Understanding solvent effects on adsorption and protonation in porous catalysts.

Solvent selection is a pressing challenge in developing efficient and selective liquid phase catalytic processes, as predictive understanding of the solvent effect remains lacking. In this work, an attenuated total reflection infrared spectroscopy technique is developed to quantitatively measure adsorption isotherms on porous materials in solvent and decouple the thermodynamic contributions of van der Waals interactions within zeolite pore walls from those of pore-phase proton transfer. While both the pore diameter and the solvent identity dramatically impact the confinement (adsorption) step, the solvent identity plays a dominant role in proton-transfer. Combined computational and experimental investigations show increasingly favorable pore-phase proton transfer to pyridine in the order: water < acetonitrile < 1,4 - dioxane. Equilibrium methods unaffected by mass transfer limitations are outlined for quantitatively estimating fundamental thermodynamic values using statistical thermodynamics.

Zeolite-Encapsulated Pt Nanoparticles for Tandem Catalysis.

Encapsulation of metal nanoparticles in a zeolite matrix is a promising route to integrate multiple sequential reactions into a one-pot and one-step tandem catalytic reaction. We report a cationic polymer-assisted synthetic strategy to encapsulate Pt nanoparticles (NPs) into MFI zeolites. Degrees of encapsulation of Pt NPs in the synthesized catalysts exceeding 90% were demonstrated via kinetic studies of model reactions involving substrates with different molecular dimensions. HZSM-5 zeolite-encapsulated Pt NPs are able to selectively mediate the tandem aldol condensation and hydrogenation of furfural and acetone to form hydrogenated C8 products with a combined yield of 87%. In contrast, hydrogenation and decarbonylation of furfural dominate on Pt NPs supported on HZSM-5 at otherwise identical conditions. The high selectivity toward the tandem reaction on the encapsulated catalyst is attributed to the distribution of metal and acid sites, which limits the access of furfural to Pt sites and promotes the acid-catalyzed aldol condensation. This is the first demonstration that the product distribution in a tandem reaction is manipulated by tailoring the architecture of catalytic materials via encapsulation.

Exhaled nitric oxide and mannitol test to predict exercise-induced bronchoconstriction.

BACKGROUND: Exercise-induced bronchoconstriction (EIB) is diagnosed via exercise challenge on a treadmill, but such testing requires complex equipment and sufficient health-care resources. The fraction of exhaled nitric oxide (FeNO) test and mannitol bronchial provocation test (BPT) may serve as a surrogate for exercise testing. METHODS: We compared the diagnostic utilities of the FeNO test and mannitol BPT in predicting EIB in asthmatic children. We retrospectively analyzed data from 60 asthmatic children aged 6-16 years. We compared the exercise BPT results, FeNO levels, and mannitol BPT data. RESULTS: All subjects were divided into exercise-positive (n = 41) or -negative (n = 19) BPT groups. Of the 41 exercise-positive patients, 32 were mannitol BPT positive and nine were mannitol BPT negative. Of the 19 exercise-negative patients, nine and 10, respectively, were mannitol BPT positive and BPT negative. The maximum % forced expiratory volume in 1 s (FEV1 ) decrease after exercise was positively correlated with FeNO (r = 0.556, P < 0.001), and with mannitol response-dose ratio (RDR; r = 0.416, P = 0.001). The receiver operating characteristic (ROC) curve for FeNO to discriminate between asthmatic subjects with and without EIB had an area under the curve (AUC) of 0.771 (95%CI: 0.643-0.870). The discriminatory ROC curve for mannitol RDR had an AUC of 0.763 (95%CI: 0.633-0.864). The AUC of FeNO and mannitol RDR did not differ significantly. CONCLUSIONS: EIB significantly correlated with both FeNO and mannitol BPT data. Given that both methods similarly predicted EIB in asthmatic children, the simpler and safer FeNO test alone may be a clinically useful diagnostic tool.

Intraparticle Diffusional versus Site Effects on Reaction Pathways in Liquid-Phase Cross Aldol Reactions.

