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π–π stacking are omnipresent interactions, crucial in many areas of chemistry, and often studied using quantum chemical methods. Here, we report a simple and computationally efficient method of estimating the binding energies of stacked polycyclic aromatic hydrocarbons based on steered molecular dynamics. This method leverages the force field parameters for accurate calculation. The presented results show good agreement with those obtained through DFT at the ωB97X-D3/cc-pVQZ level of theory. It is demonstrated that this force field-driven SMD method can be applied to other aromatic molecules, allowing insight into the complexity of the stacking interactions and, more importantly, reporting π–π stacking energy values with reasonable precision. [ABSTRACT FROM AUTHOR]

This study systematically investigates the molecular structure and electronic properties of 2-methoxy-4,6-diphenylnicotinonitrile, employing X-ray diffraction (XRD) and sophisticated computational methodologies. XRD findings validate the compound's orthorhombic crystallization in the P21212 space group, composed of a pyridine core flanked by two phenyl rings. Utilizing the three-dimensional Hirshfeld surface, the research decodes the molecule's spatial attributes, further supported by exhaustive statistical assessments. Key interactions, such as π–π stacking and H⋯X contacts, are spotlighted, underscoring their role in the crystal's inherent stability and characteristics. Energy framework computations and density functional theory (DFT) analyses elucidate the prevailing forces in the crystal and reveal geometric optimization facets and molecular reactivity descriptors. Emphasis is given to the exploration of frontier molecular orbitals (FMOs), aromaticity, and π–π stacking capacities. The research culminates in distinguishing electron density distributions, aromatic nuances, and potential reactivity hotspots, providing a holistic view of the compound's structural and electronic landscape. Concurrently, molecular docking investigates its interaction with the lipoprotein-associated phospholipase A2 protein. Notably, the compound showcases significant interactions with the protein's active site. Molecular dynamics simulations reveal the compound's influence on protein stability and flexibility. Although the molecule exhibits strong inhibitory potential against Lp-PLA2, its drug development prospects face challenges related to solubility and interactions with drug transport proteins. [ABSTRACT FROM AUTHOR]

The new Lewis acid–base adducts of general formula X(nad)B←NC5H4-C5H4N→B(nad)X [nad = 1,8-O2C10H6, X = C6H5 (2c), 3,4,5-F3-C6H2 (2d)] were synthesized in high yields via reactions of 1,8-dihydroxy naphthalene [nadH2] and 4,4′-bipyridine with the aryl boronic acids C6H5B(OH)2 and 3,4,5-F3-C6H2B(OH)2, respectively, and structurally characterized by multi-nuclear NMR spectroscopy and SCXRD. Self-assembled H-shaped Lewis acid–base adduct 2d proved to be effective in forming thermally stable host–guest complexes, 2d × solvent, with aromatic hydrocarbon solvents such as benzene, toluene, mesitylene, aniline, and m-, p-, and o-xylene. Crystallographic analysis of these solvent adducts revealed host–guest interactions to primarily occur via π···π contacts between the 4,4′-bipyridyl linker and the aromatic solvents, resulting in the formation of 1:1 and 1:2 host–guest complexes. Thermogravimetric analysis of the isolated complexes 2d × solvent revealed their high thermal stability with peak temperatures associated with the loss of solvent ranging from 122 to 147 °C. 2d, when self-assembled in an equimolar mixture of m-, p-, and o-xylene (1:1:1), preferentially binds to o-xylene. Collectively, these results demonstrate the ability of 1,8-dihydroxy naphthalene to serve as an effective building block in the selective self-assembly to supramolecular aggregates through dative covalent N→B bonds. [ABSTRACT FROM AUTHOR]

