Fine Tuning the Hydrophobicity of a New Three-Dimensional Cu2+ MOF through Single Crystal Coordinating Ligand Exchange Transformations.

The synthesis, characterization, and single-crystal-to-single-crystal (SCSC) exchange reactions of a new 3D Cu2+ MOF based on 5-aminoisophthalic acid (H2AIP), [Cu6(µ3-ΟΗ)3(ΑΙΡ)4(HΑΙΡ)]n·6nDMF·nH2O - UCY-16·6nDMF·nH2O, are reported. It exhibits a 3D structure based on two [Cu4(µ3-OH)2]6+ butterfly-like secondary building units, differing in their peripheral ligation, bridged through HAIP-/AIP2- ligands. This compound displays the capability to exchange the coordinating ligand(s) and/or guest solvent molecules through SCSC reactions. Interestingly, heterogeneous reactions of single crystals of UCY-16·6nDMF·nH2O with primary alcohols resulted not only in the removal of the lattice DMF molecules but also in an unprecedented structural alteration that involved the complete or partial replacement of the monoatomic bridging µ3-OH- anion(s) of the [Cu4(µ3-OH)2]6+ butterfly structural core by various alkoxy groups. Similar crystal-to-crystal exchange reactions of UCY-16·6nDMF·nH2O with long-chain aliphatic alcohols (CxH2x+1OH, x = 8-10, 12, 14, and 16) led to analogues containing fatty alcohols. Notably, the exchanged products with the bulkier alcohols UCY-16/n-CxH2x+1OH·S' (x = 6-10, 12, 14, and 16) do not mix with H2O being quite stable in this solvent, in contrast to the pristine MOF, and exhibit a hydrophobic/superhydrophobic surface as confirmed from the investigation of their water contact angles and capability to remove hydrophobic pollutants from aqueous media.

Just Soaping Them: The Simplest Method for Converting Metal Organic Frameworks into Superhydrophobic Materials.

The incorporation of superhydrophobic properties into metal organic framework (MOF) materials is highly desirable to enhance their hydrolytic stability, gas capture selectivity in the presence of humidity and efficiency in oil-water separations, among others. The existing strategies for inducing superhydrophobicity into MOFs have several weaknesses, such as increased cost, utilization of toxic reagents and solvents, applicability for limited MOFs, etc. Here, we report the simplest, most eco-friendly, and cost-effective process to impart superhydrophobicity to MOFs, involving a rapid (90 min) treatment of MOF materials with solutions of sodium oleate, a main component of soap. The method can be applied to both hydrolytically stable and unstable MOFs, with the porosity of modified MOFs approaching, in most cases, that of the pristine materials. Interestingly, this approach was used to isolate superhydrophobic magnetic MOF composites, and one of these materials formed stable liquid marbles, whose motion could be easily guided using an external magnetic field. We also successfully fabricated superhydrophobic MOF-coated cotton fabric and fiber composites. These composites exhibited exceptional oil sorption properties achieving rapid removal of floating crude oil from water, as well as efficient purification of oil-in-water emulsions. They are also regenerable and reusable for multiple sorption processes. Overall, the results described here pave the way for an unprecedented expansion of the family of MOF-based superhydrophobic materials, as virtually any MOF could be converted into a superhydrophobic compound by applying the new synthetic approach.

Highly efficient sorption and luminescence sensing of oxoanionic species by 8-connected alkyl-amino functionalized Zr4+ MOFs.

In the present study we provide the sorption properties of four 8-connected Zr4+ MOFs with the general formula H16[Zr6O16(RNH-BDC)4]·solvent (RNH-BDC2- = 2-alkyl-amine-terephthalate; R = ethyl-, ET-MOF; R = propyl-, PROP-MOF; R = isobutyl-, SBUT-MOF; R = n-butyl, BUT-MOF) towards toxic Cr(VI) and radionuclide-related ReO4- oxoanions. These MOFs represent superior sorbents for the removal of oxoanionic species, in terms of kinetics, sorption isotherms, selectivity and regeneration/reusability. The excellent sorption capability of the MOFs is due to a combination of surface and intra-framework sorption phenomena. The latter process proceeds via replacement of terminal water/hydroxyl ligands from the Zr6 clusters and subsequent binding of oxonanions to the Zr4+ centers, a fact that was proved via Rietveld PXRD analysis for the anion-loaded BUT-MOF. Importantly, BUT-MOF demonstrated an exceptional sorption capacity for Cr2O72- (505 mg g-1) and was further utilized in a sorption column in the form of MOF/calcium alginate beads, displaying remarkable removal efficiency towards industrial (chrome-plating) wastewater. Furthermore, the luminescence Cr(VI) sensing properties of BUT-MOF were explored in detail, presenting high sensitivity (detection limits as low as 9 ppb) and selectivity for these species against various competitive anions.

