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Heteroatom-doping is an efficient approach to extend optical absorption beyond 460 nm, which, however, often reduces crystallinity to cause a concomitant detrimental effect on photocatalytic activity. In the present study, we developed a facile approach to synthesize S-doped g-C 3 N 4 with a high crystallinity by self-assembling melamine and tri-thiocyanuric acid, followed by calcination. The resultant optimal S-doped carbon nitride (MTCN-6) exhibited a super-high H 2 -generation rate of 1511.2 μmol g −1  h -1 (about 11 times higher than that of the pristine CN) under visible light excitation (λ > 420 nm) and an excellent AQE of 3.9% at 420 nm. [ABSTRACT FROM AUTHOR]

The reaction of an equivalent amount of Ru metalla-clip B 1 b with pyrazine in the presence of excess silver triflate salt leads to the formation of macrocycle B 2 b in high yield (Scheme). GLO:1CJF/01feb20:bkcs11933-fig-0001.jpg PHOTO (COLOR): 1H NMR spectra of Ru clip 1, free pyrazine and supramolecule 2 in acetone-d6 showing the different chemical shift of only the aromatic regions. gl The pyrazine ligand is bonded through its nitrogen atoms to the ruthenium metal centers and acts as a bridge to form the cyclic structure. UV-Visible absorption properties of ruthenium clip B 1 b and the macrocycle B 2 b were studied in acetonitrile solution at room temperature (Figure S5). [Extracted from the article]

Acetoguanamine is an advantageous molecular precursor for a freshly identified N-H⋯O/N-H⋯N synthon, which is adequate for the design of novel multi-dimensional structures. Six compounds of acetoguanamine with various carboxylic acids pyridine-2,3-dicarboxylic acid 1 , phthalic acid 2 , 3,4,5-trimethoxybenzoic acid 3 , 5-chloro-2-hydroxy-benzoic acid 4 , 1,2,3,4-cyclopentane-tetracarboxylic acid 5 , terephthalic acid 6 , were synthesized and investigated. The N-H⋯O/N and C-H⋯O interactions bring about the formation of supramolecular aggregation patterns with rich structures. Compounds 1–4 are featured as 2D supramolecular structure while compounds 5 and 6 are novel 3D supramolecular aggregation patterns. Synthon strategy gives a major push to the construction of these six supermolecular compounds. The hetersynthon I R 2 2 (8) constructed by N-H⋯O/N + -H···O H-bond interaction between the deprotonated carboxyle and the protonated triazine is observed in all structures except 3 . The homosynthon III R 2 2 (8) constructed by N-H⋯N H-bond interaction between acetoguanamine is observed in all structures except 2 . What is worth mentioning, compounds 1 and 3–6 feature the 1D chain structures constructed by various synthons and in 3 , 4 and 6 the chains are positioned into infinite 2D sheets. What's more, solvent molecule play a vital role in 4 and 6 . Besides, the thermal stabilities of complexes 1 – 6 have been investigated. [ABSTRACT FROM AUTHOR]

Abstract: By solvothermal reactions of ZnSO4 ⋅ 7H2O and NiSO4 ⋅ 6H2O with 2-(3,4-dimethylphenyl)-1H-imidazole-4,5-dicarboxylic acid (3,4-DMPhH3IDC), respectively, two supramolecular complexes, [Zn(3,4-DMPhHIDC)2(H2O)2]n (I) and [Ni(3,4-DMPhHIDC)2(H2O)2]n (II) have been successfully prepared and structurally characterized by single-crystal X-ray diffraction (CIF files CCDC nos. 1440305 (I) and 1440316 (II)), elemental analyses, and IR spectroscopy. The results show that ligand 3,4-DMPhH3IDC in the two complexes has quite strong coordination ability, and the 3D solid-state supramolecular structures of I and II involve intermolecular hydrogen bonds. The thermal properties of the complexes have also been investigated and discussed. [ABSTRACT FROM AUTHOR]

A family of aromatic acids containing different binding sites, including 5-chloro-2-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, salicylic acid, 3-nitrophthalic acid, 4,5-dichlorophthalic acid, 6-hydroxy-2-naphthoic acid and tetrafluorophthalic acid, were allowed to react with 2,3-dimethylpyrazine to assemble single molecule into diverse structures. Seven cocrystals were successfully synthesized and characterized by single crystal X-ray diffraction. Crystal structure analysis shows that O H⋯N H-bonds are involved in the formation of all 1D chains of the seven cocrystals. Moreover, C H⋯O H-bonds play a crucial role in the 3D supramolecular network. In the crystal structures of cocrystals 1 , 2 and 4 , noncovalent interaction π-π stacking can be considered as a significant influencing factor. In 2, the self-assembly of 3D tessellate-type supramolecular architecture in solution is driven mainly by π-π interactions, to a lesser extent, and by weak hydrogen bond. In 3 , two carboxylic acid molecules link each other to form dimers [synthon V R 2 2 (12)] but in 7 carboxylic acid molecules and water molecules are connected to afford tetramer [synthon XVII R 4 4 (12)], further generating zig-zag chains via O H⋯N intermolecular H-bonds. What is worth mentioning, acid and alkali molecules constitute tape chains through the way of forming synthons VII R 2 2 (14) and VIII R 6 6 (30), XI R 4 4 (24) and XII R 2 2 (10) in crystals 4 and 5 , respectively. The strong orthogonally directed C H···π interactions lie in the 2D architecture of 6 . Meanwhile, solvent molecules make a significant part in preparation of supramolecular structures in 6 and 7 . Results show that solvent molecules serve as H-bond donors/acceptors to complete the various motif. [ABSTRACT FROM AUTHOR]

By employing the multifunctional organic ligand, 2-(o-bromo)phenyl-4,5-imidazole dicarboxylic acid (o-H 3 BrPhIDC), two three-dimensional supramolecular complexes, [M(o-H 2 BrPhIDC) 2 (H 2 O) 2 ]·CH 3 CH 2 OH·3H 2 O (M = Zn ( 1 ); Co ( 2 )) have been successfully solvothermally synthesized, and structurally characterized by single crystal X-ray crystallography. Their proton conduction properties have been explored under different temperature and relative humidity (RH). Compounds 1 and 2 indicate high conductivity values of 1.14 × 10 −4  S·cm −1 and 3.11 × 10 −4  S·cm −1 , respectively, at 98% RH and 100 °C. The hydrogen bonding nets inside the two complexes perform a vital function in the resultant conductivity. Variable-temperature and Variable-RH experiments of both compounds reveal that the conductivity values increase with increasing temperature and RH. The proton transfer mechanisms of the complexes have been proposed in terms of the structural analyses, activation energy calculations and PXRD determinations. [ABSTRACT FROM AUTHOR]

Nano-structures of [Zn(L)(atpt)] n ( 1 ) (L = 1,2-bis(2-methylbenzimidazol-1-ylmethyl)benzene and H 2 atpt = 2-aminoterephthalic acid) were obtained by hydrothermal and sonochemical approaches, characterized by scanning electron microscopy (SEM), IR, powder X-ray diffraction (PXRD), and elemental analysis. CP 1 features a 2D (4,4) network with the point symbol {4 4 .6 2 }, the 3D supramolecular architecture in CP 1 is controlled through π ⋯ π stacking interactions. The influence of various concentrations of initial reagents, power of ultrasound irradiation, and ultrasound time on the morphology and size of nano-structured CP 1 were studied in detail. In addition, the luminescence and photocatalytic properties of the nanoparticles of CP 1 for the degradation of methyl blue (MB) have also been investigated. [ABSTRACT FROM AUTHOR]

