A series of novel γ,γ-difluorinated Goniothalamin analogues 4a–4i and 6a–6i were synthesized. The key steps included the construction of C-5 stereocenter adjacent to gem-difluoromethylene group by way of lipase AK catalyzed kinetic resolution, the introduction of aryl group via Stille coupling, and lactonization by 1,5-oxidative cyclization. These γ,γ-difluorinated Goniothalamin analogues 4a–4i and their enantiomers 6a–6i, together with several corresponding γ-monofluorinated Goniothalamin analogues were biologically evaluated against four different cancer cell lines. Compound 7h showed a nearly equivalent potency as the parent (R)-Goniothalamin in the micromolar range. The different fluorine effects between fluoromethylene and gem-difluoromethylene on antitumor activity were discussed through the analysis of bioassay data.

A series of novel γ,γ-difluorinated Goniothalamin analogues 4a–4i and 6a–6i were synthesized by way of lipase AK catalyzed kinetic resolution, Stille coupling and 1,5-oxidative cyclization. These difluorinated analogues and several monofluorinated analogues were biologically evaluated together against four different cancer cell lines. From the analysis of bioassay data, it was found that adding one fluorine at the γ position of Goniothalamin was a better modification than introducing two fluorine atoms.

Phthalimide derivatives as nitrogen nucleophiles with α,β-unsaturated aldehydes for asymmetric aza-Michael additions have been reported. The reactions proceed smoothly to afford corresponding Michael adducts in good yields (up to 98%) and enantioselectivities (up to 95% ee).

Phthalimide derivatives as nitrogen nucleophiles with α,β-unsaturated aldehydes for asymmetric aza-Michael additions have been reported. The reactions proceed smoothly to afford corresponding Michael adducts in good yields (up to 98%) and enantioselectivities (up to 95% ee).

A low melting citric acid-urea mixture was found to be a new and effective promoting medium for the environmentally friendly synthesis of 1,8-dioxo-dodecahydroxanthene derivatives by condensation of aromatic aldehydes and cyclic 1,3-dicarbobonyl compounds. This deep eutectic solvent acts as both the reaction medium and catalyst, furnishing xanthenediones in high to excellent yields.

Low melting citric acid-urea mixture was found to be a new and effective promoting medium for the environmentally friendly synthesis of 1,8-dioxo-dodecahydroxanthene derivatives by condensation of aromatic aldehydes and cyclic 1,3-dicarbobonyl compounds. This deep eutectic solvent acts as both the reaction medium and catalyst, furnishing xanthenediones in high to excellent yield.

Polymer solar cells were fabricated based on composite films of poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylenevinylene) (MEH-PPV):fullerene derivative (6,6)-phenyl-C₆₁-butyric acid methyl ester (PCBM) with weight blend ratio of 1:3, 1:4 and 1:5, spin-coated from chloroform (CF), chlorobenzene (CB), and o-dichlorobenzene (ODCB) solutions, respectively. Photoinduced current and power conversion efficiency (PCE) of the devices show a dependence on the solvents. The solar cells have the highest PCE at 1:5 blend ratio. Transmission electron microscopy (TEM) morphology reveals that there are some voids in MEH-PPV:PCBM films. The void number decreases with the solvent from CF to CB and ODCB. We found the voids are located at the bottom of the films through electron tomography technique by TEM and film bottom-side morphology study by atomic force microscopy. The charge carrier transport efficiency and collection efficiency should decrease greatly due to the voids, and the more voids the film has, the more degree the efficiencies decrease. PCE of the solar cell prepared from CF is lower than that of the solar cells prepared from CB and ODCB. The void phenomenon of MEH-PPV:PCBM based solar cell and method to investigate the void position provide an experimental evidence and research mentality to fabricate polymer solar cell with high performance.

Some voids were found in the MEH-PPV:PCBM composite films, and the number of the voids decreases with the solvent. We found the voids are located at the bottom of the films through the electron tomography technique by transmission electron microscopy and film bottom-side morphology study by atomic force microscopy. The voids are disadvantageous to the device performance.

Cyclization is an important chemical reaction for the dipeptides containing N-alkyl groups. The cyclization mechanism has been examined by theoretical calculations. Our calculation results indicate that the most favorable mechanism is the piperidine-catalyzed stepwise mechanism, in which piperidine acts as a proton shuttle. The attack of the N-terminal amino nitrogen at the C-terminal carbonyl carbon along with the proton transfer is the rate-limiting step. The effect of the alkyl substituent on the amide N on the cyclization reaction was then examined. Finally, the influence of the solvation effect, electronic effect and steric effect on the cyclization was investigated. It is found that all of these effects contribute to the cyclization.

