Superior Adsorptive Removal of Anionic Azo Dyes from Aqueous Solutions Using Sulfonic Acid Group-Modified MIL-101@Graphene Oxide Composite.

It is critical to remove organic contaminants from wastewater released by the printing and dyeing industry for addressing water pollution issue. Therefore, the fabrication of new adsorbents with excellent removal efficiencies is an urgent task. A composite of MIL-101 partially functionalized with -SO3H (MIL-101-SO3H) and graphene oxide (GO) was prepared by assembling MIL-101-SO3H truncated octahedrons on the GO framework. The synthesized MIL-101-SO3H@GO has a superior adsorption efficiency for anionic azo dyes. The maximum adsorption capacities of MIL-101-SO3H@GO-1 for Congo red, methyl orange, acid orange 7, and acid orange G reached 2711.3, 818.8, 551.2, and 319.8 mg/g, respectively, which are considerably higher than those obtained using unmodified MIL-101. This is because additional interactions that promote azo dye adsorption, such as hydrogen bonding between the dye and the sulfonic acid groups of MIL-101-SO3H or the carboxyl groups of GO, were induced, and agglomerate pores that accommodated the dye were formed in the composite. The ultrahigh removal efficiency of the composite for azo dyes is mainly driven by hydrogen bonding, electrostatic interactions, π-π stacking between the MIL-101-SO3H@GO and dye molecules, synergistic interactions at the interface of GO and MIL-101-SO3H microcrystals, and the pore-filling effect. Understanding these driving forces for dye adsorption can contribute to the development of sustainable and functionally modified metal-organic framework composite adsorbents.

Wittig/B─H insertion reaction: A unique access to trisubstituted Z-alkenes.

The Wittig reaction, which is one of the most effective methods for synthesizing alkenes from carbonyl compounds, generally gives thermodynamically stable E-alkenes, and synthesis of trisubstituted Z-alkenes from ketones presents notable challenges. Here, we report what we refer to as Wittig/B─H insertion reactions, which innovatively combine a Wittig reaction with carbene insertion into a B─H bond and constitute a promising method for the synthesis of thermodynamically unstable trisubstituted Z-boryl alkenes. Combined with the easy transformations of boryl group, this methodology provides efficient access to a variety of previously unavailable trisubstituted Z-alkenes and thus provides a platform for discovery of pharmaceuticals. The unique Z-selectivity of the reaction is determined by the maximum overlap of the orbitals between the B─H bond of the borane adduct and the alkylidene carbene intermediate in the transition state.

Regio-controllable [2+2] benzannulation with two adjacent C(sp3)-H bonds.

Regiocontrol in traditional cycloaddition reactions between unsaturated carbon compounds is often challenging. The increasing focus in modern medicinal chemistry on benzocyclobutene (BCB) scaffolds indicates the need for alternative, more selective routes to diverse rigid carbocycles rich in C(sp3) character. Here, we report a palladium-catalyzed double C-H activation of two adjacent methylene units in carboxylic acids, enabled by bidentate amide-pyridone ligands, to achieve a regio-controllable synthesis of BCBs through a formal [2+2] cycloaddition involving σ bonds only (two C-H bonds and two aryl-halogen bonds). A wide range of cyclic and acyclic aliphatic acids, as well as dihaloheteroarenes, are compatible, generating diversely functionalized BCBs and hetero-BCBs present in drug molecules and bioactive natural products.

Catalyst-controlled site-selective methylene C-H lactonization of dicarboxylic acids.

Catalyst-controlled site-selective activation of ß- and γ-methylene carbon-hydrogen (C-H) bonds of free carboxylic acids is a long-standing challenge. Here we show that, with a pair of palladium catalysts assembled with quinoline-pyridone ligands of different chelate ring sizes, it is possible to perform highly site-selective monolactonization reactions with a wide range of dicarboxylic acids, generating structurally diverse and synthetically useful γ- and δ-lactones via site-selective ß- or γ-methylene C-H activation. The remaining carboxyl group serves as a versatile linchpin for further synthetic applications, as demonstrated by the total synthesis of two natural products, myrotheciumone A and pedicellosine, from abundant dicarboxylic acids.

Rigidified Cavitand Hosts in Water: Bent Guests, Shape Selectivity, and Encapsulation.