In this work, a nitrogen-containing bidentate ligand named 5,50-(9-octyl-9H-carbazole- 2,7-diyl)bis(1,10-phenanthroline) (OCBP) was synthesized as a nitrogen precursor for making an oxygen reduction catalyst. The 1,10-phenanthroline unit provides a coordination site for copper ions, and the resulting Cu-Nx unit may be responsible for the catalytic activities of the catalyst. Carbon black was selected as a support to improve the electroconductibility of the resulting catalyst. The metallo-supramolecule (Cu-SOCBP) was dispersed on the surface of Vulcan XC-72 carbon and was used as a catalyst (designated as Cu-SOCBP/C) for the oxygen reduction reaction (ORR). The microscope structure and surface components of the catalyst were acquired via scanning electron microscopy and X-ray photoelectron spectroscopy, as well as X-ray powder diffraction. The electrochemical property and ORR mechanism of Cu-SOCBP/C were analyzed using a variety of electroanalytical methods including cyclic voltammetry, electrochemical impedance spectroscopy, and linear sweep voltammetry. These results show that Cu-SOCBP/C was successfully synthesized and that ORR was achieved mainly via a four-electron transfer process to water. Thus, Cu-SOCBP/C was an effective catalyst and might have potential application as a cathodic catalyst in microbial fuel cells, which operate in an aqueous medium. [ABSTRACT FROM AUTHOR]

Nanoparticle (NP) structure, compositing and the nature of the NP-functionalized electrode interface have a strong influence upon electrochemical properties that are critical in applications such as sensing, photocatalysis and electrocatalysis. Existing methods to fabricate NP-functionalized electrodes do not allow or precise control over all these variables, especially the NP-electrode interface, making it difficult to understand and predict how structural changes influence electrode activity and consequently limit the application. To conquer this problem, in this study, we fabricated a stepwise construction of a novel supramolecular stabilized gold nanoparticles (AuNPs) multilayer mediated by guest molecules, yielding 3D AuNPs assembly at the electrode interface. para -Sulfonatocalix[4]arene (pSC 4 ), a water soluble macrocyclic synthetic receptor, has been served as a stabilizing ligand for preparation and gaining new insights into pSC 4 stabilized gold nanoparticles (pSC 4 -AuNPs) tethered on the electrode interface through host-guest interaction. We investigated the electrochemical properties of multilayer pSC 4 -AuNPs modified gold electrode using different core size of AuNPs with varying layer number. The electron transfer ability was characterized by electrochemical impedance spectroscopy (EIS). Electrochemical signals are significantly enhanced through the layer-by-layer assembly of pSC 4 -AuNPs due to its high conductivity and high effective area. With this innovative method, by taking the assay of a tumor marker as an example, human epidermal growth factor receptor 2 (ErbB2) was successfully measured with a detection limit of 0.5 ng/mL. Taking the advantage of the pSC 4 -AuNPs multilayer's good biocompatibility, high effective area and high electronic transmission, 3D AuNPs multilayer produced on the electrode interface suggests a portable synthetic pathway for the application into sensitive electrochemical biosensor. [ABSTRACT FROM AUTHOR]

Reduced graphene oxide (rGO) and its derivatives functionalized with 2-thiophene acetic acid (rGO- f -TAA) and grafted with poly (3-dodecylthiophene) (rGO- g -P3DDT) and poly (3-thiophene ethanol) (rGO- g -PTEt) were prepared to design the donor-acceptor supramolecular structures based on the regioregular poly (3-hexylthiophene) (P3HT). The P3HT nanofibers, which were pre-grown in a separate system and possessed the π-stacked P3HT backbones in the length of fibrils, were perpendicular to the rGO surface in the solution and, consequently, they inclined onto the substrate during solvent evaporation. Through this inclination, the orientation of P3HT chains changed from face-on to edge-on. In rGO- f -TAA systems, for either short (80 nm) or long (420 nm) P3HT nanofibers, the P3HT nanofibers were attached from their sides onto the rGO. The appearance of (020) and (002) spots in selected area electron diffraction (SAED) patterns proved a fixed edge-on orientation even after solvent evaporation. Functionalization of rGO surface with 2-thiophene acetic acid altered the tethering tendency of P3HT chains from the thiophenic rings to the hexyl side chains. Via grafting the rGO with P3DDT and PTEt, the tethered P3HT nanofibers were perpendicularly fixed onto its surface with a face-on orientation having (002) and (100) spots even after solvent evaporation, resulting in the conductivity range of 9.9–10.9 S/cm. The pre-developed large single crystals were also employed to construct the donor-acceptor supramolecules with edge-on oriented P3HTs. Further tethering of P3HT fibrils onto the rGO based micron sheets reflected a red-shifting and more intensified A 0–2 , A 0–1 , and A 0–0 peaks in the ultraviolet–visible spectra. A quenching in the photoluminescence spectra was observed in longer preparation time (18 h) based on the charge transferring from donor (P3HT) to acceptor (rGO derivatives). [ABSTRACT FROM AUTHOR]

An evanescent wave infrared chemical sensor was developed for the selective detection of odorous amino compounds in the atmosphere. To achieve this goal, cavity-containing rhenium metallacycles with multi-recognition sites were prepared and used as host molecules to modify the surface of an evanescent wave infrared (EWIR) sensing element. The unique cavity structure with hydrophobic properties of the Re metallacycle permits the selective trapping of suitably sized compounds with proper functionalities. To explore the scope of the process, two different Re metallacycles were synthesized and used to trap a series of volatile organic compounds (VOCs) with different functionalities. Based on the results, Re metallacycles are selective to detect amino compounds as evidenced by the peak shifts for C O absorption after the amino compounds had been adsorbed. The hydrophobic pocket and hydroxyl groups in the Re metallacycles were also verified to provide extra forces to stabilize the attraction of amino compounds. The efficiency of the Re metallacycles in detecting amino compounds follows the order of amine with phenyl ring > aliphatic primary amine ∼ cyclo-amine > aliphatic secondary amine > aliphatic tertiary amine. This sensor was applied to detect benzyl amine and a linear range up to 1 mg/L could be obtained with a detection limit close to 4 μg/L. [ABSTRACT FROM AUTHOR]

In this study a new calix[4]arene triazole 5 was successfully synthesized using click reaction and characterized through UV–visible, FT-IR, 1 H NMR spectroscopes and Mass Spectrometry. The supramolecular interaction of compound 5 towards commonly used drugs has been carried out using UV–Visible spectroscopy. The supramolecule 5 showed characteristic enhancement in the absorbance intensity after mixing with Cefuroxime at pH (2–12). Compound 5 displayed considerably good interactions with cefuroxime in the presence of other drugs. Compound 5 exhibits linear relationship with cefuroxime concentration in the range of (10–80 µM) with regression value of 0.9954. The standard deviation for 50 µM Cefuroxime was found to be 0.01 and the limit of detection for cefuroxime was calculated to be 2 µM. Job’s plot experiments showed 1:1 ( 5: cefuroxime) binding stoichiometry between compound 5 and cefuroxime. Supramolecule 5 displayed fairly good spectrophotometric recognition of Cefuroxime in human blood plasma and tap water thus showing that the ingredients of tap water and plasma sample was inert in the recognition of cefuroxime. [ABSTRACT FROM AUTHOR]

