Synergy of Paired Brønsted-Lewis Acid Sites on Defects of Zr-MIL-140A for Methanol Dehydration.

As a common defect-capping ligand in metal-organic frameworks (MOFs), the hydroxyl group normally exhibits Brønsted acidity or basicity, but the presence of inherent hydroxyl groups in the MOF structure makes it a great challenge to identify the exact role of defect-capping hydroxyl groups in catalysis. Herein, we used hydroxyl-free MIL-140A as the platform to generate terminal hydroxyl groups on defect sites via a continuous post-synthetic treatment. The structure and acidity of MIL-140A were properly characterized. The hydroxyl-contained MIL-140A-OH exhibited 4.6-fold higher activity than the pristine MIL-140A in methanol dehydration. Spectroscopic and computational investigations demonstrated that the reaction was initiated by the respective adsorption of two methanol molecules on the terminal-OH and the adjacent Zr vacancy. The dehydration of the adsorbed methanol molecules then occurred in the Brønsted-Lewis acid site co-participated associative pathway with the lowest energy barrier.

Fabricating defect-rich metal-organic frameworks via mixed linker-induced crystal transformation.

Defect-rich hcp UiO-66-NO2 was synthesized via mixed linker-induced crystal transformation from fcu UiO-66-NO2/NH2. The defect concentration and porosity of hcp UiO-66-NO2 can be fine-tuned by varying the BDC-NH2/BDC-NO2 ratio, which in turn endowed hcp UiO-66-NO2 with superior catalytic performance in the ring-opening reaction of epoxides with alcohols.

Macro-composition quantification combined with metabolomics analysis uncovered key dynamic chemical changes of aging white tea.

It is a common belief in China that aging could improve the quality of white tea. However, the stored-induced compositional changes remain elusive. In this study, ten subsets of white tea samples, which had been stored for 1-, 2-, 3-, 4-, 5-, 6-, 7-, 10-, 11- and 13- years, were selected. Macro-compositions were quantified firstly. As the results showed, it was interesting to find total flavonoids, thearubigins (TRs), and theabrownines (TBs) increasing, accompanied with a gradual decrease of total polyphenols, which suggest a conversion of phenolic component in the aging process. Then, nontargeted metabolomics was further conducted on selected subsets of samples, including 1-, 7- and 13- years stored to profile their conversion. As a result, most different metabolites were related to flavonol glycosides and flavone glycosides, suggesting dynamic phenolic component changes were vital in aging. The partial least-squares-discriminant analysis (PLS-DA) also identified them as markers in distinguishing.

Divergent Metal-Free [4 + 2] Cascade Reaction of 1-Indanylidenemalononitrile with 3-Benzylidenebenzofuran-2(3H)-one: Access to Spiro-dihydrofluorene-benzofuranone and Axially Chiral Fluorenylamine-phenol Derivatives.

An efficient cascade reaction of 1-indanylidenemalononitrile with 3-benzylidenebenzofuran-2(3H)-one divergently promoted by DABCO or chiral organocatalyst was developed under mild reaction conditions, and various spiro-dihydrofluorene-benzofuranones were produced in gratifying results, respectively. It is worth noting that both the spiro and axially chiral products can be obtained by tuning the reaction conditions. The mechanism of the transformation was also studied by quantum chemical calculations.

Pair Sites on Nodes of Metal-Organic Framework hcp UiO-66 Catalyze tert-Butyl Alcohol Dehydration.

On metal oxide cluster nodes of metal-organic frameworks (MOFs), sites not bonded to linkers (e.g., defects and structural vacancies) control reactivity and catalysis. Attention has been focused on isolated, individual sites, but pair sites have been largely overlooked. We now show that the MOF hcp UiO-66, which incorporates dimeric Zr6O8 nodes bridged by µ2-OH groups, is an excellent platform for identifying and controlling adjacent sites consisting of OH groups and Zr4+ sites, which catalyze tert-butyl alcohol dehydration much more rapidly than isolated single sites.

Computational Mechanistic Study of Brønsted Acid-Catalyzed Unsymmetrical 1,2,4,5-Tetrazines Synthesis.

