Degradation paths of manganese-based MOF materials in a model oxidative environment: a computational study.

Stability is the key property of functional materials. In this work we investigate computationally the degradative potential of a model Mn-BTC (BTC = benzene-1,3,5-tricarboxylate) metal-organic framework (MOF) building block in aqueous solutions under oxidative conditions. Model density functional theory calculations have shown that the direct hydrolysis of the Mn-containing moieties is more difficult than their decomposition via oxidation-induced paths. While the interaction with H2O2 species is of non-covalent nature and requires O-O-bond breaking to initiate Mn-center oxidation, open-shell O2 species readily oxidize radical Mn-centers and form bonds of σ-, π-, or δ-symmetry with the metal. The oxidative transformations of di-Mn paddle-wheel carboxylate structure-forming units are accompanied with substantial distortions of the coordination polyhedra that, together with the increased Lewis acidity of the oxidized metal centers, facilitates the hydrolysis leading to the degradation of the structure at a larger scale. Whereas such a mechanism is expected to hamper the catalytic applications of such Mn-MOFs, the associated structural response to oxidizing and radical species can create a basis for the construction of Mn-MOF-based drug delivery systems with increased bio-compatibility.

Soft x-ray free-electron laser imaging by LiF crystal and film detectors over a wide range of fluences.

LiF crystal and film detectors were used to measure the far-field fluence profile of a self-amplified spontaneous-emission free-electron laser beam and diffraction imaging with high spatial resolution. In these measurements the photoluminescence (PL) response of LiF crystal and film was compared over a wide range of soft x-ray fluences. It was found that the soft x-ray fluence dependences of LiF crystal and film differ. At low fluence, the LiF crystal shows higher PL response compared to LiF film, while this comparison is the opposite at higher fluence. Accurate measurement of LiF crystal and film PL response is important for precise characterization of the spatial, spectral, and coherence features of x-ray beams across the full profile and in localized areas. For such measurements, crucial LiF detector attributes are high spatial resolution and high dynamic range.

Degradation kinetic study of ZIF-8 microcrystals with and without the presence of lactic acid.

The zeolitic imidazolate framework ZIF-8 (Zn(mim)2, mim = 2-methylimidazolate) has recently been proposed as a drug delivery platform for anticancer therapy based on its capability of decomposing in acidic media. The concept presumes a targeted release of encapsulated drug molecules in the vicinity of tumor tissues that typically produce secretions with elevated acidity. Due to challenges of in vivo and in vitro examination, many studies have addressed the kinetics of ZIF-8 decomposition and subsequent drug release in phosphate buffered saline (PBS) with adjusted acidity. However, the presence of hydrogen phosphate anions [HPO4]2- in PBS may also affect the stability of ZIF-8. As yet, no separate analysis has been performed comparing the dissolving capabilities of PBS and various acidification agents used for regulating pH. Here, we provide a systematic study addressing the effects of phosphate anions with and without lactic acid on the degradation rate of ZIF-8 microcrystals. Lactic acid has been chosen as an experimental acidification agent, since it is particularly secreted by tumor cells. Interestingly, the effect of a lactic acid solution with pH 5.0 on ZIF-8 degradation is shown to be weaker compared to a PBS solution with pH 7.4. However, as an additive, lactic acid is able to enhance the decomposition efficacy of other solutions by 10 to 40 percent at the initial stage, depending on the presence of other ions. Additionally, we report mild toxicity of ZIF-8 and its decomposition products, as examined on HDF and A549 cell lines.

Correction to 'Holographic sol-gel monoliths: optical properties and application for humidity sensing'.

[This corrects the article DOI: 10.1098/rsos.172465.].

Holographic sol-gel monoliths: optical properties and application for humidity sensing.