ABSTRACT For verifying the influence of donor-acceptor supramolecules on photovoltaic properties, different hybrids were designed and used in organic solar cells. In this respect, reduced graphene oxide (rGO) was functionalization with 2-thiophene acetic acid (rGO- f-TAA) and grafted with poly(3-dodecylthiophene) (rGO- g-PDDT) and poly(3-thiophene ethanol) (rGO- g-PTEt) to manipulate orientation of poly(3-hexylthiophene) (P3HT) assemblies. Face-on, edge-on, and flat-on orientations were detected for assembled P3HTs on rGO and its functionalized and grafted derivatives, respectively. Alteration of P3HT orientation from face-on to flat-on enhanced current density ( Jsc), fill factor (FF), and power conversion efficiency (PCE) and thus Jsc = 7.11 mA cm−2, FF = 47%, and PCE = 2.14% were acquired. By adding phenyl-C71-butyric acid methyl ester (PC71BM) to active layers composed of pre-designed P3HT/rGO, P3HT/rGO- f-TAA, P3HT/rGO- g-PDDT, and P3HT/rGO- g-PTEt hybrids, photovoltaic characteristics further improved, demonstrating that supramolecules appropriately mediated in P3HT:PC71BM solar cells. Phase separation was more intensified in best-performing photovoltaic systems. Larger P3HT crystals assembled onto grafted rGOs (95-143 nm) may have acted as convenient templates for the larger and more intensified phase separation in P3HT:PCBM films. The best performances were reached for P3HT:P3HT/rGO- g-PDDT:PCBM ( Jsc = 9.45 mA cm−2, FF = 54%, and PCE = 3.16%) and P3HT:P3HT/rGO- g-PTEt:PCBM ( Jsc = 9.32 mA cm−2, FF = 53%, and PCE = 3.11%) photovoltaic systems. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1877-1889 [ABSTRACT FROM AUTHOR]

A study of the comparative drug carrier properties of cucurbituril[7] (CB7) and β-cyclodextrin (β-CD) with a naphthalimide derivative, [2-(2-aminoethyl)-1H-benzo[deisoquinoline-1,3(2H)-dione] (NAP) and its release in aqueous solution using micellar environment, is the key research interest of this work. The profound changes in the different spectroscopic behavior have been attributed to the formation of a 1:1 inclusion complex for NAP:CB7 system. Several experimental outcomes clearly interpreted that CB7 has better drug carrier properties for NAP compared to β-CD. It has been also focused on the systematic release of NAP molecule from CB7 by using different ionic and non ionic surfactants. Before releasing the drug molecules from CB7 the interaction between NAP and the three different types of surfactants has also been investigated separately. The selectivity of drug carrier and releaser has been monitored, using different spectroscopic techniques like absorbance, fluorescence, fluorescence decay life time and 1 H NMR spectroscopy. Besides, a theoretical approach has been followed for a proper geometrical optimized structure of NAP molecule and molecular arrangement of NAP:CB7 inclusion complex. From Density Functional Theory (DFT) it has been seen that NAP molecule is oriented as a t-bone like structure in its optimized form. [ABSTRACT FROM AUTHOR]

Sulfamethazine (SMZ) is widely present in the environment and can cause severe allergic reactions and cancer in humans. Accurate and facile monitoring of SMZ is crucial for maintaining environmental safety, ecological balance, and human health. In this work, a real-time and label-free surface plasmon resonance (SPR) sensor was devised using a two-dimensional metal-organic framework with superior photoelectric performance as an SPR sensitizer. The supramolecular probe was incorporated at the sensing interface, allowing for the specific capture of SMZ from other analogous antibiotics through host-guest recognition. The intrinsic mechanism of the specific interaction of the supramolecular probe-SMZ was elucidated through the SPR selectivity test in combination with analysis by density functional theory, including p-π conjugation, size effect, electrostatic interaction, π-π stacking, and hydrophobic interaction. This method facilitates a facile and ultrasensitive detection of SMZ with a limit of detection of 75.54 pM. The accurate detection of SMZ in six environmental samples demonstrates the potential practical application of the sensor. Leveraging the specific recognition of supramolecular probes, this direct and simple approach offers a novel pathway for the development of novel SPR biosensors with outstanding sensitivity. [Display omitted] • 2D MOF enhances SPR by increasing the plasmonic electric field of the sensing interface. • DFT analysis shows the host-guest interaction between SMZ and pSC 4 ensures the specificity of the sensor. • The host-guest interaction mechanism includes p-π conjugation, size effect, electrostatic interaction, etc. • SMZ was easily and ultrasensitively detected with a low LOD of 75.54 pM. • SMZ was accurately detected in the six environmental samples with a recovery rate of 95%− 110%. [ABSTRACT FROM AUTHOR]

• Metallocycles from Re(CO) 5 Cl and benzimidazolyl/naphthanoimidazolyl-based donor. • Neutral dinuclear π-π stacked chloro‑bridged metallocycles. • Intermolecular nontraditional H-bonding contacts stabilize the crystal structures. Neutral binuclear metallocycles of the formula, fac -[{(CO) 3 Re(µ-Cl) 2 Re(CO) 3 }Ln] were obtained using [Re(CO) 5 Cl] and ditopic flexible nitrogen donor (Ln = L1 = bis((benzimidazol-1-yl)methyl)benzene; L2 = bis((5,6-dimethylbenzimidazol-1-yl)methyl)benzene, L3 = bis((naphthanoimidazol-1-yl)methyl)benzene) in toluene under solvothermal approach. The metallocycles were characterized by ATR-IR, 1H NMR and ESI- Mass analysis. The crystal structures of 1–3 were confirmed by single crystal X-ray diffraction analysis. Non-traditional intermolecular hydrogen bonding interactions (C-H···O≡C) stabilize the solid state structures of the metallocycles. [Display omitted] [ABSTRACT FROM AUTHOR]

• Pt···Pt and π···π interactions in supramolecular structures based on the imine ligands. • Self-assembly of organoplatinum(IV) complexes via noncovalent interactions. • Oxidative addition of Pt(II) compounds for supramolecular and polymeric structures. • Pt-containing polymers and dendrimers. • Biological applications of supramolecule, polymeric, dendrimeric platinum compounds. Platinum complexes have attracted increasing attention because of their intriguing photophysical and anticancer activities. They are considered excellent building blocks for supramolecular assembly via π···π stacking, Pt···Pt and other non-covalent interactions. We have summarized the progress of platinum(II)/(IV)-based supramolecular networks, polymers and dendrimers by diverse assembling modes. Supramolecular platinum based-diimine, terpyridine, and organoplatinum complexes including σ-acetylide compounds are discussed. The introduction of supramolecular assembly involving non-covalent interactions could lead to research dimensions of unlimited possibilities and opportunities, such as response to environmental stimuli. The oxidative addition of organoplatinum(II) complexes with organohalide promoted the formation of a variety of organoplatinum polymers and supramolecular structures. Various classes of polymers with the metallic moieties in the backbone or pendent to the backbone are discussed and their properties are illustrated. While dendrimers were developed in the early 1980′s, platinum-containing dendrimers have been first reported in 1994. This review highlights the design and applications of this emerging class of macromolecules and the importance of the new generation of platinum macromolecules as anticancer drugs is highlighted. The majority of the new generation of platinum-based anticancer drugs principally relies on the platinum supramolecular, polymer and dendrimer nano drug delivery systems, which reveal better antitumor effects with negligible toxicities to major organs. The oxidative addition of cisplatin with hydrogen peroxide, and the subsequent nucleophilic reaction affords a variety of efficient functionalized Pt(IV) prodrugs followed by host–guest assembly. These new drug delivery systems are intracellular reduction-responsive with controlled release of cisplatin upon entering the cells. [ABSTRACT FROM AUTHOR]

