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1.
Appl Environ Microbiol ; 90(4): e0235523, 2024 Apr 17.
Artículo en Inglés | MEDLINE | ID: mdl-38535171

RESUMEN

Halophyte-based remediation emerges as a novel strategy for ameliorating saline soils, offering a sustainable alternative to conventional leaching methods. While bioremediation is recognized for its ability to energize soil fertility and structure, the complex interplays among plant traits, soil functions, and soil microbial diversity remain greatly unknown. Here, we conducted a 5-year field experiment involving the continuous cultivation of the annual halophyte Suaeda salsa in saline soils to explore soil microbial diversity and their relationships with plant traits and soil functions. Our findings demonstrate that a decline in soil salinity corresponded with increases in the biomass and seed yield of S. salsa, which sustained a consistent seed oil content of approximately 22% across various salinity levels. Significantly, prolonged cultivation of halophytes substantially augmented soil microbial diversity, particularly from the third year of cultivation. Moreover, we identified positive associations between soil multifunctionality, seed yield, and taxonomic richness within a pivotal microbial network module. Soils enriched with taxa from this module showed enhanced multifunctionality and greater seed yields, correlating with the presence of functional genes implicated in nitrogen fixation and nitrification. Genomic analysis suggests that these taxa have elevated gene copy numbers of crucial functional genes related to nutrient cycling. Overall, our study emphasizes that the continuous cultivation of S. salsa enhances soil microbial diversity and recovers soil multifunctionality, expanding the understanding of plant-soil-microbe feedback in bioremediation.IMPORTANCEThe restoration of saline soils utilizing euhalophytes offers a viable alternative to conventional irrigation techniques for salt abatement and soil quality enhancement. The ongoing cultivation of the annual Suaeda salsa and its associated plant traits, soil microbial diversity, and functionalities are, however, largely underexplored. Our investigation sheds light on these dynamics, revealing that cultivation of S. salsa sustains robust plant productivity while fostering soil microbial diversity and multifunctionality. Notably, the links between enhanced soil multifunctionality, increased seed yield, and network-dependent taxa were found, emphasizing the importance of key microbial taxa linked with functional genes vital to nitrogen fixation and nitrification. These findings introduce a novel understanding of the role of soil microbes in bioremediation and advance our knowledge of the ecological processes that are vital for the rehabilitation of saline environments.


Asunto(s)
Chenopodiaceae , Suelo , Suelo/química , Solución Salina , Cloruro de Sodio , Nitrificación , Plantas Tolerantes a la Sal
2.
New Phytol ; 242(3): 960-974, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38402527

RESUMEN

The link between above- and belowground communities is a key uncertainty in drought and rewetting effects on forest carbon (C) cycle. In young beech model ecosystems and mature naturally dry pine forest exposed to 15-yr-long irrigation, we performed 13C pulse labeling experiments, one during drought and one 2 wk after rewetting, tracing tree assimilates into rhizosphere communities. The 13C pulses applied in tree crowns reached soil microbial communities of the young and mature forests one and 4 d later, respectively. Drought decreased the transfer of labeled assimilates relative to the irrigation treatment. The 13C label in phospholipid fatty acids (PLFAs) indicated greater drought reduction of assimilate incorporation by fungi (-85%) than by gram-positive (-43%) and gram-negative bacteria (-58%). 13C label incorporation was more strongly reduced for PLFAs (cell membrane) than for microbial cytoplasm extracted by chloroform. This suggests that fresh rhizodeposits are predominantly used for osmoregulation or storage under drought, at the expense of new cell formation. Two weeks after rewetting, 13C enrichment in PLFAs was greater in previously dry than in continuously moist soils. Drought and rewetting effects were greater in beech systems than in pine forest. Belowground C allocation and rhizosphere communities are highly resilient to drought.


