Anion-directed assembly of a non-interpenetrated square-grid metal-organic framework with nanoscale porosity.

A non-interpenetrated square grid metal-organic framework (MOF) comprised of octahedral Zn(II) ions and linear N,N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide (DPNDI) ligands was formed in the presence of noncoordinating perchlorate counterions that occupied the cavities of the porous network by forming CH···anion hydrogen bonds with DPNDI ligands, whereas a linear coordination polymer was obtained when Zn(II)-coordinated nitrate ions were present as counterions.

Tunable electronic interactions between anions and perylenediimide.

Over the past decade anion-π interaction has emerged as a new paradigm of supramolecular chemistry of anions. Taking advantage of the electronic nature of anion-π interaction, we have expanded its boundaries to charge-transfer (CT) and formal electron transfer (ET) events by adjusting the electron-donating and accepting abilities of anions and π-acids, respectively. To establish that ET, CT, and anion-π interactions could take place between different anions and π-acids as long as their electronic and structural properties are conducive, herein, we introduce 3,4,9,10-perylenediimide (PDI-1) that selectively undergoes thermal ET from strong Lewis basic hydroxide and fluoride anions, but remains electronically and optically silent to poor Lewis basic anions, as ET and CT events are turned OFF. These interactions have been fully characterized by UV/Vis, NMR, and EPR spectroscopies. These results demonstrate the generality of anion-induced ET events in aprotic solvents and further refute a notion that strong Lewis basic hydroxide and fluoride ions can only trigger nucleophilic attack to form covalent bonds instead of acting as sacrificial electron donors to π-acids under appropriate conditions.

Controllable self-assembly of amphiphilic macrocycles into closed-shell and open-shell vesicles, nanotubes, and fibers.

Depending on functional groups, amphiphilic hexaamide macrocycles self-assemble into closed-shell and open-shell vesicles in polar solvents. In the presence of water, open-shell vesicles morph into closed-shell vesicles, whereas acidification of the medium transforms vesicles into nanotubes and fibers.

Lower rim 1,3-di{4-antipyrine}amide conjugate of calix[4]arene: synthesis, characterization, and selective recognition of Hg2+ and its sensitivity toward pyrimidine bases.

The structurally characterized lower rim 1,3-di{4-antipyrine}amide conjugate of calix[4]arene (L) exhibits high selectivity toward Hg(2+) among other biologically important metal ions, viz., Na(+), K(+), Ca(2+), Mg(2+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Ag(+) as studied by fluorescence, absorption, and ESI MS. L acts as a sensor for Hg(2+) by switch-off fluorescence and exhibits a lowest detectable concentration of 1.87 ± 0.1 ppm. The complex formed between L and Hg(2+) is found to be 1:1 on the basis of absorption and fluorescence titrations and was confirmed by ESI MS. The coordination features of the mercury complex of L were derived on the basis of DFT computations and found that the Hg(2+) is bound through an N(2)O(2) extending from both the arms to result in a distorted octahedral geometry with two vacant sites. The nanostructural features such as shape and size obtained using AFM and TEM distinguishes L from its Hg(2+) complex and were different from those of the simple mercuric perchlorate. L is also suited to sense pyrimidine bases by fluorescence quenching with a minimum detection limit of 1.15 ± 0.1 ppm in the case of cytosine. The nature of interaction of pyrimidine bases with L has been further studied by DFT computational calculations and found to have interactions through a hydrogen bonding and NH-π interaction between the host and the guest.

Benzimidazole conjugate of 1,1'-thiobis(2-naphthol) as switch-on fluorescence receptor for Ag+ and the complex as secondary recognition ensemble toward Cys, Asp, and Glu in aqueous methanolic solution: synthesis, characterization, ion and amino acid recognition, computational studies, and microscopy features.