We report the synthesis and characterization of two water-soluble container compounds (cavitand hosts) with rigidified open ends. One cavitand uses four (CH2)4's as spacers to bridge the adjacent walls, while another cavitand uses four CH2CH2OCH2CH2's bridges and features a wider open end. The spacers preorganize the deep cavitands into vase-like, receptive shapes and prevent their unfolding to the unreceptive kite-like conformation. Cycloalkane guests (C6-C8) and small n-alkanes (C5-C7) form 1:1 complexes with the cavitands and move freely in the cavitands' spaces. Hydrophilic compounds 1,4-dioxane, tetrahydrofuran, tetrahydropyran, pyridine, and 1-methylimidazole also showed good binding affinity to the new cavitands. Longer alkanes (C11-C14) and n-alcohols (C11-C16) are taken up with a -CH3 group fixed at the bottom of the cavity and the groups near the rim in compressed conformations. The methylene bridges appear to divide the cavitand into a narrow hydrophobic compartment and a broader space with exposure to the aqueous medium. Longer alkane guests (C15-C18), N,N-dimethyldioctylammonium, and dioctylamine induce the formation of capsules (2:1 host:guest complexes). The new cavitands showed selectivity for p/m-cresol isomers and xylene isomers. The cavitand with CH2CH2OCH2CH2 bridges bound long-chain α,ω-diols (C13-C15) and diamines in folded, U-shaped conformations with polar functions exposed to the aqueous medium. It was used to separate o-xylene from its isomers by using simple extraction procedures.

Selective Macrocycle Formation in Cavitands.

The traditional end-to-end cyclization of long-chain linear precursors is difficult and often unpredictable because the unfavorable entropy of macrocyclic closure allows undesired intermolecular reactions to compete. Here, we apply cavitands to the selective intramolecular aldol/dehydration reaction of long-chain α,ω-dialdehydes in aqueous solution. Hydrophobic forces drive the dialdehydes into the cavitands in folded conformations and favor macrocyclization reactions over intermolecular reactions observed in bulk solution. The macrocyclic aldol reaction products are isolated in good yields (30-85%) over a wide range (11 to 17-membered rings). Unlike conventional templates that become guests inside their assembled hosts, cavitands reverse the roles and resemble the situation in biological catalysis-the templates are hosts for guests undergoing the assisted reaction processes.

Insertion of Alkylidene Carbenes into B-H Bonds.

We have developed a protocol for insertion of alkylidene carbenes into the B-H bonds of amine-borane adducts, enabling, for the first time, the construction of C(sp2)-B bonds by means of carbene-insertion reactions. Various acyclic and cyclic alkenyl borane-amine adducts were prepared from readily accessible starting materials in good to high yields and were subsequently subjected to a diverse array of functional group transformations. The unprecedented spiro B-N heterocycles prepared in this study have potential utility as building blocks for the synthesis of pharmaceuticals. Preliminary mechanistic studies suggest that insertion of the alkylidene carbenes into the B-H bonds of the amine-borane adducts proceeds via a concerted process involving a three-membered-ring transition state.

Modulation of the driving forces for adsorption on MIL-101 analogues by decoration with sulfonic acid functional groups: superior selective adsorption of hazardous anionic dyes.

Toxic dyes pose a dramatic threat to human health and the environment when they are directly released into the water environment. Therefore, new porous materials with excellent adsorption performances are urgently needed to remove toxic dyes from wastewater. Herein, we report a sulfo-modified metal-organic framework (MIL-101-SO3H), which exhibits superior adsorption performance toward toxic dyes. The free -SO3H groups were successfully introduced into the MIL-101(Cr) skeleton to modulate the adsorption driving forces (i.e., hydrogen bonding, electrostatic attractions, and π-π stacking interactions together with adsorption spaces and steric hindrance) between the toxic dyes and MIL-101-SO3H adsorbent by varying the monosodium 2-sulfoterephthalic acid-to-terephthalic acid molar ratio in the reaction mixture. The experimental adsorption uptake by MIL-101-SO3H-1 was found to be 688.9 (methyl orange), 2592.7 (Congo red), and 213.2 (acid chrome blue K, AC) mg g-1, which was respectively 69.6, 89.6, and 51.5% higher than those of undecorated MIL-101. This adsorption behavior was attributed to the dye molecular structure, pore volumes, surface charge status, and functional groups of the adsorbents as well as the adsorption capacity of the dyes. The results revealed that the uncoordinated -SO3H groups increased the electrostatic attraction and hydrogen bonding between the MIL-101-SO3H adsorbent and linear anionic dyes. This increased the adsorption capacity toward the linear anionic dyes, overriding the effect of the pore volumes. On the other hand, the steric hindrance between the nonlinear anionic dye AC and MIL-101-SO3H adsorbent decreased the AC adsorption uptake of the latter, overriding the effects of hydrogen bonding and electrostatic attraction. In addition, the adsorption performance toward the cationic dye methylene blue increased, owing to the hydrogen bonding interactions, thereby overriding the effect of electrostatic repulsion and adsorption spaces. Thus, it is concluded that the adsorption behavior of the modified MIL-101-SO3H adsorbent is governed by the synergetic interplay between the electrostatic attraction, hydrogen bonding, and π-π stacking interactions as well as the steric hindrance and pore volumes of the adsorbent.

