core-shell particles, which were evidenced through the TEM, XPS and zeta potential analysis.

PCR-linked reverse DNA hybridization using oligonucleotide-specific probes of rpoB for identification of Mycobacterium avium and Mycobacterium intracellulare.

A PCR-linked reverse DNA hybridization method using two different specific rpoB DNA probes (Avp and Intp) of Mycobacterium avium and Mycobacterium intracellulare, respectively, were evaluated for the differentiation and identification of M. avium and M. intracellulare culture isolates. Among the 504 culture isolates tested by this method, 48 strains showed positive results for M. avium and 60 strains showed positive results for M. intracellulare. The other 396 culture isolates showed negative results for both M. avium and M. intracellulare. These results were consistent with those obtained from partial rpoB (306 bp) sequence analysis and biochemical tests. The negative strains obtained by this DNA hybridization method were identified as M. tuberculosis (366 strains), M. peregrinum (11 strains), M. abscessus (9 strains), M. fortuitum (8 strains), and M. flavescens (2 strains) by rpoB DNA sequence analysis. Due to the high sensitive and specific result obtained by this assay, we suggest that this PCR-linked reverse DNA hybridization method using two different specific rpoB DNA probes of M. avium and M. intracellulare would be used for the rapid and precise method for differentiation and identification of M. avium and M. intracellulare.

Tungsten oxide zirconia as solid superacid catalyst for esterification of waste acid oil (dark oil).

Biodiesel is a renewable fuel which can be produced through an esterification reaction. The cost of feedstock which resulted in that of biodiesel is a large problem to be resolved. Dark oil from industrial process can be a better alternative for biodiesel production because of its low price. In spite of this, the study of biodiesel production using the dark oil has not been reported. This study provides technical information and catalytic properties on this system. Among the several catalysts, WO(3)/ZrO(2) catalyst was the most effective catalyst in the esterification of the dark oil to fatty acid methyl esters (FAMEs). The catalytic reaction parameters were optimized that 20 wt.% WO(3)/ZrO(2) has a high FFA conversion of 96% at 150 degrees C, 0.4 g/ml (oil), 1:9 (oil to alcohol, molar ratio) and 2h reaction time. The physical and chemical properties of the catalyst were characterized by XRD, Raman spectrometer, BET and NH(3)-TPD.

Esterification of used vegetable oils using the heterogeneous WO3/ZrO2 catalyst for production of biodiesel.

Tungsten oxide zirconia, sulfated zirconia and Amberlyst-15 were examined as a catalyst for a conversion of used vegetable oils (VOs) to fatty acid methyl esters (FAMEs). Among them, tungsten oxide zirconia was a promising heterogeneous catalyst for the production of biodiesel fuels from used VOs because of high activity in the conversion over 93% and no leaching WO(3) in the esterification reaction. The reaction conditions were optimized. A study for optimizing the reaction parameters such as the reaction temperature, stirring speed, WO(3) loading over ZrO(2) and reaction time, was carried out. The catalyst was characterized by BET, XRD, FT-IR, and NH(3)-TPD. With increasing WO(3) loading over ZrO(2), the triclinic phase of WO(3) increased and the tetragonal phase of zirconia was clearly generated. The highest acid strength of 20 wt% tungsten oxide zirconia catalyst was confirmed by NH(3)-TPD analysis and the result was correlated to the highest catalytic activity of the esterification reaction.

Overaccumulation of higher polyamines in ripening transgenic tomato fruit revives metabolic memory, upregulates anabolism-related genes, and positively impacts nutritional quality.

Vegetables and fruits are essential components of the human diet as they are sources of vitamins, minerals, and fiber and provide antioxidants that prevent chronic diseases. Our goal is to improve durable nutritional quality of tomato fruit. We developed transgenic tomatoes expressing yeast S-adenosylmethionine decarboxylase (ySAMdc) gene driven by a fruit-specific E8 promoter to investigate the role of polyamines in fruit metabolism. Stable integration of E8-ySAMdc chimeric gene in tomato genome led to ripening-specific accumulation of polyamines, spermidine (Spd) and spermine (Spm), which in turn affected higher accumulation of glutamine, asparagine, and organic acids in the red fruit with significant decrease in the contents of valine, aspartate, sucrose, and glucose. The metabolite profiling analysis suggests that Spd/Spm are perceived as "signaling" organic-N metabolites by the fruit cells, resulting in the stimulation of carbon sequestration; enhanced synthesis of biomolecules; increased acid to sugar ratio, a good attribute for the fruit flavor; and in the accumulation of another "vital amine," choline, which is an essential micronutrient for brain development. A limited transcriptome analysis of the transgenic fruit that accumulate higher polyamines revealed a large number of differentially expressed genes, about 55% of which represented discrete functional categories, and the remaining 45% were novel, unknown, or unclassified: amino acid biosynthesis, carotenoid biosynthesis, cell wall metabolism, chaperone family, flavonoid biosynthesis, fruit ripening, isoprenoid biosynthesis, polyamine biosynthesis, signal transduction, stress/defense-related, transcription, translation, and vacuolar function. There was a good correspondence between some gene transcripts and their protein products, but not in the case of the tonoplast intrinsic protein, which showed post-transcriptional regulation. Higher metabolic activity of the transgenic fruit is reflected in higher respiratory activity, and upregulation of chaperones and mitochondrial cytochrome oxidase transcripts compared to the control. These transgenic plants are a new resource to understand the role of Spd/Spm in fruit biology. Transcriptome analysis and metabolic profiles of Spd/Spm accumulating, transgenic fruit suggest the presence of an intricate regulation and interconnection between certain metabolic pathways that are revived when Spd and Spm likely reach a certain threshold. Thus, polyamines act as antiapoptotic regulatory molecules and are able to revive metabolic memory in the tomato fruit.