Theoretical calculations were carried out to investigate the mechanism of the cyclization of dipeptides. The "proton shuttle"-catalyzed stepwise mechanism is most favored and the attack of the N-terminal amino nitrogen at the C-terminal carbonyl carbon along with the proton transfer is the rate-limiting step. The solvation effect, electronic effect and steric effect were found to contribute to the cyclization.

An effective transition-metal-free catalytic system is developed for aerobic oxidations of alcohols. Using catalytic amount of bromide-bromate coupling, H₂SO₄, and NaNO₂, together with 2,2,6,6-tetramethylpiperidine N-oxyl radical (TEMPO) in the presence of air, various alcohols could be converted into the corresponding aldehydes or ketones in good to excellent isolated yields under mild conditions.

An effective transition-metal-free catalytic system is developed for aerobic oxidations of alcohols. Using catalytic amount of bromide-bromate coupling, H₂SO₄, and NaNO₂, together with 2,2,6,6-tetramethylpiperidine N-oxyl radical (TEMPO) in the presence of air, various alcohols could be converted into the corresponding aldehydes or ketones in good to excellent isolated yields under mild conditions.

Mesoporous silica nanoparticles (MSN) were coated by pH-responsive polymer chitosan-poly (methacrylic acid) (CS-PMAA). This nano drug delivery system showed good application prospects and the polymer-coated microspheres were promising site-specific anticancer drug delivery carriers in biomedical field. A continuous detection of pH-responsive drug delivery system in cells in situ, utilizing MSN/CS-PMAA composite microspheres, was proposed. Two kinds of different cell lines, tumor cell line (Hela) and normal somatic cells (293T), were used to investigate the behaviours of the drug loaded system in the cells. Conclusions could be drawn from the fluorescent images obtained by confocal laser scanning microscopy (CLSM), modified drug-loaded microspheres (MSN/CS-PMAA) were ingested into cells more easily, the uptake of DOX@FITC-MSN/CS-PMAA by HeLa/293T cells were performed at pH 7.4/pH 6.8, DOX was released during the ingestion process, fluorescence intensity decreased with time because of efflux transport and photo-bleaching. Fluoresence detection by flow cytometry was performed as comparison. The continuous fluorescent observation in situ could be widely used in the pH-responsive releasing process of drug delivery system in the cells.

A continuous detection of pH-responsive drug delivery system in cells in situ, utilizing MSN/CS-PMAA composite microspheres, was proposed. The continuous fluorescent observation in situ could be widely used in the pH-responsive releasing process of drug delivery system in the cells.

A direct and efficient approach to 1-aminoindolizines through three-component one-pot reaction of heteroaryl aldehydes, secondary amines and terminal alkynes catalyzed by CuI under solvent-free conditions has been developed. This methodology provides a rapid access to substituted aminoindolizines with good yields (up to 97%).

A direct and efficient approach to 1-aminoindolizines through three-component one-pot reaction of heteroaryl aldehydes, secondary amines and terminal alkynes catalyzed by CuI under solvent-free conditions has been developed. This methodology provides a rapid access to substituted aminoindolizines with good yields (up to 97%).

By optimizing the reaction conditions via a careful screening of the bases and solvents, we developed an efficient transition metal-free method for CO cross-coupling of activated and unactivated heteroaryl chlorides with primary and secondary alcohols and phenols, providing a simple, efficient, and practical method for synthesis of the useful unsymmetrical heteroaryl alkyl and heteroaryl aryl ethers.

By optimizing the reaction conditions via a careful screening of the bases and solvents, we developed an efficient transition metal-free method for CO cross-coupling of activated and unactivated heteroaryl chlorides with primary and secondary alcohols and phenols, providing a simple, efficient, and practical method for synthesis of the useful unsymmetrical heteroaryl alkyl and heteroaryl aryl ethers.

Eleven triazolyl substituted tetrahydrobenzofuran derivatives were synthesized in high yields as novel H⁺/K⁺-ATPase inhibitor via one-pot CuI-catalyzed three-component click reaction of azide, secondary amine and 3-bromopropyne under mild conditions in water. Their structures were characterized by NMR, IR, ESI-MS, elemental analysis and single-crystal X-ray diffraction analysis. Most of the target compounds exhibited better H⁺/K⁺-ATPase inhibitory activity than commercial omeprazole with IC₅₀ values less than 15 µmol·L⁻¹. The initial structure-activity analysis suggested that the triazole substituted by cycloalkyl, aromatic ring or O-containing side-chain seemed to be beneficial for enhancing the activity.

Eleven triazolyl substituted tetrahydrobenzofuran derivatives were synthesized in high yields as novel H⁺/K⁺-ATPase inhibitor via one-pot CuI-catalyzed three-component click reaction under mild conditions in water, and most of them exhibited better H⁺/K⁺-ATPase inhibitory activity than commercial omeprazole with IC₅₀ values less than 15 µmol·L⁻¹.