Zr4+-terephthalate MOFs with 6-connected structures, highly efficient As(III/V) sorption and superhydrophobic properties.

The use of terephthalate ligands with CnH2n+1NH-chains (n ≥ 6) led to the isolation of the first examples of Zr4+-terephthalate MOFs with 6-connected frameworks. The material with hexyl-amino functional groups has been proved to be an exceptional sorbent for the removal of As(III/V) toxic species from aqueous media, whereas MOFs with heptyl to dodecyl-amino moieties are superhydrophobic with promising oil-water separation properties.

Robust Al3+ MOF with Selective As(V) Sorption and Efficient Luminescence Sensing Properties toward Cr(VI).

Herein, we report the synthesis and characterization of a new robust Al3+ metal-organic framework MOF, [Al(OH)(PATP)]·solvent (Al-MOF-1, with PATP2- = 2-((pyridin-2-ylmethyl)amino)terephthalate). Al-MOF-1 exhibits excellent stability from highly acidic (pH = 2) to basic (pH = 12) aqueous solutions or in the presence of oxoanionic species [As(V) and Cr(VI)]. On the contrary, the related MIL-53(Al) MOF (Al(OH) (BDC), with BDC2- = terephthalate) shows a partial structure collapse under these conditions, signifying the superior chemical robustness of Al-MOF-1. Al-MOF-1 was proved to be an effective sorbent toward As(V) with efficient sorption capacity (71.9 ± 3.8 mg As/g), rapid sorption kinetics (equilibrium time ≤1 min), and high selectivity in the presence of various competing anions. Furthermore, Al-MOF-1 revealed high sorption capacities for Cr(VI) species in both neutral (124.5 ± 8.6 mg Cr/g) and acidic (63 ± 2 mg Cr/g) aqueous media, combining fast kinetics and relatively good selectivity. The limited porosity (BET = 38 m2/g) and small pores (2-3 Å) of the material indicate that the sorption process occurs exclusively on the external surface of Al-MOF-1 particles. The driving force for the capture of oxoanions by Al-MOF-1 is the strong electrostatic interactions between the oxoanionic species and the positively charged surface of MOF particles. Aiming at a practical wastewater treatment, we have also immobilized Al-MOF-1 on a cotton substrate, coated with polydopamine. The fabric sorbent exhibited highly effective removal of the toxic oxoanionic species from aqueous media under either batch or dynamic (continuous flow) conditions. In addition, Al-MOF-1 was found to be a promising luminescence sensor for detecting trace amounts of Cr(VI) in real water samples, with Cr(VI) being successfully detected at concentrations well below the acceptable limits (<50 ppb). Moreover, Al-MOF-1 was demonstrated to be a sufficient water sensor in organic solvents (LOD ≤0.25% v/v). All the above indicate that Al-MOF-1 represents a multifunctional material with a multitude of potential applications, such as environmental remediation, industrial wastewater treatment, chemical analysis, and water determination in biofuels.

On the Development of a Novel Contrast Pulse Sequence for Polymer-Shelled Microbubbles.

Contrast agents are routinely used in ultrasound examinations. Nonlinear ultrasound imaging techniques have been developed over decades to enhance the contrast between the tissue and the blood pool after the injection of ultrasound contrast agents (UCAs). In this study, we introduce a new contrast pulse sequence, CPS4. The CPS4 combines pulse inversion (PI), subharmonic (SH), and ultraharmonic (UH) techniques to remove propagation distortion while capturing the unique SH and UH responses from UCAs. The novel CPS4 and conventional PI, SH, and UH techniques were used to detect the presence of a research-grade, thick-shell, polymer microbubble in a tissue-mimicking flow phantom. The contrast-to-tissue ratios (CTRs) obtained from the applications of all techniques were compared. The results show that the highest CTR of approximately 16 dB was obtained using CPS4, which was superior to the individual reference techniques: PI, SH, and UH techniques, in all scenarios considered in this study.

Myocardial strain indices and coronary flow reserve are only mildly affected in healthy hypertensive patients.