Removing organic dyes from contaminated wastewater resulting from industrial effluents with a cost-effective approach addresses a major global challenge. The adsorption technique onto carbon-based materials and metal oxide is one of the most effective dye removal procedures. The current work aimed to evaluate the application of calcium oxide-doped carbon nitride nanostructures (CaO-g-C3N4) to eliminate basic fuchsine dyes (BF) from wastewater. CaO-g-C3N4 nanosorbent were obtained via ultrasonication and characterized by scanning electron microscopy, X-ray diffraction, TEM, and BET. The TEM analysis reveals 2D nanosheet-like nanoparticle architectures with a high specific surface area (37.31 m2/g) for the as-fabricated CaO-g-C3N4 nanosorbent. The adsorption results demonstrated that the variation of the dye concentration impacted the elimination of BF by CaO-C3N4 while no effect of pH on the removal of BF was observed. Freundlich isotherm and Pseudo-First-order adsorption kinetics models best fitted BF adsorption onto CaO-g-C3N4. The highest adsorption capacity of CaO-g-C3N4 for BF was determined to be 813 mg. g−1. The adsorption mechanism of BF is related to the π-π stacking bridging and hydrogen bond, as demonstrated by the FTIR study. CaO-g-C3N4 nanostructures may be easily recovered from solution and were effectively employed for BF elimination in at least four continuous cycles. The fabricated CaO-g-C3N4 adsorbent display excellent BF adsorption capacity and can be used as a potential sorbent in wastewater purification. [ABSTRACT FROM AUTHOR]

The crystal structures of 1-(2,3,5,6-tetrafluoro-4-pyridyl)-3-benzylimidazolium chloride (1) and iodide (3) have been determined by single crystal X-ray diffraction. The crystal structure of 1 is similar to that of the bromide salt (2), possessing anion···C5F5N···C6H5 motifs, whilst that of 3 contains columns of alternating iodide anions and parallel tetrafluoropyridyl rings. All three crystal structures possess C(1)–H∙∙∙X− and C(2)–H∙∙∙X− hydrogen bonding. DFT calculations reveal that the strengths of the hydrogen bonding interactions lie in the order C(1)–H···X− > C(3)–H···X− > C(2)–H···X− for the same halide (X−) and Cl− > Br− > I− for each position. It is suggested that salt 3 adopts a different structure to salts 1 and 2 because of the larger size of iodide. [ABSTRACT FROM AUTHOR]

Fabricating hierarchical nanomaterials by self-assembly of rod-coil block copolymers attracts great interest. However, the key factors that affect the formation of the hierarchical nanomaterials have not been thoroughly researched. Herein, we have synthesized two diblock copolymers composed of poly(3-hexylthiophene) (P3HT) and polyethylene glycol (PEG). Through a heating, cooling, and aging process, a series of multilayered hierarchical micelles and fibers were prepared in alcoholic solutions. The transition from fibers to hierarchical micelles are strictly influenced by the strength of the π-π stacking interaction, the PEG chain length, and solvent. In isopropanol, the P3HT22-b-PEG43 could self-assemble into hierarchical micelles composed of several two-dimensional (2D) laminar layers, driven by the π-π stacking interaction and van der Waals force. The P3HT22-b-PEG43 could not self-assemble into well-defined nanostructures in methanol and ethanol, but could self-assemble into fibers in isobutanol. However, the P3HT22-b-PEG113 with a longer corona block only self-assembled into fibers in four alcoholic solutions, due to the increase in dissolving capacity and steric hindrance. The sizes and the size distributions of the nanostructures both increased with the increase in polymer concentration and the decrease in solvent polarity. This study shows a method to fabricate the hierarchical micelles. [ABSTRACT FROM AUTHOR]

Non-covalent π-π stacking interactions often play a key role in the stability of the secondary and tertiary structures of peptides and proteins, respectively, and can be a means of ensuring the binding of ligands within protein and enzyme binding sites. It is generally accepted that minor structural changes to the aromatic ring, such as substitution, can have a large influence on these interactions. Nevertheless, a thorough understanding of underpinning phenomena guiding these key interactions is still limited. This is especially true for larger aromatic structures. To expand upon this knowledge, elaborate ab initio calculations were performed to investigate the effect of halogenation on the stability of 3-methylindole stacking. 3-Methylindole served as a representation of the tryptophan side chain, and is a frequently used motif in drug design and development. Moreover, an expression is derived that is able to accurately predict the interaction stability of stacked halogenated 3-methylindole dimers as well as halogenated toluene dimers, based on monomer level calculated DFT descriptors. We aim for this expression to provide the field with a straightforward and reliable method to assess the effect of halogenation on the π-π stacking interactions between aromatic scaffolds. [ABSTRACT FROM AUTHOR]

