Weak H-bonding Interactions Research Articles

π-Conjugated Porous Polymer Nanosheets for Explosive Sensing: Investigation on the Role of H-Bonding.

Nitroaromatic explosive sensing plays a critical role in ensuring public security and environmental protection. Herein, we report 2-pyridyl-thiazolothiazole (pyTTz) integrated blue-fluorescent π-conjugated porous polymer nanosheets, NTzCMP and TzCMP for selective sensing of picric acid (PA) among nitrophenol explosives. Acid-base interactions between PA and pyTTz of CMP lead to H-bonding interactions, where the hydroxy group of PA engaged in weak H-bonding interactions with pyridine and TTz of pyTTz moiety. This led to a strong fluorescence quenching of CMPs-such formation of ground state complex was supported by linear Stern-Volmer quenching plots, unaltered excited state lifetimes, and detailed FTIR analysis of PA exposed CMPs. Interestingly, both CMPs exhibited an excellent response to smaller analytes such as o-nitrotoluene compared to electron-deficient 2,4-dinitrotoluene. Both NTzCMP and TzCMP CMPs exhibited high KSV values of 9×103 and 2.1×103 M-1 for PA and the corresponding limit of detection values were found to be 0.46 and 1.6 ppm, respectively.

An experimental and computational investigation of the cyclopentene-containing peptide-derived compounds: focus on pseudo-cyclic motifs via intramolecular interactions.

Conformational flexibility is one of the main disadvantages of peptide-based compounds. We focus on their molecular 'chameleonicity' related to forming pseudo-cyclic motifs via modulation of weak intramolecular interactions. It is an appealing strategy for controlling equilibrium between the polar open and the nonpolar closed conformations. Within this context, we report here the crystal structure of the (R)-(2-tert-butoxycarbonyl)amino-1-oxo-3-phenyl)propyl)-1-cyclopentene (1), synthesis of which in high yield was achieved by a facile multi-step protocol. Our Cambridge Structural Database (CSD) overview for the peptide-based crystals revealed the exclusivity of this compound from the viewpoint of the unusual pseudo-bicyclic system via C-H…O and C-O…π interactions, in which cyclopentene shields the amide bond. Notably, cyclopentene as a bioisostere of proline is an appealing scaffold in medicinal chemistry. An extensive combined experimental and computational study provided more profound insight into the supramolecular landscape of 1 with respect to similar derivatives deposited in the CSD, including the tendency of cyclopentene for the generation of pseudo-cyclic motifs through weak H-bonding and π-based intramolecular interactions. These weak interactions have been examined by either the quantum theory of 'atoms-in-molecules' (QTAIM) or complex Hirshfeld surface methodology, including enrichment ratios, molecular electrostatic potential surfaces and energy frameworks. In all analysed crystals, all types of H-bonded motifs involving cyclopentene are formed at all levels of supramolecular architecture. A library of cyclopentene-based H-bonding synthons is provided. A molecular docking study depicted vital interactions of cyclopentene with key amino acid residues inside the active sites of two prominent protein kinases, uncovering the therapeutic potential of 1 against breast cancer. To a large extent, dispersion forces have significance in stabilizing the supramolecular structure of both ligand and bio-complex ligand-protein. Finally, the satisfactory in silico bio-pharmacokinetic profile of 1 related to drug-likeness and blood-brain barrier permeation was also revealed.

Record Second-Harmonic Generation and Birefringence in an Ultraviolet Antimonate by Bond Engineering.

Oxides have attracted considerable attention owing to their potential for nonlinear optical (NLO) applications. Although significant progress has been achieved in optimizing the structural characteristics of primitives (corresponding to the simplest constituent groups, namely, cations/anions/neutral molecules) comprising the crystalline oxides, the role of the primitives' interaction in determining the resultant functional structure and optical properties has long been underappreciated and remains unclear. In this study, we employ a π-conjugated organic primitive confinement strategy to manipulate the interactions between primitives in antimonates and thereby significantly enhance the optical nonlinearity. Chemical bonds and relatively weak H-bonding interactions promote the formation of cis- and trans-Sb(III)-based dimer configurations in (C5H5NO)(Sb2OF4) (4-HPYSOF) and (C5H7N2)(Sb2F7) (4-APSF), respectively, resulting in very different second-harmonic generation (SHG) efficiencies and birefringences. In particular, 4-HPYSOF displays an exceptionally strong SHG response (12 × KH2PO4 at 1064 nm) and a large birefringence (0.513 at 546 nm) for a Sb(III)-based NLO oxide as well as a UV cutoff edge. Structural analyses and theoretical studies indicate that polarized ionic bond interactions facilitate the favorable arrangement of both the inorganic and organic primitives, thereby significantly enhancing the optical nonlinearity in 4-HPYSOF. Our findings shed new light on the intricate correlations between the interactions of primitives, inorganic primitive configuration, and SHG properties, and, more broadly, our approach provides a new perspective in the development of advanced NLO materials through the interatomic bond engineering of oxides.

