Functionalization and Assembling of Inorganic Nanocontainers for Optical and Biomedical Applications

Devaux, A.; Cucinotta, Fabio; Kehr, Nermin Seda; Cola, Luisa De

doi:10.1002/9783527689897.ch09

Cited by 8 publications

(13 citation statements)

References 371 publications

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“…In this way, the confining environment of the pores could not only protect the guest molecules in hostile environments, but also favour the formation of organized supramolecular systems with technologically appealing collective properties [19]. This kind of strategy has been successfully applied to the encapsulation of molecules in crystalline microporous hosts, producing hybrid devices now actually exploited in solar energy harvesting [20,21,22,23,24] and theranostics [25,26,27,28]. On the other hand, the encapsulation of a macromolecular system, such as a protein, requires larger pores size, hence the need of mesoporous silica matrices [14,29].…”

Section: Introductionmentioning

confidence: 99%

Confining a Protein-Containing Water Nanodroplet inside Silica Nanochannels

Giussani

Tabacchi

Coluccia

et al. 2019

IJMS

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Incorporation of biological systems in water nanodroplets has recently emerged as a new frontier to investigate structural changes of biomolecules, with perspective applications in ultra-fast drug delivery. We report on the molecular dynamics of the digestive protein Pepsin subjected to a double confinement. The double confinement stemmed from embedding the protein inside a water nanodroplet, which in turn was caged in a nanochannel mimicking the mesoporous silica SBA-15. The nano-bio-droplet, whose size fits with the pore diameter, behaved differently depending on the protonation state of the pore surface silanols. Neutral channel sections allowed for the droplet to flow, while deprotonated sections acted as anchoring piers for the droplet. Inside the droplet, the protein, not directly bonded to the surface, showed a behavior similar to that reported for bulk water solutions, indicating that double confinement should not alter its catalytic activity. Our results suggest that nanobiodroplets, recently fabricated in volatile environments, can be encapsulated and stored in mesoporous silicas.

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Section: Introductionmentioning

confidence: 99%

Confining a Protein-Containing Water Nanodroplet inside Silica Nanochannels

Giussani

Tabacchi

Coluccia

et al. 2019

IJMS

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“…Computer simulations (Fois et al 2010b(Fois et al , 2012(Fois et al , 2013Manzano et al 2013;Zhou et al 2013;Cucinotta et al 2014;Viani et al 2016;Insuwan et al 2017;Doungmanee et al 2018;Pintus et al 2018) revealed key aspects of the structure, properties and behaviour of zeolite L/chromophore inclusion compounds, which are important building blocks for solar energy devices, theranostic agents, and new generations of pigments (Calzaferri et al 2003;Brühwiler et al 2009;Calzaferri 2012;Devaux et al 2014;Woodtli et al 2018). On the industrial side, Ti-containing zeolites are unparalleled as mild oxidation catalysts in sustainable petrochemistry (Corma et al 2000) including biomass conversion (Luo et al 2016), and also incredibly effective in the abatement of dangerous environmental pollutants -like aromatic sulfur compounds in diesel fuels responsible of car engines corrosion (Wang et al 2018a).…”

Section: Introductionmentioning

confidence: 99%

Computational Modeling of Open Framework Silicates: Probing Straight Bond Angles in Ferrierite Reveals Intriguing Links Between Mineralogy, Nanomaterial Science and Technological Applications

