Block co-polyMOFs: morphology control of polymer-MOF hybrid materials.

The hybridization of block copolymers and metal-organic frameworks (MOFs) to create novel materials (block co-polyMOFs, BCPMOFs) with controlled morphologies is reported. In this study, block copolymers containing poly(1,4-benzenedicarboxylic acid, H2bdc) and morphology directing poly(ethylene glycol) (PEG) or poly(cyclooctadiene) (poly(COD)) blocks were synthesized for the preparation of BCPMOFs. Block copolymer architecture and weight fractions were found to have a significant impact on the resulting morphology, mediated through the assembly of polymer precursors prior to MOF formation, as determined through dynamic light scattering. Simple modification of block copolymer weight fraction allowed for tuning of particle size and morphology with either faceted and spherical features. Modification of polymer block architecture represents a simple and powerful method to direct morphology in highly crystalline polyMOF materials. Furthermore, the BCPMOFs could be prepared from both Zr4+ and Zn2+ MOFs, yielding hybrid materials with appreciable surface areas and tuneable porosities. The resulting Zn2+ BCPMOF yielded materials with very narrow size distributions and uniform cubic morphologies. The use of topology in BCPMOFs to direct morphology in block copolymer assemblies may open new methodologies to access complex materials far from thermodynamic equilibrium

Enhanced photochemical hydrogen production by a molecular diiron catalyst incorporated into a metal-organic framework.

A molecular proton reduction catalyst [FeFe](dcbdt)(CO)6 (1, dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) with structural similarities to [FeFe]-hydrogenase active sites has been incorporated into a highly robust Zr(IV)-based metal-organic framework (MOF) by postsynthetic exchange (PSE). The PSE protocol is crucial as direct solvothermal synthesis fails to produce the functionalized MOF. The molecular integrity of the organometallic site within the MOF is demonstrated by a variety of techniques, including X-ray absorption spectroscopy. In conjunction with [Ru(bpy)3](2+) as a photosensitizer and ascorbate as an electron donor, MOF-[FeFe](dcbdt)(CO)6 catalyzes photochemical hydrogen evolution in water at pH 5. The immobilized catalyst shows substantially improved initial rates and overall hydrogen production when compared to a reference system of complex 1 in solution. Improved catalytic performance is ascribed to structural stabilization of the complex when incorporated in the MOF as well as the protection of reduced catalysts 1(-) and 1(2-) from undesirable charge recombination with oxidized ascorbate

Multicomponent metal-organic framework membranes for advanced functional composites.

The diverse chemical and structural properties of metal-organic frameworks (MOFs) make them attractive for myriad applications, but their native powder form is limiting for industrial implementation. Composite materials of MOFs hold promise as a means of exploiting MOF properties in engineered forms for real-world applications. While interest in MOF composites is growing, research to date has largely focused on utilization of single MOF systems. The vast number of different MOF structures provides ample opportunity to mix and match distinct MOF species in a single composite to prepare multifunctional systems. In this work, we describe the preparation of three types of multi-MOF composites with poly(vinylidene fluoride) (PVDF): (1) co-cast MOF MMMs, (2) mixed MOF MMMs, and (3) multilayer MOF MMMs. Finally, MOF MMMs are explored as catalytic membrane reactors for chemical transformations

Prevalence and causes of dysphonia in a large treatment-seeking population

Journal ArticleObjective: To determine the prevalence and common causes of dysphonia as diagnosed by primary care physicians (PCPs) and otolaryngologists, and to evaluate differences in etiologies offered by these providers. Study Design: Retrospective analysis of data from a large, nationally representative administrative U.S. claims database. Methods: Patients were identified as dysphonic based on ICD-9-CM codes from January 1, 2004 to December 31, 2008. Data regarding age, gender, geographic location, and type of physician providing the dysphonia diagnosis were collected. Overall and age-related prevalence rates, as well as frequency of specific etiologies by provider type were calculated. Results: Of the almost 55 million individuals in the database, 536,943 patients, ages 0 to > 65 years, were given a dysphonia diagnosis (point prevalence rate of 0.98%). The prevalence rate was higher among females as compared to males (1.2% versus 0.7%) and among those > 70 years of age (2.5%). The most frequent diagnoses overall were acute laryngitis, non-specific dysphonia, benign vocal fold lesions, and chronic laryngitis. PCPs more commonly diagnosed acute laryngitis, whereas otolaryngologists more commonly diagnosed non-specific dysphonia and laryngeal pathology. Gastro-esophageal reflux was more commonly diagnosed as a comorbid condition by otolaryngologists than by PCPs. Overall laryngeal cancer prevalence in this treatment-seeking population was 2.2% and was greatest among males > 70 years of age. Conclusion: This analysis of insurance claims data from a nationally representative database represents the largest study of its kind. Important differences in dysphonia prevalence related to age, gender, diagnosis, and physician type were identified. Word count: 248, Evidence level: level 2b. Introduction: The public health impact of vocal dysfunction is becoming increasingly recognized. Dysphonia adversely impacts communication with physical, social, and workrelated effects. Patients suffer social isolation, depression, impaired disease-specific and general quality of life, and work absenteeism.1-4 Thus, voice disorders negatively impact individuals and burden society

