Thermally Hypsochromic or Bathochromic Emissions? The Silver Nuclei Does Matter.

Structural modulation of core-shell silver nanoclusters from the inside is a huge challenge but of great importance in their syntheses. Herein, two silver nanoclusters [Ag3 S9 @Ag42 ] (SD/Ag45b) and [Ag9 S9 @Ag42 ] (SD/Ag51a) are isolated in the presence of different kinds of sulfonic acids. Uniquely, SD/Ag45b and SD/Ag51a show typical core-shell structures with the similar Ag42 shell but different cores. The outer shell of 42 silver atoms comprises two Ag3 trigons at two poles encircled by three equatorial distorted square cupolas (J4 , Ag12 ). The core in SD/Ag45b is a silver trigon ligated by nine S2- ions (Ag3 S9 ), while a tricapped triangular prismatic Ag9 also ligated by the same amount of S2- ions (Ag9 S9 ) is observed in the inner core of SD/Ag51a. The electrospray ionization mass spectrometry (ESI-MS) indicates that the introduction of p-toluenesulfonic acid can realize the transformation from SD/Ag45b to Ag51 . SD/Ag45b and SD/Ag51a show inverse luminescence thermochromic behaviors in the near-infrared (NIR) region, mainly dictated by the inner silver cores. This work not only realizes the synthesis of new silver nanoclusters by core modulation but also provides a prototype to get molecular-level insight into the correlation between structure and luminescence thermochromism.

Chirality Inversion in Self-Assembled Nanocomposites Directed by Curvature-Mediated Interactions.

Nanoscale curvature-dependent interactions are of paramount importance in biological systems. Here, we report that nanoscale curvature plays an important role in regulating the chirality of self-assembled nanocomposites from chiral organic molecules and achiral nanoparticles. Specifically, we show that the supramolecular chirality of the nanocomposites markedly depends on the nanoparticle curvature, where small-sized nanoparticles of high curvature and large-sized nanoparticles of low curvature lead to nanocomposites with opposite chirality. Quantitative kinetic experiments and molecular dynamics simulations reveal that nanoparticle curvature plays a key role in promoting the pre-nucleation oligomerization of chiral molecules, which consequently regulates the supramolecular chirality of the nanocomposites. We anticipate that this study will aid in rational design of an artificial cooperative system giving rise to emergent assembling phenomena that can be surprisingly rich and often cannot be understood by studying the conventional noncooperative systems.

Study of the effects of ultrafine carbon black on the structure and function of trypsin.

Due to the rapid development of industrial society, air pollution is becoming a serious problem which has being a huge threat to human health. Ultrafine particles (UFPs), one of the major air pollutants, are often the culprits of human diseases. At present, most of the toxicological studies of UFPs focus on their biological effects on lung cells and tissues, but there are less researches taking aim at the negative effects on functional proteins within the body. Therefore, we experimentally explored the effects of ultrafine carbon black (UFCB) on the structure and function of trypsin. After a short-term exposure to UFCB, the trypsin aromatic amino acid microenvironment, protein backbone and secondary structure were changed significantly, and the enzyme activity showed a trend that rose at first, then dropped. In addition, UFCB interacts with trypsin in the form of a complex. These studies demonstrated the negative effects of UFCB on trypsin, evidencing potential effects on animals and humans.

Control Viscoelasticity of Polymer Networks with Crosslinks of Superposed Fast and Slow Dynamics.

Depending on the dynamics of the crosslinks, polymer networks can have distinct bulk mechanical behaviors, from viscous liquids to tough solids. Here, by means of designing a crosslink with variable molecular dynamics, we show the control of viscoelasticity of polymer networks in a broad range quantitatively. The hexanoate-isoquinoline@cucurbit[7]uril (HIQ@CB[7]) crosslink exhibits in a combination of protonated and deprotonated states of similar association affinity but distinct molecular dynamics. The molecular property of this crosslink is contributed by linear combination of the parameters at the two states, which is precisely tuned by pH. Using this crosslink, we achieve the quantitative control of viscoelasticity of quasi-ideal networks in 5 orders of magnitude, and we show the reversible control of mechanical response, such as stiffness, strength and extensibility, of tough random polymer networks. This strategy offers a way to tailor the mechanical properties of polymer networks at the molecular level and paves the way for engineering "smart" responsive materials.

Hydrogen bonded co-assembly of aromatic amino acids and bipyridines that serves as a sacrificial template in superstructure formation.