Density functional theory (DFT) calculations were conducted to gain insight into the reaction mechanism of the Brønsted acid-catalyzed unsymmetrical 1,2,4,5-tetrazine synthesis. Various possible reaction pathways were considered, and the most favorable one can be characterized via sequential six steps, including addition of DCM to hydrazine 1 giving complex IM4, N-H bond activation in IM4 mediated by sulfur, AcOH-assisted substitution of 3 with sulfur-activated hydrazine 2, HNO2-assisted addition of nitrile to intermediate 8, cyclization, and intramolecular elimination leading to the final product 7. Among the six steps, sulfur activation of IM4 N-H bond is found to be the rate-determining step (RDS). The mechanism rationalizes the experimental observation that 2 equiv of sulfur leads to the best yield of product. Furthermore, we disclosed that the Brønsted acid additives (i.e., acetic acid and nitrous acid) served triple roles as catalyst, proton shuttle, and hydrogen bond donor and acceptor in the whole catalysis.

Mechanistic Study of the N-Quaternized Pyridoxal-Catalyzed Biomimetic Asymmetric Mannich Reaction: Insights into the Origins of Enantioselectivity and Diastereoselectivity.

Density functional theory calculations have been performed to gain insights into the catalytic mechanism of the N-quaternized pyridoxal (i.e., 1a)-mediated biomimetic asymmetric Mannich reaction of tert-butyl glycinate 3 with N-diphenylphosphinyl imine 2a to give the diamino acid ester 4a in high yield with excellent enantiomeric and diastereomeric selectivity (Science 2018, 360, 1438). The study reveals that the whole catalysis can be characterized via three stages: (i) the catalyst 1a reacts with the tert-butyl glycinate 3 to generate the active carbanion complex IM3. (ii) IM3 then reacts with the N-diphenylphosphinyl imine 2a giving the imine intermediate IM8. (iii) IM8 undergoes hydrolysis to give the final product anti-4a and regenerate the catalyst 1a for the next catalytic cycle. Each stage is kinetically and thermodynamically feasible for experimental realization. The hydrolysis step in the stage III is predicted to be the rate-determining step during the whole catalytic cycle. Furthermore, the origins of the enantioselectivity and diastereoselectivity for the target reaction, as well as the deactivation of the catalyst 1b, are also discussed.

Mechanistic study of the cooperative palladium/Lewis acid-catalyzed transfer hydrocyanation reaction: the origin of the regioselectivity.

Density functional theory (DFT) calculations have been performed to gain insights into the catalytic mechanism of the palladium/Lewis acid-catalyzed transfer hydrocyanation of terminal alkenes to reach the linear alkyl nitrile with excellent anti-Markovnikov selectivity. The study reveals that the whole catalysis can be characterized via three stages: (i) oxidative addition generates the π-allyl complex IM2, followed by ß-hydride elimination leading to the intermediate IM4, (ii) ligand exchange followed by Pd-H migratory alkene insertion gives the anti-Markovnikov intermediate IM6 and (iii) IM6 undergoes a reductive elimination step to form the linear terminal nitrile 3a and regenerates the active species for the next catalytic cycle. Each stage is kinetically and thermodynamically feasible. The oxidative addition step, with a barrier of 30.9 kcal mol-1, should be the rate-determining step (RDS) in the whole catalysis, which agrees with the experimental high temperature of 110 °C. Furthermore, the origin of the high regioselectivity of the product with excellent anti-Markovnikov selectivity is discussed.

Preparation of graphene oxide-modified palygorskite nanocomposites for high-efficient removal of Co(II) from wastewater.

Removing Co(II) from wastewater is urgent due to the threat to the environment and human health. In the work, the nanocomposite of graphene oxide-modified palygorskite (mPal-GO) is synthesized by cross-linking one-dimensional palygorskite (Pal) with two-dimensional material graphene oxide (GO), and used to remove Co(II) from wastewater. Its structure is characterized by Fourier transformed infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area measurement. The parameters, such as mass ratio (GO:mPal), temperature, pH, and contact time, are carefully investigated. The results indicate that pseudo-second-order equation and Langmuir isotherm model are the best fitting one in the adsorption process of Co(II) onto mPal-GO. The maximum adsorption capacity achieves 16.9 mg/g at pH = 6.0 and T = 298 K according to the Langmuir model analysis. Furthermore, mPal-GO can be reused more than 5 times with a slight decrease according to the adsorption-desorption cycle experiments. Finally, mPal-GO with the low-cost and easy separation is a promising candidate for removing of Co(II) from wastewater.