A simple-structured 4-(2-pyridylazo)resorcinol (PAR) system presents interesting properties with dual fluorescent outputs. Modulated by solution pH two kinds of reversible switch behaviors, "ON-OFF" and "OFF-ON", were realized with the PAR system. Stimulated by different combination of external stimulus, such as metal ions, UV irradiation and solution pH, the PAR system could perform multiple logic functions including three inputs AND, two inputs INHIBIT and combinatorial "NOR/AND" in parallel. The operation of the designed system is very simple and detected with a high sensitive fluorescent signal.

Stimulated by different combination of external stimulus, including metal ions, UV irridiation and solution pH, the PAR system could perform multiple logic functions, presenting great potential for the construction of molecular devices.

Bismuthinite (Bi₂S₃) nanostructures were prepared by a hydrothermal method with sodium ethylenediaminetetraacetate (EDTA-Na₂). The morphology of Bi₂S₃ nanostructures was changed from a nanorod to a nanoplate by presence of the EDTA-Na₂. The altered morphology was caused by the capping effect of EDTA-Na₂ with Bi³⁺ ions, which induces the suboptimal growth direction due to partially blocking the preferential orientation direction. When the EDTA-Na₂/Bi³⁺ molar ratio=1, the growth of Bi₂S₃ nanostructures was not allowed due to the chelating effect of EDTA-Na₂. The obtained Bi₂S₃ nanorods, stacked nanorods, nanoplates and nanoparticles were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) pattern. A possible formation mechanism of these morphologies was proposed. The successful synthesis of various morphologies of nanostructured Bi₂S₃ may open up new possibilities for thermoelectric, electronic and optoelectronic uses of nanodevices based on Bi₂S₃ nanostructure.

Bismuthinite (Bi₂S₃) nanostructures were prepared by a hydrothermal method with sodium ethylenediaminetetraacetate (EDTA-Na₂). The successful synthesis of various morphologies of nanostructured Bi₂S₃ may open up new possibilities for thermoelectric, electronic and optoelectronic uses of nanodevices based on Bi₂S₃ nanostructure.

A novel (4-ferrocenylethyne) phenylamine functionalized graphene sheets (FEPA-GR), coupling with chitosan (CS) were used as a signal amplification platform for simultaneous and sensitive determination of dopamine (DA) and acetaminophen (AC). In this work, FEPA used as electron transfer mediator can be immobilized on GR surface via strong π-π stacking interaction between the conjugate chain of FEPA and GR, which effectively prevents FEPA electron mediator leaking from the electrode surface and amplified the signal. Transmission electron microscopy, FT-IR spectroscopy, UV-vis spectroscopy and electrochemical experiments results are all demonstrated the strong π-π stacking interaction between FEPA and GR. The resulted biosensor exhibited a fast response, remarkable electrocatalytic activity, perfect anti-interference ability and good stability for simultaneous detection of DA and AC. Under the optimum conditions, the oxidation peak currents of DA and AC were linearly correlated to their concentrations in the range of 2.0–135.0 µmol·L⁻¹ and 0.3–80.0 µmol·L⁻¹, respectively. The lower detection limits for DA and AC were 0.30 and 0.05 µmol·L⁻¹, respectively. The feasibility of the proposed method was validated by successfully applied to the simultaneous determination of DA and AC in serum samples with the standard addition method.

A dual signal amplification platform for simultaneous and sensitive determination of dopamine (DA) and acetaminophen (AC) is proposed by the synergistic effect of graphene (GR) and (4-ferrocenylethyne) phenylamine (FEPA). The synthesized FEPA serves as an electron mediator for amplification of the detection signals, and it can be strongly adsorbed on GR surface via the strong π-π stacking interaction between the conjugate chain of FEPA and GR. The proposed strategy provided a stable electronic mediator immobilization method on electrode surfaces for electrochemical analysis.

Affinity core-shell magnetic nanoparticles (MNPs) were prepared for identifying the target proteins of drugs in the cell lysate when used in combination with nano-high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS)-based shotgun proteomic analysis. A number of new potential targets of cyclosporine A (CsA) could be identified, owing to the high efficacy of the affinity MNPs in drug target identification. To the best of our knowledge, this is the first time to reveal such an abundant target spectrum of CsA.

Selective benzoylation of secondary hydroxyl on sugar moiety of various ribosides including N-ribosides, O-ribosides and 2′-deoxy-N-riboside was investigated by using benzoyl chloride and Na₂CO₃ in aqueous CH₃CN. The influence of the aglycone and sugar moiety on the selectivity of benzoylation was discussed as well. A most efficient method for preparation of 2′,3′-O-dibenzoylnucleosides was developed.