A novel cocrystal of picric acid/acetophenone was prepared by solvent evaporation method and the crystal structure was characterized by single crystal X-ray diffraction. Analysis of the crystal structure shows that the hydrogen bonding, van der Waals and π-π stacking are the main driving forces for the cocrystal formation. Density functional theory (DFT) calculation was performed to better understand the formation mechanism and properties of the cocrystal. The results suggest that π-π stacking is more important than hydrogen bonding considering their interaction energies. Furthermore, Mulliken charge analysis shows picric acid becomes less sensitive after cocrystallization with other compounds because of the electron transfer. [ABSTRACT FROM AUTHOR]

Micelle is mainly used for drug delivery and is prepared from amphiphilic block copolymers. It can be formed into an obvious core-shell structure that can incorporate liposoluble drugs. However, micelles are not suitable for the encapsulation of water-soluble drugs, and it is also difficult to maintain stability in the systemic circulation. To solve these problems, a type of polymer material, Fmoc-Lys-PEG and Fmoc-Lys-PEG-RGD, was designed and synthesized. These copolymers could self-assemble into micelles driven by π–π stacking and the hydrophobic interaction of 9-fluorenylmethoxycarbony (Fmoc) and, at the same time, form a framework for a hydrogen-bonding environment in the core. Mitomycin C (MMC), as a water-soluble drug, can be encapsulated into micelles by hydrogen-bonding interactions. The interaction force between MMC and the polymers was analyzed by molecular docking simulation and Fourier transform infrared (FTIR). It was concluded that the optimal binding conformation can be obtained, and that the main force between the MMC and polymers is hydrogen bonding. Different types of MMC nanoparticles (NPs) were prepared and the physicochemical properties of them were systematically evaluated. The pharmacodynamics of the MMC NPs in vitro and in vivo were also studied. The results show that MMC NPs had a high uptake efficiency, could promote cell apoptosis, and had a strong inhibitory effect on cell proliferation. More importantly, the as-prepared NPs could effectively induce tumor cell apoptosis and inhibit tumor growth and metastasis in vivo. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations were used to quantitatively investigate the interactions between the twenty proteinogenic amino acids and C60. The conserved amino acid backbone gave a constant energetic interaction ~5.4 kcal mol−1, while the contribution to the binding due to the amino acid side chains was found to be up to ~5 kcal mol−1 for tryptophan but lower, to a point where it was slightly destabilizing, for glutamic acid. The effects of the interplay between van der Waals, hydrophobic, and polar solvation interactions on the various aspects of the binding of the amino acids, which were grouped as aromatic, charged, polar and hydrophobic, are discussed. Although π–π interactions were dominant, surfactant-like and hydrophobic effects were also observed. In the molecular dynamics simulations, the interacting residues displayed a tendency to visit configurations (i.e., regions of the Ramachandran plot) that were absent when C60 was not present. The amino acid backbone assumed a "tepee-like" geometrical structure to maximize interactions with the fullerene cage. Well-defined conformations of the most interactive amino acids (Trp, Arg, Met) side chains were identified upon C60 binding. [ABSTRACT FROM AUTHOR]