Asunto(s)
Pinus , Resiliencia Psicológica , Ecosistema , Rizosfera , Resistencia a la Sequía , Suelo , Bosques , Carbono/metabolismo , Árboles/fisiología , Sequías , Ácidos Grasos/metabolismo , Fosfolípidos/metabolismo , Pinus/metabolismo , Microbiología del Suelo
3.
J Exp Bot ; 75(2): 594-604, 2024 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-37882632

RESUMEN

Root architectural phenotypes are promising targets for crop breeding, but root architectural effects on microbial associations in agricultural fields are not well understood. Architecture determines the location of microbial associations within root systems, which, when integrated with soil vertical gradients, determines the functions and the metabolic capability of rhizosphere microbial communities. We argue that variation in root architecture in crops has important implications for root exudation, microbial recruitment and function, and the decomposition and fate of root tissues and exudates. Recent research has shown that the root microbiome changes along root axes and among root classes, that root tips have a unique microbiome, and that root exudates change within the root system depending on soil physicochemical conditions. Although fresh exudates are produced in larger amounts in root tips, the rhizosphere of mature root segments also plays a role in influencing soil vertical gradients. We argue that more research is needed to understand specific root phenotypes that structure microbial associations and discuss candidate root phenotypes that may determine the location of microbial hotspots within root systems with relevance to agricultural systems.


Asunto(s)
Raíces de Plantas , Rizosfera , Raíces de Plantas/metabolismo , Microbiología del Suelo , Fitomejoramiento , Suelo/química
4.
Chemistry ; 30(6): e202303673, 2024 Jan 26.
Artículo en Inglés | MEDLINE | ID: mdl-37963087

RESUMEN

Separation and reuse of the catalytically active metal complexes are persistent issues in homogeneous catalysis. Supported Ionic Liquid Phase (SILP) catalysts, where the catalytic center is dissolved in a thin film of a stable ionic liquid, deposited on a solid support, present a promising alternative. However, the dissolution of the metal center in the film leaves little control over its position and its activity. We present here four novel, task-specific ionic liquids [FPhn ImH R]I (n=1, 2; R=PEG2 , C12 H25 ), designed to self-assemble on a silica surface without any covalent bonding and offering a metal binding site in a controlled distance to the support. Advanced multinuclear solid-state NMR spectroscopic techniques under Magic Angle Spinning, complemented by molecular dynamics (MD) simulations, allow us to determine their molecular conformation when deposited inside SBA-15 as a model silica support. We provide here conceptual proof for a rational design of ionic liquids self-assembling into thin films, opening an avenue for a second, improved generation of SILP catalysts.

5.
Langmuir ; 40(25): 12853-12867, 2024 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-38861921

RESUMEN

We have developed a comprehensive strategy for quantitatively assessing the hydrophilicity/hydrophobicity of nanoporous materials by combining advanced adsorption studies, novel liquid intrusion techniques, and solid-state NMR spectroscopy. For this, we have chosen a well-defined system of model materials, i.e., the highly ordered mesoporous silica molecular sieve SBA-15 in its pristine state and functionalized with different amounts of trimethylsilyl (TMS) groups, allowing one to accurately tailor the surface chemistry while maintaining the well-defined pore structure. For an absolute quantification of the trimethylsilyl group density, quantitative 1H solid-state NMR spectroscopy under magic angle spinning was employed. A full textural characterization of the materials was obtained by high-resolution argon 87 K adsorption, coupled with the application of dedicated methods based on nonlocal-density functional theory (NLDFT). Based on the known texture of the model materials, we developed a novel methodology allowing one to determine the effective contact angle of water adsorbed on the pore surfaces from complete wetting to nonwetting, constituting a powerful parameter for the characterization of the surface chemistry inside porous materials. The surface chemistry was found to vary from hydrophilic to hydrophobic as the TMS functionalization content was increased. For wetting and partially wetting surfaces, pore condensation of water is observed at pressures P smaller than the bulk saturation pressure p0 (i.e., at p/p0 < 1) and the effective contact angle of water on the pore walls could be derived from the water sorption isotherms. However, for nonwetting surfaces, pore condensation occurs at pressures above the saturation pressure (i.e., at p/p0 > 1). In this case, we investigated the pore filling of water (i.e., the vapor-liquid phase transition) by the application of a novel, liquid water intrusion/extrusion methodology, allowing one to derive the effective contact angle of water on the pore walls even in the case of nonwetting. Complementary molecular simulations provide density profiles of water on pristine and TMS-grafted silica surfaces (mimicking the tailored, functionalized experimental silica surfaces), which allow for a molecular view on the water adsorbate structure. Summarizing, we present a comprehensive and reliable methodology for quantitatively assessing the hydrophilicity/hydrophobicity of siliceous nanoporous materials, which has the potential to optimize applications in heterogeneous catalysis and separation (e.g., chromatography).