Binding selectivity and separation of p-functionalized toluenes with a metallo-cavitand in water.

A metallo-cavitand (1-2Pd) showed unprecedented binding selectivity and sequestration of p-functionalized toluene isomers in water. The host-guest complexation was studied using 1H and COSY NMR methods and xylene-isomer complexes were examined by using DFT calculations. A liquid-liquid extraction scheme was developed for the separation of p-functionalized toluenes.

The LAMMER kinase is involved in morphogenesis and response to cell wall- and DNA-damaging stresses in Candida albicans.

Dual specificity LAMMER kinase has been reported to be conserved across species ranging from yeasts to animals and has multiple functions. Candida albicans undergoes dimorphic switching between yeast cells and hyphal growth forms as its key virulence factors. Deletion of KNS1, which encodes for LAMMER kinase in C. albicans, led to pseudohyphal growth on YPD media and defects in filamentous growth both on spider and YPD solid media containing 10% serum. These cells exhibited expanded central wrinkled regions and specifically reduced peripheral filaments. Among the several stresses tested, the kns1Δ strains showed sensitivity to cell-wall and DNA-replicative stress. Under fluorescent microscopy, an increase in chitin decomposition was observed near the bud necks and septa in kns1Δ cells. When the expression levels of genes for cell wall integrity (CWI) and the DNA repair mechanism were tested, the kns1 double-deletion cells showed abnormal patterns compared to wild-type cells; The transcript levels of genes for glycosylphosphatidylinositol (GPI)-anchored proteins were increased upon calcofluor white (CFW) treatment. Under DNA replicative stress, the expression of MluI-cell cycle box binding factor (MBF)-targeted genes, which are expressed during the G1/S transition in the cell cycle, was not increased in the kns1 double-deletion cells. This strain showed increased adhesion to the surface of an agar plate and zebrafish embryo. These results demonstrate that Kns1 is involved in dimorphic transition, cell wall integrity, response to DNA replicative stress, and adherence to the host cell surface in C. albicans.

Rhodium-Catalyzed B-H Bond Insertion Reactions of Unstabilized Diazo Compounds Generated in Situ from Tosylhydrazones.

Although transition-metal-catalyzed B-H bond insertion of carbenes into stable borane adducts has emerged as a promising method for organoborane synthesis, all the diazo compounds used to date as carbene precursors have had an electron-withdrawing group to stabilize them. Herein, we report a protocol for rhodium-catalyzed B-H bond insertion reactions of unstabilized diazo compounds generated in situ from tosylhydrazones. In addition, by using chiral dirhodium catalysts, we also achieved an asymmetric version of the reaction with good to excellent enantioselectivities (up to 98:2 e.r.). This is the first enantioselective heteroatom-hydrogen bond insertion reaction to use unstabilized diazo compounds as carbene precursors. The protocol exhibited good functional group tolerance and could be carried out on a gram scale. It also enabled one-pot transformation of a carbonyl group to a boryl group enantioselectively. The B-H bond insertion products could be easily transformed into chiral alcohols and other widely used organoboron reagents with enantiomeric fidelity.

Effect of surface charge status of amorphous porous coordination polymer particles on the adsorption of organic dyes from an aqueous solution.

