One-dimensional self-assembly of perylene-diimide dyes by unidirectional transit of zeolite channel openings

Confined supramolecular architectures of chromophores are key components in artificial antenna composites for solar energy harvesting and storage. A typical fabrication process, based on the insertion of dye molecules into zeolite channels, is still unknown at the molecular level. We show that slipping of perylene diimide dyes into the one-dimensional channels of zeolite L and travelling inside is only possible because of steric-interaction-induced cooperative vibrational modes of the host and the guest. The funnel-like structure of the channel opening, larger at the entrance, along with a directionally asymmetric entrance\u2013exit probability, ensures a favorable self-assembly process of the perylene units

Confining a protein-containing water nanodroplet inside silica nanochannels

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.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

On the Compatibility Criteria for Protein Encapsulation inside Mesoporous Materials

The properties of the enzyme pepsin, relevant to its incorporation inside the channels of mesoporous silica materials in the preparation of bioinorganic hybrids, are highlighted by molecular dynamics simulations of aqueous solutions of the protein under conditions optimal for encapsulation in SBA-15. The protein size, shape, flexibility and surface properties are calculated with the aim of deriving general accessibility/compatibility criteria favouring encapsulation inside mesoporous systems

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

Transition metal complexes with \u3b2-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn \u3b2-diketonate-diamine complex Zn(hfa)2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N\u2032,N\u2032-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures

Energy Transfer from Magnetic Iron Oxide Nanoparticles: Implications for Magnetic Hyperthermia

Magnetic iron oxide nanoparticles (IONPs) have gained momentum in the field of biomedical applications. They can be remotely heated via alternating magnetic fields, and such heat can be transferred from the IONPs to the local environment. However, the microscopic mechanism of heat transfer is still debated. By X-ray total scattering experiments and first-principles simulations, we show how such heat transfer can occur. After establishing structural and microstructural properties of the maghemite phase of the IONPs, we built a maghemite model functionalized with aminoalkoxysilane, a molecule used to anchor (bio)molecules to oxide surfaces. By a linear response theory approach, we reveal that a resonance mechanism is responsible for the heat transfer from the IONPs to the surroundings. Heat transfer occurs not only via covalent linkages with the IONP but also through the solvent hydrogen-bond network. This result may pave the way to exploit the directional control of the heat flow from the IONPs to the anchored molecules─i.e., antibiotics, therapeutics, and enzymes─for their activation or release in a broader range of medical and industrial applications

Supramolecular organization of water–ethanol solution in ferrierite under pressure

Turning disorder into organization is a key issue in science. In particular, supramolecular organization induced by external stimuli has opened new paths for the bottom-up fabrication of nanostructures. By using a combined strategy based on the synergy of X-ray powder diffraction experiments and modeling studies [1], we showed that high pressure - in combination with the shape and space constraints of a hydrophobic all-silica zeolite - separate an ethanol–water liquid mixture into ethanol dimer wires and water tetramer squares (Figure 1). Separation of ethanol from water was accomplished in an all-silica ferrierite (Si-FER), by using as pressure transmitting medium a mixture of (1:3) ethanol and water in the 0.20 to 1.34 GPa pressure range. The system was studied in situ by high-pressure synchrotron X-ray powder diffraction at BM01 beamline at ESRF and refined via first principles modeling. Upon separation, the confined supramolecular blocks alternate in a binary two-dimensional architecture that remains stable upon complete pressure release. This unique architecture might rationalize the high selectivity of Si-FER in the separation of alcohol–water mixtures, a key issue in biofuel production. Moreover, as ferrierite is an exceptionally selective catalyst for biofuel synthesis in its hydrophilic Brønsted acid form, while only its pore entrances are actually exploited, we suggest that pressure could also be beneficial for the catalytic performance by enforcing the intrusion of reactants. These results support the combined use of high pressures and porous networks as a viable strategy for driving the organization of molecules or nano-objects towards complex, pre-defined patterns relevant for the realization of novel functional nanocomposites. [1] Arletti, R., Fois, E., Gigli, L., Vezzalini, G., Quartieri, S., Tabacchi, G. (2017) Angewandte Chemie, DOI: 10.1002/anie.20170021

Differential penetration of ethanol and water in Si-chabazite: high pressure dehydration of azeotrope solution..

