Controlling crystal morphology of anisotropic zeolites with elemental composition

O.V. acknowledges the support of Charles University through the project “Grant Schemes at CU” (Reg. no. CZ.02.2.69/0.0/0.0/19_073/0016935). J.Č. acknowledges the support of the Czech Science Foundation through the project ExPro (19-27551X). W.J.R. acknowledges the financial support from the National Science Centre Poland, grant number 2020/37/B/ST5/01258. M.S. acknowledges the support of the Ministry of Education, Youth and Sports of the Czech Republic through ERC_CZ project LL 2104. This work was also supported by Ministerstvo Školství, Mládeže a Tělovýchovy as ERDF/ESF project TECHSCALE (Nos. CZ.02.01.01/00/22_008/0004587). R.E.M. acknowledges the European Research Council for funding through the AdG 787073 “ADOR” programme.The morphology of zeolite crystals strongly affects their textural, catalytic, and mechanical attributes. However, controlling zeolite crystal morphology without using modifiers or structure-directing agents remains a challenging task because of our limited understanding of the relationships between zeolite crystal shape, crystallization mechanism, and composition of the starting synthesis mixture. In this study, we aimed at developing a general method for controlling the morphology of zeolites by assessing the impact of the Si/T molar ratio of the synthesis gel on the growth rate of zeolite crystals in various crystallographic directions and on the final crystal morphology of the UTL germanosilicate with a 2D system of intersecting 14- and 12-ring pores. Our results showed that flat UTL crystals progressively thicken with the Si/Ge molar ratio, demonstrating that Ge concentration controls the relative rate of crystal growth in the perpendicular direction to the pore system. The morphology of other zeolites and zeotypes with an anisotropic structure, including AFI (12R), IFR (12R), MWW (10–10R), and IWW (12–10–8R), can also be predicted based on their Si/T ratio, suggesting a systematic pattern across zeolite structures and in a wide range of zeolite framework elements. Combined, these findings introduce a facile and cost-efficient method for directly controlling crystal morphology of zeolites with anisotropic structures with a high potential for scale-up while providing further insights into the role of elemental composition in zeolite crystal growth.Peer reviewe

Norleucine, a natural occurrence in a novel ergot alkaloid γ-ergokryptinine

A novel natural peptide ergot alkaloid γ-ergokryptinine containing norleucine has been isolated from ergot sclerotia of the field-growing parasitic fungus Claviceps purpurea CCM 8059. Its structure was deduced from the NMR and mass spectral data. The final structural proof was provided by the crystal structure determination, which is the first X-ray structure of a natural Nle-containing secondary metabolite. The conformations of three ergopeptinines: γ-ergokryptinine, ergoladinine, and α-ergokryptinine were compared. © Springer-Verlag 2005

Predicted climate change will increase the truffle cultivation potential in central Europe.

Climate change affects the distribution of many species, including Burgundy and Périgord truffles in central and southern Europe, respectively. The cultivation potential of these high-prized cash crops under future warming, however, remains highly uncertain. Here we perform a literature review to define the ecological requirements for the growth of both truffle species. This information is used to develop niche models, and to estimate their cultivation potential in the Czech Republic under current (2020) and future (2050) climate conditions. The Burgundy truffle is already highly suitable for cultivation on ~ 14% of agricultural land in the Czech Republic (8486 km2), whereas only ~ 8% of the warmest part of southern Moravia are currently characterised by a low suitability for Périgord truffles (6418 km2). Though rising temperatures under RCP8.5 will reduce the highly suitable cultivation areas by 7%, the 250 km2 (3%) expansion under low-emission scenarios will stimulate Burgundy truffles to benefit from future warming. Doubling the moderate and expanding the highly suitable land by 352 km2 in 2050, the overall cultivation potential for Périgord truffles will rise substantially. Our findings suggest that Burgundy and Périgord truffles could become important high-value crops for many regions in central Europe with alkaline soils. Although associated with uncertainty, long-term investments in truffle cultivation could generate a wide range of ecological and economic benefits