Two heteroleptic NiII complexes combined the redox-active catecholate and 2,2′- bipyridine ligand platforms were synthesized to observe a photoinduced intramolecular ligand-to-ligand charge transfer (LL'CT, HOMOcatecholate → LUMOα-diimine). A molecular design of compound [NiII(3,6-Cat)(bipy)]∙CH3CN (1) on the base of bulky 3,6-di-tert-butyl-o-benzoquinone (3,6-DTBQ) was an annelation of the ligand with an electron donor glycol fragment, producing derivative [NiII(3,6-Catgly)(bipy)]∙CH2Cl2 (2), in order to influence the energy of LL'CT transition. A substantial longwave shift of the absorption peak was observed in the UV-Vis-NIR spectra of 2 compared with those in 1. In addition, the studied NiII derivatives demonstrated a pronounced negative solvatochromism, which was established using a broad set of solvents. The molecular geometry of both compounds can be ascribed as an insignificantly distorted square-planar type, and the π–π intermolecular stacking of the neighboring α-diimines is realized in a crystal packing. There is a lamellar crystal structure for complex 1, whereas the perpendicular T-motifs with the inter-stacks attractive π–π interactions form the packing of complex 2. The redox-active nature of ligand systems was clearly shown through the electrochemical study: a quasi-reversible one-electron reduction of 2,2′-bipyridine and two reversible successive one-electron oxidative conversations ("catecholate dianion—o-benzosemiquinonato radical anion—neutral o-benzoquinone") were detected. [ABSTRACT FROM AUTHOR]

A real-time sensor for the detection of amyl butyrate (AB) utilising human olfactory receptor 2AG1 (OR2AG1), a G-protein coupled receptor (GPCR) consisting of seven transmembrane domains, immobilized onto a graphene resistor is demonstrated. Using CVD graphene as the sensor platform, allows greater potential for more sensitive detection than similar sensors based on carbon nanotubes, gold or graphene oxide platforms. A specific graphene resistor sensor was fabricated and modified via non-covalent π–π stacking of 1,5 diaminonaphthalene (DAN) onto the graphene channel, and subsequent anchoring of the OR2AG1 receptor to the DAN molecule using glutaraldehyde coupling. Binding between the target odorant, amyl butyrate, and the OR2AG1 receptor protein generated a change in resistance of the graphene resistor sensor. The functionalized graphene resistor sensors exhibited a linear sensor response between 0.1–500 pM and high selectively towards amyl butyrate, with a sensitivity as low as 500 fM, whilst control measurements using non-specific esters, produced a negligible sensor response. The approach described here provides an alternative sensing platform that can be used in bioelectronic nose applications. [ABSTRACT FROM AUTHOR]

Aquatic contamination by heavy metals is a major concern for the serious negative consequences it has for plants, animals, and humans. Among the most toxic metals, Cd(II) stands out since selective and truly efficient methodologies for its removal are not known. We report a novel multidentate chelating agent comprising the heterocycles thiadiazole and benzisothiazole. 3-((5-(trifluoromethyl)-1,3,4-thiadiazol-2-yl)amino)benzo[d]isothiazole 1,1-dioxide (AL14) was synthesized from cheap saccharin and characterized by different techniques, including single crystal X-ray crystallography. Our studies revealed the efficiency and selectivity of AL14 for the chelation of dissolved Cd(II) (as compared to Cu(II) and Fe(II)). Different spectral changes were observed upon the addition of Cd(II) and Cu(II) during UV-Vis titrations, suggesting different complexation interactions with both metals. [ABSTRACT FROM AUTHOR]

The pronouncedly low thermal conductivity of polymers in the range of 0.1–0.2 W m−1 K−1 is a limiting factor for their application as an insulating layer in microelectronics that exhibit continuously higher power-to-volume ratios. Two strategies can be applied to increase the thermal conductivity of polymers; that is, compounding with thermally conductive inorganic materials as well as blending with aromatic units arranged by the principle of π-π stacking. In this study, both strategies were investigated and compared on the example of epoxy-amine resins of bisphenol A diglycidyl ether (BADGE) and 1,2,7,8-diepoxyoctane (DEO), respectively. These two diepoxy compounds were cured with mixtures of the diamines isophorone diamine (IPDA) and o-dianisidine (DAN). The epoxy-amine resins were cured without filler and with 5 wt.-% of SiO2 nanoparticles. Enhanced thermal conductivity in the range of 0.4 W·m−1·K−1 was observed exclusively in DEO-based polymer networks that were cured with DAN (and do not contain SiO2 fillers). This observation is argued to originate from π-π stacking of the aromatic units of DAN enabled by the higher flexibility of the aliphatic carbon chain of DEO compared with that of BADGE. The enhanced thermal conductivity occurs only at temperatures above the glass-transition point and only if no inorganic fillers, which disrupt the π-π stacking of the aromatic groups, are present. In summary, it can be argued that the bisphenol-free epoxy-amine resin with an epoxy compound derivable from natural resources shows favorably higher thermal conductivity in comparison with the petrol-based bisphenol-based epoxy/amine resins. [ABSTRACT FROM AUTHOR]