Design and fabrication of superstructures are intriguing yet challenging tasks, which require delicate operations at micro/nanoscale such as template-directed seeding or etching processes. In this study, we prepared integrated one dimensional (1D) microrods from co-assembled N-terminated aromatic amino acids and bipyridines that could serve as sacrificial templates for micro-superstructure formation. Organic polar solvents were utilized for generating a co-assembly that showed selectivity to both molecular topology of building blocks and solvent environments via thermodynamic and kinetic manners. The addition of specific transition metal ions would extract bipyridines from crystalline microrods, leading to well-aligned engraved motifs along the 1D direction as well as the emergence of ordered packed nanostructures on microrod surfaces. Responsive to types of metal ions, diverse superstructures such as etched sculptures and surface-encapsulated heterojunctions of metal-bipyridine coordination polymers were constructed. This study offers a proof-of-concept exploration in the rational design of 1D crystalline micro-superstructures via non-covalent complexation towards potential applications in electrical and optical applications.

High-Nuclear Organometallic Copper(I)-Alkynide Clusters: Thermochromic Near-Infrared Luminescence and Solution Stability.

Cu(CF3 COO)2 reacts with tert-butylacetylene (tBuC≡CH) in methanol in the presence of metallic copper powder to give two air-stable clusters, [CuI15 (tBuC≡C)10 (CF3 COO)5 ]⋅tBuC≡CH (1) and [CuI16 (tBuC≡C)12 (CF3 COO)4 (CH3 OH)2 ] (2). The assembly process involves in situ comproportionation reaction between Cu2+ and Cu0 and the formation of two different clusters is controlled by reactants concentration. The clusters consist of Cu15 and Cu16 cores co-stabilized by strong by σ- and π-bonded tert-butylethynide and CF3 COO- (together with methanol molecule in 2). Their stabilities in solution were confirmed using electrospray ionization mass spectrometry in which the cluster core remains intact for 1 in chloroform and acetone, and for 2 in acetonitrile. Strong thermochromic luminescence in the near infrared (NIR) region was observed in the solid-state. Of particular interest, the emission maximum of 1 is red-shifted from 710 nm at 298 K to 793 nm at 93 K, along with a 17-fold fluorescence enhancement. In contrast, 2 exhibits red shift from 298 to 123 K followed by blue shift from 123 to 93 K. The emission wavelength was correlated with the structural parameters using variable-temperature X-ray single-crystal analyses. The rich cuprophilic interaction plays a significant role in the formation of 3 LMCT (tBuC≡C→Cux ) excited state mixed with cluster-centered (3 CC) characters, which can be considerably influenced by temperature, leading to thermochromic luminescence. The present work provides 1) a new synthetic protocol for the high-nuclear CuI -alkynyl clusters; 2) a comprehensive insight into the mechanism of thermochromic luminescence; 3) unusual emissive materials with the characters of NIR and thermochromic luminescence simultaneously.

Near-Infrared Emitters: Stepwise Assembly of Two Heteropolynuclear Clusters with Tunable Ag(I):Zn(II) Ratio.

Two 3d-4d heteropolynuclear clusters with Ag-Zn ratios of 9:2 and 9:4 were stepwise constructed from a robust nonanuclear silver cluster. Their crystal structures consist of a common bucket-shaped [Ag9(mba)9](9-) (H2mba = 2-mercaptobenzoic acid) core with different numbers of Zn(II) connected by different exo-oriented carboxylates. Most fascinating is the observation of emission (∼703 nm) in the near-infrared (NIR) region at 300 K that may be compared to the related Ag9Zn3 cluster with aliphatic polyamine as auxiliary ligand that emits from the visible (∼580 nm). The shift is associated with the change of ligand field of the 2,2'-bipyridine. The emission intensity and lifetime were dramatically enhanced along with the slight bathochromic shift upon cooling from 300 K to 80 K. The results raise two significant issues: (a) the structural and electronic effects of the secondary metal binding to the metalloligand and the factors influencing the heteropolynuclear cluster assembly and (b) the use of NIR fluorescence, introduced by integrating two luminophores into one heteropolynuclear entity, in detecting free-moving zinc in biological systems both in vivo and in vitro.