Correction to "Monitoring the Hierarchical Evolution from a Double-Stranded Helix to a Well-Defined Microscopic Morphology Based on a Turbine-like Aromatic Molecule".

[This corrects the article DOI: 10.1021/acsomega.0c01443.].

Monitoring the Hierarchical Evolution from a Double-Stranded Helix to a Well-Defined Microscopic Morphology Based on a Turbine-like Aromatic Molecule.

1H-Indazolo[1,2-b]phthalazine-5,10-dione IPDD with an approximate turbine-like spatial structure, primary assembled double-stranded helices at the first level, was predicted by quantum chemical calculations and confirmed by atomic force microscopy. The higher-dimensional hierarchical architectures including fibrils, helical fibers, spherical shells, and porous prismatic structures were observed in sequence by the scanning electron microscopy technique. The final porous prismatic structures sensitive to NH3 vapors have the potential to be applied in gas sensing and absorbing materials.

Complex emulsions for shape control based on mass transfer and phase separation.

Complex emulsions are used to fabricate new morphologies of multiple Janus droplets, evolving from non-engulfing to complete engulfing core/shell configuration. The produced droplets contain an aqueous phase of dextran (DEX) solution and an oil phase, which is mixed with ethoxylated trimethylolpropane triacrylate (ETPTA) and poly(ethylene glycol) diacrylate (PEGDA). The PEGDA in the oil phase is transferred into the aqueous phase to form complex morphologies due to the phase separation of PEGDA and DEX. The effects are investigated including the ratio of oil to aqueous phase, the content of initial PEGDA, DEX and surfactants, and the type of surfactants. DEX/PEGDA-ETPTA core/shell-single phase Janus droplets are formed with an increasing engulfed oil droplet into the aqueous droplet while the ratio of oil to aqueous phase increases or the initial PEGDA content increases. The high DEX content leads to the DEX-PEGDA-ETPTA doublet Janus. The use of surfactants polyglycerol polyricinoleate (PGPR) and Span 80 results in the formation of DEX/PEGDA/ETPTA single core/double shell and DEX/PEGDA-ETPTA core/shell-single phase Janus droplets, respectively. These complex emulsions are utilized to fabricate solid particles of complex shapes. This method contributes to new material design underpinned by mass transfer and phase separation, which can be extended to other complex emulsion systems.

Preparation of Silica@Silica Core-Shell Microspheres Using an Aqueous Two-Phase System in a Novel Microchannel Device.

In the present work, a novel microchannel device was developed and used for the preparation of core-shell microspheres combining with a dextran/poly(ethylene glycol) diacrylate (DEX/PEGDA) aqueous two-phase system. Silica@silica core-shell microspheres were prepared as a model material. Silica@silica core-shell microspheres with different sizes of cores and thicknesses of shells were prepared by using different flowrate ratios of DEX/silica and PEGDA/silica aqueous solutions. The content of colloidal silica and the calcination temperature have a significant effect on the texture properties of the prepared core-shell microspheres. The surface area decreased from 199 to 177 m2/g with an increase in the colloidal silica content from 30 to 60 wt %. For a specific colloidal silica content (50 wt %), with the increase in calcination temperature from room temperature to 650 °C, the total pore volume went through a maximum of 0.7 cm3 g-1 with a surface area of 178 m2 g-1 and pore size of 7.32 nm at 450 °C. Due to the accumulation of metal nanoparticles in DEX, different metal nanoparticles (Ni and Pd) were successfully introduced into the core of the core-shell microspheres for the preparation of silica/metal nanoparticles@silica core-shell microsphere catalysts. The catalysts showed similar catalytic performance as the metal nanoparticles for hydrogenation of 4-nitrophenol with a conversion higher than 95%. However, the core-shell microsphere catalyst is much easier to recover. The reuse experiments indicated that the core-shell catalyst has high stability.

Shape-Anisotropic Diblock Copolymer Particles with Varied Internal Structures.