We synthesized and studied the polymeric compound {[Cu2(µ4-EDTA)(Him)2] 2H2O}n (1). The single-crystal structure is reported along with an in depth characterization of its thermal stability (TGA), spectral properties (FT-IR, Vis-UV and RSE), and magnetic behavior. The crystal consists of infinite 2D-networks built by centrosymmetric dinuclear motifs, constructed by means of a bridging anti,syn-carboxylate group from each asymmetric unit. Each layer guides Him ligands toward their external faces. They are connected by intermolecular (Him)N-H···O(carboxylate) bonds and antiparallel π–π stacking between symmetry related pairs of Him ligands, and then pillared in a 3D-network with parallel channels, where disordered water molecules are guested. About half of the labile water is lost from these channels over a wide temperature range (r.t. to 210 °C) before the other one, most strongly retained by the cooperating action of (water)O1-H(1A)···O(carboxylate) and (water) O1-H(1B)···π(Him) interactions. The latter is lost when organic ligands start to burn. ESR spectra and magnetic measurements indicated that symmetry related Cu(II) centers connected by the bridging carboxylate groups behave magnetically not equivalently, enabling an exchange interaction larger than their individual Zeeman energies. [ABSTRACT FROM AUTHOR]

Affinity biosensors based on graphene field-effect transistor (GFET) or resistor designs require the utilization of graphene's exceptional electrical properties. Therefore, it is critical when designing these sensors, that the electrical properties of graphene are maintained throughout the functionalization process. To that end, non-covalent functionalization may be preferred over covalent modification. Drop-cast 1,5-diaminonaphthalene (DAN) was investigated as a quick and simple method for the non-covalent amine functionalization of carbon-based surfaces such as graphene, for use in biosensor development. In this work, multiple graphene surfaces were functionalized with DAN via a drop-cast method, leading to amine moieties, available for subsequent attachment to receptor molecules. Successful modification of graphene with DAN via a drop-cast method was confirmed using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and real-time resistance measurements. Successful attachment of receptor molecules also confirmed using the aforementioned techniques. Furthermore, an investigation into the effect of sequential wash steps which are required in biosensor manufacture, on the presence of the DAN layer, confirmed that the functional layer was not removed, even after multiple solvent exposures. Drop-cast DAN is thus, a viable fast and robust method for the amine functionalization of graphene surfaces for use in biosensor development. [ABSTRACT FROM AUTHOR]

To characterize the interfacial microstructure and interaction at a nanoscale has a significant meaning for the interface improvement of the nanocomposites. In this study, the interfacial microstructure and features of aligned multiwalled carbon nanotube (MWNT) and conjugated polymer polyimide (PI) with three molecular structures were investigated using small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and fluorescence emission spectroscopy. It was found that aligned MWNT/PI nanocomposites had a nonideal two-phase system with the interfaces belonging to long period stacking ordered structure. Attributed to the π–π stacking effect, MWNT/BTDA-MPD presented the most regular arrangement verified by fractal dimension. By adopting a one-dimension correlation function, each phase dimension in aligned MWNT/PI nanocomposites was calculated and verified by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The π–π stacking was demonstrated to be an important interaction between MWNT and PI via WAXD and fluorescence emission spectroscopy, and it was influenced by the linkage bond between benzene rings in PIs. This work is of significance to reveal the interfacial features between conjugated polymer and carbon nanotubes (CNTs), which is favorable for the interface design of CNT-based high performance nanocomposites. [ABSTRACT FROM AUTHOR]