Sol-gel monoliths based on SiO2, TiO2 and ZrO2 with holographic colourful diffraction on their surfaces were obtained via a sol-gel synthesis and soft lithography combined method. The production was carried out without any additional equipment at near room temperature and atmospheric pressure. The accurately replicated wavy structure with nanoscale size of material particles yields holographic effect and its visibility strongly depends on refractive index (RI) of materials. Addition of multi-walled carbon nanotubes (MWCNTs) in systems increases their RI and lends absorbing properties due to extremely high light absorption constant. Further prospective and intriguing applications based on the most successful samples, MWCNTs-doped titania, were investigated as reversible optical humidity sensor. Owing to such property as reversible resuspension of TiO2 nanoparticles while interacting with water, it was proved that holographic xerogels can repeatedly act as humidity sensors. Materials which can be applied as humidity sensors in dependence on holographic response were discovered for the first time.

Diphenylalanine-Based Microribbons for Piezoelectric Applications via Inkjet Printing.

Peptide-based nanostructures are very promising for nanotechnological applications because of their excellent self-assembly properties, biological and chemical flexibility, and unique multifunctional performance. However, one of the limiting factors for the integration of peptide assemblies into functional devices is poor control of their alignment and other geometrical parameters required for device fabrication. In this work, we report a novel method for the controlled deposition of one of the representative self-assembled peptides-diphenylalanine (FF)-using a commercial inkjet printer. The initial FF solution, which has been shown to readily self-assemble into different structures such as nano- and microtubes and microrods, was modified to be used as an efficient ink for the printing of aligned FF-based structures. Furthermore, during the development of the suitable ink, we were able to produce a novel type of FF conformation with high piezoelectric response and excellent stability. By using this method, ribbonlike microcrystals based on FF could be formed and precisely patterned on different surfaces. Possible mechanisms of structure formation and piezoelectric effect in printed microribbons are discussed along with the possible applications.

Silica Foams for Fire Prevention and Firefighting.

We report the new development of fire-extinguishing agents employing the latest technology of fighting and preventing fires. The in situ technology of fighting fires and explosions involves using large-scale ultrafast-gelated foams, which possess new properties and unique characteristics, in particular, exceptional thermal stability, mechanical durability, and full biocompatibility. We provide a detailed description of the physicochemical processes of silica foam formation at the molecular level and functional comparison with current fire-extinguishing and fire-fighting agents. The new method allows to produce controllable gelation silica hybrid foams in the range from 2 to 30 s up to 100 Pa·s viscosity. Chemical structure and hierarchical morphology obtained by scanning electron microscopy and transmission electron microscopy images develop thermal insulation capabilities of the foams, reaching a specific heat value of more than 2.5 kJ/(kg·°C). The produced foam consists of organized silica nanoparticles as determined by X-ray photoelectron spectroscopy and X-ray diffraction analysis with a narrow particle size distribution of ∼10-20 nm. As a result of fire-extinguishing tests, it is shown that the extinguishing efficiency exhibited by silica-based sol-gel foams is almost 50 times higher than that for ordinary water and 15 times better than that for state-of-the-art firefighting agent aqueous film forming foam. The biodegradation index determined by the time of the induction period was only 3 d, while even for conventional foaming agents this index is several times higher.

Synthesis of Thrombolytic Sol-Gel Coatings: Toward Drug-Entrapped Vascular Grafts.

As is evident from numerous investigations, drug-eluting vascular grafts and stents have not solved the main problems associated with thrombosis and due to drug release only postpone their advance for a longer period. Here we point to a potential solution of this problem by developing thrombolytic sol-gel coatings which potentially could lead to drug-entrapped vascular grafts: urokinase-type plasminogen activator was entrapped within a porous alumina sol-gel film with a subsequent deposition on a polymer graft.

Single-shot extreme ultraviolet laser imaging of nanostructures with wavelength resolution.

We have demonstrated near-wavelength resolution microscopy in the extreme ultraviolet. Images of 50 nm diameter nanotubes were obtained with a single ~1 ns duration pulse from a desktop-size 46.9 nm laser. We measured the modulation transfer function of the microscope for three different numerical aperture zone plate objectives, demonstrating that 54 nm half-period structures can be resolved. The combination of near-wavelength spatial resolution and high temporal resolution opens myriad opportunities in imaging, such as the ability to directly investigate dynamics of nanoscale structures.