Chemo- and regioselectivity in a heterogeneously catalyzed cross aldol reaction were directed by tuning the nature of the sites, textural properties, and reaction conditions. Catalysts included sulfonic acid-functionalized resins or SBA-15 with varying particle size or pore diameter, H-BEA zeolites, and Sn-BEA zeotype; conditions were 25 °C to 170 °C in organic media. Benzaldehyde and 2-butanone yielded branched (reaction at -CH2 - of butanone) and linear (reaction at -CH3 ) addition and condensation products; and fission of the branched aldol led to ß-methyl styrene and acetic acid. Strong acids promoted the dehydration step, and regioselectivity originated from preferred formation of the branched aldol. Both, resins and functionalized SBA-15 materials yielded predominantly the branched condensation product, unless particle morphology or temperature moved the reaction into the diffusion-limited regime, in which case more fission products were formed, corresponding to Wheeler Type II selectivity. For H-form zeolites, fission of the branched aldol competed with dehydration of the linear aldol, possibly because weaker acidity or steric restrictions prevented dehydration of the branched aldol.

Ultra-selective high-flux membranes from directly synthesized zeolite nanosheets.

A zeolite with structure type MFI is an aluminosilicate or silicate material that has a three-dimensionally connected pore network, which enables molecular recognition in the size range 0.5-0.6 nm. These micropore dimensions are relevant for many valuable chemical intermediates, and therefore MFI-type zeolites are widely used in the chemical industry as selective catalysts or adsorbents. As with all zeolites, strategies to tailor them for specific applications include controlling their crystal size and shape. Nanometre-thick MFI crystals (nanosheets) have been introduced in pillared and self-pillared (intergrown) architectures, offering improved mass-transfer characteristics for certain adsorption and catalysis applications. Moreover, single (non-intergrown and non-layered) nanosheets have been used to prepare thin membranes that could be used to improve the energy efficiency of separation processes. However, until now, single MFI nanosheets have been prepared using a multi-step approach based on the exfoliation of layered MFI, followed by centrifugation to remove non-exfoliated particles. This top-down method is time-consuming, costly and low-yield and it produces fragmented nanosheets with submicrometre lateral dimensions. Alternatively, direct (bottom-up) synthesis could produce high-aspect-ratio zeolite nanosheets, with improved yield and at lower cost. Here we use a nanocrystal-seeded growth method triggered by a single rotational intergrowth to synthesize high-aspect-ratio MFI nanosheets with a thickness of 5 nanometres (2.5 unit cells). These high-aspect-ratio nanosheets allow the fabrication of thin and defect-free coatings that effectively cover porous substrates. These coatings can be intergrown to produce high-flux and ultra-selective MFI membranes that compare favourably with other MFI membranes prepared from existing MFI materials (such as exfoliated nanosheets or nanocrystals).

High neutrophil : lymphocyte ratio is associated with refractory Kawasaki disease.

BACKGROUND: The clinical significance of the neutrophil : lymphocyte ratio (NLR) has not yet been fully elucidated in Kawasaki disease (KD). The purpose of this study was to investigate the relationship between NLR and response to i.v. immunoglobulin (IVIG), and its effect on coronary abnormalities in KD. METHODS: A total of 196 KD patients treated with IVIG were analyzed. Baseline NLR was evaluated immediately before IVIG therapy and the patients classified into two groups according to NLR. The clinical data, other inflammatory biomarkers, and coronary complications were also assessed. RESULTS: Kawasaki disease patients with NLR ≥ 5 had a greater incidence of IVIG refractoriness than the NLR < 5 group (31.7% vs 4.3%, P < 0.001), but this was not related to the development of coronary abnormalities. The change in NLR after IVIG (i.e. ΔNLR) was significantly decreased in the coronary abnormality group (2.65 ± 1.88 vs 3.81 ± 2.55, P = 0.042). On multivariate analysis, high NLR and CRP were independent predictors of IVIG refractoriness during the acute phase of KD (P = 0.032 in NLR; P = 0.029 in CRP, respectively). CONCLUSIONS: High NLR was closely associated with resistance to IVIG, but it was not related to the occurrence of coronary abnormalities in KD. Low ΔNLR after IVIG, however, was significantly associated with coronary artery abnormalities.

Anal Human Papillomavirus Infection among HIV-Infected Men in Korea.