6.
Arthroscopy ; 2024 Jun 04.
Artículo en Inglés | MEDLINE | ID: mdl-38844015

RESUMEN

PURPOSE: To compare the sagittal position of the tibial tubercle in relation the trochlea groove in patients with and without trochlear dysplasia (TD). METHODS: All patients between January 2017 and December 2020 with high-grade TD (Dejour type B, C and D) who underwent patellar stabilizing surgery for patellar instability at a single institution were included in the current study. Patients without preoperative magnetic resonance imaging (MRI), any prior osteotomy on the affected lower extremity or cruciate ligament insufficiency were excluded. Patients who underwent knee arthroscopy for meniscal repair/debridement without any signs of TD or any of the above-mentioned criteria served as control group. Preoperative magnetic-resonance imaging (MRI) was retrospectively assessed to compare common patellofemoral anatomic parameters including patellar angle, patellar tilt, patella morphology according to Wiberg, Caton-Deschamps index (CDI), PF index, trochlear sulcus angle, sulcus depth, lateral inclination angle of the trochlea, tibiofemoral rotation, TTTG and sTTTG distance, between both groups. The sTTTG is measured as the distance between the nadir point of the cartilaginous trochlear groove and the most anterior point of the tibial tubercle on an axial MRI. Independent predictors for the sTTTG were assessed for patients with TD. RESULTS: Patients with high-grade TD (n=82) showed an increased patellar tilt, CDI, trochlear sulcus angle, lateral tibiofemoral rotation angle, TTTG and sTTTG (9.16 ± 4.47 mm vs. 2.66 ± 4.21 mm) compared to the control group (n=83) (p<0.001). Patellar angle, PF index, sulcus depth and lateral inclination angle of the trochlear were significantly decreased in the TD group (p<0.001). The sTTTG was similar in all TD groups (n.s.). Among patients with TD, both tibiofemoral rotation and patellar height were independent predictors of the sTTTG (p<0.05). CONCLUSION: Patients with high-grade TD show not only abnormal values in common patellofemoral instability risk factors, but also a significantly increased sTTTG compared to patients without TD. LEVEL OF EVIDENCE: Retrospective case comparative study, III.

7.
Knee Surg Sports Traumatol Arthrosc ; 32(5): 1179-1186, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38504510

RESUMEN

PURPOSE: The multifactorial nature of patellofemoral instability requires a comprehensive assessment of the affected patients. While an association between tibial tuberosity (TT) torsion and patellofemoral instability is known, its specific effect has not yet been investigated. This study investigated the effect of TT torsion on patellofemoral instability. METHODS: This retrospective cohort study compared patients who underwent surgical intervention for patellofemoral instability and asymptomatic controls. TT torsion was measured in addition to other commonly assessed risk factors for patellofemoral instability using standardised computed tomography (CT) data of the lower extremities. The diagnostic performances of the assessed parameters were evaluated using receiver operating characteristic curve analysis and odds ratios (ORs) were calculated. RESULTS: The patellofemoral instability group consisted of 79 knees, compared to 72 knees in the asymptomatic control group. Both groups differed significantly in all assessed parameters (p < 0.001), except for tibial torsion (n.s.). Among all parameters, TT torsion presented the best diagnostic performance for predicting patellar instability with an area under the curve of 0.95 (95% confidence interval [CI], 0.91-0.98; p < 0.001). A cut-off value of 17.7° yielded a 0.87 sensitivity and 0.89 specificity to predict patellar instability (OR, 55.2; 95% CI, 20.5-148.6; p < 0.001). CONCLUSION: Among the evaluated risk factors, TT torsion had the highest predictive value for patellofemoral instability. Patients with TT torsions ≥ 17.7° showed a 55-fold increased probability of patellofemoral instability. Therefore, TT torsion should be included in the assessment of patients with patellofemoral instability. LEVEL OF EVIDENCE: Level III.


