Secondary Amine Groups Research Articles

Molecular structure, spectroscopic properties, and Hirshfeld surface analysis of chlorobis(N-methyl-1,3-propanediamine)copper(II) tetrafluoroborate and azidobis(2,2-dimethyl-1,3-propanediamine)copper(II) azide

Two new copper (II) complexes, [Cu(N-Metn)2Cl]BF4 (1) and [Cu(Me2tn)2(N3)]N3 (2) (N-Metn = N-methyl-1,3-propanediamine; Me2tn = 2,2-dimethyl-1,3-propanediamine), have been prepared, fully characterized, and their structures established by X-ray single-crystal analysis from synchrotron diffraction data. For these complexes, the Cu(II) ions are five-coordinate in an axially elongated square-pyramidal environment, with the four amine N atoms at the equatorial positions and the Cl atom (1) or N atom of one azide (2) at an apical site. The CuN bond lengths for amine N atoms in the complex 1 (2.0198(13)–2.0735(12) A°) and complex 2 (2.0239(9)–2.0489(9) Å) are typical, but the axial ligands are coordinated with a CuCl bond length of 2.5962 (7) Å for complex 1, and the CuN (azido) bond length is 2.1990 (10) Å for complex 2, adopting square-planar geometry around the Cu(II) with four N atoms from two N-Metn or Me2tn ligands. The crystals are stabilized by a three-dimensional network of intermolecular hydrogen bonds that are formed between the primary and secondary amine groups of the N-Metn ligands, the Cl ligands, and the F atoms of BF4− anion in 1, and by the primary amine groups of the Me2tn ligands and the N atoms of the azido ligand and azide ion in 2. Hirshfeld surface analysis with 2D fingerprint plots revealed that the H⋯H, F⋯H, Cl⋯H contacts in 1 and the H⋯H and N⋯H contacts in 2 are the main intermolecular interactions. The electronic absorption and IR spectral properties are also discussed.

Stable pH responsive layer-by-layer assemblies of partially hydrolysed poly(2-ethyl-2-oxazoline) and poly(acrylic acid) for effective prevention of protein, cell and bacteria surface attachment

Polyoxazolines have received increasing attention as low-fouling materials with good stability and ease of functional group incorporation. We investigated layer-by-layer (LbL) assembly of poly(2-ethyl-2-oxazoline) (PEOX) with poly(acrylic acid) (PAA) to incorporate PEOX into thin conformal coatings with controllable thicknesses ranging from the nano- to micron range. Partial hydrolysis of PEOX (to form PEOX-I) was used to introduce secondary amine groups that enable post-assembly multilayer stabilization by heat-induced crosslinking. While as-assembled multilayers dissolve in aqueous solutions at pH 5 and above, thermally crosslinked multilayers were stable against film loss and instead exhibit pH responsive swelling. The anti-fouling properties of crosslinked coatings were assessed by evaluating the resistance of PEOX-I containing multilayers to fouling by proteins, cells and bacteria. Our study of multilayers with thicknesses ranging from ∼12nm to ∼1.5μm revealed thickness dependence of surface fouling resistance to BSA. Crosslinked multilayers of ∼220nm were found to be highly effective in suppressing surface adsorption of bovine serum albumin (BSA), while thinner or thicker layers were increasingly susceptible to BSA adsorption. We further found that coatings of ∼220nm and above were all highly effective at preventing surface attachment of fibroblasts, gram-positive (S. aureus) and gram-negative (E. coli) bacteria.

Metal Complexes with a Hexadentate Macrocyclic Diamine-Tetracarbene Ligand.