The toughening of epoxy resins is important for their applications in coatings, adhesives, and composite materials. In our previous study, we introduced polyrotaxane (PR), which comprises poly- ε -caprolactone (PCL)-grafted α -cyclodextrins (α -CDs) and a polyethylene glycol (PEG) axial chain, into epoxy resins as an additive and observed that the presence of PR causes an additional viscoelastic relaxation and enhances the mechanical toughness. In this study, we modified the side chain ends of PR with epoxy groups (PR-E) to enable incorporation into crosslinked epoxy networks. The chemical bonding of PR-E to the epoxy resins suppressed the local dynamics of the PCL graft chains and enhanced the mechanical properties. [Display omitted] • Epoxy-Modified Polyrotaxane (PR-E) is incorporated into cross-linked epoxy networks. • Dynamics of the PCL chains was suppressed by end-reaction of PR-E with epoxy matrix. • Chemical binding between PR-E and epoxy matrix can reinforce the interfaces. • Containing of PR-E in epoxy resins can improve the mechanical properties. [ABSTRACT FROM AUTHOR]

Lysosomal DNase is essential for maintaining cellular DNA synthesis and metabolic homeostasis, and their abnormal activity leads to a variety of diseases such as cancer and immune abnormalities. Herein, a biosensor named PTC-G4 has been constructed to detect lysosomal DNase activity in solution and living organisms. This biosensor consists of a cyanine dye (PTC) supramolecule and an exogenous G-quadruplex (G4) DNA, both of which are highly targeted to lysosomes in live cells, while PTC is highly specific for the G4 structure. Lysosomal DNase activity was evaluated by monitoring the double-channel fluorescence of PTC monomers and aggregates in response to G4 hydrolysis. PTC-G4 can not only be used as a tool for monitoring lysosomal DNase in vivo, but also can distinguish the difference between tumor cells and normal cells, making it promising in tumor screening or auxiliary diagnosis. • A biosensor is constructed to detect lysosomal DNase activity in vivo. • The biosensor is composed of cyanine dye supramolecules and G-quadruplex DNA. • The biosensor has been applied to living cells and zebrafish. • It can distinguish the difference between normal cells and tumor cells. [ABSTRACT FROM AUTHOR]

In this study, we found that the hydrogel containing cross-linking points of amylose/PCL graft chain inclusion complexes was obtained by vine-twining polymerization using a water-soluble chitosan- graft-poly(ε-caprolactone) (chitosan- g-PCL). When phosphorylase-catalyzed enzymatic polymerization was performed in the presence of chitosan- g-PCL, the reaction mixture turned into a gel form. The IR spectrum of the sample obtained by lyophilization of the hydrogel indicated that amylose included the PCL graft chains in the intermolecular (chitosan- g-PCL)s to produce cross-linking points. The evaluation of the hydrogels obtained under various conditions was conducted by the shear-viscosity measurement. Because amylose, chitosan, and PCL are known to be enzymatically hydrolyzed, we have investigated enzymatic disruption behaviors of the hydrogels by hydrolysis of these components catalyzed by the corresponding enzymes, i.e., β-amylase, chitosanase, and lipase, respectively. In all cases, the hydrogels were transformed into solution or suspension states, indicating the occurrence of enzymatic disruption of hydrogels. Furthermore, the hydrogel was reproduced when the vine-twining polymerization was carried out in the presence of phosphorylase in the resulting solution by the β-amylase treatment. [ABSTRACT FROM AUTHOR]

Supramolecular slide-ring (SR) elastomers without solvent were fabricated by cross-linking of polymer-grafted polyrotaxane in which α -cyclodextrins (CDs) with poly- ε -caprolactone (PCL) side chains are threaded on a polyethylene glycol (PEG) axial linear chain. The cross-links in the SR elastomers are capable of sliding along the backbone in response to applied stress. Mechanical properties of the SR elastomers with different cross-linking densities were compared with those of fixed cross-link (FC) elastomers prepared from PCL-grafted hydroxypropyl cellulose (HPC) to understand the influence of the slidable cross-links. The SR elastomers are found to undergo less strain-hardening at large strains and demonstrate higher strains at break than the conventional FC elastomers with the same Young's moduli. [ABSTRACT FROM AUTHOR]

Two novel complexes $$\{\hbox {(Pepy)}[\hbox {Cu}_{2}\hbox {(SCN)}_{4}]\}_{\mathrm{n}}$$ ( 1) and $$\{\hbox {(Pepy)}[\hbox {Cu}_{2}\hbox {Br}_{4}]\}_{\mathrm{n}}$$ ( 2) [Pepy=1-2-(Pyridinium-1-yl)-1-ethenyl) pyridinium] based on vinylpyridinium organic cation and cuprous salts have been synthesized and characterized by X-ray diffractometry. Compound 1 has a 2D polypseudorotaxane structure and compound 2 presents a 1D chain structure. Furthermore, the thermal gravimetric analysis (TGA), UV-Vis diffuse reflectance spectra, the morphology and the photocatalytic performances were studied carefully. Remarkably, both 1 and 2 exhibited good photocatalytic degradation abilities towards some dyes. Graphical Abstract: Two novel complexes $$\{\hbox {(Pepy)}[\hbox {Cu}_{2}\hbox {(SCN)}_{4}]\}_{\mathrm{n}}$$ and $$\{\hbox {(Pepy)}[\hbox {Cu}_{2}\hbox {Br}_{4}]\}_{\mathrm{n}}$$ [Pepy=1-2-(Pyridinium-1-yl)-1-ethenyl) pyridinium] based on vinylpyridinium cation and cuprous salts have been synthesized. They exhibited diverse structures and good photocatalytic properties. [ABSTRACT FROM AUTHOR]

Four new network organic-inorganic hybrid supramolecular compounds [PWO](CHN)·6HO (1), [PMoO](CHN)·6HO (2), [HSiWO][CNOH][CNOH][CNH]·39HO (3) and [HVWO] (CHNO)(CHO)·4HO (4) composed by keggin type heteropolyanion and O/N-containing organic groups of 1H-1,2,4-Triazole or 2,3-Pyridinedicarboxylic acid have been successfully synthesized by hydrothermally method, and characterized by infrared spectrum (IR), thermogravimetric-differentialthermal analysis (TG-DTA), cyclic voltammetry (CV) and single crystal X-ray diffraction (XRD). Compounds 1-4 exhibit three dimensional supramolecular network via hydrogen bonds and/or π-π stacking interactions. These compounds exhibit good thermal stability and catalytic ability. They are active for catalytic oxidation of methanol in a continuous-flow fixed-bed micro-reactor, when the initial concentration of methanol is 2.5 g m in air and flow rate is 10 mL min, the corresponding elimination rates of methanol are 65% (125 °C), 85% (125 °C), 94% (150 °C), and 80% (125 °C), respectively. [ABSTRACT FROM AUTHOR]