Post-synthesis incorporation of Al into germanosilicate ITH zeolites : the influence of treatment conditions on the acidic properties and catalytic behavior in tetrahydropyranylation

M. S. thanks the Czech Science Foundation for support through the project 14-30898P. M. O. acknowledges the Czech Science Foundation for the project 13-17593P. R. E. M. thanks the EPSRC for funding (EP/K025112/1 and EP/L014475/1).Post-synthesis alumination of germanosilicate medium-pore ITH zeolites was shown to be an effective procedure for tuning their acidity. Treatment of ITH zeolites synthesized with different chemical compositions (i.e. Si/Ge = 2.5, 4.4 and 5.8) with aqueous Al(NO3)3 solution led to the formation of strong Brønsted and Lewis acid sites and an increasing fraction of ultramicro- and meso-pores in Ge-rich ITH samples (Si/Ge = 2.5 and 4.4). The concentration of Al incorporated into the framework increases with decreasing Si/Ge ratio of the parent ITH. The increasing temperature of alumination from 80 to 175 °C (HT conditions) resulted in (1) a 1.5-2-fold increase in the concentration of Brønsted acid sites formed and (2) a decreasing fraction of framework Al atoms detectable with base probe molecules (i.e. pyridine, 2,6-di-tert-butylpyridine), i.e. an increased concentration of the "inner" acid sites. The activity of prepared Al-substituted ITH zeolites in tetrahydropyranylation of alcohols is enhanced with increasing amount of accessible acid sites in bulky crystals (e.g. alumination at lower temperature) or with increasing total concentration of acid centres within tiny ITH crystals (e.g. alumination under HT conditions). This trend became more prominent with increasing kinetic diameter of the substrate molecules under investigation (methanol <1-propanol <1-hexanol).PostprintPeer reviewe

Structural analysis of IPC zeolites and related materials using positron annihilation spectroscopy and high-resolution argon adsorption

ETH authors thanks for the grant ETH 33 15-1. PE and JČ acknowledge the financial support from the Czech Science Foundation (P106/12/0189). JPR and JČ gratefully acknowledge the financial support from the European Union Seventh Framework Programme (FP7/ 2007-2013) under grant agreement no. 604307. HRTEM characterization was performed at the Advanced Microscopy Laboratory (LMA) and the research leading to these results has received funding from the European Union Seventh Framework Programme under Grant Agreement 312483 – ESTEEM2 (Integrated Infrastructure Initiative-I3).The advanced investigation of pore networks in isoreticular zeolites and mesoporous materials related to the IPC family was performed using high-resolution argon adsorption experiments coupled with the development of a state-of-the-art non-local density functional theory approach. The optimization of a kernel for model sorption isotherms for materials possessing the same layer structure, differing only in the interlayer connectivity (e.g. oxygen bridges, single- or double-four-ring building units, mesoscale pillars etc.) revealed remarkable differences in their porous systems. Using high-resolution adsorption data, the bimodal pore size distribution consistent with crystallographic data for IPC-6, IPC-7 and UTL samples is shown for the first time. A dynamic assessment by positron annihilation lifetime spectroscopy (PALS) provided complementary insights, simply distinguishing the enhanced accessibility of the pore network in samples incorporating mesoscale pillars and revealing the presence of a certain fraction of micropores undetected by gas sorption. Nonetheless, subtle differences in the pore size could not be discriminated based on the widely-applied Tao-Eldrup model. The combination of both methods can be useful for the advanced characterization of microporous, mesoporous and hierarchical materials.PostprintPeer reviewe

Differences in Activities of Antioxidant Superoxide Dismutase, Glutathione Peroxidase and Prooxidant Xanthine Oxidoreductase/Xanthine Oxidase in the Normal Corneal Epithelium of Various Mammals