A new 1,1'-thiobis(2-naphthoxy)-based receptor molecule (L) containing a benzimidazole moiety has been synthesized and characterized by (1)H NMR, ESI-MS, and elemental analysis. The selectivity of L has been explored in aqueous methanol, resulting in selective (7.5 ± 0.5)-fold switch-on fluorescence response toward Ag(+) among 14 different transition, alkali, and alkaline earth metal ions studied. The complexation of Ag(+) by L has been addressed by ESI-MS, (1)H NMR, and UV-vis spectra. Microstructural features of L and its Ag(+) complex have been measured by AFM and TEM. The morphological features of L alone and L in the presence of Ag(+) differ dramatically both in shape and size, and the ion induces the formation of chains owing to its coordinating ability toward benzimidazole. Further, the in situ [Ag(+)-L] complex was titrated against 20 naturally occurring amino acids and found that this complex acts as a secondary recognition ensemble toward Cys, Asp, and Glu by switch-off fluorescence.

Study on gelatin-silver nanoparticle composite towards the development of bio-based antimicrobial film.

Nano-scale silver particle stabilized by gelatin protein was prepared through the reduction of aqueous silver nitrate solution by sodium borohydride. Gelatin concentration was varied against a fixed concentration of silver nitrate to optimize the gelatin to metal ratio. Gelatin-protected Ag-nanoparticle was characterized by UV-VIS spectroscopy and transmission electron microscopy (TEM). All the samples exhibited similar yellow color with a characteristic plasmonic band of silver nanoparticles at 412 nm. TEM micrographs also showed the presence of nanoscale silver particles of approximately 3.9 nm. Since silver has strong bactericidal properties and at the same time relatively less toxic to human cell, silver in various forms is ideally suited for a wide range of applications in consumer, industrial and medical products The antimicrobial properties of gelatin-silver nanocomposites were tested by 'cup-plate zone of inhibition' method. The nanocomposites exhibited significant antibacterial and antifungal activity.

Carbohydrate assisted fluorescence turn-on gluco-imino-anthracenyl conjugate as a Hg(II) sensor in milk and blood serum milieu.

A new anthracenyl-imino-glucosyl conjugate (L) selectively senses Hg(2+) by turn-on fluorescence with a 13 ± 1 fold enhancement by forming a 2 : 1 complex in pH 5 to 10 even in the presence of several biologically and ecologically relevant metal ions, with a 25 ± 2% fluorescence enhancement at the EPA limit of 2 ppb. L is equally sensitive towards Hg(2+) in the presence of albumin proteins and in blood serum and milk.

Interaction of aromatic imino glycoconjugates with jacalin: experimental and computational docking studies.

Altering the lectin properties by chemically modified glycoconjugates can have profound effect on their biological applications. In the present case, jacalin has been chosen to study the binding aspects toward glycoconjugates modified by connecting aromatic moieties through imine conjugation at their C-1- or C-2-positions. Out of 10 glycoconjugates, the galactosyl-naphthyl imine (1c) was found to be most effective toward agglutination inhibition (260 times better than galactose), quenching fluorescence intensity, and exhibiting greater binding (K(a), 1.3 × 10(4)M(-1)) with jacalin. The specific binding of galactose conjugates and the nonspecific binding of other conjugates have been demonstrated based on ITC. Changes in the secondary structures have been addressed by far- and near-UV CD spectroscopy. The present studies demonstrated that galactose-based conjugates bind at carbohydrate recognition domain (CRD) mainly through polar interactions in addition to exhibiting some nonpolar/hydrophobic interactions, whereas the conjugates other than galactose primarily interact through hydrophobic interactions. Binding of galactosyl conjugates at CRD has been further demonstrated by rigid docking.

Nanofibers formed through pi...pi stacking of the complexes of glucosyl-C2-salicyl-imine and phenylalanine: characterization by microscopy, modeling by molecular mechanics, and interaction by alpha-helical and beta-sheet proteins.