Interplay between anion-receptor and anion-solvent interactions in halide receptor complexes characterized with ultrafast infrared spectroscopies.

The competition between host-guest binding and solvent interactions is a crucial factor in determining the binding affinities and selectivity of molecular receptor species. The interplay between these competing interactions, however, have been difficult to disentangle. In particular, the development of molecular-level descriptions of solute-solvent interactions remains a grand experimental challenge. Herein, we investigate the prototypical halide receptor meso-octamethylcalix[4]pyrrole (OMCP) complexed with either chloride or bromide anions in both dichloromethane (DCM) and chloroform (trichloromethane, TCM) solvent using ultrafast infrared transient absorption and 2D IR spectroscopies. OMCP·Br- complexes in both solvents display slower vibrational relaxation dynamics of the OMCP pyrrole NH stretches, consistent with weaker H-bonding interactions with OMCP compared to chloride and less efficient intermolecular relaxation to the solvent. Further, OMCP·Br- complexes show nearly static spectral diffusion dynamics compared to OMCP·Cl-, indicating larger structural fluctuations occur within chloride complexes. Importantly, distinct differences in the vibrational spectra and dynamics are observed between DCM and TCM solutions. The data are consistent with stronger and more perturbative solvent effects in TCM compared to DCM, despite DCM's larger dielectric constant and smaller reported OMCP·X- binding affinities. These differences are attributed to the presence of weak H-bond interactions between halides and TCM, in addition to competing interactions from the bulky tetrabutylammonium countercation. The data provide important experimental benchmarks for quantifying the role of solvent and countercation interactions in anion host-guest complexes.

Copper(I) Complexes of Amide Functionalized Bisphosphine: Proximity Enhanced Metal-Ligand Cooperativity and Its Catalytic Advantage in C(sp3)-H Bond Activation of Unactivated Cycloalkanes in Dehydrogenative Carboxylation Reactions.

The reactions of amide functionalized bisphosphine, o-Ph2PC6H4C-(O)N(H)C6H4PPh2-o (1) (BalaHariPhos), with copper salts is described. Treatment of 1 with CuX in a 1:1 molar ratio yielded chelate complexes of the type [CuX{(o-Ph2PC6H4C(O)N(H)C6H4PPh2-o)}-κ2-P,P] (X = Cl, 2; Br, 3; and I, 4), which on subsequent treatment with KOtBu resulted in a dimeric complex [Cu(o-Ph2PC6H4C(O)(N)C6H4PPh2-o)]2 (5). Interestingly, complexes 2-4 showed weak N-H···Cu interactions. These weak H-bonding interactions are studied in detail both experimentally and computationally. Also, CuI complexes 2-5 were employed in the oxidative dehydrogenative carboxylation (ODC) of unactivated cycloalkanes in the presence of carboxylic acids to form the corresponding allylic esters. Among complexes 2-5, halide-free dimeric CuI complex 5 showed excellent metal-ligand cooperativity in the oxidative dehydrogenative carboxylation (ODC) in the presence of carboxylic acids to form the corresponding allylic esters through C(sp3)-H bond activation of unactivated cycloalkanes. Mechanistic details of the catalytic process were established by isolating the precatalyst [Cu{(o-Ph2PC6H4C(O)(NH)C6H4PPh2-o)-κ2-P,P}(OOCPh)] (6) and fully characterized by mass spectrometry, NMR data, and single-crystal X-ray analysis. Density functional theory-based calculations further provided a quantitative understanding of the energetics of a series of H atom transfer steps occurring in the catalytic cycle.

Effect of Bacterial Amyloid Protein Phenol-Soluble Modulin Alpha 3 on the Aggregation of Amyloid Beta Protein Associated with Alzheimer's Disease.