An aspect of nanochemistry that has attracted significant attention is the formation of nanoarchitectures from the self-assembly of metal complexes, based on the design of compounds having cooperative functionalities. This technique is currently seen as important within the field of nanomaterials. In the present review, we describe the methods that allow tuning of the intermolecular interactions between spin crossover (SCO) complexes in various media. These approaches include the use of lipophilic derivatives, lipids, and diblock copolypeptide amphiphiles. The resulting supramolecular assemblies can enhance the solubility of various SCO complexes in both organic and aqueous media. In addition, amphiphilic modifications of coordination systems can result in metastable structures and dynamic structural transformations leading to unique solution properties, including spin state switching. The supramolecular chemistry of metal complexes is unprecedented in its scope and potential applications, and it is hoped that the studies presented herein will promote further investigation of dynamic supramolecular devices. [ABSTRACT FROM AUTHOR]

A supramolecular cobalt phthalocyanine ( CoPc ) bearing four redox active cobaloxime ( CoDMG ) substituents (( CoDMG ) 4 - CoPc ) was synthesized and electrochemically characterized in order to determine its functionalities for practical usages as effective electrocatalysts. Voltammetric analyses of CoDMG , CoPc , and ( CoDMG ) 4 - CoPc indicated redox activity of each compounds and supported substitution of CoPc with CoDMG . ( CoDMG ) 4 - CoPc showed three CoPc based reduction processes and two CoDMG based reduction processes. While CoDMG showed two reduction and one oxidation processes, CoPc illustrated three reduction and two oxidation processes. Binding of CoDMG to CoPc increased the reduction processes to five. Multi-electron and metal and/or ring based redox processes showed worthy of the ( CoDMG ) 4 - CoPc for using as an electrocatalyst. Shifting of the proton reduction reaction toward the positive potentials indicated electrocatalytic activities of the complexes for the hydrogen evolution reaction ( HER ). Among CoDMG , CoPc , and ( CoDMG ) 4 - CoPc , modified glassy carbon electrode with ( CoDMG ) 4 - CoPc illustrated the highest electrocatalytic activity and it decreased the over-potential of the bare electrode about 360 mV and increased the current density of the electrode about 10-fold. [ABSTRACT FROM AUTHOR]

Mesoporous polymers derived from supramolecules of phenolic resins (PRs) and block copolymers (BCPs) containing highly uniform pores with sizes down to a few nanometers, are expected to deliver promising membrane separation performances. Here we report on the preparation of mesoporous phenolic membranes exhibiting tight ultrafiltration properties through a pore-filling strategy. Solutions of PR/BCP supramolecules are filled into the macropores of polyvinylidene fluoride (PVDF) microfiltration membranes (substrates), followed by thermopolymerization to solidify the solution in the pores. Subsequently, the filled PVDF substrates are treated in hot H 2 SO 4 to remove the BCP components, thus producing mesopores in the PR framework. The produced composite membranes are mechanical robust and ductile as mesoporous phenolic resins are tightly embedded in the pores of the PVDF matrix. The mesoscale porosity in the PR phases endow the composite membrane a tight ultrafiltration performance with the molecular-weight-cut-off (MWCO) down to 2350 Da. The separation properties can be tuned simply by adjusting the dosage of supramolecule solutions used to fill the macroporous substrates. Considering the tight and uniform pore sizes and the robustness of phenolic resins, this strategy opens a new avenue to ultrafiltration membranes with low MWCOs or even nanofiltration membranes. [ABSTRACT FROM AUTHOR]

Wireframe, polyhedral, supramolecular complexes made of DNA have uniform sizes, defined three-dimensional shapes, porous facets, hollow interiors, good biocompatibilities, and chemical functionalizability. They confer great potentials in bottom-up nanoengineering towards various applications. In this review, we summarize recent advances in the rational design and programmed assembly of DNA wireframe polyhedra. Their assembly is based on three distinctively different strategies: individual strands-based assembly, tile-based assembly, and scaffolded DNA origami. Applications of these polyhedral structures in templated nanomaterial assembly and in-vivo cargo delivery are discussed. In the future, expanding the structural complexity and exploring their applications, especially in nanomaterials science and biomedicines, should be a primary focus of this rapidly developing and evolving activity of structural DNA nanotechnology. [ABSTRACT FROM AUTHOR]

By using solvent evaporation method, 2,4,6-triaminopyrimidine (TAPI) is employed to crystallize with a variety of acids, including 3,5-dihydroxybenzoic acid (HDHBA), 3-nitrophthalic acid (H 2 NPA), 5-amino-2,4,6-triiodoisophthalic acid (H 2 ATIPIA), 2,5-dibromoterephthalic acid (H 2 DBTPA), 1,5-naphthalenedisulfonic acid (H 2 NDSA), sebacic acid (H 2 SA), 1,2,4-benzenetricarboxylic acid (H 3 BTA), and biphenyl-2,2′,5,5'-tetracarboxylic acid (H 4 BPTA). In all eight complexes, protons are completely exchanged from O atom of acid to nitrogen of TAPI in 1 , 3 , 4 , and, 5 , partly transferred in 2, 6, 7 , and 8 . The crystal structure of all eight complexes exhibit that classical robust hydrogen bonds X-H⋯X (X = O/N) direct the molecular crystals to bind together in a stacking modes. Classical hydrogen bond N H⋯O is participated in forming all eight organic salts, while hydrogen bonding O H⋯O are found in constructing the diversity structures in salts 1 , 2 , 3 , 4 , 6 , and 7 . The analysis shows that some classical supramolecular synthons, such as I R 2 2 (8), V R 2 4 (12), and VI S(6), are observed again in the construction of hydrogen-bonding networks. In the formation of layered and reticular structure, strong hydrogen bonds between water molecules and ligands having well-refined hydrogen atoms have been considered. Water molecules play an important role in building supramolecular structures of 1 , 2 , 3 , 4 , 7 , and 8 . Moreover, salts 1-8 are further characterized and analyzed by element analysis, infrared radiation, thermogravimetric analysis, proton nuclear magnetic resonance spectra, and mass spectra. [ABSTRACT FROM AUTHOR]

Polydiacetylenes (PDAs) are intrinsically supramolecular conjugated polymers that are prepared by polymerisation of self-assembled diacetylene (DA) supramolecules. Owing to their highly aggregating nature and insolubility, fabrication of transparent and homogeneous films has been challenging. By taking advantage of multiple hydrogen bonding, a transparent and thin PDA film was readily prepared with an aminopyridine-containing DA monomer. The PDA film displayed an irreversible blue-to-red colour change between 30 and 90 °C and a reversible red-to-yellow thermochromism between 30 and 190 °C. Micropatterned colour and fluorescence PDA images were readily fabricated by employing a simple photolithographic approach. [ABSTRACT FROM AUTHOR]

Novel nanorods of a lead(II) 3D metal-organic coordination system {[Pb(μ-NO)].(hmta).HO} (1) (hmta = hexamethylenetetramine) were synthesized by a sonochemical method. The new nanostructure was characterized using scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, elemental analysis, and thermogravimetric analysis. The single-crystal X-ray structure shows that 1 is a three dimensional (3D) coordination compound. This is further self-assembled into a 3-D supramolecular structure by weak directional intermolecular interactions. The coordination number of the Pb(II) ions is eight (PbO). PbO nanoparticles were obtained by the thermolysis of 1 at 180 °C using oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by the Scherrer equation to be 30 nm. The morphology and size of the prepared PbO samples were also observed using SEM. [ABSTRACT FROM AUTHOR]

