Selective Adsorption and Separation of <i>o</i>‑Xylene Using an Aluminum-Based Metal–Organic Framework

Separation and purification of C8 aromatics is still a great challenge owing to their similar boiling point and molecular size. Herein, an aluminum-based metal–organic framework was synthesized to investigate the ability of discriminating C8 aromatics. Both the single-component and multicomponent experiments exhibited the preferential adsorption of o-xylene with the adsorption order of o-xylene > p-xylene > m-xylene > ethylbenzene. Especially, the separation selectivity of o-xylene over m-xylene can reach as high as 8.1, which exceeds the reported values using MOFs in the liquid phase. The results of the experiment in combination of calculations revealed that the interaction between polarity groups of frameworks and guests besides the stacking interaction among guest molecules is the main interaction. The cooperative effect of μ-OH groups and the aluminum-metal cluster can strengthen the electrostatic interactions for o-xylene. With the help of density function theory calculations, it is believed that the difference in binding affinities with the framework endows this MOF with excellent selective adsorption and separation of o-xylene from the C8 mixture

pH and H₂S Dual-Responsive Magnetic Metal–Organic Frameworks for Controlling the Release of 5‑Fluorouracil

Along with the increasing cancer incidence, developing suitable drug delivery systems (DDSs) is becoming urgent to control drug release and further enhance therapeutic efficiency. Herein, a Fe–Zn bimetallic MOF-derived ferromagnetic nanomaterial was synthesized by a one-step method. The successful preparation of ferromagnetic Fe-ZIF-8 was verified by scanning electron microscopy, powder X-ray diffraction, Brunauer–Emmett–Teller, X-ray photoelectron spectroscopy, and physical property measurement system characterizations. Furthermore, the release behaviors of 5-FU from the ferromagnetic carrier were investigated in a simulative cancer microenvironment of PBS buffer solution (PBS = phosphate-buffered saline, pH = 5.8) and NaHS solution. The vehicle in PBS solution of pH = 5.8 and NaHS solution of 500 μM can rapidly release 5-FU with the cumulative release percentages of 68 and 36%, respectively, within two hundred minutes. The release mechanism in the weak acid environment can be mainly attributed to the decomposition of the Fe-ZIF-8. However, the strong interaction between Zn and Fe atoms in Fe-ZIF-8 and the S atom in H2S plays an important role in the release process in the simulated H2S cancer microenvironment. The investigation of release kinetic models indicates that the 5-FU release in the PBS solutions and NaHS solution of 500 μM can be accurately fitted by a second-degree polynomial model and first-order model, respectively. In addition, the decomposition products, zinc, iron, and 2-MeIM, are endogenous and show low toxicity values [LD50 (Zn) = 0.35 g·kg–1, LD50 (Fe) = 30 g·kg–1, and LD50 (2-MeIM) = 1.4 g·kg–1]. Therefore, the low-toxicity, pH and H2S dual-stimuli-responsive, and ferromagnetic nature make the obtained Fe-ZIF-8 an ideal candidate in the field of bioactive molecule delivery

Chromatin regulators in the TBX1 network confer risk for conotruncal heart defects in 22q11.2DS

Congenital heart disease (CHD) affecting the conotruncal region of the heart, occurs in 40–50% of patients with 22q11.2 deletion syndrome (22q11.2DS). This syndrome is a rare disorder with relative genetic homogeneity that can facilitate identification of genetic modifiers. Haploinsufficiency of TBX1, encoding a T-box transcription factor, is one of the main genes responsible for the etiology of the syndrome. We suggest that genetic modifiers of conotruncal defects in patients with 22q11.2DS may be in the TBX1 gene network. To identify genetic modifiers, we analyzed rare, predicted damaging variants in whole genome sequence of 456 cases with conotruncal defects and 537 controls, with 22q11.2DS. We then performed gene set approaches and identified chromatin regulatory genes as modifiers. Chromatin genes with recurrent damaging variants include EP400, KAT6A, KMT2C, KMT2D, NSD1, CHD7 and PHF21A. In total, we identified 37 chromatin regulatory genes, that may increase risk for conotruncal heart defects in 8.5% of 22q11.2DS cases. Many of these genes were identified as risk factors for sporadic CHD in the general population. These genes are co-expressed in cardiac progenitor cells with TBX1, suggesting that they may be in the same genetic network. The genes KAT6A, KMT2C, CHD7 and EZH2, have been previously shown to genetically interact with TBX1 in mouse models. Our findings indicate that disturbance of chromatin regulatory genes impact the TBX1 gene network serving as genetic modifiers of 22q11.2DS and sporadic CHD, suggesting that there are some shared mechanisms involving the TBX1 gene network in the etiology of CHD.</p