A hexadentate macrocyclic N-heterocyclic carbene (NHC) ligand precursor (H4L)(PF6)4 containing four benzimidazolium and two secondary amine groups, has been synthesized and characterized. Coordination chemistry of this new macrocyclic diamine-tetracarbene ligand has been studied by the synthesis of its Ag(I), Au(I), Ni(II), and Pd(II) complexes. Reactions of (H4L)(PF6)4 with different equiv of Ag2O result in Ag(I) complexes [Ag(H2L)](PF6)3 (1) and [Ag2(H2L)](PF6)4 (2). A mononuclear Au(I) complex [Au(H2L)](PF6)3 (3) and a trinuclear Au(I) complex [Au3(H2L)(Cl)2](PF6) (4) are obtained by transmetalation of 1 and 2 with AuCl(SMe2), respectively. Reactions of (H4L)(PF6)4 with Ni(OAc)2 and Pd(OAc)2 in the presence of NaOAc yield [Ni(L)](PF6)2 (5) and [Pd(L)](PF6)2 (6), respectively, containing one Ni(II) and Pd(II) ion with distorted square-planar geometry. Using more NaOAc results in the formation of unusual dinuclear complexes [Ni2(L-2H)](PF6)2 (7) and [Pd2(L-2H)](PF6)2 (8) (L-2H = deprotonated ligand after removing two H+ ions from two secondary amine groups in L), respectively, featuring a rare M2N2 core formed by two bridging amides. 7 is also formed by the reaction of 5 with 1.0 equiv of Ni(OAc)2·4H2O in the presence of NaOAc. Transmetalation of 2 with 2.0 equiv of Ni(PPh3)2Cl2 gives [Ni2(L)(μ-O)](PF6)2 (9), the first example of a dinuclear Ni(II) complex with a singly bridging oxo group. 9 is converted to 7 in good yield through the treatment with NaOAc.

Leachable diphenylguanidine from rubber closures used in pre-filled syringes: A case study to understand solid and solution interactions with oxytocin

Leachables derived from multi-component drug-device syringe systems can result in changes to the quality of drug products. Diphenylguanidine (DPG), a leachable released from styrene butadiene rubber syringe plungers, interacts with Oxytocin to form protein-adducts. This study investigated the mechanism and kinetics of this interaction in both solid and solution states through in-vitro tests and spectroscopic methods For solid state interaction, the protein-adducts with DPG were characterized using SEM, XRD, DSC, FTIR, 13C ss NMR, and dissolution analysis. For solution state interaction, LC–HRMS was used to assess stability of Oxytocin solutions in presence of various concentrations of DPG at 25°C and 40°C for 4 weeks. Moreover, molecular docking analysis was used to identify possible molecular configurations of the interaction.Results were consistent with the formation of a new solid state with distorted surface morphology for oxytocin-DPG adducts, in which the oxytocin carbonyl group(s) and the secondary amine groups of DPG interact. This interaction was also confirmed by molecular docking analysis through hydrogen bonding (2.31Å) and Van der Waal attraction (3.14Å). Moreover, LC–HRMS analysis revealed an increase in Oxytocin stability and suppression of Oxytocin dimerization by DPG. A potential reduction in the rate of Oxytocin dissolution from the formed adducts was indicative of its strong association with DPG. Hence, the leaching potential of DPG from rubber closures and plungers should be monitored and controlled to maintain the quality and stability of the pharmaceutical product.

In-silico & In-vitro Identification of Structure-Activity Relationship Pattern of Serpentine & Gallic Acid Targeting PI3Kγ as Potential Anticancer Target.

Natural products showed anticancer activity and often induce apoptosis or autophagy in cancer cells through the PI3K/Akt/mTOR signaling pathways. The potential of natural products as PI3Ks inhibitors has been reported, which suggest PI3Ks a promising anticancer target. Phosphoinositide 3-kinase is a family of related intracellular signal transducer enzymes or lipid kinases that regulate different cellular processes involved in cancer. To identify the molecular reason behind the similar target based activity of selected shikimate pathway metabolites on PI3Kγ, a detail structure-activity relationship study was performed. In the studied work, anticancer potential of plant molecules gallic acid and serpentine was evaluated against PI3Kγ isoform and compared with wortmannin, a steroid metabolite of the fungi and a non-specific covalent known inhibitor of PI3Ks by using in-silico QSAR, docking, ADMET, chemical isolation from plant, NMR and in-vitro activity. A predictive QSAR model was developed by applying multiple linear regression which revealed identification of key structural properties regulating the inhibitory activity of serpentine and gallic acid on PI3Kγ. The model exhibited acceptable statistical parameters such as r2 0.76, r2CV 0.72, and q2 0.55. Structural elucidation was done through NMR studies. Predicted activities were further evaluated through in-vitro testing of gallic acid and serpentine targeting PI3Kγ. The identified chemical features modulating the activity were amide, amine, and secondary amine groups counts, highest occupied molecule orbital (HOMO) energy and valence connectivity index (order 2). In-silico ADME and toxicity risk assessment was done for pharmacokinetic and bioavailability compliance evaluation.