New Insights into the Toxicity of n-Butanol to Trypsin: Spectroscopic and Molecular Docking Descriptions.

n-Butanol has been widely used and its residue exists extensively in the environment. It could lead to conformational and functional changes of trypsin by forming a complex with it. Docking method and spectrographic technique were employed to the study of the complex of trypsin and n-butanol. The fluorescence results indicated that n-butanol can form a complex with trypsin and change the distance between tryptophan and fluorescence quenchers. The conformational changes of trypsin were proved by UV-visible absorption and synchronous fluorescence spectroscopy indicating that n-butanol had little effect on the conformation of trypsin at a low concentration while denatured and coagulated the trypsin at a high concentration. The binding site was displayed by molecular modeling, which gave information about distances and binding forces between n-butanol and trypsin. The results were in accordance with spectroscopic experiments. Besides, enzyme activity assay gave the dose-response relationship of n-butanol with trypsin.

Covalently linked perylenetetracarboxylic diimide dimers and trimers with rigid "J-type" aggregation structure.

Covalently linked perylenetetracarboxylic diimide (PDI) dimers (D1 and D2) and trimers (T1 and T2) with slipped "face-to-face" stacked structure are prepared and their molecular structures are characterized by 1H NMR, MALDI-TOF mass spectroscopy and elemental analysis. The rigid molecular structures of these compounds make it easier to establish a direct correlation between the aggregate structure and the photophysical properties. The minimized molecular structures of these compounds reveal that they are all "face-to-face" stacked aggregates with large longitudinal displacement. Their absorption spectra show red-shifted bands, suggesting the presence of "J" type excitonic coupling between the PDI subunits in these compounds. However, their steady state and time resolved fluorescence spectra revealed that the emission from the "excimer-like" states dominates the fluorescence of these compounds, this is similar to that of "H-type" aggregates and may be ascribed to the "face-to-face" stacked structure. In the fluorescence spectra of these compounds, a minor "J-type" emission can be identified for the compounds with a relatively large longitudinal displacement. An increase in the number of subunits in one aggregate from 2 to 3 also brings about distinctive changes in their photophysical properties, which can be ascribed to the changes in the stacking structure caused by the steric hindrance.

Pnictogen bonding in imide derivatives for chiral folding and self-assembly.

Pnictogen bonding (PnB) is an attraction interaction that originates from the anisotropic distribution of electron density of pnictogen elements, which however has been rarely found in nitrogen atoms. In this work, for the first time, we unveil the general presence of N-involved PnB in aromatic or aliphatic imide groups and reveal its implications in chiral self-assembly of folding. This long-neglected interaction was consolidated by Cambridge structural database (CSD) searching as well as subsequent computational studies. Though the presence of PnB has limited effects on spectroscopic properties in the solution phase, conformation locking effects are sufficiently expressed in the chiral folding and self-assembly behavior. PnB anchors the chiral conformation to control the emergence and inversion of chiroptical signals, while intramolecular PnB induces the formation of supramolecular tilt chirality. It also enables the chiral folding of imide-containing amino acid or peptide derivatives, which induces the formation of unique secondary structural sequences such as ß-sheets. Finally, the effects of PnB in directing folded helical structures were revealed. Examples of cysteine and cystine derivatives containing multiple N⋯O and N⋯S PnBs constitute an α-helix like secondary structure with characteristic circular dichroism. This work discloses the comprehensive existence of imide-involved PnB, illustrates its important role in folding and self-assembly, and sheds light on the rational fabrication of conformation-locked compounds and polymers with controllable chiroptical activities.

Photoresponsive chiral vesicles as a light harvesting matrix with tunable chiroptical properties.

A chiral vesicle system with photo-regulated chiroptical properties including Cotton effects and circularly polarized luminescence (CPL) was reported. Photoresponsive cyanostilbene was conjugated to the cholesteryl group, which provides chiral centers and lipophilic domain for the flexible vesicle membrane formation. The building block self-assembled into vesicles with exciton Cotton effects and CPL. The high dissymmetry g-factor of CPL at 10-2 order of magnitude was achieved. Upon UV light irradiation, Cotton effects were enhanced with an elevated g-factor by 3-fold, while the CPL dissymmetry factor showed a light irradiation resistance. A hydrophobic fluorescent dye (Nile Red) was loaded into vesicle membranes to allow energy transfer and chirality transfer to give red color CPL with retained high g-factor, while resistance to the UV light irradiation of vesicles was enhanced after loading the fluorescent dye. This study highlights the fabrication of the chiral vesicle system with noninvasively stimulus-responsive chiroptical properties, which may provide new thoughts for the fabrication of smart chiroptical materials in aqueous media.

Toxic mechanism of pyrene to catalase and protective effects of vitamin C: Studies at the molecular and cell levels.