Since the proposal of the brainstem axis theory, increasing research attention has been paid to the interactions between bacterial amyloids produced by intestinal flora and the amyloid β-protein (Aβ) related to Alzheimer's disease (AD), and it has been considered as the possible cause of AD. Therefore, phenol-soluble modulin (PSM) α3, the most virulent protein secreted by Staphylococcus aureus, has attracted much attention. In this work, the effect of PSMα3 with a unique cross-α fibril architecture on the aggregation of pathogenic Aβ40 of AD was studied by extensive biophysical characterizations. The results proposed that the PSMα3 monomer inhibited the aggregation of Aβ40 in a concentration-dependent manner and changed the aggregation pathway to form granular aggregates. However, PSMα3 oligomers promoted the generation of the β-sheet structure, thus shortening the lag phase of Aβ40 aggregation. Moreover, the higher the cross-α content of PSMα3, the stronger the effect of the promotion, indicating that the cross-α structure of PSMα3 plays a crucial role in the aggregation of Aβ40. Further molecular dynamics (MD) simulations have shown that the Met1-Gly20 region in the PSMα3 monomer can be combined with the Asp1-Ala2 and His13-Val36 regions in the Aβ40 monomer by hydrophobic and electrostatic interactions, which prevents the conformational conversion of Aβ40 from the α-helix to β-sheet structure. By contrast, PSMα3 oligomers mainly combined with the central hydrophobic core (CHC) and the C-terminal region of the Aβ40 monomer by weak H-bonding and hydrophobic interactions, which could not inhibit the transition to the β-sheet structure in the aggregation pathway. Thus, the research has unraveled molecular interactions between Aβ40 and PSMα3 of different structures and provided a deeper understanding of the complex interactions between bacterial amyloids and AD-related pathogenic Aβ.

Interaction of Atomically Precise Thiolated Copper Nanoclusters with Proteins: A Comparative Study.

A facile synthesis of glutathione-stabilized copper nanoclusters (CuNCs) is carried out in H2O/ tetrahydrofuran medium. The photophysical and morphological studies performed with as-synthesized CuNCs revealed the formation of green-emissive, stable, and smaller nanoclusters. The precise composition of these as-synthesized CuNCs was predicted with the aid of electrospray ionization mass spectrometry analysis as Cu12(SG)9. Furthermore, the systematic studies of the interaction of synthesized CuNCs with three plasmatic proteins, namely, bovine serum albumin (BSA), lysozyme (Lys), and hemoglobin (Hb) have been performed by using a series of spectroscopic studies. The conformational changes in these proteins upon interacting with CuNCs and their binding stoichiometries have been investigated from the combination of UV-visible and steady-state fluorescence measurements. The changes in the microenvironment of proteins caused by CuNCs were investigated by circular dichroism spectroscopy. Among these three proteins, BSA and Lys had a minor effect on the luminescence of CuNCs, which makes them suitable candidates for biological applications. There are no drastic changes in the microenvironment of NCs as well as proteins because of the possibilities of weak electrostatic and H-bonding interactions of CuNCs with BSA and Lys. The feasibility of strong metallophic interaction between the Fe2+ present in the heme group of Hb and Cu(I) or -S atoms present in the CuNCs brings considerable changes in the photophysical activity of CuNCs and their interactions with Hb. The functional groups on NCs as well as active amino acid residues present in proteins play a crucial role in determining their interactions. This work shed a piece of knowledge on designing NCs for specific biological applications.

Recent advancements of photo- and electro-active hydrogen-bonded organic frameworks

The development of hydrogen-bonded organic frameworks (HOFs) with predictable topologies and robust structures for targeted functionality was initially hindered by the relatively weak H-bonding interactions as many HOFs would collapse upon guest solvent removal. Recently, the design of tectons with large π-conjugated systems that form intermolecular shape-fitted π–π stacking interactions has proven to be an effective strategy to create chemically and thermally stable HOFs. More importantly, these HOFs with large π-conjugated tectons exhibit accelerated redox hopping processes due to more favorable through-space orbital overlap interactions. These intrinsic photoelectric properties render HOFs an appealing and unique class of photoactive and electroactive porous materials for catalysis, sensing, and biomedical applications. Based on shape-fitted π–π stacking strategy, various robust photoactive and electroactive HOFs have been built from tectons containing both photosensitive or redox-active organic cores and hydrogen bonding sites. This review summarizes the recent advancements, including synthetic methods and diverse applications, in the development of photo- and electro-active HOFs. Considering the numerous photo- and electro-active organic units available, as well as the virtually unlimited potential combinations of organic cores and hydrogen bonding sites, we anticipate that this review will inspire scientists in a range of disciplines, ranging from porous materials to organic photoelectric materials and catalysis scientists, to further explore functional photo- and electro-active HOF materials.