The surface charge status of coordination polymer particles (CPPs) from negative electrification through electrically neutral to positive electrification was achieved by varying the amount of acetic acid. The adsorption capacity of CPPs-1 with a negatively charged framework for the anionic dye Congo red (CR) is much higher than that of the CPPs-5, which possess a positively charged framework, because of different adsorption mechanisms. This is the first reported example of negatively charged CPPs exhibiting excellent adsorption performance toward anionic organic dyes. Broadly, the obtained results shed light on the mechanism of organic dye adsorption on CPPs. The CPP nanostructures exhibit excellent adsorption capabilities for the CR dye, with a maximum capacity of 1033.2 mg g-1, which is higher than that of most reported materials. The influences of variables such as initial pH, organic dye concentration, and contact time were investigated. The results indicate that the CPPs-1 nanostructures have promising application in CR dye-containing wastewater treatment.

Adsorptive removal of organic dyes from aqueous solution by a Zr-based metal-organic framework: effects of Ce(iii) doping.

Herein, we report the synthesis and characterization of Ce(iii)-doped UiO-66 nanocrystals, revealing their potential to efficiently remove organic dyes such as methylene blue (MB), methyl orange (MO), Congo red (CR), and acid chrome blue K (AC) from aqueous solutions. Specifically, the room-temperature adsorption capacities of Ce(iii)-doped UiO-66 equaled 145.3 (MB), 639.6 (MO), and 826.7 (CR) mg g-1, exceeding those reported for pristine UiO-66 by 490, 270, and 70%, respectively. The above behavior was rationalized based on zeta potential and adsorption isotherm investigations, which revealed that Ce(iii) doping increases the number of adsorption sites and promotes π-π interactions between the adsorbent and the adsorbate, thus improving the adsorption capacity for cationic and anionic dyes and overriding the effect of electrostatic interactions. The obtained results shed light on the mechanism of organic dye adsorption on metal-organic frameworks, additionally revealing that the synergetic interplay of electrostatic, π-π, and hydrophobic interactions results in the operation of two distinct adsorption regimes depending on adsorbate concentration.

A facile approach to fabricate an immobilized-phosphate zirconium-based metal-organic framework composite (UiO-66-P) and its activity in the adsorption and separation of organic dyes.

A novel immobilized-phosphate zirconium-based metal-organic framework composite, denoted as UiO-66-P, was synthesized by a solvothermal method using UiO-66 nanoparticles and Na3PO4 ligands. The products were characterized by powder X-ray diffraction, energy dispersive spectrometry, field emission scanning electron microscopy, thermogravimetric analysis, infrared spectroscopy, zeta potential analysis, and gas adsorption measurements. The UiO-66-P nanocrystals, which comprised negatively charged frameworks, exhibited high stability, excellent porosity, and efficient charge-selective capture and separation of the cationic dye Methylene Blue (MB). An uptake capacity of 91.1mgg-1 was achieved at room temperature over 24h when 5mg of UiO-66-P was immersed in 40mL of a 500mgL-1MB solution. This capacity is much higher than that of UiO-66 (24.5mgg-1). The adsorption capability of UiO-66-P for MB was improved by 272% compared to that of pristine UiO-66. The effects of variables such as initial pH, MB concentration, and contact time were investigated. In addition, the as-obtained UiO-66 nanocrystals exhibited excellent adsorption capability for the anionic dyes Congo Red, Acid Chrome Blue K, and Methyl Orange.

Catalytic B-H Bond Insertion Reactions Using Alkynes as Carbene Precursors.

Herein, we report transition-metal-catalyzed B-H bond insertion reactions between borane adducts and alkynes to afford organoboron compounds in excellent yields under mild reaction conditions. This successful use of alkynes as carbene precursors in these reactions constitutes a new route to organoboron compounds. The starting materials are safe and readily available, and the reaction exhibits 100% atom-economy. Moreover, an asymmetric version catalyzed by chiral dirhodium complexes produced chiral boranes with excellent enantioselectivity (up to 96% ee). This is the first report of highly enantioselective heteroatom-hydrogen bond insertion reactions of metal carbenes generated in situ from alkynes. The chiral products of the reaction could be easily transformed to widely used borates and diaryl methanol compounds without loss of optical purity, which demonstrates its potential utility in organic synthesis. A kinetics study indicated that the Cu-catalyzed B-H bond insertion reaction is first order with respect to the catalyst and the alkyne and zero order with respect to the borane adduct, and no kinetic isotopic effect was observed in the reaction of the adduct. These results, along with density functional theory calculations, suggest that the formation of the Cu carbene is the rate-limiting step and that the B-H bond insertion is a fast, concerted process.

Facile water-stability evaluation of metal-organic frameworks and the property of selective removal of dyes from aqueous solution.