The proton transfer between equimolar amounts of [Cd(H2EDTA)(H2O)] and 2,6-diaminopurine (Hdap) yielded crystals of the out-of-sphere metal complex H2(N3,N7)dap[Cd(HEDTA)(H2O)]·H2O (1) that was studied by single-crystal X-ray diffraction, thermogravimetry, FT-IR spectroscopy, density functional theory (DFT) and quantum theory of "atoms-in-molecules" (QTAIM) methods. The crystal was mainly dominated by H-bonds, favored by the observed tautomer of the 2,6-diaminopurinium(1+) cation. Each chelate anion was H-bonded to three neighboring cations; two of them were also connected by a symmetry-related anti-parallel π,π-staking interaction. Our results are in clear contrast with that previously reported for H2(N1,N9)ade [Cu(HEDTA)(H2O)]·2H2O (EGOWIG in Cambridge Structural Database (CSD), Hade = adenine), in which H-bonds and π,π-stacking played relevant roles in the anion–cation interaction and the recognition between two pairs of ions, respectively. Factors contributing in such remarkable differences are discussed on the basis of the additional presence of the exocyclic 2-amino group in 2,6-diaminopurinium(1+) ion. [ABSTRACT FROM AUTHOR]

Herein, we report the surface functionalization of carbon nano-onions (CNOs) through an amidation reaction that occurs between the oxidized CNOs and 4-(pyren-4-yl)butanehydrazide. Raman and Fourier transform infrared spectroscopy methods were used to confirm the covalent functionalization. The percentage or number of groups in the outer shell was estimated with thermal gravimetric analysis. Finally, the potential applications of the functionalized CNOs as electrode materials in supercapacitors were evaluated by cyclic voltammetry and electrochemical impedance spectroscopy. Functionalization increased the specific capacitance by approximately 138% in comparison to that of the pristine CNOs, while acid-mediated oxidation reduced the specific capacitance of the nanomaterial by 24%. [ABSTRACT FROM AUTHOR]

The pronouncedly low thermal conductivity of polymers in the range of 0.1-0.2 W m -1 K -1 is a limiting factor for their application as an insulating layer in microelectronics that exhibit continuously higher power-to-volume ratios. Two strategies can be applied to increase the thermal conductivity of polymers; that is, compounding with thermally conductive inorganic materials as well as blending with aromatic units arranged by the principle of π-π stacking. In this study, both strategies were investigated and compared on the example of epoxy-amine resins of bisphenol A diglycidyl ether (BADGE) and 1,2,7,8-diepoxyoctane (DEO), respectively. These two diepoxy compounds were cured with mixtures of the diamines isophorone diamine (IPDA) and o -dianisidine (DAN). The epoxy-amine resins were cured without filler and with 5 wt.-% of SiO 2 nanoparticles. Enhanced thermal conductivity in the range of 0.4 W·m -1 ·K -1 was observed exclusively in DEO-based polymer networks that were cured with DAN (and do not contain SiO 2 fillers). This observation is argued to originate from π-π stacking of the aromatic units of DAN enabled by the higher flexibility of the aliphatic carbon chain of DEO compared with that of BADGE. The enhanced thermal conductivity occurs only at temperatures above the glass-transition point and only if no inorganic fillers, which disrupt the π-π stacking of the aromatic groups, are present. In summary, it can be argued that the bisphenol-free epoxy-amine resin with an epoxy compound derivable from natural resources shows favorably higher thermal conductivity in comparison with the petrol-based bisphenol-based epoxy/amine resins.

In this study, a novel system was set up by preparing a magnetic flocculant combining with ultraviolet/H 2 O 2 to realize the rapid enrichment and degradation of diclofenac sodium (DCFS). For the magnetic flocculant, template anion polyacrylamide (TAPAM) with anion micro-block structure was prepared. Thereafter, polydopamine was used to modify TAPAM, Fe 3 O 4 nanoparticles was grafted to the modified TAPAM by chelation, named template anion polyacrylamide-polydopamine-Fe 3 O 4 (TAPAM-PDA-Fe 3 O 4 ). Furthermore, the TAPAM-PDA-Fe 3 O 4 preparation protocol was optimized by the response surface method (RSM). In the DCFS enrichment section, the rapid separation of flocs from water was realized by an external magnetic field and it indicated that the π-π stacking effect was dominant in neutral/alkaline condition, whereas charge neutralization was favored in acidic conditions. Meanwhile, a DCFS enrichment kinetic curve was much fitted by the pseudo-second-order kinetic model and DCFS enrichment isothermal curve was close to the Freundlich isothermal model, indicating the dependence of DCFS quantity enriched by TAPAM-PDA-Fe 3 O 4 and a multilayer heterogeneous enrichment process. The degradation experiment confirmed that DCFS was effectively degraded by ultraviolet/H 2 O 2 /TAPAM-PDA-Fe 3 O 4 and the maximum value of DCFS degradation efficiency reached 98.1%. Furthermore, the regeneration experiment showed that the enrichment and degradation efficiency of DCFS could maintain a relatively high level in the initial three recycles.