Asunto(s)
Inestabilidad de la Articulación , Articulación Patelofemoral , Tibia , Tomografía Computarizada por Rayos X , Humanos , Inestabilidad de la Articulación/cirugía , Inestabilidad de la Articulación/diagnóstico , Masculino , Femenino , Estudios Retrospectivos , Adulto , Articulación Patelofemoral/diagnóstico por imagen , Articulación Patelofemoral/cirugía , Tibia/cirugía , Tibia/diagnóstico por imagen , Valor Predictivo de las Pruebas , Adulto Joven , Factores de Riesgo , Anomalía Torsional/cirugía , Anomalía Torsional/diagnóstico , Anomalía Torsional/diagnóstico por imagen , Curva ROC , Adolescente
8.
J Am Chem Soc ; 144(29): 13079-13083, 2022 07 27.
Artículo en Inglés | MEDLINE | ID: mdl-35819401

RESUMEN

Using EPR and HYSCORE spectroscopies in conjunction with ab initio calculations, we assess the structure of framework-bound monomeric hydroxo-CuII in copper-loaded chabazite (CHA). The species is an interfacial distorted square-planar [CuIIOH(O-8MRs)3] complex located at eight-membered-ring windows, displaying three coordinating bonds with zeolite lattice oxygens and the hydroxo ligand hydrogen-bonded to the cage. The complex has a distinctive EPR signature with g = [2.072 2.072 2.290], CuA= [30 30 410] MHz, and HA = [-13.0 -4.5 +11.5] MHz, distinctively different from other CuII species in CHA.


Asunto(s)
Zeolitas , Cobre/química , Cristalografía por Rayos X , Ligandos
9.
Mol Ecol ; 30(17): 4305-4320, 2021 09.
Artículo en Inglés | MEDLINE | ID: mdl-34160856

RESUMEN

Despite the importance of soil microorganisms for ecosystem services, long-term surveys of their communities are largely missing. Using metabarcoding, we assessed temporal dynamics of soil bacterial and fungal communities in three land-use types, i.e., arable land, permanent grassland, and forest, over five years. Soil microbial communities remained relatively stable and differences over time were smaller than those among sites. Temporal variability was highest in arable soils. Indications for consistent shifts in community structure over five years were only detected at one site for bacteria and at two sites for fungi, which provided further support for long-term stability of soil microbial communities. A sliding window analysis was applied to assess the effect of OTU abundance on community structures. Partial communities with decreasing OTU abundances revealed a gradually decreasing structural similarity with entire communities. This contrasted with the steep decline of OTU abundances, as subsets of rare OTUs (<0.01%) revealed correlations of up to 0.97 and 0.81 with the entire bacterial and fungal communities. Finally, 23.4% of bacterial and 19.8% of fungal OTUs were identified as scarce, i.e., neither belonging to site-cores nor correlating to environmental factors, while 67.3% of bacterial and 64.9% of fungal OTUs were identified as rare but not scarce. Our results demonstrate high stability of soil microbial communities in their abundant and rare fractions over five years. This provides a step towards defining site-specific normal operating ranges of soil microbial communities, which is a prerequisite for detecting community shifts that may occur due to changing environmental conditions or anthropogenic activities.