A facile and universal method was developed to evaluate the relative water stability of porous MOFs and morphological evolution was achieved by controlling the volume ratio of DMF and H2O. The relative water stability of the studied MOFs is in the order HKUST-1 > MOF-505 ∼ UMCM-150 > NOTT-101 > DUT-23(Cu) > [Zn2(BPnDC)2(DABCO)] ∼ [Cu3(TPTrC)2(DABCO)] > MOF-5. In addition, DUT-23(Cu) [Cu6(BTB)4(BPY)3] (H3BTB = 4,4',4''-benzene-1,3,5-triyl-tribenzoic acid, BPY = 4,4'-bipyridine) nanoparticles obtained with a volume ratio of DMF and H2O of 18 : 2 show excellent adsorption capacity for methylene blue (MB) (814 mg g(-1)) with high selectivity compared with methyl orange, rhodamine B, and acid chrome blue K dyes due to the size and the electrostatic repulsion effects in aqueous solution.

Facile fabrication of MIL-103(Eu) porous coordination polymer nanostructures and their sorption and sensing properties.

Nano/microscale lanthanide porous coordination polymer MIL-103(Eu) [Eu(BTB)] (H3BTB = 4,4',4''-benzene-1,3,5-triyl-tribenzoic acid) crystals have been fabricated at room temperature by a facile, convenient and environmentally friendly method. The structures of the products were confirmed by powder X-ray diffraction, and the crystal morphologies, including microrods, nanorods and nanospheres, were characterized by scanning electron microscopy. It is found that the addition of sodium acetate and the concentration of the reactants have an important impact on the morphology and size of the MIL-103(Eu) crystals. Gas adsorption measurements reveal that the products show high specific surface areas among the rare earth based coordination polymers and the MIL-103(Eu) nanorods can selectively adsorb CO2 over N2 under ambient conditions. Furthermore, all the products exhibit red emission corresponding to the (5)D0→(7)F2 transition of the Eu(iii) ion, and MIL-103(Eu) nanorods display sensitive and selective sensing for Cu(ii) ions and acetone molecules in solution.

Iron-catalyzed arylation of α-aryl-α-diazoesters.

An iron-catalyzed arylation of α-aryl-α-diazoesters with electron-rich benzene rings was developed, which provides an efficient method for the preparation of 1,1-diarylacetates with high yields and excellent chemo- and regio-selectivities.

Morphology evolution and gas adsorption of porous metal-organic framework microcrystals.

A facile and controllable synthesis of porous framework [Cu3(L)2(DABCO)] (1) (H3L = 1,1':3,1''-terphenyl]-4,4'',5'-tricarboxylic acid; DABCO = 1,4-diazabicyclo[2.2.2]octane) microcrystals was realized with morphology evolution from a tetragonal plate to an elongated tetragonal bipyramid, and the particle size changes by tuning the volume ratio of mixed solvents of DMF and H2O. Interestingly, the exposed high-energy {103} crystal facet can be easily tuned by controlling the supersaturation through the increase of the solution concentration, resulting in the formation of spindle microcrystals. It was found that both H2O and HCl play important roles in the morphology evolution process. The gas adsorption properties were found to be dependent on the morphology of microcrystals, and the elongated tetragonal bipyramidal microcrystals show the largest BET surface area.

M-CSF from Cancer Cells Induces Fatty Acid Synthase and PPARß/δ Activation in Tumor Myeloid Cells, Leading to Tumor Progression.

We investigate crosstalk between cancer cells and stromal myeloid cells. We find that Lewis lung carcinoma cells significantly induce PPARß/δ activity in myeloid cells in vitro and in vivo. Myeloid cell-specific knockout of PPARß/δ results in impaired growth of implanted tumors, and this is restored by adoptive transfer of wild-type myeloid cells. We find that IL-10 is a downstream effector of PPARß/δ and facilitates tumor cell invasion and angiogenesis. This observation is supported by the finding that the CD11blowIL-10+ pro-tumoral myeloid cell is scarcely detected in tumors from myeloid-cell-specific PPARß/δ knockout mice, where vessel densities are also decreased. Fatty acid synthase (FASN) is shown to be an upstream regulator of PPARß/δ in myeloid cells and is induced by M-CSF secreted from tumor cells. Our study gives insight into how cancer cells influence myeloid stromal cells to get a pro-tumoral phenotype.