This study is aimed to shed light on the mechanisms at the basis of the differential penetration of alcohol and water in hydrophobic zeolites at ambient (Pamb) and non-ambient pressure. Here we report the effects of the penetration of water and alcohol in an all-silica chabazite (Si-CHA) compressed with an ethanol/water azeotrope solution (ethanol: water=95.63 : 4.37 by mass %). We collected in situ synchrotron X-ray Powder Diffraction (XRPD) data in order to monitor the structural modifications induced by the fluid penetration and to investigate the guest-guest and host-guest interactions. First principles molecular dynamics simulations allowed to complete the structural description at high pressure, providing an atomistic level description of the guest-guest hydrogen bond network. For a comprehensive understanding of the processes involving the Si-CHA + azeotrope interactions, both the zeolite and the alcohol/water solution were firstly investigated separately under pressure. The results obtained prove that both H2O and ethanol penetrate Si-CHA porosities even at Pamb. However, while in these conditions the H2O/ethanol ratio adsorbed inside Si-CHA is similar to that of the external azeotrope solution, under pressure the zeolite extra-framework content corresponds to a composition much richer in H2O than the azeotrope one. Hence, our results suggest that a dehydration effect occurred on the azeotrope solution, promoted by pressure. In addition, the experiment performed to test the elastic behavior of Si-CHA with a nonpenetrating pressure transmitting medium interestingly indicates that Si-pure chabazite is the most compressible zeolite among those up to now studied in silicone oil

Unravelling the High-Pressure Behaviour of Dye-Zeolite L Hybrid Materials

Self-assembly of chromophores nanoconfined in porous materials such as zeolite L has led to technologically relevant host-guest systems exploited in solar energy harvesting, photonics, nanodiagnostics and information technology. The response of these hybrid materials to compression, which would be crucial to enhance their application range, has never been explored to date. By a joint high-pressure in situ synchrotron X-ray powder diffraction and ab initio molecular dynamics approach, herein we unravel the high-pressure behaviour of hybrid composites of zeolite L with fluorenone dye. High-pressure experiments were performed up to 6 GPa using non-penetrating pressure transmitting media to study the effect of dye loading on the structural properties of the materials under compression. Computational modelling provided molecular-level insight on the response to compression of the confined dye assemblies, evidencing a pressure-induced strengthening of the interaction between the fluorenone carbonyl group and zeolite L potassium cations. Our results reveal an impressive stability of the fluorenone-zeolite L composites at GPa pressures. The remarkable resilience of the supramolecular organization of dye molecules hyperconfined in zeolite L channels may open the way to the realization of optical devices able to maintain their functionality under extreme conditions

Manganese(II) Molecular Sources for Plasma-Assisted CVD of Mn Oxides and Fluorides: From Precursors to Growth Process

A viable route to manganese-based materials of high technological interest is plasma-assisted chemical vapor deposition (PA-CVD), offering various degrees of freedom for the growth of high-purity nanostructures from suitable precursors. In this regard, fluorinated \u3b2-diketonate diamine Mn(II) complexes of general formula Mn(dik)2\ub7TMEDA [TMEDA = N,N,N\u2032,N\u2032-tetramethylethylenediamine; Hdik = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (Hhfa), or 1,1,1-trifluoro-2,4-pentanedione (Htfa)] represent a valuable option in the quest of candidate molecular sources for PA-CVD environments. In this work, we investigate and highlight the chemico-physical properties of these compounds of importance for their use in PA-CVD processes, through the use of a comprehensive experimental\u2013theoretical investigation. Preliminary PA-CVD validation shows the possibility of varying the Mn oxidation state, as well as the system chemical composition from MnF2 to MnO2, by simple modulations of the reaction atmosphere, paving the way to a successful utilization of the target compounds in the growth of manganese-containing nanomaterials for different technological applications

Precision molecular threading/dethreading

Abstract: The general principles guiding the design of molecular machines based on interlocked structures are well known. Nonetheless, the identification of suitable molecular components for a precise tuning of the energetic parameters that determine the mechanical link is still challenging. Indeed, what are the reasons of the \u201call-or-nothing\u201d effect, which turns a molecular \u201cspeed-bump\u201d into a stopper in pseudorotaxane-based architectures? Here we investigate the threading and dethreading processes for a representative class of molecular components, based on symmetric dibenzylammonium axles and dibenzo[24]crown-8 ether, with a joint experimental-computational strategy. From the analysis of quantitative data and an atomistic insight, we derive simple rules correlating the kinetic behaviour with the substitution pattern, and provide rational guidelines for the design of modules to be integrated in molecular switches and motors with sophisticated dynamic feature