Aggregation induced emission by pyridinium–pyridinium interactions

Non-covalent intermolecular interactions between pyridinium subunits in a crystal-state are an efficient means to accomplish aggregation induced emission and avoid aggregation caused quenching.

Non-covalent intermolecular pyridinium–pyridinium and pyridinium–arene-π system interactions result in aggregation induced emission (AIE).     

Rhodium(iii)-catalyzed annulation of enamides with sulfoxonium ylides toward isoquinolines

An efficient rhodium(iii)-catalyzed C–H activation followed by intermolecular annulation between enamides and sulfoxonium ylides has been developed. The transformation proceeds smoothly with a broad range of substrates, affording a series of isoquinoline derivatives in moderate to good yields under additive-free conditions.

An efficient rhodium(iii)-catalyzed C–H activation followed by intermolecular annulation between enamides and sulfoxonium ylides has been developed.     

Quantitative analysis of hydrogen and chalcogen bonds in two pyrimidine-5-carbonitrile derivatives,potential DHFR inhibitors: an integrated crystallographic and theoretical study

Two potential bioactive pyrimidine-5-carbonitrile derivatives have been synthesized and characterized by spectroscopic techniques (¹H and ¹³C-NMR) and the three dimensional structures were elucidated by single crystal X-ray diffraction at low temperature (160 K). In both structures, the molecular conformation is locked by an intramolecular C–H⋯C interaction involving the cyano and CH of the thiophene and phenyl rings. The intermolecular interactions were analyzed in a qualitative manner based on the Hirshfeld surface and 2D-fingerprint plots. The results suggest that the phenyl and thiophene moieties have an effect on the crystal packing. For instance, the chalcogen bonds are only preferred in the thiophene derivative. However, both structures uses a common N–H⋯O hydrogen bond motif. Moreover, the structures of 1 and 2 display 1D isostructurality and molecular chains stabilize by intermolecular N–H⋯O and N–H⋯N hydrogen bonds. The nature and extent of different non-covalent interactions were further characterized by the topological parameters derived from the quantum theory of atoms-in-molecules approach. This analysis indicates that apart from N–H⋯O hydrogen bonds, other non-covalent interactions are closed-shell in nature. A strong and linear N–H⋯O hydrogen bond shows intermediate bonding character between shared and closed-shell interactions. The molecular docking analysis suggests that both compounds display potential inhibitory effect against the dihydrofolate reductase (DHFR) enzyme from humans and Staphylococcus aureus.

Qualitative and quantitative analyses of hydrogen and chalcogen bonds in two pyrimidine-5-carbonitrile derivatives are described.     

Highly covalent molecular cage based porous organic polymer: pore size control and pore property enhancement

It remains a great challenge to effectively control the pore size in porous organic polymers (POPs) because of the disordered linking modes. Herein, we used organic molecular cages (OMCs), possessing the properties of fixed intrinsic cavities, high numbers of reactive sites and dissolvable processability, as building blocks to construct a molecular cage-based POP (TPP-pOMC) with high valency through covalent cross coupling reaction. In the formed TPP-pOMC, the originating blocking pore channels of TPP-OMC were “turned on” and formed fixed pore channels (5.3 Å) corresponding to the connective intrinsic cavities of cages, and intermolecular pore channels (1.34 and 2.72 nm) between cages. Therefore, TPP-pOMC showed significant enhancement in Brunauer–Emmett–Teller (BET) surface area and CO₂ adsorption capacity.

By utilizing the cage to framework strategy, the blocking pores of the cage itself were “turned on” to construct a highly covalent molecular cage based porous organic polymer.     

Alcohol functionality in the fatty acid backbone of sphingomyelin guides the inhibition of blood coagulation

Cell-surface sphingomyelin (SM) inhibits binary and ternary complex activity of blood coagulation by an unknown mechanism. Here we show the OH functionality of SM contributes in forming the close assembly through intermolecular H-bond and through Ca²⁺ chelation, which restricts the protein–lipid/protein–protein interactions and thus inhibits the coagulation procedure.

Cell-surface sphingomyelin (SM) inhibits binary and ternary complex activity of blood coagulation.     

Rhodium(iii)-catalyzed C–H annulation of 2-acetyl-1-arylhydrazines with sulfoxonium ylides: synthesis of 2-arylindoles

An efficient Rh(iii)-catalyzed synthesis of 2-arylindole derivatives via intermolecular C–H annulation of arylhydrazines with sulfoxonium ylides was accomplished. A variety of 2-acetyl-1-arylhydrazines with sulfoxonium ylides were converted into 2-arylindoles in satisfactory yields. Excellent selectivity and good functional group tolerance of this transformation were also observed.