Methylation as an effective way to generate SOD-activity in copper complexes of scorpiand-like azamacrocyclic receptors

Methylation of the secondary amine groups of a scorpiand-type ligand consisting of a pyridine spacer connected through methylene groups to a tris(2-aminomethyl) unit with the pendant arm further functionalised with a 3-pyridine unit leads to a ligand whose Cu(II) complex exhibits threefold enhanced SOD activity with respect to the non-methylated ligand. Potentiometric studies indicate the formation of [CuL]2+ species with a stability three orders of magnitude lower than that formed with the related non-methylated ligand. Kinetic studies indicate that methylation of the secondary nitrogens causes a deceleration of both the complex formation and the acid-induced dissociation of the metal ion. The reduction in stability associated to the poorer σ-donor ability of the tertiary amino groups shifts the Cu(II)/Cu(I) redox potentials towards more positive values permitting a better cycling between both states needed for the dismutation of superoxide radicals.

Cationic Polypeptoids with Optimized Molecular Characteristics toward Efficient Nonviral Gene Delivery.

The rational design of gene vectors relies on the understanding of their structure-property relationship. Polypeptoids, which are structural isomers of natural polypeptides, hold great potential as gene delivery vectors due to their facile preparation, structural tunability, and most importantly, their desirable proteolytic stability. We herein designed a library of polypeptoids with different cationic side-chain terminal groups, degree of polymerizations (DPs), side-chain lengths, and incorporated aliphatic side chains, to unravel the structure-property relationships so that gene delivery efficiency can be maximized and cytotoxicity can be minimized. In HeLa cells, a polypeptoid bearing a primary amine side-chain terminal group exhibited remarkably higher transfection efficiency than that of its analogues containing secondary, tertiary, or quaternary amine groups. Elongation of the polypeptoid backbone length (from 28 to 251 mer) led to enhanced DNA condensation as well as cellular uptake levels, however it also caused higher cytotoxicity. Upon a proper balance between DNA uptake and cytotoxicity, the polypeptoid with a DP of 46 afforded the highest transfection efficiency. Elongating the aliphatic spacer between the backbone and side amine groups enhanced the hydrophobicity of the side chains, which resulted in notably increased membrane activities and transfection efficiency. Further incorporation of hydrophobic decyl side chains led to an improvement in transfection efficiency of ∼6 fold. The top-performing material identified, P11, mediated successful gene transfection under serum-containing conditions, outperforming the commercial transfection reagent poly(ethylenimine) by nearly 4 orders of magnitude. Reflecting its excellent serum-resistant properties, P11 further enabled effective transfection in vivo following intratumoral injection to melanoma-bearing mice. This study will help the rational design of polypeptoid-based gene delivery materials, and the best-performing material identified may provide a potential supplement to existing gene vectors.

One-electron oxidation of chloroquine, cymanquine, and related aminoquinolines in nonaqueous media

The anodic oxidation of a series of secondary-amine-substituted chloroquinoline derivatives, 1–5, has been studied in dichloromethane/0.05M [NBu4][B(C6F5)4]. Compounds 4 and 5 contain organometallic moieties of the cymantrene family as part of the amine group. All five compounds undergo an electrochemically irreversible one-electron oxidation. For compounds 2–4, this occurs at the secondary amine group (0.86 to 0.98V vs ferrocene). The oxidations of others occur at tertiary amines located either in the side chain of the quinoline secondary amine (1, 0.68V) or in the cyclopentadienyl ring of the cymantrene moiety (5, 0.82V). The anodic reaction products have been isolated and shown to be ring-nitrogen protonated aminochloroquinolinium ions. Abstraction of a hydrogen atom from the solvent by the putative aminochloroquinoline radical cation is thought to be responsible for formation of the protonated oxidation product. Cathodic reduction of the latter regenerates the neutral starting material in an overall chemically reversible process that mimics a simple acid/base reaction at the quinoline ring nitrogen.