A polyoxometalate-based, inorganic–organic hybrid compound containing a helical structure along theaaxis, [Ag(pyttz)2][H2PW12O40]·2H2O (p-pyttz = 3-(pyrid-4-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl), has been isolated and structurally characterized. Single-crystal X-ray diffraction analysis reveals that the new compound possesses two helical channels constructed by the left- and right-handed helical chains, respectively, which are fused together through sharing POMs dimer fabricating a 3-D framework with {44·53·63} {44·53·63} topolopy. The new compound displays good acid-catalytic activity toward the synthesis of Aspirin and good oxidation-catalytic activity to the decomposition of Rhodamine B dye; the catalytic reaction kinetics are discussed. [ABSTRACT FROM AUTHOR]

A six-coordinate Mn(IV) complex, [Mn(H2L)2] (1) [H4L = 2-methoxy-6-(tris(hydroxymethyl)methyliminomethyl)phenol], was synthesized and characterized by elemental analysis, single-crystal X-ray crystallography, FTIR, UV–Vis electronic absorption, and EPR spectroscopy. The single-crystal structural determination reveals that the complex crystallizes in tetragonal space groupP41212 and the tridentate Schiff base ligands are arranged inmerconfiguration chelating manganese, which exhibits as slightly distorted octahedral coordination sphere with a N2O4chromophore. Weak hydrogen bonding interactions of uncoordinated hydroxyl groups result in a 2-D supramolecular structure. The UV–Vis electronic absorption and IR spectral data of1have been compared with the results obtained by employing DFT and time-dependent density functional theory calculation using B3LYP, B3PW91, and MPW1PW91 functionals, with 6-31G (d-p) and LanL2MB basis sets. The results of these calculations are functional-dependent and, among those used, B3PW91 proved to better reproduce the experimental results. [ABSTRACT FROM AUTHOR]

The supramolecular palladium dithiolate complexes, [Pd 2 (dppe) 2 {S(C 6 H 4 ) n S}] 2 (OTf) 4 and [Pd 2 (dppe) 2 (SCH 2 C 6 H 4 CH 2 S)] 4 (OTf) 8 (dppe = 1,2-bis(diphenylphosphino)ethane) has been investigated as highly stable and robust catalysts in Heck C-C coupling reactions. The arylation of butyl acrylate and styrene with various aryl bromides under optimized catalytic systems, showed excellent yield and turnover number (410,000) of the products. The tetranuclear complexes showed slightly higher catalytic activity than the octanuclear complex. [ABSTRACT FROM AUTHOR]

Chlorosomes are major light-harvesting antenna apparatuses in green photosynthetic bacteria. Chlorosomes contain a large amount of bacteriochlorophyll(BChl)- c , d , e and f molecules and the supramolecular nanostructures of their self-assemblies are suggested to be rods with 5-nm or 10-nm diameters and/or lamellas with approximately 2-nm spacing. BChls- c were extracted, isolated and purified from cultured cells of a green sulfur photosynthetic bacterium, Chlorobaculum ( Cba. ) tepidum . Self-assemblies of the natural composite BChls- c as well as each pure homolog/epimer were prepared in a hydrophobic hexane-based solution and the resulting self-assembled solids were investigated by spectroscopic and microscopic techniques. Visible and near-infrared absorption and circular dichroism spectra of the in vitro self-assemblies of the natural composite BChls- c on a quartz substrate were closely similar to those in cells of Cba. tepidum in an aqueous buffer solution. Self-assemblies of (3 1 R )-epimerically pure BChl- c molecules showed a wider Qy absorption band with increase in the steric bulkiness of hydrocarbon substituents at the 8- and 12-positions, which were effective for capturing wider wavelength light. (3 1 S )-BChls- c gave similar self-assembly bands, but more monomeric and/or dimeric species than (3 1 R )-BChls- c . Atomic force microscopic images of in vitro self-assemblies of natural composite BChls- c showed a rod with a 5-nm height and bundles of fibrils with 1–2-nm heights. Spectroscopic and microscopic analysis suggested that the 8 2 -methylation enhanced π–π stacking of self-assemblies by hydrophobic interaction, but the 12 1 -methylation slightly weakened the intermolecular interactions due to its steric bulkiness. [ABSTRACT FROM AUTHOR]

Supramolecular hydrogel as a novel drug carrier was prepared from N -(9-Fluorenylmethoxycarbonyl) (Fmoc) modified l -phenylalanine. Its different properties like stability at different pH, temperature and rheology were evaluated in reference to salicylic acid (SA) as a model drug, entrapped in the supramolecular hydrogel network. The release behaviour of SA drug in supramolecular hydrogel was investigated by UV–vis spectroscopy. The influence of hydrogelator, pH values of the accepting media, temperature and concentration of SA drug on the release behaviour was investigated under static conditions. The results indicated that the release rate of SA in the supramolecular hydrogels was slightly retarded with an increase of the hydrogelator concentration. Also, the release rates of SA increased with an increase of temperature and its concentration. Furthermore, the release behaviour of SA was found to be different at various pH values in buffers. The study of the release kinetics indicated that the release behaviour of SA from the carrier was in accord with the Peppas model and the diffusion controlled mechanism involved in the Fickian model. [ABSTRACT FROM AUTHOR]

Liquid-crystalline nanoparticles represent an exciting class of new materials for a variety of potential applications. By combining supramolecular ordering with the fluid properties of the liquid-crystalline state, these materials offer the possibility to organise nanoparticles into addressable 2-D and 3-D arrangements exhibiting high processability and self-healing properties. Herein, we review the developments in the field of discrete thermotropic liquid-crystalline nanoparticle hybrids, with special emphasis on the relationship between the nanoparticle morphology and the nature of the organic ligand coating and their resulting phase behaviour. Mechanisms proposed to explain the supramolecular organisation of the mesogens within the liquid-crystalline phases are discussed.

Conjugates consisting of stigmasterol and L-phenylalanine, interconnected through short-chained dicarboxylic acyls by ester and amide bonds, respectively, were synthesized as potential low molecular weight/mass organic gelators (LMWGs/LMMGs). Their physico-chemical properties were subjected to investigation, especially their ability to form gels reversibly based on changes of the environmental conditions. Other self-assembly properties detectable by UV-VIS traces were measured in systems consisting of two miscible solvents (water/acetonitrile) with varying solvent ratios and using constant concentrations of the studied compounds. Partition and diffusion coefficients and solubility in water were calculated for the target conjugates. The conjugate 3a was the only compound from this series capable of forming a gel in 1-octanol. All three conjugates 3a–3c displayed supramolecular characteristics in the UV-VIS spectra.

Ionophore incorporated PVC membrane sensors are well-established analyticaltools routinely used for the selective and direct measurement of a wide variety of differentions in complex biological and environmental samples. Potentiometric sensors have someoutstanding advantages including simple design and operation, wide linear dynamic range,relatively fast response and rational selectivity. The vital component of such plasticizedPVC members is the ionophore involved, defining the selectivity of the electrodes' complexformation. Molecular recognition causes the formation of many different supramolecules.Different types of supramolecules, like calixarenes, cyclodextrins and podands, have beenused as a sensing material in the construction of ion selective sensors. Schiff's bases andcrown ethers, which feature prominently in supramolecular chemistry, can be used assensing materials in the construction of potentiometric ion selective electrodes. Up to now,more than 200 potentiometric membrane sensors for cations and anions based on Schiff'sbases and crown ethers have been reported. In this review cation binding and anioncomplexes will be described. Liquid membrane sensors based on Schiff's bases and crownethers will then be discussed.