Design Rules of Hydrogen-Bonded Organic Frameworks with High Chemical and Thermal Stabilities.

Hydrogen-bonded organic frameworks (HOFs), self-assembled from strategically pre-designed molecular tectons with complementary hydrogen-bonding patterns, are rapidly evolving into a novel and important class of porous materials. In addition to their common features shared with other functionalized porous materials constructed from modular building blocks, the intrinsically flexible and reversible H-bonding connections endow HOFs with straightforward purification procedures, high crystallinity, solution processability, and recyclability. These unique advantages of HOFs have attracted considerable attention across a broad range of fields, including gas adsorption and separation, catalysis, chemical sensing, and electrical and optical materials. However, the relatively weak H-bonding interactions within HOFs can potentially limit their stability and potential use in further applications. To that end, this Perspective highlights recent advances in the development of chemically and thermally robust HOF materials and systematically discusses relevant design rules and synthesis strategies to access highly stable HOFs.

Nature of excited-state dependent hydrogen bonds and their critical role in determining the photophysical properties of aromatic thioketones.

In this work, how the excited-state dependent hydrogen bond (H-bond) interactions control photophysical processes have been uncovered by accurate electronic structure calculations for the five lowest-lying states (S0, S1, S2, T1, and T2) of three aromatic thioketones and their isomers. The difference in the H-bond nature between S2 and S1 gives rise to ultrafast S2 → S1 internal conversion via the two-state conical intersection. Strong S2 fluorescence observed usually in thiocarbonyl compounds is absent in aromatic thioketones with intramolecular H-bonds. Meanwhile, the relatively weak H-bond interactions in S1 and T1 states make the S1, T2, and T1 states degenerate or quasi-degenerate. As a result, the T2 state acts as a relay and enables both forward S1 → T1 and reverse T1 → S1 processes to occur efficiently, which provides new insights into the mechanism of thermally activated delayed fluorescence (TADF), and could be used to improve the design principle of purely organic TADF materials.

Solvation and Ion-Pairing Effects of Choline Acetate Electrolyte in Protic and Aprotic Solvents Studied by NMR Titrations.

Choline‐based electrolytes have been proposed as environmentally friendly and low‐cost alternatives for secondary zinc air batteries. Choline acetate [Ch]+[OAc]− in protic (D2O) and aprotic (DMSO‐d6) solvents has been studied by means of concentration‐dependent 1H NMR, viscosity, and density measurements. The viscosities have been calculated on the basis of the Jones‐Dole equation and showed that the dominant contribution originates from short‐range ion‐solvent interactions. Site‐specific association affinities were assigned from NMR chemical shift titrations. In DMSO‐d6, the hydroxyl group of choline was found to have the smallest dissociation constant followed by the methyl group of acetate. The corresponding Gibbs energies at low concentration were found to be in agreement with a solvent‐separated ion pair (2SIP) configuration, whereas at concentrations above 300 mM, a solvent‐shared ion pair (SIP) configuration was assigned. For [Ch]+[OAc]− in D2O, association effects were found to be weaker, attributed to the high dielectric constant of the solvent. On time scales on the order of 100 ms, NMR linewidth perturbations indicated a change in the local rotational dynamics of the ions, attributed to short‐range cation‐solvent interactions and not to solvent viscosity. At 184 mM, ∼ 40 % of the cations in DMSO‐d6 and ∼ 10 % in D2O were found to exhibit short‐range interactions, as indicated by the linewidth perturbations. It was found that at about 300 mM, the ions in DMSO‐d6 exhibit a transition from free to collective translational dynamics on time scales on the order of 400 ms. In DMSO‐d6, both ions were found to be almost equally solvated, whereas in D2O solvation of acetate was stronger, as indicated by the obtained effective hydrodynamic radii. For [Ch]+[OAc]− in DMSO‐d6, the results suggest a solvent‐shared ion association with weak H‐bonding interactions for concentrations between 0.3–1 M. Overall, the extent of ion association in solvents such as DMSO is not expected to significantly limit charge transport and hinder the performance of choline‐based electrolytes.

Probing the Hydrogen-Bonding Environment of Individual Bases in DNA Duplexes with Isotope-Edited Infrared Spectroscopy.