Rh(iii)-catalyzed intermolecular C–H annulation of arylhydrazines with sulfoxonium ylides for synthesis of 2-arylindole derivatives was well established.     

Highly fluorescent aryl-cyclopentadienyl ligands and their tetra-nuclear mixed metallic potassium–dysprosium clusters

Two alkyl substituted triaryl-cyclopentadienyl ligands [4,4′-(4-phenylcyclopenta-1,3-diene-1,2-diyl)bis(methylbenzene) (1) and 4,4′,4′′-(cyclopenta-1,3-diene-1,2,4-triyl)tris(methylbenzene) (2)] have been synthesized via cross-aldol condensation followed by Zn-dust mediated cyclization and acid catalyzed dehydration reactions. The fluorescence properties of 1 and 2 have been studied in solution and solid state. The ligands exhibited aggregation-induced emission enhancement (AIEE) in THF/water solution. 1 and 2 have been found to be significantly more fluorescent in the solid state than in their respective solutions. This phenomenon can be attributed to the strong intermolecular CH⋯π interactions present in 1 and 2 which leads to the tight packing of molecules in their solid-state. Both 1, 2 and their corresponding anions have been studied by theoretical calculations. Ligands 1 and 2 have been shown to react with anhydrous DyCl₃ in the presence of potassium metal at high temperature to afford two fluorescent chloride-bridged tetra-nuclear mixed potassium–dysprosium metallocenes [(Me₂Cp)₄Dy₂^IIICl₄K₂]·3.5(C₇H₈) (5) and [(Me₃Cp)₄Dy₂^IIICl₄K₂]·3(C₇H₈) (6), respectively in good yields.

Alkyl substituted triaryl-cyclopentadienyl ligands with aggregation-induced emission enhancement (AIEE) properties and their applications in the syntheses of novel chloride bridged tetra-nuclear mixed potassium–dysprosium metallocenes.     

Computational insights into Ir(iii)-catalyzed allylic C–H amination of terminal alkenes: mechanism,regioselectivity, and catalytic activity

Computational studies on Ir(iii)-catalyzed intermolecular branch-selective allylic C–H amination of terminal olefins with methyl dioxazolone have been carried out to investigate the mechanism, including the origins of regioselectivity and catalytic activity difference. The result suggests that the reaction proceeds through generation of active species, alkene coordination, allylic C–H activation, decarboxylation, migratory insertion, and protodemetalation. The presence of AgNTf₂ could thermodynamically promote the formation of catalytically active species [Cp*Ir(OAc)]⁺. Both the weaker Ir–C(internal) bond and the closer interatomic distance of N⋯C(internal) in the key allyl-Ir(v)-nitrenoid intermediate make the migratory insertion into Ir–C(internal) bond easier than into the Ir–C(terminal) bond, leading to branch-selective allylic C–H amidation. The high energy barrier for allylic C–H activation in the Co system could account for the observed sluggishness, which is mainly ascribed to the weaker coordination capacity of alkenes to the triplet Cp*Co(OAc)⁺ and the deficient metal⋯H interaction to assist hydrogen transfer.

DFT studies on Ir(iii)-catalyzed branch-selective allylic C–H amination of terminal olefins with methyl dioxazolone have been carried out to investigate the mechanism, including the origins of regioselectivity and catalytic activity difference.     

Recognition and optical sensing of amines by a quartz-bound 7-chloro-4-quinolylazopillar[5]arene monolayer

Covalent bonding of 7-chloro-4-quinolylazo-octamethoxypillar[5]arene molecules to silylated quartz substrates readily produced a new chromogenic reusable pillararene-coated quartz slide, for the direct UV detection of “transparent” analytes in solution. This device provides an analyte-selective optical response towards linear (di)amines with a highly reproducible optical read-out.

Pillar[5]arene-decorated quartz slides for the direct detection of linear amines and diamines are now available.     