Curing kinetics of epoxy cured by cardanol-based phenalkamines synthesized from different polyethylenepolyamines by Mannich reaction

Phenalkamines with different structures are expected to affect the curing reaction of epoxy, yet the exact mechanism remains to be elucidated. In this study, four cardanol-based phenalkamines (named PK1, PK2, PK3, and PK4, respectively), synthesized from ethylenediamine, diethylenetriamine, triethylenetetramine, and pentaethylenehexamine, were used as curing agents in diglycidyl ether of bisphenol A (DGEBA) epoxy system. The phenalkamines were characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and time-of-flight secondary ion mass spectrometry. The curing behaviors and kinetics were investigated by non-isothermal differential scanning calorimetry, and the activation energies of the reactions (E α ) were determined using Kissinger–Akahira–Sunose (KAS) and Starink methods. The results indicate a similar curing mechanism for all four phenalkamines. All E α values remain almost constant in the range of 0.05 ≤ α ≤ 0.6, and increase dramatically after α > 0.6 due to greater viscosity of the reaction systems. The diffusion of reactive groups plays an increasingly important role in determining the curing kinetics. In addition, DGEBA/PK1 and DGEBA/PK2 have lower initial E α values than DGEBA/PK3 and DGEBA/PK4, because PK1 and PK2 have lower viscosity than PK3 and PK4. When α is high, DGEBA/PK1 and DGEBA/PK2 have higher E α values than DGEBA/PK3 and DGEBA/PK4, because more tertiary amine groups can be formed in the reactions between the epoxy and secondary amine groups in the DGEBA/PK3 and DGEBA/PK4 systems, which catalyze the curing reaction and it thus lowers energetic barrier.

Thiourea-Based Bifunctional Ionic Liquids as Highly Efficient Catalysts for the Cycloaddition of CO2 to Epoxides

A series of thiourea-based ionic liquids (TBILs) were developed as efficient catalysts for the synthesis of cyclic carbonates by the cycloaddition of CO2 with epoxides under metal-, cocatalyst- and solvent-free conditions. Different substituted groups including electron donating and withdrawing groups were introduced onto the para-position of the aromatic ring in cation of TBILs. The effect of the catalyst structures on the reaction activity was systematically investigated. Among the ionic liquids, TBIL3 with substituted OCH3 group showed the best performance with 99% propylene oxide conversion as well as 99% propylene carbonate selectivity under mild conditions (1.5 MPa, 130 °C and 3 h) without any co-solvent. It was demonstrated that two secondary amine groups of the thiourea unit could dually activate the epoxides and CO2 and have a synergetic effect with the halide anion.

Preparation, Characterization and Properties of Alginate/Poly(γ-glutamic acid) Composite Microparticles.

Alginate (Alg) is a renewable polymer with excellent hemostatic properties and biocapability and is widely used for hemostatic wound dressing. However, the swelling properties of alginate-based wound dressings need to be promoted to meet the requirements of wider application. Poly(γ-glutamic acid) (PGA) is a natural polymer with high hydrophility. In the current study, novel Alg/PGA composite microparticles with double network structure were prepared by the emulsification/internal gelation method. It was found from the structure characterization that a double network structure was formed in the composite microparticles due to the ion chelation interaction between Ca2+ and the carboxylate groups of Alg and PGA and the electrostatic interaction between the secondary amine group of PGA and the carboxylate groups of Alg and PGA. The swelling behavior of the composite microparticles was significantly improved due to the high hydrophility of PGA. Influences of the preparing conditions on the swelling behavior of the composites were investigated. The porous microparticles could be formed while compositing of PGA. Thermal stability was studied by thermogravimetric analysis method. Moreover, in vitro cytocompatibility test of microparticles exhibited good biocompatibility with L929 cells. All results indicated that such Alg/PGA composite microparticles are a promising candidate in the field of wound dressing for hemostasis or rapid removal of exudates.

Polyethylenimine Applications in Carbon Dioxide Capture and Separation: From Theoretical Study to Experimental Work

AbstractSolid absorbents made with polyethylenimine (PEI), which is loaded on different porous substrates, are promising for postcombustion carbon dioxide capture. Herein, theoretical studies of polyamine applications, including PEI for carbon dioxide capture, are reviewed and the development of experimental work on carbon dioxide capture by using PEI summarized. The mechanisms of carbon dioxide capture are discussed at different reaction sites of the polyamines, such as primary, secondary, and tertiary amine groups. Experimental achievements in carbon dioxide capture are investigated by the incorporation of PEI with different support materials, such as mesoporous silica; nanotubes; membranes; and other materials, such as alumina, zeolite, resin, metal–organic frameworks, and glass fibers, through impregnation, grafting, and synthesis. The excellent carbon dioxide capture capacity and great stability of PEI‐impregnated nanomaterials highlight PEI as one of the greatest candidates for carbon dioxide capture from flue gas or air.