Regioselective protection of secondary hydroxyl groups on ribosides and 2′-deoxyribosides was investigated. A most simple and efficient method for preparation of 2′,3′-di-O-benzoylribonucleosides was developed.

In this paper a label-free fluorescent sensor for probing the interaction between heparin and protein was reported. Heparin, the bioactive polyanions, formed supramolecular assemblies with cationic surfactant cetyltrimethyl ammonium bromide (CTAB). The environment-dependent dye pyrene, encapsulated in hydrophobic interiors of the supramolecular assemblies worked as the fluorescence probe. Once the heparin-binding protein was added, competing interactions of protein with heparin would weaken the interaction between CTAB and heparin. As a result, the noncovalently sequestered pyrene would be released upon disassembly and the fluorescence of the released pyrene was subsequently decreased. The binding events were exemplified by protamine and Tat peptide, these processes were also verified by DLS and TEM. Such a strategy is appealing as organic synthesis was traded off against supramolecular assembly. This label-free fluorescent system is simple, selective, convenient, and can serve as a good complement to other existing methods, also this method has the potential for preprimary drug screening.

The sensor was based on supramolecular assemblies composed of heparin and CTAB, the dye pyrene worked as the fluorescence probe. Once the target protein was added, heparin was taken away by protein, resulting in the decreasing of fluorescence intensity. The binding events were exemplified by protamine and Tat peptide.

A novel series of eight SMS and sPLA2 dual inhibitors containing indole and α-amino cyanide fragments of different length and substitution position was synthesized and evaluated by three different in vitro assays. Biological evaluation showed that all compounds provided inhibitory effects against SMS (about 50% inhibition at 100 µmol/L) and sPLA2 (14–32 µmol/L). All the compounds had the SMS activity better than the positive control compound D609 in SMS2 homogenate, with compounds 5b and 5e ideal for liver homogenate and SMS2 high expression cell homogenate, respectively.

The secretory phospholipase A2 (sPLA2) and sphingomyelin (SMS) are the key enzymes to atherosclerosis. In this paper, we combined the single sPLA2 and SMS inhibitors with a carbon chain to get a series of dual inhibitors. The biological evaluation showed these compounds had the moderate inhibition against both enzymes.

The cover picture shows the binding gradient effect of two hydrogen bonding-driven foldamer-dirived molecular tweezers. For a pentafluorophenyl-appended pyridine ligand, in the cavity of the tweezer, two binding interactions, i.e., the N-Zn(II) coordination and zinc porphyrin-pentafluorobenzene donor-acceptor interactions stabilize the encapsulation of the ligand in the cavity of the tweezers. After the binding in the cavity take places, further coordination of the ligand from outside the tweezer becomes much less favorable due to the interaction occurring in the cavity, which is evidenced by the UV-vis and ¹H and ¹⁹F NMR experiments. More details are discussed in the article by Li et al. on page 582–588.

Cyclodextrins (CDs) are regarded as one kind of the most important and promising macrocyclic oligosaccharides, which contain hydrophobic internal cavities capable of hosting various guest molecules. CDs are water-soluble, non-toxic, commercially available as well as low-cost. Because of these favorable characteristics, cyclodextrin chemistry has created a great number of interesting works covering different fields, in particular CD-based porous nanocapsules (CDPNCs). Chemical cross-linking is an important way developed to prepare CDPNCs. CDPNCs can be obtained using different cross-linkers and preparation methods, such as homogeneous method, miniemulsion polymerization, and emulsion-solvent evaporation method. Because of cross-linking, a three-dimensional network is built which forms the porous structure in CDPNCs with the cavities of CDs. Attributed to the porous structure, CDPNCs exhibit excellent performances in encapsulation of targeted molecules and realization of controllable release, indicating a promising prospect in applications such as drug delivery systems and environment protection.

CD-based porous nanocapsules (CDPNCs) are a class of covalently cross-linked networks based on CDs with a three-dimensional structure. Chemical cross-linking is an important way developed to prepare CDPNCs. CDPNCs can be obtained using different cross-linkers and preparation methods, such as homogeneous method, miniemulsion polymerization, and emulsion-solvent evaporation method. Because of cross-linking, a three-dimensional network is built which forms the porous structure in CDPNCs with the cavities of CDs. CDPNCs not only take on the merits of CDs, including host-guest interaction, molecular recognition, stability, and biocompatibility, but also possess new functions given by the porous structure. CDPNCs are promising nanomaterials which are expected to be applied in diverse fields.