Ethanol vs. water: influence of the terminal functional group of the alkyl chain and environment of the self-assembly process on electron transport through the thiol layer

Self-assembly of alkanethiol chains on metallic surfaces is a spontaneous process which leads to the formation of highly ordered layers. However, the organization of the thiol chains on the surface strongly depends on the intermolecular interactions between the terminal groups in the chain. The solution environment also plays an important role. In this paper we present the effect of solution solvent (water and ethanol) and the presence of various hydrophilic terminal groups (–OH, –NH₂ and –COOH) on the quality and electrochemical properties of the formed alkanethiol layers. In the studies we applied voltammetry, atomic force microscopy and quartz crystal microbalance to characterize the morphology, packing density and ability to electron exchange through the thiol layer. The blocking properties of the formed SAMs expressed as the electron-transfer rate constant as well as their organization have been examined using a model electrochemical probe, Fe(CN)₆³⁻. With the increase in the polarity of the terminal functional group the regularity of the thiol layer decreased.

The organization of the thiol chains on the surface strongly depends on the intermolecular interactions between the terminal groups in the chain and the solution environment.     

Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study

It is very important to develop multiple C–H substitution reactions of simple alkenes to obtain complex unsaturated components. The present study focuses on a theoretical investigation of the plausible mechanism in the Fe(OTf)₃-catalyzed tandem amidomethylative reactions of α-phenylstyrene. Bis(tosylamido)methane is activated by Fe(OTf)₃ to form tosylformaldimine and its Fe(OTf)₃-adduct. The Fe(OTf)₃-adduct undergoes an intermolecular aza-Prins reaction with α-phenylstyrene to form allylamide. The DFT data support the formation of the hexahydropyrimidine derivative from allylamide, and “condensation/iminium homologation/intramolecular aza-Prins” is the optimal reaction path. At the same time, a possible reaction pathway for the conversion of the hydrolysate 1,3-diamide derivative to the hexahydropyrimidine (HHP) derivative is given. This work is thus instructive for understanding Fe(iii)-based tandem catalysis for the amidomethylative multiple-substitution reactions of alkenes.

It is very important to develop multiple C–H substitution reactions of simple alkenes to obtain complex unsaturated components.     

Continuous flow synthesis of diaryl ketones by coupling of aryl Grignard reagents with acyl chlorides under mild conditions in the ecofriendly solvent 2-methyltetrahydrofuran

An efficient continuous flow sequential synthesis of diaryl ketones was achieved by coupling of aryl Grignard reagents with acyl chlorides in the bio-derived “green” solvent 2-methyltetrahydrofuran (2-MeTHF) under mild reaction conditions (ambient temperature, 1 hour), allowing a safe and on-demand generation of 2-(3-benzoylphenyl)propionitrile with a productivity of 3.16 g hour⁻¹.

Continuous flow method for parallel synthesis of diaryl ketones using commercially available reagents.     

Synthesis of tetrahydro-β-carbolines from 2-indolylmethyl azides and propargylic alcohols

A facile and efficient route to tetrahydro-β-carbolines from 2-indolylmethyl azides and propargylic alcohols via acid-catalyzed dehydrative annulation reactions is described. This reaction proceeds through a cascade sequence of Friedel–Crafts-type alkylation followed by intramolecular “Click” reaction, involving the formation of multiple chemical bonds in a single operation with excellent atom-economy and broad functional group tolerance.

The synthesis of tetrahydro-β-carbolines from 2-indolylmethyl azides and propargylic alcohols via acid-catalyzed dehydrative [4 + 2]-annulation reaction is described.     

Structure-flexible DNA origami translocation through a solid-state nanopore

Nanopore detection is a label-free detection method designed to analyze single molecules by comparing specific translocation events with high signal-to-noise ratios. However, it is still challenging to understand the influences of structural flexibility of 100 nm DNA origami on nanopore translocations. Here, we used solid-state nanopores to characterize the translocation of “nunchaku” origami structures, the flexibility of which can be regulated by introducing specific DNA strands and streptavidin protein. The structural changes can result in significant variations in the translocation signals and distributions. It is anticipated that such a method of the flexible DNA origami translocation through a solid-state nanopore will find further applications in molecular detection as well as biosensing.

Using a solid-state nanopore to characterize the translocation of “nunchaku” origami with tunable-structures.     

Polymorphism of hydrogen-bonded star mesogens – a combinatorial DFT-D and FT-IR spectroscopy study

A comprehensive study combining detailed computational analyses with temperature-variable FT-IR experiments was performed in order to elucidate the structure of the hydrogen-bonded liquid crystals based on phloroglucinol and azopyridine in their mesophase. Conformational analysis revealed three relevant conformers: star, λ- and E-shape. The results demonstrate an entropy-driven unfolding mechanism of the assembly. The stability of the conformers is given by intermolecular π–π and dispersion interactions of the azopyridine side chains. Correlating the calculated vibrational frequency with experimental FT-IR spectra suggests a λ-folded conformation of the assemblies as the predominant species in the mesophase.