[Display omitted] • A thiacalix[4]arene functionalized XG was fabricated as an efficient adsorbent system. • ECH-modified TC4As bonded to Fe 3 O 4 @XG-NH 2 to get the TC4As-XG@Fe 3 O 4. • Great adsorption capacity (769.23 and 833.33 mg/g) of CPF and CV from water was achieved. • Pseudo second-order kinetic and freundlich isotherm well described the adsorption data. • The TC4As-XG@Fe 3 O 4 exhibited regeneration ability at least for three cycles. A novel thiacalixarene-functionalized biopolymer nanocomposite hydrogel was designed and prepared as an efficient adsorbent system to elimination of aquatic areas from chlorpyrifos (CPF) and crystal violet (CV). This adsorbent system was conducted by multi-step including; preparation of Fe 3 O 4 @XG hydrogel through in-situ magnetization of XG, amine modification of Fe 3 O 4 @XG hydrogel by using 3-aminopropyltriethoxysilane (APTES) to get Fe 3 O 4 @XG-NH 2, the synthesis of TC4As supramolecule, its functionalization with epichlorohydrin (ECH) and eventually covalently attachment of ECH-modified TC4As onto as-prepared Fe 3 O 4 @XG-NH 2 to obtain the TC4As-XG@Fe 3 O 4 nanocomposite hydrogel. Several characterization techniques including FTIR, XRD, FESEM, VSM, TGA, and BET demonstrated the successful synthesis of TC4As-functionalized XG nanocomposite hydrogel. The result of characterization demonstrated that the TC4As-XG@Fe 3 O 4 adsorbent system showed superparamagnetic property with magnetic saturation (Ms) of 9.10 emu/g and high thermal stability with 73 % char yields. The XRD pattern of TC4As-XG@Fe 3 O 4 nanocomposite showed characteristic peaks of Fe 3 O 4 MNPs and XG, but with enhanced crystallinity in compared to neat XG as result of in-situ magnetization of XG as well as its functionalization with TC4As. The BET surface area of Fe 3 O 4 @XG and TC4As-XG@Fe 3 O 4 hydrogels was measured approximately 45.32 and 17.30 m2/g, which was higher than neat XG. Then, the constructed adsorbent system was assessed for removing a CPF as an organophosphorus pesticide and CV as cationic dye from aqueous. The batch adsorption experiments were conducted to optimize the effective adsorption parameter i.e., solution pH, adsorbent dosage, contact time, CPF and CV initial concentration. Furthermore, Freundlich isotherm mode was well-fitted model and by utilizing prepared adsorbent, and the maximum adsorption capacities of CPF and CV (at optimum conditions: 298 K, pH 7.0 and 9.0) were found to be about 769.230 and 833.33 mg/g, respectively. The adsorption kinetic study revealed that experimental data were well-fitted by the pseudo-second-order model. Based on proposed mechanism, the CPF and CV were adsorbed onto hydrogel nanocomposite mainly through π–π interactions, electrostatic interaction and hydrogen bonding. The regeneration experiments up to three cycles were best achieved for two studied pollutants. [ABSTRACT FROM AUTHOR]

• The recent progress in dynamic supramolecular system in electrical conductive and magnetic [Ni(dmit)2] salts has been summarized. • Various molecular rotator and its application for dipole rotator has been exhibited. • Ferroelectrics coupled with dipole rotator in magnetic [Ni(dmit)2] salts has been summarized. • Design of dynamic structural units in magnetic [Ni(dmit)2] salts has been summarized. • The existing challenges and the future prospects of dynamic molecular system in the conductive and magnetic molecular materials are discussed. Supramolecular cation (SC) structures with high degrees of chemically designed freedoms are one of the most effective building blocks for controlling the dynamic and physical properties of molecular assemblies. Various SC structures, ranging from simple metal ions with different sizes, valences, and magnetic spins to organic ammoniums with diverse molecular structures, can be formed via complexation of crown ether derivatives with different ring sizes, which can be introduced into the π-planar Ni-coordination complexes using electrically conductive and magnetic [Ni(dmit) 2 ] salts (dmit2− = 2-thioxo-1,3-dithiole-4,5-dithiolate). Various dynamics such as ion transport, molecular rotation, and molecular oscillation coexist in a single crystal of [Ni(dmit) 2 ], affecting its electrical conductivity, magnetic behavior, dielectric response, and ferroelectricity. Unlike the physical properties exhibited by a static crystal lattice, the physical properties of a dynamic system depends on external factors such as temperature and the presence of an electric field. These properties are governed by factors such as the motional symmetry, amplitude, and frequency of the dynamic SC units in the crystal lattice. In particular, the dynamics of the polar structural units is particularly prominent in the dielectric response and ferroelectricity. The dipole rotator structure is an example of achieving macroscopic physical properties of ferroelectrics along with microscopic molecular dynamics. Structural and functional control of dynamic molecular assemblies using the SC approach is fundamental to the fabrication of next-generation molecular electronic and mechatronic devices. [ABSTRACT FROM AUTHOR]

Electrochemical detection of water contaminants driven by polyoxometalate-based materials provides a promising approach for environmental safety and diseases prevention. Herein, three polyoxotungstate-based supramolecular complexes were synthesized with formulas of [Cd 3 (H 2 O) 2 (trz) 6 ][HSiW 12 O 40 ] 2 ·17H 2 O (1) , [Cd(imi) 6 ] 2 [SiW 12 O 40 ]·24H 2 O (2) , [Himi] 4 [SiW 12 O 40 ]·H 2 O (3) , (Htrz ​= ​1-H-1,2,4-triazole; imi ​= ​Imidazole), which were employed as multifunctional sensors for the detection of various contaminants in water. Structural analysis showed that in compound 1 , the trinuclear cadmium cluster [Cd 3 (Htrz) 6 ]6+ links [SiW 12 O 40 ]4- anion to form a dumbbell-shaped fragment, which interacts with each other via abundant hydrogen bonds to extend the structure into three-dimensional supramolecular network. In compound 2 , the windmill-shaped [Cd(imi) 6 ]2+ cations interact with [SiW 12 O 40 ]4- anion via electrostatic interactions and hydrogen bonding to form 3-D supramolecular structure. Compound 3 displays an 'inorganic core-organic hell' hybrid supramolecular structure constructed by [SiW 12 O 40 ]4- anion cluster and four protonated organic [Himi]+ cations. Three compounds as electrochemical sensors exhibited favorable electrocatalytic activities for the detection of hexavalent chromium Cr(VI), NO 2 − and H 2 O 2 with remarkable anti-interference capacity. As for the determination of Cr(VI), compound 1 shows the lowest limit of detection (LOD) of 0.86 ​μM and high sensitivity of 39.3 ​μA ​mM−1 among three compounds, which meets the WHO standard for the minimum concentration of Cr(VI) in drinking water (less than 0.962 ​μM). Moreover, the LODs of compound 1 towards NO 2 − and H 2 O 2 detection are 3.74 ​μM and 1.39 ​μM along with sensitivities of 4.81 ​μA ​mM−1 for NO 2 − ion and 37.2 ​μA ​mM−1 for H 2 O 2 , respectively. This work provides some important insights into the design of efficient POMs-based electrochemical sensors for environmental applications. Three polyoxotungstate-based supramolecular complexes show favorable electrochemical activities for detecting water contaminants including Cr(VI), NO 2 − and H 2 O 2. [Display omitted] • Three polyoxotungstate-based supramolecular complexes were constructed. • Crystals 1–3 show favorable electrochemical activities for detecting water contaminants. • The detection limits for Cr(VI), NO 2 − and H 2 O 2 over compound 1 are 0.86, 3.74 and 1.39 ​μM. • The synergistical effect between [SiW 12 O 40 ]4- and Cd-organic fragments plays important role. [ABSTRACT FROM AUTHOR]