Trudu¹,

Tabacchi²,

Fois³

2019

Preprint

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For several decades, zeolites have acted as a porous bridge intimately connecting mineralogy to advanced technology through industrial applications. Such a key linkage between mineral and material science has been reinvigorated by the numerous successes of computational modeling. The intriguing<br>relationships between synthetic zeolites and their natural counterparts unveiled by theoretical studies have greatly contributed to improve the properties and practical applications of zeolite-based materials in various technological areas ranging from industrial catalysis, to environmental protection, up to<br>advanced optics, electronics, and solar energy harvesting. To pinpoint the key role of modeling in zeolite science, we focus herein on a simple yet instructive example of computational-driven problemsolving: can tetrahedral frameworks sustain straight (i.e. 180°) Si-O-Si bond angles? Indeed, the true crystal symmetry of zeolite ferrierite, especially in its all-silica form, has been intensely debated for 30 years before being solved in the Pmnn space group. Yet there are indications that an Immm structure, featuring energetically unfavourable flat (180°) Si-O-Si angles, could be formed at high temperature. To provide insight on this issue, we perform density functional theory optimizations and frequency calculations of all-silica ferrierite in both the Pmnn and Immm space groups. Our results indicate that Pmnn is more stable than Immm, in line with experiments. While the Pmnn structure is a true minimum in the free energy profile of ferrierite, the Immm structure has four imaginary frequency vibrations, two of which are localized on the 180° Si-O-Si angles. This suggest that ferrierites with Immm symmetry may be classified as metastable phases. Such a designation is also supported by firstprinciples molecular dynamics on Immm FER, evidencing that the average value of 180° actually results from Si-O-Si angle inversion. An exciting implication of this study with interesting geological and technological consequences is the possible association of flat Si-O-Si angles experimentally detected in open-framework silicates to metastable structures characterized by pore openings more circular than in the corresponding equilibrium structures. Such a lower channel ellipticity might play an important role in sorption phenomena, which are ubiquitous in geological processes and industrial applications alike. More in general, this work underlines how highly complex processes involving zeolite materials can be understood and accurately captured using theoretical techniques.<div><br></div><div><br></div>

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“…For these reasons, the realization of organized supramolecular systems in nanoporous frameworks is a steadily growing research area 9 . Zeolite cages have long been exploited to create confined nanostructures for optoelectronics 11 , like metal clusters, [12][13][14] quantum dots, 10,15,16 or lanthanide complexes 17 , and the practical applications of zeolite-based functional composites from effect pigments 18 , to theranostic agents 19,20 , keep on increasing in number and performances.…”

Section: Introductionmentioning

confidence: 99%

“…In contrast, the implementation of zeolite L hybrids (framework type: LTL) 72 has already accomplished practical application in strategic areas such as solar energy harvesting, 5,[73][74][75][76][77][78][79] photonics, [80][81][82] and nano-medical technology. 19,[83][84][85] The fabrication of confined architectures of chromophores for photon transport 5,9,57,[86][87][88] and other light-operated systems 17,19,89 has made impressive progresses in the last few years. On the other hand, it is still to clarify how the microscopic interactions within the cages govern the peculiar behavior of guest species, and thus the commercially useful features of zeolite L devices.…”

Section: Introductionmentioning

confidence: 99%

The Different Organization of Water in Zeolite L and Its MOF Mimic

Tabacchi¹,

Fois²

2019

Preprint

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Abstract:<div>Confinement of molecules inside one dimensional arrays of channel-shaped cavities has led to an impressive number of technologically interesting materials. However, the interactions governing the properties of the supramolecular aggregates still remain obscure, even in the case of the most common guest molecule: water. Herein, we use computational chemistry methods (#compchem) to study the water organization inside two different channel-type environments: zeolite L – a widely used matrix for inclusion of dye molecules, and ZLMOF – the closest metal-organic-framework mimic of zeolite L. In ZLMOF, the methyl groups of the ligands protrude inside the channels, creating nearly isolated nanocavities. These cavities host well-separated ring-shaped clusters of water molecules, dominated mainly by water-water hydrogen bonds. ZLMOF channels thus provide arrays of „isolated supramolecule“ environments, which might be exploited for the individual confinement of small species with interesting optical or catalytic properties. In contrast, the one dimensional nanochannels of zeolite L contain a continuous supramolecular structure, governed by the water interactions with potassium cations and by water-water hydrogen bonds. Water molecules impart a significant energetic stabilization to both materials, which increases by increasing the water content in ZLMOF, while the opposite trend is observed in zeolite L. The water network in zeolite L contains an intriguing hyper-coordinated structure, where a water molecule is surrounded by 5 strong hydrogen bonds. Such a structure, here described for the first time in zeolites, can be considered as a water pre-dissociation complex and might explain the experimentally detected high proton activity in zeolite L nanochannels. </div>

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Functionalization and Assembling of Inorganic Nanocontainers for Optical and Biomedical Applications

Cited by 8 publications

References 371 publications

Confining a Protein-Containing Water Nanodroplet inside Silica Nanochannels

Confining a Protein-Containing Water Nanodroplet inside Silica Nanochannels

Computational Modeling of Open Framework Silicates: Probing Straight Bond Angles in Ferrierite Reveals Intriguing Links Between Mineralogy, Nanomaterial Science and Technological Applications

The Different Organization of Water in Zeolite L and Its MOF Mimic

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