Anisotropic polymer particles have promising applications in various fields, whereas their preparation usually suffers from tedious procedures. Here, we introduce a facile strategy to fabricate novel shape-anisotropic particles with varied internal structures via self-assembly of block copolymers (BCPs), with perfluorooctane (PFO) as the liquid template in emulsion droplets. By increasing the volume ratio of PFO to polystyrene- block-poly(4-vinylpyridine) (PS- b-P4VP) or decreasing the initial concentration of the BCPs, the self-assembled polymer particles change from spherical core-shell structures to anisotropic particles. Moreover, the anisotropic shape and internal structure of the polymer particles, including cone-like particles with alternative PS and P4VP lamellas, crescent-shaped particles with cylindrical P4VP domains, and plate-like particles with spherical P4VP domains, can be obtained by changing the block ratio or molecular weight or by adding a hydrogen-bonding agent. Based on the in situ optical microscopy investigation of the morphology evolution of the emulsion droplet, we conclude that both kinetic and thermodynamic factors during emulsion evolution determine the formation of shape-anisotropic polymeric particles with controllable internal structures.

Kinetically Controlled Self-Assembly of Block Copolymers into Segmented Wormlike Micelles in Microfluidic Chips.

Kinetically controlled self-assembly of block copolymers (BCPs) in solution is an efficient route to fabricate complex hierarchical colloids which are of great importance for nanoencapsulation, microreactors, and biomimics. Herein, segmented wormlike micelles (SWMs) with controllable size are generated by the self-assembly of polystyrene- block-poly(4-vinyl pyridine) in microfluidic channel. Different from the assembly of BCPs off-chip at the same solution properties, it is found that the fabricated SWMs are kinetically controlled assemblies with thermodynamic metastable structures, which are formed by the orderly aggregation of preformed spherical micelles because of the fast mixing process in microfluidic channels. Moreover, by manipulating the total flow velocity of water and BCPs solution or their flow velocity ratio, both of the percentages of SWMs among the whole assemblies and their sizes can be effectively tuned. On the basis of electron microscopy and dynamic light scatting investigations, a product diagram of micellar morphologies associated to initial polymer concentration and flow velocity ratio of water/BCPs solution was constructed, which is important for the rational design and fabrication of complex hierarchical BCP colloids.

Regulating Block Copolymer Assembly Structures in Emulsion Droplets through Metal Ion Coordination.

In this report, we demonstrate the metal ion coordination-induced morphological transition of block copolymer assemblies under three-dimensional (3D) confinement. Polystyrene- block-poly(4-vinyl pyridine) (PS- b-P4VP) aggregates with various morphologies can be obtained by emulsion-solvent evaporation in the presence of metal ions (e.g., Pb(II) or Fe(III) ions) in the aqueous phase. Due to the coordination interaction between 4VP units and metal ions, the overall shape, internal structure, and surface composition of the particles can be tailored by varying the type and concentration of the metal ions. For example, when Pb(II) ions were employed, morphological transition of the assemblies occurred due to the formation of P4VP-Pb(II) complexes. More interestingly, when Fe(III) ions were added, hydrolysis of Fe(III) caused the reduction of the pH value of the aqueous phase, leading to the protonation of 4VP units. As a result, interfacial instability took place to trigger the splitting of emulsion droplets and then formation of nanosized micelles. Therefore, metal ion coordination is a facile strategy to tune the structure of assemblies under 3D confinement and offers an alternative approach for the design of organic-inorganic hybrid assemblies with well-tunable structures.

Fabrication of PAA-PETPTA Janus Microspheres with Respiratory Function for Controlled Release of Guests with Different Sizes.