Asunto(s)
Microbiota , Micobioma , Bacterias/genética , Hongos/genética , Microbiota/genética , Micobioma/genética , Suelo , Microbiología del Suelo
10.
Hautarzt ; 72(6): 528-532, 2021 Jun.
Artículo en Alemán | MEDLINE | ID: mdl-33180178

RESUMEN

Chronic prurigo is characterized by persistent itching und partly accompanied by secondary skin excoriation. Diagnostic evaluation is of special relevance and atopic diathesis is a frequent pathogenic factor. We present a patient with prurigo of multifactorial etiology (atopic diathesis, impaired kidney function, diabetes and polyneuropathy). After several unsuccessful prior treatment approaches, the patient was treated with dupilumab, which resulted in a tremendous improvement of itching, skin lesions, and quality of life.


Asunto(s)
Prurigo , Anticuerpos Monoclonales Humanizados , Humanos , Prurigo/diagnóstico , Prurigo/tratamiento farmacológico , Prurito/tratamiento farmacológico , Calidad de Vida
11.
Bioinformatics ; 34(23): 4027-4033, 2018 12 01.
Artículo en Inglés | MEDLINE | ID: mdl-29912385

RESUMEN

Motivation: Correct taxonomic identification of DNA sequences is central to studies of biodiversity using both shotgun metagenomic and metabarcoding approaches. However, no genetic marker gives sufficient performance across all the biological kingdoms, hampering studies of taxonomic diversity in many groups of organisms. This has led to the adoption of a range of genetic markers for DNA metabarcoding. While many taxonomic classification software tools can be re-trained on these genetic markers, they are often designed with assumptions that impair their utility on genes other than the SSU and LSU rRNA. Here, we present an update to Metaxa2 that enables the use of any genetic marker for taxonomic classification of metagenome and amplicon sequence data. Results: We evaluated the Metaxa2 Database Builder on 11 commonly used barcoding regions and found that while there are wide differences in performance between different genetic markers, our software performs satisfactorily provided that the input taxonomy and sequence data are of high quality. Availability and implementation: Freely available on the web as part of the Metaxa2 package at http://microbiology.se/software/metaxa2/. Supplementary information: Supplementary data are available at Bioinformatics online.


Asunto(s)
Código de Barras del ADN Taxonómico , Marcadores Genéticos , Metagenómica , Filogenia , Programas Informáticos , Biología Computacional
12.
PLoS Biol ; 14(2): e1002378, 2016 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-26871440

RESUMEN

Almost all higher organisms, including plants, insects, and mammals, are colonized by complex microbial communities and harbor a microbiome. Emerging studies with plants reveal that these microbiomes are structured and form complex, interconnected microbial networks. Within these networks, different taxa have different roles, and keystone species have been identified that could be crucial for plant health and ecosystem functioning. A new paper in this issue of PLOS Biology by Agler et al. highlights the presence of microbial hubs in these networks that may act as mediators between the plant and its microbiome. A next major frontier is now to link microbiome composition to function. In order to do this, we present a number of hypothetical examples of how microbiome diversity and function potentially influence host performance.


Asunto(s)
Arabidopsis/microbiología , Microbiota
13.
Ecol Appl ; 29(7): e01971, 2019 10.
Artículo en Inglés | MEDLINE | ID: mdl-31302945

RESUMEN

The international seed trade is considered relatively safe from a phytosanitary point of view and is therefore less regulated than trade in other plants for planting. However, the pests carried by traded seeds are not well known. We assessed insects and fungi in 58 traded seed lots of 11 gymnosperm and angiosperm tree species from North America, Europe, and Asia. Insects were detected by X-raying and molecular methods. The fungal community was characterized using high-throughput sequencing (HTS) and by growing fungi on non-selective agar. About 30% of the seed lots contained insect larvae. Gymnosperms contained mostly hymenopteran (Megastigmus spp.) and dipteran (Cecidomyiidae) larvae, while angiosperms contained lepidopteran (Cydia latiferreana) and coleopteran (Curculio spp.) larvae. HTS indicated the presence of fungi in all seed lots and fungi grew on non-selective agar from 96% of the seed lots. Fungal abundance and diversity were much higher than insect diversity and abundance, especially in angiosperm seeds. Almost 50% of all fungal exact sequence variants (ESVs) found in angiosperms were potential pathogens, in comparison with around 30% of potentially pathogenic ESVs found in gymnosperms. The results of this study indicate that seeds may pose a greater risk of pest introduction than previously believed or accounted for. A rapid risk assessment suggests that only a small number of species identified in this study is of phytosanitary concern. However, more research is needed to enable better risk assessment, especially to increase knowledge about the potential for transmission of fungi to seedlings and the host range and impact of identified species.