This paper deals with the self-assembly of the 1:1 complex of two different amphiphiles, namely, a glucosyl-salicyl-imino conjugate (L) and phenylalanine (Phe), forming nanofibers over a period of time through pi...pi interactions. Significant enhancement observed in the fluorescence intensity of L at approximately 423 nm band and the significant decrease observed in the absorbance of the approximately 215 nm band are some characteristics of this self-assembly. Matrix-assisted laser desorption ionization/time of flight titration carried out at different time intervals supports the formation of higher aggregates. Atomic force microscopy (AFM), transmission electron microscopy, and scanning electron miscroscopy results showed the formation of nanofibers for the solutions of L with phenylalanine. In dynamic light scattering measurements, the distribution of the particles extends to a higher diameter range over time, indicating a slow kinetic process of assembly. Similar spectral and microscopy studies carried out with the control molecules support the role of the amino acid moiety over the simple -COOH moiety as well as the side chain phenyl moiety in association with the amino acid, in the formation of these fibers. All these observations support the presence of pi...pi interactions between the initially formed 1:1 complexes leading to the fiber formation. The aggregation of 1:1 complexes leading to fibers followed by the formation of bundles has been modeled by molecular mechanics studies. Thus the fiber formation with L is limited to phenylalanine and not to any other naturally occurring amino acid and hence a polymer composed of two different biocompatible amphiphiles. AFM studies carried out between the fiber forming mixture and proteins resulted in the observation that only BSA selectively adheres to the fiber among the three alpha-helical and two beta-sheet proteins studied and hence may be of use in some medical applications.

Role of the orientation of -OH groups in the sensitivity and selectivity of the interaction of M(2+) with ribosyl- and galactosyl-imino-conjugates.

Three glyco-conjugates, viz., L(1), L(2) and L(3), which differ either in their carbohydrate moiety or in their aromatic moiety or both, were synthesized and characterized and were shown to have beta-anomeric form based on (1)H NMR and optical rotation studies. Metal ion interaction studies carried out in solution by emission and absorption spectral techniques exhibited selectivity towards Cu(2+) in HEPES buffer and a two fold higher sensitivity for L(2) as compared to L(1). The composition of the complexed species has been established based on ESI MS. Dinuclear-Cu(II) complexes of all these conjugates have been synthesized and characterized based on analytical and spectral methods including FTIR, (1)H NMR, FAB MS, EPR, ORD, CD and magnetism, and the structures of and have been established based on single crystal XRD. The structures revealed subtle differences present in the orientation of the -OH groups and also their ion binding preferences both at the molecular level as well as at the lattice levels. In the dinuclear-Cu(II) complexes, while C3-O(-) of ribosyl acts as a bridging moiety in , it is the C2-O(-) of galactosyl that bridges in and the Cu(2)O(2) cores are stabilized by two intra-complex H-bond interactions formed using C4-OH in the case of and C3-OH in the case of . While the glyco-moiety is poised perpendicular to the average plane of the Cu(2)O(2) core in , this is in plane in the case of 3.

Synthesis of small atomic copper clusters in microemulsions.

We report evidence of the formation of small atomic copper clusters, Cu(n), by the microemulsion technique, and how their size can be controlled by adjusting the percentage of the reducing agent used. Copper clusters were characterized by UV-visible spectrophotometry and atomic force microscopy. Photoluminescent copper clusters, Cu(n), with n less, similar 13, can be obtained using very low percentages of the reducing agent (<10% of the stochiometric amount). Photoluminescent clusters disappear for larger percentages of reducing agent, giving rise to larger copper clusters (0.8-2.0 nm), showing a red-shift of their UV-visible absorption bands as they grow in size. Finally, by using near stoichiometric amounts, nanoparticles of 2.9 +/- 1.1 nm in size, displaying the characteristic plasmon band, can be obtained.

C(1)-/C(2)-aromatic-imino-glyco-conjugates: experimental and computational studies of binding, inhibition and docking aspects towards glycosidases isolated from soybean and jack bean.