Crystallographic aspects of hydrated salts of 4,6-diaminopyrimidine with the first five dicarboxylic acids

Abstract The preparation, X-ray single-crystal structure determination and vibrational spectroscopic characterisation of five novel salts, i.e. bis(4,6-diaminopyrimidinium(1+)) oxalate tetrahydrate; 4,6-diaminopyrimidinium(1+) hydrogen malonate monohydrate; bis(4,6-diaminopyrimidinium(1+)) succinate octahydrate; bis(4,6-diaminopyrimidinium(1+)) glutarate dihydrate and bis(4,6-diaminopyrimidinium (1+)) adipate octahydrate, are presented. It is the first crystallographic study with the title cation. All the structures are centrosymmetric. The oxalate, succinate and adipate anions are situated about inversion centres in their respective structures. The dependence on the parity of the number of carbon atoms in the anions is apparent in the interplanar angles of the carboxylate or carboxylic groups. In all of the structures, there are intermolecular N–H···N, N–H···Oacid, N–H···Owater, Owater–H···Oacid and Owater–H···Owater hydrogen-bonds of moderate strength. The most common graph set motif, R 2 2(8), describes the arrangement of the involved carboxylic as well as of the primary- and secondary-amine groups. There is a growing complexity of arrangement of water molecules in the structures with longer anionic molecules. In 4,6-diaminopyrimidinium(1+) hydrogen malonate monohydrate, there is an intramolecular Oacid–H···Oacid bond, and the conformation of the hydrogen malonate ions with non-parallel carboxylic and carboxylate groups is not often observed. The structural parameters of the carboxylic or carboxylate groups in the dicarboxylic acids or their derivatives found in the Cambridge Structural Database (CSD) are compared with the title structures.

Degradation of poly(β-amino ester) gels in alcohols through transesterification: A method to conjugate drugs to polymer matrices.

Poly(β amino ester) polymers have received growing attention in the literature, owing to their ease of synthesis, versatile co-monomer selection, and highly tunable degradation kinetics. As such, they have shown extensive potential in many biomedical applications as well. In this work, it is demonstrated for the first time that PβAE polymers containing primary and secondary amine groups can undergo degradation by primary alcohols via transesterification mechanism. While this work emphasizes an important aspect of solvent compatibility of these networks, it also represents an interesting, simple mechanism for post synthesis drug incorporation, with riboflavin conjugation being demonstrated as a model compound.

Aromaticity of peri- and para-Substituted Naphthalene-1-carbaldehyde. Comparison with 1-Nitronaphthalene.

Aromaticity of the naphthalene ring substituted by formyl or nitro and secondary amine groups in peri and para positions has been investigated. HOMA (harmonic oscillator model of aromaticity) index of the naphthalene rings has been used to characterize the aromaticity of the investigated molecules. Ellipticity of C2-C3 (C6-C7) bonds, obtained by means of topological analysis of the electron density, has been used as a measure of the through-resonance effect between the para substituents. Dependence of the HOMA values on the rotation angle of formyl and nitro groups to the aromatic plane for naphthalene-1-carbaldehyde and their derivatives with dimethylamino group in para position has been analyzed. It has been shown that the nitro group has a stronger resonance effect and causes greater decrease of aromaticity than the formyl group only for planar or close to planar conformation. The attractive and repulsive peri interactions have been analyzed by using the QTAIM and NCI methods. Interrelation between the peri and para interactions has been discussed.