Measuring the strength of the hydrogen bonds between DNA base pairs is of vital importance for understanding how our genetic code is physically accessed and recognized in cells, particularly during replication and transcription. Therefore, it is important to develop probes for these key hydrogen bonds (H-bonds) that dictate events critical to cellular function, such as the localized melting of DNA. The vibrations of carbonyl bonds are well-known probes of their H-bonding environment, and their signals can be observed with infrared (IR) spectroscopy. Yet, pinpointing a single bond of interest in the complex IR spectrum of DNA is challenging due to the large number of carbonyl signals that overlap with each other. Here, we develop a method using isotope editing and infrared (IR) spectroscopy to isolate IR signals from the thymine (T) C2=O carbonyl. We use solvatochromatic studies to show that the TC2=O signal’s position in the IR spectrum is sensitive to the H-bonding capacity of the solvent. Our results indicate that C2=O of a single T base within DNA duplexes experiences weak H-bonding interactions. This finding is consistent with the existence of a third, noncanonical CH···O H-bond between adenine and thymine in both Watson–Crick and Hoogsteen base pairs in DNA.

Self-Assembly of Switchable Protein Nanocages via Allosteric Effect

Protein cages have promising applications in highly efficient gene transportation. Many methods of engineering protein–interface interactions have been developed to build such viral mimics. Missing...

An insight into the role of supramolecular interactions to stabilize the solid state structure of an octahedral nickel(II) diamine complex

A mononuclear octahedral nickel(II) complex, [Ni(dmpn)2(NCS)2], where dmpn = 2,2-dimethyl-1,3-propanediamine, has been synthesized and characterized by elemental and spectral analyses. The structure of the complex has been confirmed by single crystal X-ray diffraction. The complex forms an infinite chain in the solid state, where the NH groups participate in weak H-bonding interactions with the thiocyanate ligands. The DFT study is devoted to the analysis of the hydrogen bonds and additional CH•••HC interactions that are important in the solid state structure of the complex. Moreover, these supramolecular contacts have been studied and characterized using the QTAIM computational tool.

Long-Range Ordered Water Correlations between A–T/C–G Nucleotides

Summary The interactions between complementary base pairs are crucial to the helical duplex structure of DNA. Although base-base interactions have been widely reported, the study of long-range interactions in the base-pairing processes is still a major challenge in this field. Here, we first study the long-range interactions between the base pairs by atomic force microscopy-based single-molecule force spectroscopy (SMFS). The SMFS results of A–T/C–G imply that there are weak long-range interactions between them, which have a range of 15–25 nm. Raman spectroscopy results imply that these weak interactions can be attributed to multiplex hydrogen bond interaction of ordered water structure between A–T/C–G nucleotides. In addition, the theoretical calculations deduce that the ideal structure of these water molecules exhibits a specific helical structure. Our findings might open up a new understanding of biological assembly processes and provide helpful strategies for bio-nanotechnology.

Crystallographic Elucidation of Stimuli-Controlled Molecular Rotation for a Reversible Sol-Gel Transformation.

To get an idea about the most probable microporous supramolecular environment in the gel state, gelator molecule 1 has been crystallized from its gelling solvent (dimethylformamide). Crystal structure analysis of 1 shows a strong π···π stacking interaction between the electron-deficient pentafluorophenyl ring and electron-rich naphthyl ring. The gelling solvent situated in the "molecular pocket" stitches the gelators through weak H-bonding interactions to facilitate the formation of an organogel. Scanning electron microscopy analysis exhibits a ribbonlike fibrous morphology that resembles the supramolecular arrangement of 1 in its crystalline state, as evidenced by powder X-ray diffraction. In the presence of external stimuli (tetrabutylammonium fluoride), the organogel of 1 disassembles into sol. This sol-gel transformation phenomenon has been explained on the basis of X-ray single-crystal analysis. Single crystals obtained from the sol state show that naphthylic -OH of 1 gets deprotonated, resulting in C-C bond rotation that plays a major role in the sol-gel transformation. Gelator 1 exhibits weak green fluorescence in the gel state, whereas it shows highly intense yellow fluorescence in the sol state. Furthermore, a reversible sol-gel transformation associated with changes in the spectroscopic properties has been observed in the presence of acids and fluoride ions, respectively.