Enhanced aging properties of HKUST-1 in hydrophobic mixed-matrix membranes for ammonia adsorption.

Metal-organic frameworks (MOFs) in their free powder form have exhibited superior capacities for many gases when compared to other materials, due to their tailorable functionality and high surface areas. Specifically, the MOF HKUST-1 binds small Lewis bases, such as ammonia, with its coordinatively unsaturated copper sites. We describe here the use of HKUST-1 in mixed-matrix membranes (MMMs) prepared from polyvinylidene difluoride (PVDF) for the removal of ammonia gas. These MMMs exhibit ammonia capacities similar to their hypothetical capacities based on the weight percent of HKUST-1 in each MMM. HKUST-1 in its powder form is unstable toward humid conditions; however, upon exposure to humid environments for prolonged periods of time, the HKUST-1 MMMs exhibit outstanding structural stability, and maintain their ammonia capacity. Overall, this study has achieved all of the critical and combined elements for real-world applications of MOFs: high MOF loadings, fully accessible MOF surfaces, enhanced MOF stabilization, recyclability, mechanical stability, and processability. This study is a critical step in advancing MOFs to a stable, usable, and enabling technology

Postsynthetic modification of coordination networks

Belgium Herbarium image of Meise Botanic Garden

Activation of sulfonate ester based matrix metalloproteinase proinhibitors by hydrogen peroxide

This study details the development of matrix metalloproteinase inhibitor prodrugs (proMMPi) that are activated in the presence of reactive-oxygen species (ROS). Conventional matrix metalloproteinase inhibitors (MMPi) utilize a zinc-binding group (ZBG) that chelates to the catalytic zinc(II) ion of matrix metalloproteinases (MMPs) to inhibit their activity. To create ROS-sensitive prodrugs, sulfonate esters were used as a protecting group for the ZBG to block their metal binding ability. Surprisingly, these sulfonate esters were found to be cleaved by H2O2 only when the ZBG contained an N-oxide donor atom moiety. Sulfonate ester derivatives of full-length MMPi based on these ROS-triggerable systems were synthesized. It was found that proMMPi with sulfonate ester protecting groups showed relatively high rates of cleavage in the presence of H2O2 to release the active MMPi. In vitro MMP inhibition studies confirmed a significant increase in inhibitory activity of proMMPi upon addition of H2O2, demonstrating the use of sulfonate esters to act as cleavable triggers for ROS-activated prodrugs

Complexity of multi-dimensional spontaneous EEG decreases during propofol induced general anaesthesia

Emerging neural theories of consciousness suggest a correlation between a specific type of neural dynamical complexity and the level of consciousness: When awake and aware, causal interactions between brain regions are both integrated (all regions are to a certain extent connected) and differentiated (there is inhomogeneity and variety in the interactions). In support of this, recent work by Casali et al (2013) has shown that Lempel-Ziv complexity correlates strongly with conscious level, when computed on the EEG response to transcranial magnetic stimulation. Here we investigated complexity of spontaneous high-density EEG data during propofol-induced general anaesthesia. We consider three distinct measures: (i) Lempel-Ziv complexity, which is derived from how compressible the data are; (ii) amplitude coalition entropy, which measures the variability in the constitution of the set of active channels; and (iii) the novel synchrony coalition entropy (SCE), which measures the variability in the constitution of the set of synchronous channels. After some simulations on Kuramoto oscillator models which demonstrate that these measures capture distinct ‘flavours’ of complexity, we show that there is a robustly measurable decrease in the complexity of spontaneous EEG during general anaesthesia