Two rigid macrocyclic CTV-based porous organic polymers, Click-POP-1 and Click-POP-2, have been synthesized by Click reaction of a cyclotriveratrylene analogue with alkyne groups and aromatic azides in one pot. FTIR, solid ¹³C NMR and elemental analysis confirmed the formation of the polymers. Both of them possess high thermo-stability which is up to 410 and 900°C, respectively, and moderate hydrogen storage properties with 0.46 wt% at 77 K. Their nitrogen uptake showed type-I isotherm with BET surface areas up to 342 and 317 m²·g⁻¹.

Two porous organic polymers were synthesized by Click reaction of rigid macrocyclic CTV-alkyne with azide. These polymers showed high thermal-stability and moderate hydrogen uptake.

By introducing two and three zinc porphyrin units to one side of hydrogen bonding-induced aromatic amide foldamers, two new molecular tweezers 1 and 2 have been prepared. To explore new possible binding patterns, a leucine-based pyridine ligand 3 that bears a pentafluorophenyl group has been prepared. UV-Vis and ¹H NMR experiments reveal that 1 and 2 favorably complex one or two molecules of 3. UV-Vis titration experiments show that the apparent association constants of the complexes of the zinc porphyrin units of the two receptors and 3 are considerably higher than that of the complex between a simple control zinc porphyrin and 3. In the presence of excess of 3, the left zinc porphyrin unit of 1 and 2 can bind one more molecule of 3, which is, however, stabilized only by the single Zn-N coordination.

Although the tweezers bear two and three zinc porphyrin units, respectively, 1:1 and 1:2 binding patterns are favored in which the coordination and stacking interaction promote each other.

We herein report the synthesis and metal-directed coordination self-assembly behaviors of three new macrocyclic azacalix[4]aromatics that comprise various numbers of pyridine and pyrazine rings bridged by N-CH₃ groups. Structural characterization of 1–3 explored that their conformations are fluxional in solution and each adopts a 1,3-alternate configuration in crystalline solids. The macrocyclic skeletons in azacalixaromatic 1–3 afford a good platform to designedly arrange coordination sites in a unique way relative to conventional multidentate ligands. Solid-state structures of three coordination self-assembled silver complexes (13–15) of 1–3 determined by X-ray crystallography suggest that the nitrogen atoms on procumbent aromatics have better coordination ability than those on perpendicular aromatics and dictate the whole coordination self-assemblies. Unique discrete and 1D chain-like structures were thus obtained. This system may afford a deeper insight into the coordination self-assembly studies of heteroatom-bridged calixaromatics, possibly extending potential application of this novel macrocyclic polydentate organic compounds in the synthesis of functional metal organic framework formation.

Three new macrocyclic azacalix[4]aromatics that comprise various numbers of pyridine and pyrazine rings bridged by N-CH₃ groups were synthesized. Structural characterization explored that their conformations are fluxional in solution and each adopts a 1,3-alternate configuration in crystalline solids.

A π-conjugated phenylaza-15-crown-5-triazol-substituted coumarin fluoroionophore 1 was synthesized by copper(I)-catalyzed Huisgen alkyne-azide 1,3-dipolar cycloaddition (CuAAC "click" reaction). 1 can display selective fluorescence enhancement toward Fe³⁺ over Hg²⁺, Cr³⁺ and the other metal ions in aqueous solution. In sharp contrast, the fluorescence behavior between Fe³⁺ and Hg²⁺ is completely reversed in EtOH. That is, Hg²⁺ gives the largest fluorescence enhancement over Cr³⁺, Fe³⁺ and the other metal ions.

A π-conjugated phenylaza-15-crown-5-triazol-substituted coumarin fluoroionophore 1 was synthesized. 1 can display selective fluorescence enhancement toward Fe³⁺ over Hg²⁺, Cr³⁺ and the other metal ions in aqueous solution. In sharp contrast, Hg²⁺ gives the largest fluorescence enhancement over Cr³⁺, Fe³⁺ and the other metal ions in EtOH.

Irradiation of cyclohexyl phenyl ketone (1) results in either intra- or intermolecular hydrogen abstraction to afford compounds 1-phenylhept-6-en-1-one (2) and α-cyclohexyl benzyl alcohol (3) as photoproducts, in which 3 has a pair of enantiomers. Herein, two types of chiral hexagonal liquid crystals were prepared to direct the enantioselective photochemical reaction of 1. One of the hexagonal liquid crystals is composed of 1-tetradecyl-3-methylimidazolium bromide/p-xylene/H₂O with the modification by a chiral inductor. The other one is formed by chiral (S)-3-hexadecyl-1-(1-hydroxy-propan-2-yl)-imidazolium bromide/p-xylene/H₂O. The product analysis shows that the latter one can be used as a microreactor to achieve stereoselective photochemical reaction, while the former one produced compound 3 with no enantioselectivity at all.