Polycyclic aromatic hydrocarbons, distributing extensively in the soil, would potentially threaten the soil organisms (Eisenia fetida) by triggering oxidative stress. As a ubiquitous antioxidant enzyme, catalase can protect organisms from oxidative damage. To reveal the potential impact of polycyclic aromatic hydrocarbon pyrene (Pyr) on catalase (CAT) and the possible protective effect of Ascorbic acid (vitamin C), multi-spectral and molecular docking techniques were used to investigate the influence of structure and function of catalase by pyrene. Fluorescence and circular dichroism analysis showed that pyrene would induce the microenvironmental changes of CAT amino acid residues and increase the α-helix in the secondary structure. Molecular simulation results indicated that the main binding force of pyrene around the active center of CAT is hydrogen bonding force. Furthermore, pyrene inhibited catalase activity to 69.9% compared with the blank group, but the degree of inhibition was significantly weakened after vitamin C added into the research group. Cell level experiments showed that pyrene can increase the level of ROS in the body cavity cell of earthworms, and put the cells under the threat of potential oxidative damage. Antioxidants-vitamin C has a protective effect on catalase and maintains the stability of intracellular ROS levels to a certain extent.

Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level.

Although chirality is an ever-present characteristic in biology and some artificial molecules, controlling the chirality and demystifying the chirality origin of complex assemblies remain challenging. Herein, we report two homochiral Ag14 nanoclusters with inherent chirality originated from identical rotation of six square faces on a Ag8 cube driven by intra-cluster π···π stacking interaction between pntp- (Hpntp = p-nitrothiophenol) ligands. The spontaneous resolution of the racemic (SD/rac-Ag14a) to homochiral nanoclusters (SD/L-Ag14 and SD/R-Ag14) can be realized by re-crystallizing SD/rac-Ag14a in acetonitrile, which promotes the homochiral crystallization in solid state by forming C-H···O/N hydrogen bonds with nitro oxygen atoms in pntp- or aromatic hydrogen atoms in dpph (dpph = 1,6-bis(diphenylphosphino)hexane) on Ag14 nanocluster. This work not only provides strategic guidance for the syntheses of chiral silver nanoclusters in an all-achiral environment, but also deciphers the origin of chirality at molecular level by identifying the special effects of intra- and inter-cluster supramolecular interactions.

Solvent-Processed Circularly Polarized Luminescence in Light-Harvesting Coassemblies.

As a kinetic factor, solvent polarity functioning in regulating/enhancing chiroptical properties of supramolecular chiral self-assemblies including handedness, dissymmetry factor, and luminescent color has not been realized. Here, we introduce a delicate solvent control over self-assembly pathways of a dynamer into four soft matters comprising gel, liposome, helix, and particles respectively, where a fluorescent dye as an acceptor was loaded to allow efficient circularly polarized light harvesting. Though no apparent chirality transfer from chiral assemblies to acceptors occurred at ground state based on the circular dichroism spectra, efficient energy transfer at photoexcited state was observed, demonstrating considerable dependence on solvent polarity and constitution. As the acceptor orientated without chiral sense in coassemblies, circularly polarized light migration from donor to acceptor is reasonably expected. In apolar decane, thixotropic gels with left-handed circularly polarized luminescence were given, and luminescent colors could be controlled from green to red (510-600 nm) via adjusting molar fraction of acceptor, affording a high dissymmetry factor at 1 × 10-2 order of magnitude. The crucial role of ordered structures in the emergence of circularly polarized luminescence was also validated. The present work provides a solvent-processed manner to rationally regulate the dissymmetry factor, colors, and handedness by feat of circularly polarized light harvesting and migration, avoiding the tedious construction of a building block and enantiomer library.

Fluorescent Imprintable Hydrogels via Organic/Inorganic Supramolecular Coassembly.

Photoresponsive hydrogels with on/off luminescence show a promising application potential in writable information recording and display materials. However, it still remains a tremendous challenge to fabricate such hydrogels on account of the intrinsic fluorescence quenching effect and the lack of suitable responsive groups. Herein, we present fluorescent imprintable hydrogels constructed via organic/inorganic supramolecular coassembly. A photoisomeric cyanostilbene conjugated cationic surfactant exhibited an aggregation-induced emission behavior upon clay (laponite) complexation, along with excellent thixotropism brought by laponite. Macrocyclic cucurbituril[7] and ß-cyclodextrin rings capable of forming host-guest complexes with the surfactant were utilized to give ternary hybrid hydrogels with luminescence and photoresponsive properties. On the account of trans-cis photoisomerization of the cyanostilbene unit, the fluorescence of the multicomponent hydrogels could undergo rapid quenching within a short irradiation period under UV light and be recovered when subjected to an annealing process. According to these properties, the imprinted fluorescent patterns using the hybrid hydrogels were erasable and rewritable. Thus, this research successfully integrates host-guest complexation and supramolecular coassembly into the fabrication of fluorescent imprintable hydrogels.