Several C(1)-imino conjugates of D: -galactose, D: -lactose and D: -ribose, where the nitrogen center was substituted by the salicylidene or naphthylidene, were synthesized and characterized. Similar C(2)-imino conjugates of D: -glucose have also been synthesized. All the glyco-imino-conjugates, which are transition state analogues, exhibited 100% inhibition of the activity towards glycosidases extracted from soybean and jack bean meal. Among these, a galactosyl-napthyl-imine-conjugate (1c) showed 50% inhibition of the activity of pure alpha-mannosidase from jack bean at 22 +/- 2.5 microM, and a ribosyl-naphthyl-imine-conjugate (3c) showed at 31 +/- 5.5 microM and hence these conjugates are potent inhibitors of glycosidases. The kinetic studies suggested non-competitive inhibition by these conjugates. The studies are also suggestive of the involvement of aromatic, imine and carbohydrate moieties of the glyco-imino-conjugates in the effective inhibition. The binding of glyco-imino-conjugate has been established by extensive studies carried out using fluorescence emission and isothermal titration calorimetry. The conformational changes resulted in the enzyme upon interaction of these derivatives has been established by studying the fluorescence quench of the enzyme by KI as well as from the secondary structural changes noticed in CD spectra. All these studies revealed the difference in the binding strengths of the naphthylidene vs. salicylidene as well as galactosyl vs. lactosyl moieties present in these conjugates. The differential inhibition of these glyco-conjugates has been addressed by quantifying the specific interactions present between the glyco-conjugates and the enzyme by using rigid docking studies.

Thermodynamics of the interaction of globular proteins with powdered stearic acid in acid pH.

Adsorption isotherms of different globular proteins and gelatin on strearic acid particles have been studied as a function of biopolymer concentration, ionic strength of the medium, and temperature. The effect of neutral salts including CaCl2, Na3PO4, and urea on the adsorption isotherms has been also investigated. It is observed that the extent of adsorption (Gamma2(1)) increases in two steps with the increase of biopolymer concentration (C2) in the bulk. Gamma2(1) increases with an increase of C2 until a steady maximum value Gamma2(m) is reached at a critical concentration C2(m). After initial saturation, Gamma2(1) again increases from Gamma2(m) without reaching any limiting value due to the surface aggregation of the protein. The values of the standard free energy change for adsorption have been calculated on the basis of the Gibbs equation. The standard entropy and enthalpy changes are also calculated.

Nanogel formation consisting of DNA and poly(amido amine) dendrimer studied by static light scattering and atomic force microscopy.

Binding of a poly(amido amine) dendrimer with salmon testes DNA in an aqueous solution of 0.01 M NaCl at pH 6.5 has been investigated. It was shown from the physicochemical experiments of static light scattering and ultra-violet and circular dichroism spectroscopy that at a 0.2 mixing ratio of dendrimer/DNA (number ratio of NH2 groups in dendrimer vs phosphate groups in DNA) significant conformational change of the DNA occurred owing to the binding of dendrimers on the DNA chain. The dendrimer/DNA complexes formed aggregates (nanogels) when the mixing ratio was increased above 0.2. Weight-averaged molecular weight, radius of gyration, and turbidity measurements revealed that the size of the aggregates increased up to a mixing ratio of 0.8. Atomic force microscopic images certified the formation of complexes and the morphology of the nanogels.

Synthesis and characterization of nanoporous silica using dendrimer molecules.

A water soluble porogen, e.g., poly(amido amine) dendrimer, has been used as a structure-directing agent to introduce porosity of nanometer scale in silica-based nanocomposite materials. Hydrothermal synthesis was carried out at different elevated temperatures (343-413 K) in a closed teflon-lined stainless steel autoclave under autogenerated pressure. The synthesis time varied from 2 to 6 days, depending upon pH, synthesis temperature, concentration of porogen, etc. X-ray diffraction, transmission and scanning electron microscopic analyses, as well as infrared absorption spectroscopic measurements, were carried out to characterize these materials. Mostly disordered mesostructures were observed. The porous silica particles with sphere-like morphology varied from 30 to 200 nm in size were prepared depending upon the conditions of preparation. The structure and nanoporosity were preserved after the removal of structure-directing porogen through calcination at 823 K. The pore size was in the range of the dendrimer molecule as a template, indicating the structure-directing role of the terminal amino groups in the dendrimer molecule for the synthesis of nanoporous silica, since the nanoporous silica could be prepared by the hydrogen bonding or electrostatic interaction of dendrimer amino groups and tetraethyl orthosilicate.