Triptycene-derived cylindrical macrotricyclic host with two dibenzo-30-crown-10 cavities could form stable 1:1 complexes with not only polyether linked bisparaquat derivative but also a self-folding A-D-A guest in solution and/or solid state. Moreover, it was found that switchable processes between the host and both the bisparaquat derivative and the self-folding guest could be further controlled by potassium ions.

Triptycene-derived cylindrical macrotricyclic host with a large central cavity could form stable 1:1 complexes with not only polyether linked bisparaquat derivative but also a self-folding A-D-A guest. Moreover, switchable processes between the host and both the bisparaquat derivative and the self-folding guest could be controlled by potassium ions.

A highly efficient one-pot procedure for the preparation of fluorescein-based dyes with relatively high yield was investigated. Significantly, introduction of these fluoro and chloro functional groups and forming host-guest complexes with cyclodextrins partially enhanced the photostability of these dyes.

A highly efficient one-pot synthesis of fluorescein-based halogenated dyes with relatively high yield was reported. Introduction of fluoro and chloro functional groups and forming host-guest complexes with cyclodextrins enhanced their photostability.

Macrocyclic CTV-Br₃ reacted with the linear benzene-1,4-diboronic acid and 1,4-diethynylbenzene via Suzuki and Sonogashira-Hagihara coupling reactions producing the rigid porous materials CTV-CMP-1 and CTV-CMP-2. The porous materials have good thermal and chemical stability. The Brunauer-Emmet-Teller specific surface areas of CTV-CMP-1 and CTV-CMP-2 are 314 and 218 cm²·g⁻¹, respectively. Physical properties of the porous materials were investigated, CTV-CMP-1 showed moderate hydrogen adsorption about 0.81 wt% at 1.13 bar while CTV-CMP-2 showed lower hydrogen adsorption about 0.51 wt%. These materials are analogs to activated carbons which could be potentially used in gas separation and organic compound adsorption.

Two rigid porous materials CTV-CMP-1 and CTV-CMP-2 have been synthesized via Sonogashira-Hagihara and Suzuki coupling reactions which showed both microporous and mesoporous properties and moderate hydrogen adsorption about 0.81 wt% at 1.13 bar.

The complexation of alkyl-substituted pillar[5]arenes with primary ammonium salts is investigated. 1,4-Bis(methoxy)pillar[5]arene (MeP5) can form strong complexes with the primary ammonium salts in CDCl₃. However, 1,4-bis(ethoxy)pillar[5]arene (EtP5) shows weak interaction with these guests, and 1,4-bis(butoxy)pillar[5]arene (BuP5) can not form such a complex at all. These results indicate that the modified alkyl chains of pillar[5]arene play an important role in the complexation selectivity.

1,4-Bis(methoxy)pillar[5]arene MeP5 can form complexes with primary ammonium salts, but 1,4-bis(butoxy)pillar[5]arene BuP5 can not form such complexes. The length of the alkyl chains of pillar[5]arenes plays an important role for the high selectivity in their host-guest interactions.

Two novel photochromic macrocycles 1 and 2 bearing dithienylethene units and urea building blocks have been synthesized, and their photochromic properties are described. Macrocycle 2 shows good photochromic properties, while the relatively smaller size of macrocycle 8b exhibits photochemically inactive properties due to the unfavourable ring conformational constraint. Moreover, the crystal structures of the urea-protected precursor macrocyles 3a, 3b, and 8b are presented.

Two novel photochromic macrocycles 1 and 2 bearing dithienylethene units and urea building blocks have been synthesized, and their photochromic properties are described.

Structural information on the crystalline forms of mebendazole, an anti-parasitic drug, is limited, although three polymorphic forms of this drug have been reported. The present work investigates the structures and properties of different crystalline forms of mebendazole with a series of n-alkyl carboxylic acids, including trifluroacetic acid (1), formic acid (2), acetic acid (3), propanoic acid (4), butanoic acid (5), valeric acid (6) and hexanoic acid (7). These compounds were characterized by thermogravimetric analysis, IR spectra, as well as powder and single-crystal X-ray diffraction analysis. The R₂²(8) structural motif was detected in all the seven products, which was formed by a pair of NH···O/OH···N hydrogen bonds between mebendazole and carboxylic acid. Forms 3–7 were found to be neutral solvate, while in forms 1 and 2, proton transfer was observed from carboxylic acid to mebendazole.

The cocrystallization of mebendazole with a series of n-alkyl carboxylic acids generated two salts of 1–2 and five solvates of 3–7, and their structures and thermal stabilities were investigated. Compounds 1–7 provide new solid forms of mebendazole for improvement of its physical and chemical properties.