Asunto(s)
Bosques , Árboles , Animales , Europa (Continente) , América del Norte , Semillas
15.
New Phytol ; 217(4): 1737-1748, 2018 03.
Artículo en Inglés | MEDLINE | ID: mdl-29243821

RESUMEN

Ancient DNA from historical and subfossil wood has a great potential to provide new insights into the history of tree populations. However, its extraction and analysis have not become routine, mainly because contamination of the wood with modern plant material can complicate the verification of genetic information. Here, we used sapwood tissue from 22 subfossil pines that were growing c. 13 000 yr bp in Zurich, Switzerland. We developed and evaluated protocols to eliminate surface contamination, and we tested ancient DNA authenticity based on plastid DNA metabarcoding and the assessment of post-mortem DNA damage. A novel approach using laser irradiation coupled with bleaching and surface removal was most efficient in eliminating contaminating DNA. DNA metabarcoding confirmed which ancient DNA samples repeatedly amplified pine DNA and were free of exogenous plant taxa. Pine DNA sequences of these samples showed a high degree of cytosine to thymine mismatches, typical of post-mortem damage. Stringent decontamination of wood surfaces combined with DNA metabarcoding and assessment of post-mortem DNA damage allowed us to authenticate ancient DNA retrieved from the oldest Late Glacial pine forest. These techniques can be applied to any subfossil wood and are likely to improve the accessibility of relict wood for genome-scale ancient DNA studies.


Asunto(s)
ADN de Plantas/aislamiento & purificación , Bosques , Fósiles , Pinus/genética , Madera/genética , ADN de Plantas/genética , Descontaminación , Picea/genética , Pinus/clasificación , Especificidad de la Especie
16.
Ecology ; 99(3): 714-723, 2018 03.
Artículo en Inglés | MEDLINE | ID: mdl-29323701

RESUMEN

Biodiversity enhances ecosystem functions such as biomass production and nutrient cycling. Although the majority of the terrestrial biodiversity is hidden in soils, very little is known about the importance of the diversity of microbial communities for soil functioning. Here, we tested effects of biodiversity on the functioning of methanotrophs, a specialized group of soil bacteria that plays a key role in mediating greenhouse gas emissions from soils. Using pure strains of methanotrophic bacteria, we assembled artificial communities of different diversity levels, with which we inoculated sterile soil microcosms. To assess the functioning of these communities, we measured methane oxidation by gas chromatography throughout the experiment and determined changes in community composition and community size at several time points by quantitative PCR and sequencing. We demonstrate that microbial diversity had a positive overyielding effect on methane oxidation, in particular at the beginning of the experiment. This higher assimilation of CH4 at high diversity translated into increased growth and significantly larger communities towards the end of the study. The overyielding of mixtures with respect to CH4 consumption and community size were positively correlated. The temporal CH4 consumption profiles of strain monocultures differed, raising the possibility that temporal complementarity of component strains drove the observed community-level strain richness effects; however, the community niche metric we derived from the temporal activity profiles did not explain the observed strain richness effect. The strain richness effect also was unrelated to both the phylogenetic and functional trait diversity of mixed communities. Overall, our results suggest that positive biodiversity-ecosystem-function relationships show similar patterns across different scales and may be widespread in nature. Additionally, biodiversity is probably also important in natural methanotrophic communities for the ecosystem function methane oxidation. Therefore, maintaining soil conditions that support a high diversity of methanotrophs may help to reduce the emission of the greenhouse gas methane.