To investigate changes in two-dimensional myocardial strain echocardiography (2DSTE) indices following a dipyridamole stress test (DIPSE) in relatively healthy hypertensive patients and healthy controls. Forty-seven male hypertensive patients (aged 57±9 years) with normal ejection fraction and without left ventricular (LV) hypertrophy and 20 healthy male subjects were studied with conventional and 2DSTE echocardiography at rest and post DIPSE. Coronary flow reserve (CFR) in the left anterior descending artery following DIPSE was also evaluated. Global longitudinal strain (GLS) and TWIST were higher while UNTWIST rate was lower in hypertensives versus controls (p < 0.05 for all); TWIST remained higher in hypertensives (p = 0.021) after adjustment for differences in age and body mass index (BMI) between the groups. CFR was higher in controls compared to hypertensives even after adjustment for confounders (4.14 vs. 2.53, p = 0.001). DIPSE-induced changes did not differ between the groups after adjustment for age and BMI (p > 0.05 for all). DIPSE-induced improvement in GLS was associated with higher CFR only in hypertensive patients (r - 0.372, p = 0.010). The current study showed that well controlled hypertensive patients have only mild echocardiographic differences compared to controls; some of these differences appear to depend on age and BMI. A 'hyper-rotation' phenomenon (i.e. higher TWIST) early in hypertension may be a compensatory mechanism to preserve global systolic LV function. Coronary microcirculatory function was impaired in hypertensive patients, albeit within normal range, and was associated with DIPSE-induced changes in myocardial long-axis systolic function.

Hypertrophic cardiomyopathy in a patient with Crohn's disease: a case report.

Cardiac manifestations of Crohn's disease are rare; the most common is pericarditis. In the present report we briefly describe a 56-year-old man with Crohn's disease who presented to the emergency department due to paroxysmal atrial flutter. A transthoracic echocardiographic study revealed asymmetric left ventricular hypertrophy without outflow pressure gradient. Reviewing the literature, hypertrophic cardiomyopathy has not been previously described in patients with Crohn's disease.

QT interval prolongation associated with venlafaxine administration.

A significant number of non-antiarrhythmic drugs including psychotropic agents have been shown to prolong cardiac repolarization increasing the risk for torsade de pointes ventricular tachycardia. We briefly describe a 60-year-old woman who admitted to the hospital due to hypertension and mild dyspnea having a prolonged QT interval (QTc: 582 ms). The patient had a known history of depression treated with venlafaxine. The QT interval normalised a few days after cessation of the antidepressant agent. This is the first report of venlafaxine-induced QT interval prolongation.

Spontaneous coronary artery dissection associated with oral contraceptive use: a case report and review of the literature.

Spontaneous coronary artery dissection (SCAD) represents a rare cause of acute coronary syndromes with complex pathohysiology. We briefly describe a 50-year-old woman, without traditional cardiovascular risk factors, hospitalized for an acute ST-elevation myocardial infarction and treated with thrombolytic therapy. Notably, the patient was on oral contraceptives for the past 10 years. Coronary angiography showed a dissection of the distal left anterior descending artery. She was treated conservatively and her clinical status improved without evidence of continuing ischemia, while a repeated catheterization 6 months later showed a complete resolution of the dissection. It has been speculated that the female hormones may be responsible for the increased incidence of SCAD among women particularly during the peripartum period or during the exogenous administration of such agents. A systematic review of the literature revealed 4 further cases reporting an association of SCAD with oral contraceptive use.

Acute myocardial infarction with normal coronary arteries in a patient with Hodgkin's disease: a late complication of irradiation and chemotherapy.

We describe the case of a 31-year-old man who experienced an acute myocardial infarction 16 years after undergoing radiation and vinca alkaloid therapy for Hodgkin's disease. Even though coronary artery disease is a well-established complication after mediastinal radiation therapy, this adult patient had normal coronary angiographic results, with no traditional risk factors for coronary artery disease, and no hematologic or other abnormality associated with hypercoagulability.

Effect of atrial pressure increase on sinus node automaticity.

There is evidence suggesting that atrial electrophysiological properties may be changed by an acute increase in atrial pressure. The aim of the present study was to investigate the effect of alteration, in atrial pressure on sinus node recovery time. Twelve patients (8 men and 4 women, mean age 61.3 +/- 14.1 years) were included in this study. None of the patients had organic heart disease. Sinus node recovery time (SNRT) was measured following atrial pacing and atrioventricular (AV) pacing at sequential cycle lengths of 600, 545, 500, 461, 428, and 400 ms with two different AV intervals (150, 0 ms). Peak and minimal atrial pressure increased significantly from 8.5 +/- 2.8 to 20.1 +/- 2.9 mmHg (11.56 +/- 3.8 to 27.3 +/- 3.9 cmH2O) ( P=0.001) and from 2.06 +/- 1.69 to 5.33 +/- 2.9 mmHg (2.8 +/- 2.29 to 7.2 +/- 3.9 cmH2O), respectively (P=0.002) during AV interval modification. Sinus node recovery time did not change despite the increase in atrial pressure. Autonomic blockade had no effect on SNRT. This study demonstrates that atrial pressure increase does not significantly affect sinus node automaticity expressed by SNRT.