New imidazolium/benzimidazolium-containing receptors (R)-1–(R)-6 were developed as multifunctional receptors for both chromogenic and chiral anion recognition through multichannel. The ?uorescence spectra of (R)-1 showed a distinct and intense peak at 454, 474 nm with AcO⁻ and F⁻, respectively, indicating that (R)-1 can be applied to the detection of fluoride and acetate ions by naked eye. Receptor (R)-5, containing a lipophilic dodecyl appendage at imidazolium nitrogen, exhibited larger fluorescent responses than (R)-1. The ratio of fluorescence enhancement for (R)-5 with AcO⁻ (I₄₆₀/I₃₆₉=16) and F⁻ (I₄₈₅/I₃₆₉=11) was 32-fold and 18-fold over (R)-1 with AcO⁻ (I₄₅₄/I₃₆₉=0.5) and F⁻ (I₄₇₄/I₃₆₉=0.6), respectively. Less electron-deficient benzimidazolium receptor (R)-2 only gave fluorescence enhance at 555 nm for F⁻. Only chelation enhanced quenching (CHEQ) effect was obtained in the case of mono-imidazolium receptor (R)-4. Furthermore, (R)-1 and (R)-5 displayed a remarkable binding ability for the t-Boc alanine anion with interesting enantioselectivity [K_L/K_D=4.5 for (R)-1 and 4.1 for (R)-5)], whereas only negligible enantioselectivity ability (K_L/K_D=1.1) was obtained by using C₁ symmetric receptor (R)-4.

An effective strategy to create anions probes by conjugating imidazolium with BINOL derivatives has been achieved, and this method enabled naked eye and dual channel (absorption and fluorescence) detection of F⁻ and AcO⁻ ions. More importantly, introduction of a lipophilic dodecyl appendage at imidazolium nitrogen ((R)-5) led to dramatic enhancement of the interaction with anions.

A series of aromatic oligoamide foldamers based on 8-fluoro amino-quinoline carboxyl acid have been synthesized and characterized. Studies show that these foldamers self-assemble to form well-defined twisted helical microfibers in chloroform-methanol (1:1, V/V) binary solvent due to the intermolecular π-π stacking and van der Waals forces of aliphatic chains, which are supported by SEM, TEM and XRD. It is also revealed that the assembly morphologies show strong dependence on the length of alkyl chains.

A non-natural aromatic foldamer with unique 'S'-styled helical supersecondary structures does self-assemble to well-defined twisted helical microfibers in binary solvent.

Cyclodextrins (CDs) show functionality, biocompatibility, and host-guest inclusion capacity with a variety of molecules. These unique properties offer great potential for the exploitation of CDs as drug delivery systems. An easy, green, and effective synthetic approach was described to develop CD-based porous nanospheres (CDPNSs) with a size distribution from 100 to 400 nm. A new cross-linker tris(2-aminoethyl)amine was used to cross-link modified β-CD at room temperature. The resulting CD-based polymers (CDPs) were reshaped from a random morphology into a spherical shape during a dialysis process, and CDPNSs were obtained. The morphologies of CDPs and CDPNSs were observed with scanning electron microscopy. The average diameter and the size distribution of CDPNSs were determined by dynamic light scattering. The structures of the resulting products were characterized by using Fourier transform infrared spectroscopy, ¹H NMR spectroscopy, solid-state ¹³C CP/MAS NMR spectroscopy, and X-ray diffraction. Furthermore, a study was conducted on drug loading and in vitro release behavior of CDPNSs, which was monitored by ultraviolet spectroscopy. The prepared CDPNSs show the potential as drug delivery systems.

A green, simple, and effective approach was developed to synthesize biocompatible cyclodextrin-based porous nanospheres (CDPNSs). The cross-linking is allowed to take place at room temperature in N,N-dimethylformamide (DMF) with tris(2-aminoethyl)amine (TAA) as the cross-linker. The resulting CD-based polymers (CDPs) were reshaped from a random morphology into a spherical shape during a dialysis process, and CDPNSs were formed with the average diameter of 237±93 nm and the size distribution of 100–400 nm. Furthermore, a study on drug loading and in vitro release behavior of CDPNSs was carried out, where acridine red (AR) was chosen as a drug model. The loading capacity is up to (9.8±0.2) wt% and the encapsulation efficiency is up to (40.2±0.8) wt%. With regard to the release of AR from CDPNSs in vitro, (82.3±0.2)% of AR was released within 24 h. It is expected that CDPNSs will find potential applications as drug delivery systems in the future.