Summary Under normal conditions, antioxidants at the corneal surface are balanced with the production of reactive oxygen species without any toxic effects. Danger from oxidative stress appears when natural antioxidants are overwhelmed leading to antioxidant/prooxidant imbalance. The aim of the present study was to examine the activities of enzymes contributing to the antioxidant/prooxidant balance in normal corneal epithelium of various mammals. The enzyme activities of antioxidant superoxide dismutase and glutathione peroxidase, as well as prooxidant xanthine oxidoreductase/xanthine oxidase were examined using biochemical methods. Results show that superoxide dismutase activity is high in rabbits and guinea pigs, whereas in pigs the activity is low and in cows it is nearly absent. In contrast, glutathione peroxidase activity is high in cows, pigs and rabbits, whereas in guinea pigs the activity is low. As far as prooxidant enzymes are concerned, elevated xanthine oxidoreductase/xanthine oxidase activities were found in rabbits, lower activities in guinea pigs, very low activity in cows and no activity in pigs. In conclusion, the above results demonstrate inter-species variations in activities of enzymes participating in antioxidant/prooxidant balance in the corneal epithelium. It is suggested that the levels of antioxidant and prooxidant enzymes studied in the corneal epithelium might be associated with the diurnal or nocturnal activity of animals. UV rays decompose hydrogen peroxide to damaging hydroxyl radicals and perhaps for this reason large animals with diurnal activity (cow, pig) require more effective peroxide removal (high glutathione peroxidase activity) together with the suppression of peroxide production (low superoxide dismutase activity, low xanthine oxidoreductase activity)

Synthesis and Characterisation of Hierarchically Structured Titanium Silicalite‐1 Zeolites with Large Intracrystalline Macropores

The successful synthesis of hierarchically structured titanium silicalite‐1 (TS‐1) with large intracrystalline macropores by steam‐assisted crystallisation of mesoporous silica particles is reported. The macropore topology was imaged in 3D by using electron tomography and synchrotron radiation‐based ptychographic X‐ray computed tomography, revealing interconnected macropores within the crystals accounting for about 30 % of the particle volume. The study of the macropore formation mechanism revealed that the mesoporous silica particles act as a sacrificial macropore template during the synthesis. Silicon‐to‐titanium ratio of the macroporous TS‐1 samples was successfully tuned from 100 to 44. The hierarchically structured TS‐1 exhibited high activity in the liquid phase epoxidation of 2‐octene with hydrogen peroxide. The hierarchically structured TS‐1 surpassed a conventional nano‐sized TS‐1 sample in terms of alkene conversion and showed comparable selectivity to the epoxide. The flexible synthesis route described here can be used to prepare hierarchical zeolites with improved mass transport properties for other selective oxidation reactions

Synthesis of ‘unfeasible’ zeolites

R.E.M. thanks the Royal Society and the E.P.S.R.C. (Grants EP/L014475/1, EP/K025112/1 and EP/K005499/1) for funding work in this area. J.Č. and P.N. acknowledge the Czech Science Foundation for the project of the Centre of Excellence (P106/12/G015) and the European Union Seventh Framework Programme (FP7/ 2007-­‐2013) under grant agreement n°604307. The research leading to these results has received funding from the European Union Seventh Framework Programme under Grant Agreement 312483 – ESTEEM2 (Integrated Infrastructure Initiative–I3). We thank Professor Wuzong Zhou and Dr. Fengjiao Yu for their expertise in TEM and Daniel Dawson for help with NMR.Zeolites are porous aluminosilicate materials that have found applications in many different technologies. However, although simulations suggest that there are millions of possible zeolite topologies, only a little over 200 zeolite frameworks of all compositions are currently known, of which about 50 are pure silica materials. This is known as the zeolite conundrum - why have only so few of all the possible structures been made? Several criteria have been formulated to explain why most zeolites are unfeasible synthesis targets. Here we demonstrate the synthesis of two such 'unfeasible' zeolites, IPC-9 and IPC-10, through the assembly-disassembly-organization-reassembly mechanism. These new high-silica zeolites have rare characteristics, such as windows that comprise odd-membered rings. Their synthesis opens up the possibility of preparing other zeolites that have not been accessible by traditional solvothermal synthetic methods. We envisage that these findings may lead to a step change in the number and types of zeolites available for future applications.PostprintPeer reviewe