Template-Free Synthesis of an Interlocked Covalent Organic Molecular Cage

An interlocked covalent organic molecular cage with a trigonal-prismatic structure based on anthracene units and imine bonds was synthesized by a template-free and one-pot reaction in a relatively good yield. By comparing the single-crystal structures of the interlocked cage and two additional monomeric cages as reference compounds, a cause of weak supramolecular interaction-induced synthesis was proposed; π···π interactions induce the triphenylbenzene units as the core and anthracenes as side parts close to each other, which provides a possibility of the preorganization for the formation of the interlocked structure

Chromatin regulators in the TBX1 network confer risk for conotruncal heart defects in 22q11.2DS

Congenital heart disease (CHD) affecting the conotruncal region of the heart, occurs in 40–50% of patients with 22q11.2 deletion syndrome (22q11.2DS). This syndrome is a rare disorder with relative genetic homogeneity that can facilitate identification of genetic modifiers. Haploinsufficiency of TBX1, encoding a T-box transcription factor, is one of the main genes responsible for the etiology of the syndrome. We suggest that genetic modifiers of conotruncal defects in patients with 22q11.2DS may be in the TBX1 gene network. To identify genetic modifiers, we analyzed rare, predicted damaging variants in whole genome sequence of 456 cases with conotruncal defects and 537 controls, with 22q11.2DS. We then performed gene set approaches and identified chromatin regulatory genes as modifiers. Chromatin genes with recurrent damaging variants include EP400, KAT6A, KMT2C, KMT2D, NSD1, CHD7 and PHF21A. In total, we identified 37 chromatin regulatory genes, that may increase risk for conotruncal heart defects in 8.5% of 22q11.2DS cases. Many of these genes were identified as risk factors for sporadic CHD in the general population. These genes are co-expressed in cardiac progenitor cells with TBX1, suggesting that they may be in the same genetic network. The genes KAT6A, KMT2C, CHD7 and EZH2, have been previously shown to genetically interact with TBX1 in mouse models. Our findings indicate that disturbance of chromatin regulatory genes impact the TBX1 gene network serving as genetic modifiers of 22q11.2DS and sporadic CHD, suggesting that there are some shared mechanisms involving the TBX1 gene network in the etiology of CHD.</p

Triazine-Based Conjugated Microporous Polymers for Efficient Hydrogen Production

Developing visible-light-active porous organic polymers with high photocatalytic efficiency is highly desirable. Here, two triazine-based conjugated microporous polymers were synthesized. The structures were controllably adjusted to explore the structure–photocatalytic activity relationship. T-CMP-1 containing more triazine units exhibited a hydrogen evolution rate of 3214.3 μmol h–1 g–1, much higher than that of T-CMP-2 (242.1 μmol h–1 g–1). The increasing contents of triazine units bring better hydrogen evolution efficiency

Ultrafastly Interweaving Graphdiyne Nanochain on Arbitrary Substrates and Its Performance as a Supercapacitor Electrode

A moderate method is first developed here for superfast (in seconds) growth of an ultrafine graphdiyne (GDY) nanochain on arbitrary substrates in the atmosphere. This is an environmentally friendly and metal-catalyst-free method, efficiently eliminating extraneous contaminations for the carbon materials. The seamless GDY coating on any substrates demonstrates that an all-carbon GDY possesses outstanding controllability and processability, perfectly compensating for the drawbacks of prevailing all-carbon materials. After the decoration of 3D GDY nanostructures, the substrates become superhydrophobic with contact angles high up to of 148° and can be used as outstanding frameworks for storing organic pollution. Because of the reasonable porous and 3D continuous features, the as-prepared samples can be applied as high-performance binder-free supercapacitor electrodes with high area capacitance of up to 53.66 mF cm ^–2, prominent power performance, and robust long-term retention (99% after 1300 cycles)

Ultrasensitive Photodetectors Based on Strongly Interacted Layered-Perovskite Nanowires

Metal-halide layered perovskites, self-assembled quantum wells with alternating insulating interlayer organic cations, and conductive perovskite layers boost the incorporation of multiple functionalities into a single-phase material. Optoelectronic performances in layered perovskites are more sensitive to crystallinity than their 3D counterparts due to the traps and insulating barriers introduced by interlayer cations. Here, we combine the capillary-bridge lithography method for the fabrication of single-crystalline nanowire arrays with strongly interacted layered perovskites for the enhancement of crystallinity and crystallographic orientation purity. Due to regulated nucleation and growth of layered perovskites in capillary bridges and the sulfur–sulfur interaction between interlayer cations, nanowires with pure (101) orientation are realized for underpinning insulating crystal interiors and photoconductive layer edges. Based on these nanowires, ultrasensitive photodetectors are reached with an ultralow dark current of below 10–12 A, an average responsivity of 7.3 × 103 A W–1, an average specific detectivity of 3.9 × 1015 Jones, and a 3 dB bandwidth of 10.3 kHz