Ulcerative colitis(UC) is a recurrent, intractable inflammatory bowel disease. Coptidis Rhizoma and Bovis Calculus, serving as heat-clearing and toxin-removing drugs, have long been used in the treatment of UC. Berberine(BBR) and ursodeoxycholic acid(UDCA), the main active components of Coptidis Rhizoma and Bovis Calculus, respectively, were employed to obtain UDCA-BBR supramolecular nanoparticles by stimulated co-decocting process for enhancing the therapeutic effect on UC. As revealed by the characterization of supramolecular nanoparticles by field emission scanning electron microscopy(FE-SEM) and dynamic light scattering(DLS), the supramolecular nanoparticles were tetrahedral nanoparticles with an average particle size of 180 nm. The molecular structure was described by ultraviolet spectroscopy, fluorescence spectroscopy, infrared spectroscopy, high-resolution mass spectrometry, and hydrogen-nuclear magnetic resonance(H-NMR) spectroscopy. The results showed that the formation of the supramolecular nano-particle was attributed to the mutual electrostatic attraction and hydrophobic interaction between BBR and UDCA. Additionally, supramolecular nanoparticles were also characterized by sustained release and pH sensitivity. The acute UC model was induced by dextran sulfate sodium(DSS) in mice. It was found that supramolecular nanoparticles could effectively improve body mass reduction and colon shortening in mice with UC(P<0.001) and decrease disease activity index(DAI)(P<0.01). There were statistically significant differences between the supramolecular nanoparticles group and the mechanical mixture group(P<0.001, P<0.05). Enzyme-linked immunosorbent assay(ELISA) was used to detect the serum levels of tumor necrosis factor-α(TNF-α) and interleukin-6(IL-6), and the results showed that supramolecular nanoparticles could reduce serum TNF-α and IL-6 levels(P<0.001) and exhibited an obvious difference with the mechanical mixture group(P<0.01, P<0.05). Flow cytometry indicated that supramolecular nanoparticles could reduce the recruitment of neutrophils in the lamina propria of the colon(P<0.05), which was significantly different from the mechanical mixture group(P<0.05). These findings suggested that as compared with the mechanical mixture, the supramolecular nanoparticles could effectively improve the symptoms of acute UC in mice. The study provides a new research idea for the poor absorption of small molecules and the unsatisfactory therapeutic effect of traditional Chinese medicine and lays a foundation for the research on the nano-drug delivery system of traditional Chinese medicine.

Rhenium(I)-based supramolecular coordination complexes were obtained using Re2(CO)10, (2-hydroxyphenyl)benzimidazole-derived bis-chelating N?O donors and a benzimidazolyl-derived ditopic monodentate N-donor possessing Troger's base spacer in a one-pot approach.

In this work, we have investigated the photophysical properties of methyl 2-hydroxy-3-naphthoate (MHN23) in two different types of heterogeneous microenvironments, micelles and niosomes formed by nonionic surfactant (Tween-80) by using the steady state and time-resolved fluorescence spectroscopy. The transmission electron microscopy (TEM) technique was also employed to confirm the formation of Tween-80/PEG-6000 niosomes. The experimental results indicate that in the confined systems both the absorption and the fluorescence intensity have been enhanced. The fluorescence intensity and fluorescence lifetime of MHN23 in niosomes were enhanced more than that in micelles. The enhanced fluorescence intensity and lifetime of MHN23 arise from the more rigid and confined microenvironment of niosomes. However, with the increasing of the surfactant concentration in micelles, the fluorescence lifetime of MHN23 in micelles gets longer gradually than that in niosomes. Consequently, it has been demonstrated that the photophysical properties of probes could be significantly affected by both the confined microenvironment and the concentration of surfactants. [ABSTRACT FROM AUTHOR]

We demonstrated high performance non-volatile pentacene based OFET memory devices using charge-transfer (CT) supramolecules of poly(4-vinylpyridine) (P4VP) with two different chromophores, 3-(dicyanomethylidene)indan-1-one (1CN-IN) and 1,3-bis(dicyanomethylidene)indan (2CN-IN), respectively. The intermolecular CT interaction effectively introduced the chromophores as charge trapping sites into the P4VP matrix, leading to a controllable flash-type memory behavior. The electron-trapping ability of the supramolecular electrets was increased with enhancing the chromophore composition in the supramolecules. The experimental molar ratio x of chromophores binding to the repeating unit of P4VP, however, was limited to 0.30 for P4VP(1CN-IN) x or 0.45 for P4VP(2CN-IN) x . The 2CN-IN with one more electron-withdrawing dicyanomethylene group, compared to 1CN-IN, provided a better electron-trapping ability and thus obtained a larger memory window. The device based on P4VP(2CN-IN) 0.30 electret exhibited the largest memory window (79 V) with the excellent retention ability of up to 10 7 s and endurance of over 100 cycles. The study revealed that the CT supramolecular electret could be as a facile and simple approach for future organic memory device applications. [ABSTRACT FROM AUTHOR]

Two new 3D network organic-inorganic hybrid supramolecular complexes {[Na 6 (CoEDTA) 2 (H 2 O) 13 ]·(H 2 SiW 12 O 40 )·xH 2 O}n (1) and [CoH 4 EDTA(H 2 O)] 2 (SiW 12 O 40 )·15H 2 O (2) (H 4 EDTA=Ethylenediamine tetraacetic acid) have been successfully synthesized by solution method, and characterized by infrared spectrum (IR), thermogravimetric-differential thermal analysis (TG-DTA), cyclic voltammetry (CV) and single − crystal X-ray diffraction (XRD). Both of the complexes are the supramolecules, but with different liking mode, they are two representative models of supramolecule. complex (1) is a 3D infinite network supramolecular coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through coordinate-covalent bonds. While complex (2) is normal supramolecule, which linked by non-covalent interactions, such as H-bonding interaction, electrostatic interaction and van der waals force. Both of complex (1) and (2) exhibit good catalytic activities for catalytic oxidation of methanol, when the initial concentration of methanol is 3.0 g m −3 , flow rate is 10 mL min −1 , and the quality of catalyst is 0.2 g, for complex (1) and complex (2) the maximum elimination rates of methanol are 85% (150 °C) and 92% (120 °C), respectively. [ABSTRACT FROM AUTHOR]

Silver nanoparticles are synthesized in the medium of an aqueous cysteine-silver solution at different рН values using sodium borohydride as a reductant. Dynamic light scattering, electron spectroscopy, and transmission electron microscopy are applied to find that the size and stability of nanoparticles in this system depend on рН, which is regulated by alkali, and on the concentration of the cysteine-silver solution. Under certain conditions, it is possible to obtain a unimodal distribution for silver nanoparticles with an average size of ~40 nm. [ABSTRACT FROM AUTHOR]