The design and self-assembly of pyrene-modified rhomboidal metallodendrimers R1–R6 via directional metal-ligand bonding approach is described. By employing pyrene-containing 120° di-Pt(II) acceptor and appropriate 60° dendritic dipyridyl donors, a variety of [G-1]–[G-3] pyrene-modified rhomboidal metallodendrimers with well-defined shape and size were prepared under mild conditions in high yields. The supramolecular dendrimers were characterized with multinuclear NMR (¹H and ³¹P) and mass spectrometry (CSI-TOF-MS). Isotopically resolved mass spectrometry data support the existence of the pyrene-modified dendrimers with rhomboidal cavities, and NMR data were consistent with the formation of all ensembles. The shape and size of all rhomboidal dendrimers were investigated with the PM6 semiempirical molecular orbital method. Their primary photochemical properties were studied as well.

A series of novel rhomboidal pyrene-modified metallodendrimers R1–R6 were constructed via directional metal-ligand bonding approach.

A series of cyclic receptors 1–5 based on bis-benzimidazolium group were designed and synthesized. Their anion recognition properties were investigated by UV-vis, fluorescent spectroscopy, ¹H NMR and MALDI-TOF mass spectrometry. The UV-vis and fluorescent spectroscopic studies showed that the receptors 1–5 had different binding abilities for various anions such as fluoride, chloride, bromide, iodide and acetate. The high selectivity of the receptors for fluoride and acetate anions is attributed to their basicity. Job plot and MALDI-TOF mass spectrometry demonstrated that the receptors form 1:1 complex with fluoride. DFT calculation and ¹H NMR studies indicated that the receptors bind anions through (CH)⁺···X⁻ hydrogen bond.

The tris(2-aminoethyl)amine (tren)-based tris(4-pyridylurea) receptor L has been synthesized and its anion binding properties were studied. The ligand forms a 2:1 (host/guest) complex with MgSO₄, [SO₄²⁻⊂L₂], in which a sulfate ion is encapsulated by six urea groups from the two ligands through multiple hydrogen bonds. The metal ions do not coordinate to the pyridyl groups but exist as the hydrate [Mg(H₂O)₆]²⁺ and interact with the [SO₄⊂L₂] capsules in the outer coordination sphere to form a three dimensional extended structure. The anion binding behavior of ligand L in solution was studied.

The tripodal tris(4-pyridylurea) receptor (L) was synthesized and its anion binding properties studied. The ligand forms a 2:1 (H/G) complex with MgSO₄, [SO₄²⁻⊂L₂], in which a sulfate ion is encapsulated by six urea groups as in the analogous complex of the 3-pyridyl-substituted ligand. The anion binding behavior of ligand L in solution was studied.

Tetraamido-oxacalix[4]arene derivatives have been synthesized via the reactions of tetraamino-oxacalix[4]arene with excess butyryl chloride, octanoyl chloride, benzoyl chloride and p-toluenesulfonyl chloride, respectively. ¹H NMR results suggest that these oxacalix[4]arene derivatives preferentially adopt the 1,3-alternate (saddle-like) conformation in solution, which were also the case in the solid state as demonstrated by single crystal X-ray analysis. A dimerized slipped capsule could be formed by tetra-butyramido-oxacalix[4]arene in the solid state via intermolecular hydrogen bond interactions under the assistance of two encapsulated methanol molecules. On the other hand, a molecular cavity was formed by tetra-p-toluenesulfonamido-oxacalix[4]arene which can encapsulate a solvent molecule of ethyl acetate.

Tetraamido-oxacalix[4]arene derivatives have been synthesized and their structural and assembly properties have been discussed.

An intramolecularly hydrogen-bonded crescent aromatic oligoamide 1 bearing two coumarin residues was synthesized. The results from UV-vis and fluorescent spectra upon metal ions complexation demonstrated that the two fluorophores serving as parts of the shape-persistent backbone provided the molecule with high selectivity and sensitivity for recognition of Th⁴⁺ over other lanthanide and uranyl ions. A 48-fold fluorescent enhancement in the intensity was observed at 505 nm upon adding Th⁴⁺, while other metal cations failed to induce such a significant change. A visual detection for Th⁴⁺ was achieved by color change. The stoichiometry of the complex formed by 1 and Th⁴⁺ was found to be 1:1 with the stability constant of (2.0±0.6)×10⁶ L·mol⁻¹.

A significant fluorescent enhancement was observed upon adding Th⁴⁺ for a crescent aromatic oligoamide, allowing a visual detection for Th⁴⁺ over some other lanthanide and uranyl ions under UV-light (365 nm).

Fluorous gold nanoparticle (Fluo-NP), i.e. gold nanoparticle covered by fluorous ponytail (C₈F₁₇-) was prepared and found to self-assemble into supra-structures covered by carbohydrates (named supraF-NP), due to the strong fluorous interaction. More importantly, the re-dispersed supraF-NP (diameter around 200 nm) in water provided an alternative strategy to detect carbohydrate-protein interaction in solution by naked eye.

Self-assembled fluorous gold nanoparticles in water with carbohydrates covered on surface showing reversible binding ability to lectin.