Synthesis, crystal structure and antibacterial activity of manganese(III) and cobalt(III) complexes containing pentadentate Schiff bases of a common amine and thiocyanate

Four new mononuclear Schiff base manganese(III) and cobalt(III) complexes viz. [Mn(L1)(NCS)] (1), [Mn(L2)(NCS)] (2), [Co(L3)(NCS)] (3), and [Co(L4)(NCS)]·0.5CH3OH·0.5H2O (4), containing thiocyanate as a common pseudohalide ion are reported. The pentadentate Schiff base ligands H2L1, H2L2, H2L3, and H2L4 were obtained by the condensation of substituted salicylaldehydes with N-(3-aminopropyl)-N-methylpropane-1,3-diamine. The syntheses of the complexes have been achieved by the reaction of manganese(II) perchlorate or cobalt(II) perchlorate with the respective Schiff bases in the presence of thiocyanate in methanol medium. Complexes 1–4 have been characterized by microanalytical, spectroscopic, single-crystal X-ray diffraction and other physicochemical studies. Structural studies reveal that 1–4 adopt nearly similar structures containing the MN4O2 (M = Mn, Co) chromophore in which each central M(III) ion adopts a distorted octahedral geometry. Weak intermolecular H-bonding interactions are operative in these complexes to bind the molecular units. The antibacterial activity of 1–4 and their constituent Schiff bases has been tested against some common bacteria.

Modulating Morphologies and Surface Properties of Nanoparticles from Cellulose-Grafted Bottlebrush Copolymers Using Complementary Hydrogen-Bonding between Nucleobases.

Herein we report the synthesis of a cellulose-grafted bottlebrush copolymer with nucleobases as hydrophobic moieties. Well-defined spherical micelles from this bottlebrush copolymer were fabricated via a solvent switch method. A morphological transition from spheres to worms was only observed to occur when a diblock copolymer with a complementary nucleobase functionality was introduced. Hydrophobic interaction is not capable of triggering the morphological transformation, and the diblock copolymer with the heterogeneous acrylamide nucleobase monomer can induce the morphological transition at higher A:T molar ratios, which might be caused by the weak H-bonding interaction. This supramolecular "grafting to" method enables the preparation of a series of nanoparticles with similar shapes and dimensions but distinct surface properties such as zeta potentials. Moreover, reversible morphological transitions between worm-like micelles and spheres can be achieved using a reversible collapsing and swelling of a thermoresponsive polymer. This work highlights that a supramolecular "grafting to" approach between complementary nucleobases can be utilized to tune morphologies and surface properties of nanoparticles.

Pesticide application inhibit the microbial carbonic anhydrase-mediated carbon sequestration in a soil microcosm.

Heterotrophic system for carbon sequestration is gaining importance in the recent decades. Carbonic anhydrase (CA) is a major enzyme involved in carbon sequestration and biomineralization process. In this paper, we evaluate the effect of pesticide on CA activity using inhibitory assay. 2,4-D, being one of the most extensively used pesticide, being deleterious to soil health, its usage should be minimized to regain the soil health. Maximum inhibitory constant (Ki) was observed for 5% 2,4-D (49.53 mM) followed by 5% glyphosate (43.92 mM). The maximum Km increase with increase in pesticide concentration by 3.05-fold was in case of glyphosate which was higher than that of 2,4-D (2.08-fold) and dichlorvos (2.38-fold). Moreover, we evaluated the carbon sequestration using CA enzyme in the soil microcosm. In the present study, we identified the negative impact of 2,4-D on carbonic anhydrase produced by Bacillus halodurans PO15. The inhibition was a mixed type and had significantly lowered the carbon reduction to about 2.38 ± 0.17% in a soil microcosm study. Based on the molecular docking, the inhibition was contributed due to weak H-bonding interaction with amino acid residues (Gly65, Gly95, Val147, Ser150 and Gly65, Ser146, and Ser150).

Negative Solvatochromism in a N-Linked p-Pyridiniumcalix[4]arene Derivative.

In this paper, we report the synthesis, structural characterization, and solvatochromic properties of a N-linked p-pyridiniumcalix[4]arenediol derivative 1. In the solid state, 1 forms a dimeric assembly stabilized by a network of weak H-bonding interactions involving acetonitrile solvent molecules. In solution, 1 shows a peculiar negative solvatochromism which was rationalized with the aid of TD-DFT calculations. The species responsible for this phenomenon is the monodeprotonated betainic form of 1 which is easily formed at pH close to neutrality.