Asunto(s)
Metano , Microbiología del Suelo , Bacterias/clasificación , Biodiversidad , Filogenia
17.
Nanotechnology ; 29(3): 035203, 2018 Jan 19.
Artículo en Inglés | MEDLINE | ID: mdl-29176051

RESUMEN

The electrical transport properties of short-channel transistors based on single-walled carbon nanotubes (CNT) are significantly affected by bundling along with solution processing. We report that especially high off currents of CNT transistors are not only related to the incorporation of metallic CNTs but also to the incorporation of CNT bundles. By applying device passivation with poly(4-vinylpyridine), the impact of CNT bundling on the device performance can be strongly reduced due to increased gate efficiency as well as reduced oxygen and water-induced p-type doping, boosting essential field-effect transistor performance parameters by several orders of magnitude. Moreover, this passivation approach allows the hysteresis and threshold voltage of CNT transistors to be tuned.

18.
J Chem Phys ; 148(19): 193837, 2018 May 21.
Artículo en Inglés | MEDLINE | ID: mdl-30307227

RESUMEN

A new synthesis route for the zeolitic imidazolate framework ZIF-4 using imidazolium imidazolate is reported. Additionally, the ionic liquid-derived material is compared to conventional ZIF-4 with respect to the powder X-ray diffraction pattern pattern, nitrogen uptake, particle size, and separation potential for olefin/paraffin gas mixtures. Higher synthesis yields were obtained, and the different particle size affected the performance in the separation of ethane and ethylene.

19.
Molecules ; 23(3)2018 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-29543777

RESUMEN

Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here, we present such data, obtained by monitoring the chain length dependence of the uptake of n-alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n-butane was observed, followed by an increase for n-pentane, and another decrease for n-hexane. This observation was confirmed by uptake measurements with n-butane/n-pentane mixtures, which yield faster uptake of n-pentane. Further evidence is provided by the observation of overshooting effects, i.e., by transient n-pentane concentrations exceeding the (eventually attained) equilibrium value. Accompanying grand canonical Monte Carlo simulations reveal, for the larger n-alkanes, significant differences between the adsorbed and gas phase molecular configurations, indicating strong confinement effects within ZIF-4, which, with increasing chain length, may be expected to give rise to configurational shifts facilitating molecular propagation at particular chain lengths.


Asunto(s)
Alcanos/química , Estructuras Metalorgánicas/química , Zeolitas/química , Estructura Molecular , Método de Montecarlo
20.
Molecules ; 23(4)2018 Apr 11.
Artículo en Inglés | MEDLINE | ID: mdl-29641508

RESUMEN

In this study, two zeolitic imidazolate frameworks (ZIFs) called ZIF-4 and ZIF-zni (zni is the network topology) were characterized by sorption studies regarding their paraffin/olefin separation potential. In particular, equilibrated pure and mixed gas adsorption isotherms of ethane and ethene were recorded at 293 K up to 3 MPa. ZIF-4 exhibits selectivities for ethane in the range of 1.5-3, which is promising for continuous pressure swing adsorption (PSA). ZIF-4 shows high cycle stability with promising separation potential regarding ethane, which results in purification of the more industrial desired olefin. Furthermore, both ZIF materials were implemented in Matrimid to prepare a mixed matrix membrane (MMM) and were used in the continuous separation of a propane/propene mixture. The separation performance of the neat polymer is drastically increased after embedding porous ZIF-4 crystals in the Matrimid matrix, especially at higher feed pressures (3-5 barg). Due to the smaller kinetic diameter of the olefin, the permeability is higher compared to the paraffin.


Asunto(s)
Alquenos/aislamiento & purificación , Imidazoles/química , Parafina/química , Zeolitas/química , Adsorción , Etano/química , Membranas Artificiales , Modelos Moleculares , Porosidad
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