Correlative 3D cryo X-ray imaging reveals intracellular location and effect of designed antifibrotic protein–nanomaterial hybrids

Revealing the intracellular location of novel therapeutic agents is paramount for the understanding of their effect at the cell ultrastructure level. Here, we apply a novel correlative cryo 3D imaging approach to determine the intracellular fate of a designed protein–nanomaterial hybrid with antifibrotic properties that shows great promise in mitigating myocardial fibrosis. Cryo 3D structured illumination microscopy (cryo-3D-SIM) pinpoints the location and cryo soft X-ray tomography (cryo-SXT) reveals the ultrastructural environment and subcellular localization of this nanomaterial with spatial correlation accuracy down to 70 nm in whole cells. This novel high resolution 3D cryo correlative approach unambiguously locates the nanomaterial after overnight treatment within multivesicular bodies which have been associated with endosomal trafficking events by confocal microscopy. Moreover, this approach allows assessing the cellular response towards the treatment by evaluating the morphological changes induced. This is especially relevant for the future usage of nanoformulations in clinical practices. This correlative super-resolution and X-ray imaging strategy joins high specificity, by the use of fluorescence, with high spatial resolution at 30 nm (half pitch) provided by cryo-SXT in whole cells, without the need of staining or fixation, and can be of particular benefit to locate specific molecules in the native cellular environment in bio-nanomedicine.

A novel 3D cryo correlative approach locates designed therapeutic protein–nanomaterial hybrids in whole cells with high specificity and resolution. Detection of treatment-induced morphological changes, crucial for pre-clinical studies, are revealed.     

Synthesis of molybdenum(V) and molybdenum(VI) derivatives of 5,15-diphenyl-2,8,12,18-tetra-n-butyl-3,7,13,17-tetramethylporphyrin

The methoxo-oxomolybdenum(V), diperoxomolybdenum(VI) and cis-dioxomolybdenum(VI) derivatives of 5,15-diphenyl-2,8,12,18-tetra-n-butyl-3,7,13,17-tetramethylporphyrin ( 4a, 5c, 6a ) have been prepared and characterized by uv, ir, pmr, mass and esr spectra. The structure of the molybdenum(V) porphyrin was confirmed by X-ray analysis.     

The Néel temperature of TMMC in large magnetic fields

The Néel temperature of TMMC has been determined as a function of applied field. T_N is found to increase by more than a factor of three from zero field up to 66 kOe. The results are compared to available theories.     

Adsorption of butane isomers and SF6 on Kureha activated carbon: 1. Equilibrium

Adsorption equilibria of butane isomers and SF6 on Kureha activated carbon were investigated using the volumetric method and the tapered element oscillating microbalance (TEOM) technique. The isotherm data of the butane isomers measured by the TEOM technique are in good agreement with those determined by the volumetric method. Single-component adsorption isotherms are reported at temperatures in the range from 298 to 393 K and at pressures up to 120 kPa. SF6 molecules are mainly adsorbed in the larger micropores, resulting in a lower adsorption capacity. The amount adsorbed for n-butane is slightly higher than that for isobutane in the whole range investigated. This is attributed to the fact that the linear n-butane molecule can adsorb in the smaller micropores. The T6th model appropriately describes the equilibrium data of the butane isomers, while the isotherm data of SF6 can be fitted by the Langmuir model. The isosteric heats associated with adsorption for these three adsorptives show different loading dependences. The present study indicates that the activated carbon can be well characterized by the probe molecules having different molecular sizes.     

A Grassmannian band method approach to the Nehari-Takagi problem

The band method is a flexible method for solving a variety of interpolation and extension problems which has evolved into increasing levels of sophistication over the past two decades. This article enhances the Grassmannian version of the band method to handle the Nehari-Takagi problem rather than merely the Nehari problem.     

MR angiography with pulsatile flow.

To achieve acceptable scan times, current multiple thin slice and 3D MR angiography (MRA) methods usually are based on continuous data acquisition, without ECG-synchronization. The purpose of this work is to study consequences of pulsatile blood flow for the 2D inflow method. Arterial blood flow and blood signal intensity versus cardiac phase were studied by a 2D phase based method with retrospective cardiac synchronization. Such studies were performed in different parts of the body and with different excitation flip angles. As expected, a clear relation between intensity enhancement and time dependent flow can be demonstrated. The raw data of these multiphase studies was used to simulate alternative inflow MRA data acquisition strategies to improve image quality, without the excessive increase in scan time implied by standard cardiac triggering. The alternatives investigated were data collection during part of the cardiac cycle and cardiac-ordered phase encoding. Simulation results indicate that the best results are obtained by a combination of both strategies. This method was implemented on Philips Gyroscan systems to compare it with standard nontriggered 2D inflow in practical MRA studies. For highly pulsatile flow, much better MR angiograms were obtained in this way.     

Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design

The introduction of synthetic zeolites has led to a paradigm shift in catalysis, separations, and adsorption processes, due to their unique properties such as crystallinity, high-surface area, acidity, ion-exchange capacity, and shape-selective character. However, the sole presence of micropores in these materials often imposes intracrystalline diffusion limitations, rendering low utilisation of the zeolite active volume in catalysed reactions. This critical review examines recent advances in the rapidly evolving area of zeolites with improved accessibility and molecular transport. Strategies to enhance catalyst effectiveness essentially comprise the synthesis of zeolites with wide pores and/or with short diffusion length. Available approaches are reviewed according to the principle, versatility, effectiveness, and degree of reality for practical implementation, establishing a firm link between the properties of the resulting materials and the catalytic function. We particularly dwell on the exciting field of hierarchical zeolites, which couple in a single material the catalytic power of micropores and the facilitated access and improved transport consequence of a complementary mesopore network. The carbon templating and desilication routes as examples of bottom-up and top-down methods, respectively, are reviewed in more detail to illustrate the benefits of hierarchical zeolites. Despite encircling the zeolite field, this review stimulates intuition into the design of related porous solids (116 references).     

Direct demonstration of enhanced diffusion in mesoporous ZSM-5 zeolite obtained via controlled desilication

A 2 orders of magnitude gas transport improvement in a medium pore ZSM-5 zeolite has been achieved upon introduction of intracrystalline mesoporosity in gradient-free crystals by desilication post-treatment in alkaline medium.     

In situ monitoring of desilication of MFI-type zeolites in alkaline medium

In situ pH and Attenuated Total Reflection (ATR) infrared techniques have been successfully applied in order to gain insights into the dissolution process connected to mesopore formation occurring upon alkaline treatment of ZSM-5 zeolites. Online pH measurements reveal a similar consumption of OH(-) ions in the initial stage of the reaction independent of the Si/Al ratio of the zeolite. In view of the greatly different mesoporosity development, the extraction of polymeric silica entities is anticipated, its structure depending on the framework Si/Al ratio. In agreement, ATR-IR experiments have confirmed dissolution of polymeric silicon-containing species that in the course of the alkaline treatment disintegrate into smaller entities. A direct relation between the type of porosity developed and the process of silicon extraction as measured in the liquid phase cannot be drawn.