The HIV nucleocapsid protein NCp7 was previously shown to play a number of roles in the viral life cycle and was previously identified as a potential target for small molecule intervention. In this work, the synthesis of the previously unreported complexes [Au(dien)(1MeCyt)]3+, [Au(N-Medien)(1MeCyt)]3+, and [Au(dien)(Cyt)]3+ is detailed, and the interactions of these complexes with the models for NCp7 are described. The affinity for these complexes with the target interaction site, the "essential" tryptophan of the C-terminal zinc finger motif of NCp7, was investigated through the use of a fluorescence quenching assay and by 1H-NMR spectroscopy. The association of [Au(dien)(1MeCyt)]3+ as determined through fluorescence quenching is intermediate between the previously reported DMAP and 9-EtGua analogs, while the associations of [Au(N-Medien)(1MeCyt)]3+ and [Au(dien)(Cyt)]3+ are lower than the previously reported complexes. Additionally, NMR investigation shows that the self-association of relevant compounds is negligible. The specifics of the interaction with the C-terminal zinc finger were investigated by circular dichroism spectroscopy and electrospray-ionization mass spectrometry. The interaction is complete nearly immediately upon mixing, and the formation of AuxFn+ (x = 1, 2, or 4; F = apopeptide) concomitant with the loss of all ligands is observed. Additionally, oxidized dimerized peptide was observed for the first time as a product, indicating a reaction via a charge transfer mechanism. [ABSTRACT FROM AUTHOR]

Organic semiconductor materials composed of π–π stacking aromatic compounds have been under intense investigation for their potential uses in flexible electronics and other advanced technologies. Herein we report a new family of seven π–π stacking compounds of silver(I) bis-N-(4-pyridyl) benzamide with varying counterions, namely [Ag(NPBA)2]X, where NPBA is N-(4-pyridyl) benzamine, X = NO3− (1), ClO4− (2), CF3SO3− (3), PF6− (4), BF4− (5), CH3PhSO3− (6), and PhSO3− (7), which form extended π−π stacking networks in one-dimensional (1D), 2D and 3D directions in the crystalline solid-state via the phenyl moiety, with average inter-ring distances of 3.823 Å. Interestingly, the counterions that contain π–π stacking-capable groups, such as in 6 and 7, can induce the formation of mesomorphic phases at 130 °C in dimethylformamide (DMF), and can generate highly branched networks at the mesoscale. Atomic force microscopy studies showed that 2D interconnected fibers form right after nucleation, and they extend from ~30 nm in diameter grow to reach the micron scale, which suggests that it may be possible to stop the process in order to obtain nanofibers. Differential scanning calorimetry studies showed no remarkable thermal behavior in the complexes in the solid state, which suggests that the mesomorphic phases originate from the mechanisms that occur in the DMF solution at high temperatures. An all-electron level simulation of the band gaps using NRLMOL (Naval Research Laboratory Molecular Research Library) on the crystals gave 3.25 eV for (1), 3.68 eV for (2), 1.48 eV for (3), 5.08 eV for (4), 1.53 eV for (5), and 3.55 eV for (6). Mesomorphic behavior in materials containing π–π stacking aromatic interactions that also exhibit low-band gap properties may pave the way to a new generation of highly branched organic semiconductors. [ABSTRACT FROM AUTHOR]