The structure of hydrogen-bonded star mesogens is investigated using modern quantum chemistry methods in combination with infrared spectroscopy.     

Rapid detection of staphylococcal enterotoxin B in milk samples based on fluorescence hybridization chain reaction amplification

A rapid, simple, and sensitive method has been developed to detect staphylococcal enterotoxin B (SEB). To establish the hybridization chain reaction-based aptasensor, we described the new probes of two hairpins (H1 and H2), which were first designed based on the partial complementary sequence of the SEB aptamer (cDNA). The H1 labeled with a fluorophore and a quencher can act as a molecular fluorescence “switch”. Hence, in the presence of SEB, the aptamer binds SEB, while the unbound cDNA triggers HCR to carry out the cyclic hybridization of H1 and H2 so as to turn “ON” the fluorescence through forming long nicked DNA. By using this new strategy, SEB can be sensitively detected within the range of 3.13 ng mL⁻¹ to 100 ng mL⁻¹ with a detection limit of 0.33 ng mL⁻¹ (S/N = 3). Furthermore, the developed method could facilitate the detection of SEB effectively in milk samples.

A new competitive aptasensor combined with HCR was developed for SEB detection.     

A new red fluorophore with aggregation enhanced emission by an unexpected “One-step” protocol

In this work, a triphenylamine-benzothiadiazole-based new fluorophore is obtained from a facile “one-step” protocol. A possible reduction mechanism is proposed, and an amine containing α-H plays a key role in the reduction reaction. The resultant product A1H2 exhibits bright red emission in solid state, with an absolute quantum yield of 44.5%. Aggregation induced emission enhancement of A1H2 is also observed with the increased water fraction in THF-H₂O mixture. The nanoparticles of A1H2 reveal good stability and biocompatibility, which are successfully applied in cellular cytoplasm imaging.

Compound A1H2 was synthesized via the reductive Knoevenagel alkylation, whose nanoparticles exhibit bright red emission in aqueous solution.     

Solvent influence on molecular interactions in the bulk of fluorene copolymer films

The effect of intermolecular interactions between the chains of the amorphous PFO–MEH-PPV films built from toluene and tetrahydrofuran (THF) were studied by atomistic molecular dynamics simulations, applying a successive solvent removal procedure. In the good solvent toluene, the incidence of topological entanglements is more significant. While in the poor solvent, coplanar interactions between neighbouring segments of the chains were also found, which is characteristics of cohesional entanglements. Structure factor curves of the films showed three peaks associated with the microstructure of the film, as previously reported by WAX diffractogram measurements. Moreover, the good solvent promotes more flexibility in dihedral angles, and the chains become nearer to each other.

The effect of intermolecular interactions between the chains of the amorphous PFO–MEH-PPV films built from toluene and tetrahydrofuran (THF) were studied by atomistic molecular dynamics simulations, applying a successive solvent removal procedure.     

The spirobichroman-based polyimides with different side groups: from structure–property relationships to chain packing and gas transport performance

Spirobichroman-based polymers with high gas permeability and selectivity are promising for their applications as membranes in gas separation. In this study, three spirobichroman-based polyimides (PIs; 6FDA-FH, 6FDA-DH, and 6FDA-MH) were synthesised by the polyreaction between diamines containing different substituents (benzene ring, pyridine ring, and methyl group) and 4,4′-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA). The physical properties, gas transport behaviour, d-spacing, dihedral angle of molecules, and fractional free volume of the PIs were investigated through experiments and molecular simulations. The PIs exhibited excellent thermal stability and good solubility in common organic solvents. The gas permeability of the PIs was investigated; the results highlighted the critical role of the substituents in the enhancement of the gas separation performance of polymer membranes. Detailed analysis of the PIs showed that 6FDA-FH exhibits the highest gas permeability. This can be ascribed to the loose packing of the polymer chain owing to the increased dihedral angle between the two planes. However, the methyl substituent in 6FDA-MH disrupts the polymer chain packing rather than changing the dihedral angle between the two planes, thus enhancing the gas permeability of 6FDA-MH. Furthermore, 6FDA-DH exhibited the highest CO₂/CH₄ selectivity, which is attributed to the CO₂ affinity of the polymer containing the pyridine unit.

Effect of substituents on the dihedral angle and chain packing plays a critical role in the enhancement in the gas separation performance of polymer membranes.