Searching for a bisphenol A substitute: Effects of bisphenols on catalase molecules and human red blood cells.

Some countries are limiting the use of BPA. To meet the challenge of finding a suitable alternative requires safety assessments of the common analogs of BPA. Bisphenol S (BPS), Bisphenol F (BPF) and Bisphenol B (BPB) are increasingly used as substitutes and the aim of this study is to assess their human health implications. By comparing the effects on hemoglobin spectroscopically, the least toxic possibility is using BPB as a substitute for BPA. In this paper, the effects of BPS, BPF and BPB on catalase were compared at the molecular level and the same result was found. To further enhance our understanding of BPB, the impact of BPB on antioxidant defense system, structure (hemolysis rate) and function (ATPase activity) of red blood cell (RBCs) were analyzed at the cellular level. It has been found that low concentrations (below 0.1 µM) of BPB slightly increased the activity of T-AOC (112.7%), GST (118.4%) and T-SOD (131.8%) while high concentrations decreased the activity of T-AOC (90.2%), T-SOD (67.8%), GST (74.7%) and GSH-Px (61.7%). It also has been shown that BPB had little effect on MDA (100%-101.6%) and CAT activity (100%-100.5%) with reduced activity of ATPase (100%-27.7%). In conclusion, BPB may possibly be used as the BPA substitute in the manufacture, and the concentration of BPB should be controlled within 1 µM.

The effect of sarafloxacin on Cu/ZnSOD structure and activity.

The effect of sarafloxacin to Cu/ZnSOD was evaluated via investigating the change in Cu/ZnSOD structure and the structure basis activity upon sarafloxacin binding. Multi-spectroscopic methods, isothermal titration microcalorimetry (ITC) and molecular docking method were adopted in this study. Sarafloxacin binds to Cu/ZnSOD mainly through hydrophobic and hydrogen bond forces and tends to be saturated as the molar ratio of sarafloxacin to Cu/ZnSOD reaches 4. The binding changed the microenvironment around Tyr and the secondary structure of Cu/ZnSOD but did not affect the activity of Cu/ZnSOD. Molecular docking study revealed that sarafloxacin binds into a hydrophobic area with possibility to form hydrogen bonds with Tyr 108, Asp 25, Pro 100 and Ser 103 of Cu/ZnSOD. The binding area locates on the surface of ß-barrel close to the second Greek key loop (GK2) and V-loop but far away from the active site and active site channel of Cu/ZnSOD. These promoted the understanding of the experiment phenomenons. The binding of sarafloxacin does not affect the activity of Cu/ZnSOD should attribute to the binding not to change the microenvironment of Cu/ZnSOD active site and active site channel.

Potential toxicity of sarafloxacin to catalase: spectroscopic, ITC and molecular docking descriptions.

The interaction between sarafloxacin and catalase (CAT) was studied by fluorescence spectroscopy, UV-visible absorption spectroscopy, circular dichroism (CD) spectroscopy, isothermal titration microcalorimetry (ITC) and molecular docking method. After deducting the inner filter effect, the fluorescence of CAT was quenched regularly by different concentrations of sarafloxacin. The quenching mechanism was studied by lifetime measurement, and it was proved to be mostly due to static quenching. The formation of sarafloxacin-CAT complex alters the micro-environment of amide moieties and tryptophan (Trp) residues, reduces the α-helix content of the enzyme, changes the peripheral substituents on the porphyrin ring of heme and leads to the inhibition of the enzyme activity. Molecular docking study reveals that sarafloxacin is located between two α-helix of CAT near to Trp 182 and Trp 185 residues, which supports the experimental results and helps to have a more clear understanding about the interaction mechanism. The change in the relative position of His 74 to heme induced by the variation of secondary structure is considered to be the major reason for the reduction of CAT activity. Moreover, sarafloxacin binds into a hydrophobic area of CAT mainly through hydrophobic interactions, which is consistent with the ITC analysis.