Poly(acrylic acid)-poly(ethoxylated trimethylolpropane triacrylate) (PAA-PETPTA) Janus microspheres with "respiratory" function for controlled release were prepared by polymerization of acrylic acid-ethoxylated trimethylolpropane triacrylate (AA-ETPTA) Janus microdroplets in a continuous oil phase in a simple capillary-based microfluidic device with the assistance of UV radiation. The flow rate ratios of AA and ETPTA phases and surfactant content in the continuous oil phase have a significant effect on the structure of the Janus microspheres. PAA part in the Janus microspheres has respiratory function for loading and release due to the different stimuli responses to different pHs. The hollow structure of PETPTA part with different sizes of opening serves as the host materials for PAA and could control release rate further due to the different opening sizes. The obtained PAA-PETPTA Janus microspheres showed high rhodamine B (RhB) loading of 860 mg g-1 and different controlled-release behavior in water with different pHs. The release rate increases with the increase of pH and the contact area of PAA part with water. The maximum controlled-release time for RhB was about 3 h in water with pH of 5. In addition, the Janus microspheres also showed controlled-release behavior for larger size guests, e.g., 150 nm polystyrene beads, which indicated a wide range of application. The loading and release behaviors for guests, for instance, for RhB, have almost no change even after six times of reuse, which indicated a high stability.

Shaping metal-organic framework materials with a honeycomb internal structure.

A self-assembly technology allows metal-organic framework materials to constitute a honeycomb internal structure while being shaped into millimeter-scale spheres. The ZIF-8 load is up to 83 wt% through solidification of chitosan (CS). This approach can be expanded to other morphologies (fibers) or crystals and is transformative for industrial manufacturing of nanomaterials.

Two-Phase Diffusion Technique for the Preparation of Ultramacroporous/Mesoporous Silica Microspheres via Interface Hydrolysis, Diffusion, and Gelation of TEOS.

Honeycombed hierarchical ultramacroporous/mesoporous silica microspheres were prepared via the hydrolysis of TEOS in the oil-water interface, with subsequent diffusion and gelation in the acidic water-phase microdroplets with the assistance of a simple homemade microdevice. The diffusion of furfuryl alcohol (FA) also happened at a relatively high rate during the hydrolysis and diffusion of TEOS. Therefore, plenty of FA will be inside of the water microdroplets and form a decent number of polyfurfuryl alcohol (PFA) microparticles, thereby obtaining honeycombed hierarchical porosity silica microspheres with abundant ultramacroporous cavities and mesopores after calcination. It was found that the concentration of FA, residence time, and reaction temperature have significant effects on the porosity and pore size due to the influence on the diffusion rate and amount of FA in water-phase microdroplets. The honeycombed silica microspheres have obvious microscopic visible ultramacroporous cavities with the submicrometer cavity diameter as high as 85% porosity based on the rough overall volume of microsphere. N2 adsorption-desorption isotherms show that the honeycombed hierarchical porosity silica microspheres have a high surface area of 602 m2 g-1, a mesopore volume of 0.77 cm3/g, and a mesopore porosity of 99.6% based on the total pore volume of N2 adsorption-desorption. On the basis of the experiment results, a rational formation process of the honeycombed hierarchical porosity silica microspheres was deduced.

Complex Emulsions by Extracting Water from Homogeneous Solutions Comprised of Aqueous Three-Phase Systems.

Multiple emulsions can be obtained by binary and ternary liquid phase separation. And the use of the aqueous two-phase system provides a simple route to prepare water-in-water-in-oil (W/W/O) or water-in-water-in-water (W/W/W) multiple emulsions. It is thus expected that we can fabricate more complex emulsions by using an aqueous three-phase system. Herein, we present a simple and versatile method to generate complex emulsions based on phase separation in homogeneous droplets made up of aqueous three-phase system: poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA) and dextran (DEX) through extracting water from droplets. We examine the formation process and the effect of mass ratio of each two components in the three phase system. Emulsion droplets with five types of morphologies, i.e., binary-core/shell, core/shell-single phase Janus, ellipsoid Janus, multicore-in-matrix and single core-double shell morphologies can be formed, depending on the mass ratio of each two components and modification of PEG with Fe3O4 nanoparticles. We observe transition of core/shell-single phase Janus to binary-core/shell and single core-double shell to core/shell-single phase Janus geometry with prolongation of extracting time, and obtain the geometry map for the formation of different shaped droplets. Due to different affinities of PEG, PVA and DEX to certain materials, we functionalize each compartment in the complex emulsion droplets, and apply the resulting droplet for glucose sensing and the construction of antibody-mediated targeting drug delivery. This emulsion generation method is simple and the choice for the component of the aqueous three-phase system is broad, which can be further extended to generate complex emulsions from aqueous multiphase systems.