BACKGROUND: Little is known about the epidemiology on human papillomavirus (HPV) infection among HIV-infected men in Korea. The objective of this study was to determine the prevalence, genotype distribution and risk factors associated with anal HPV infection among HIV-infected men in Korea. METHODS: A single-center cross-sectional study was conducted with HIV-infected men in Korea. Participants completed a detailed sexual behavior risk factor questionnaire. Anal samples were collected for cytology and HPV genotyping. Factors associated with anal HPV infection were assessed using multivariable logistic regression, stratifying by sexual behaviour. RESULTS: A total of 201 HIV-infected men were included in the study: 133 were from men who have sex with men (MSM) and 68 from men who have sex with women (MSW). Any anal HPV infection was detected in 82.7% of HIV-infected MSM and in 51.5% of HIV- infected MSW (P < 0.001). High-risk HPV (HR-HPV) prevalence was higher among MSM (47.4%) than MSW (25.0%; P = 0.002). The HR-HPV types identified most frequently were HPV 16 (11%), HPV 18 (9.9%), and HPV 58 (5%) in MSM, and HPV 58(11%) and HPV 16 (8.9%) in MSW. Prevalence of any HPV types in 9-valent vaccine types was higher among MSM than MSW (47.4% vs 22.1%. P = 0.001). Abnormal anal cytology was more commonly detected in MSM than MSW (42.9% vs.19.1%, P < 0.001). In HIV-infected MSM, higher number of lifetime male sex partners was significantly associated with any anal HPV infection, but age was a significant risk factor associated with anal HR-HPV infection. CONCLUSION: Anal HPV infection was highly prevalent in HIV-infected MSM in Korea, and also commonly found in HIV-infected MSW. In HIV-infected MSM, the significant risk factor for being infected with any HPV infection was lifetime number of male sexual partners, and with anal oncogenic HPV infection was age.

Antimicrobial Activity of Silver Ions Released from Zeolites Immobilized on Cellulose Nanofiber Mats.

In this study, we exploit the high silver ion exchange capability of Linde Type A (LTA) zeolites and present, for the first time, electrospun nanofiber mats decorated with in-house synthesized silver (Ag(+)) ion exchanged zeolites that function as molecular delivery vehicles. LTA-Large zeolites with a particle size of 6.0 µm were grown on the surface of the cellulose nanofiber mats, whereas LTA-Small zeolites (0.2 µm) and three-dimensionally ordered mesoporous-imprinted (LTA-Meso) zeolites (0.5 µm) were attached to the surface of the cellulose nanofiber mats postsynthesis. After the three zeolite/nanofiber mat assemblies were ion-exchanged with Ag(+) ions, their ion release profiles and ability to inactivate Escherichia coli (E. coli) K12 were evaluated as a function of time. LTA-Large zeolites immobilized on the nanofiber mats displayed more than an 11 times greater E. coli K12 inactivation than the Ag-LTA-Large zeolites that were not immobilized on the nanofiber mats. This study demonstrates that by decorating nanometer to micrometer scale Ag(+) ion-exchanged zeolites on the surface of high porosity, hydrophilic cellulose nanofiber mats, we can achieve a tunable release of Ag(+) ions that inactivate bacteria faster and are more practical to use in applications over powder zeolites.

Photocatalytic degradation of 17α-ethinylestradiol (EE2) in the presence of TiO2-doped zeolite.

Current design limitations and ineffective remediation techniques in wastewater treatment plants have led to concerns about the prevalence of pharmaceutical and personal care products (PPCPs) in receiving waters. A novel photocatalyst, TiO2-doped low-silica X zeolite (TiO2-LSX), was used to study the degradation of the pharmaceutical compound, 17α-ethinylestradiol (EE2). The catalyst was synthesized and characterized using XRD, BET surface analysis, SEM-EDAX, and ICP-OES. The effects of different UV light intensities, initial EE2 concentrations, and catalyst dosages on the EE2 removal efficiency were studied. A higher EE2 removal efficiency was attained with UV-TiO2-LSX when compared with UV-TiO2 or UV alone. The EE2 degradation process followed pseudo-first-order kinetics. A comprehensive empirical model was developed to describe the EE2 degradation kinetics under different conditions using multiple linear regression analysis. The EE2 degradation mechanism was proposed based on molecular calculations, identification of photoproducts using HPLC-MS/MS, and reactive species quenching experiments; the results showed that oxidative degradation pathways initiated by hydroxyl radicals were predominant. This novel TiO2-doped zeolite system provides a promising application for the UV disinfection process in wastewater treatment plants.