Exploiting biosynthetic gold nanoparticles for improving the aqueous solubility of metal-free phthalocyanine as biocompatible PDT agent

Increasing the limit of dispersion of metal-free phthalocyanine (H2Pc) in an aqueous medium using biosynthetic gold nanoparticles for photodynamic therapy (PDT) is investigated. Gold nanoparticles (Au NPs) are biosynthesized in one step using Potatoes (Solanum tuberosum) extract and are characterized by UV/VIS spectrophotometry, Fourier transformer infrared spectroscopy (FTIR), and transmission electron microscopy (TEM). The metal-free phthalocyanine is conjugated to the surface of the gold nanoparticles in a side to side regime through the secondary amine groups of H2Pc. The clear violet solution of phthalocyanine-gold (Pc-Au) nanoconjugates is investigated by UV–VIS, FTIR and TEM techniques. Disappearance of the absorption band of the secondary amine in the Pc-Au nanoconjugates compared to that of the parent H2Pc, and detection of the absorption band of H2Pc in the aqueous medium confirmed the dispersion of H2Pc and consequently the loading of H2Pc on the surface of Au NPs. The cytotoxic effect of biosynthetic gold nanoparticles and Pc-Au nanoconjugates compared to chemically synthesized gold nanoparticles on buffalo epithelial cells has been studied in vitro. Interestingly, the results showed that the biosynthetic Au NPs as well as Pc-Au nanoconjugates have no effect on buffalo epithelial cells viability, which indicating their biocompatibility contrary to the chemically synthesized Au NPs. This work will open the door, for the first time, for using H2Pc suspended in water for PDT and other phototherapeutic applications.

Synthesis, metal coordination and structural studies of trisubstituted P{CH2-1-N(H)naphthyl}3 ligands

The two-step synthesis of new naphthyl based P{CH2-1-NHC10H6(4-R)}3 ligands (R=H, L1; R=Cl, L2; R=Br, L3) by initial condensation of [P(CH2OH)4]Cl with 4equiv of 1-NH2C10H6(4-R) in EtOH, followed by reduction with tBuOK in MeOH, is described. Oxidation of L1 with elemental S or grey Se gave SP{CH2-1-NHC10H6(4-H)}3SL1 or SeP{CH2-1-NHC10H6(4-H)}3SeL1 respectively. The two-coordinate Au(I) complex [AuCl(L1)] 4 was prepared from [AuCl(tht)] (tht=tetrahydrothiophene) and one equiv. of L1 in 83% yield. Chloro-bridge cleavage of [RuCl(μ-Cl)(η6-C10H14)]2 or [IrCl(μ-Cl)(η5-Cp∗)]2 with L1, in CH2Cl2, gave the mononuclear complexes [RuCl2(η6-C10H14)L1] 5 and [IrCl2(η5-Cp∗)L1] 6 respectively. Similarly chloro-bridge cleavage of the cyclometallated compounds [Pd(μ-Cl)(κ2-C6H4CH2NMe2)]2 or [Pd(μ-Cl)(κ2-C10H6NMe2)]2 with L1–L3 gave the κ2-PN-chelate complexes [PdCl(κ2-C6H4CH2NMe2)L1–L3] (8–10) or [PdCl(κ2-C10H6NMe2)L1] 11 respectively. Reaction of two equiv. of L1–L3 with [PtCl2(cod)] (M=Pt, cod=cycloocta-1,5-diene), in CH2Cl2, afforded the complexes [MCl2(L1–L3)2] (11–13) as the cis isomers. In contrast, reaction of two equiv. of L1 with [PdCl(CH3)(cod)] gave [PdCl(CH3)(L1)2] 14 exclusively as the trans isomer. All compounds have been characterised by multinuclear NMR, FT-IR, mass spectrometry and microanalysis. Single crystal X-ray studies have been performed on compounds L1, 4, 6·CDCl3·OEt2, 8–10 and 11·CDCl3·OEt2. Intermolecular and/or intramolecular H-bonding is observed in various instances involving the secondary amine groups.

Self-Assembly of a Bile Acid Dimer in Aqueous Solutions: From Nanofibers to Nematic Hydrogels.

A mixture of a cholic acid dimer with a secondary amine group and formic acid at a molar ratio of 1/1 is regarded as an organic salt, and it self-assembles in aqueous solutions to form monodisperse nanofibers. The nanofibers are separated at low concentrations of the mixture but entangle with each other at high concentrations to form well-dispersed and randomly arranged 3D fibrous networks. Above the minimum gelation concentration of the dimer, the fibrous network is strong enough to gelate the aqueous solutions to form a hydrogel. Hydrogels obtained from the dimer salt at a lower concentration are isotropic and show extinction between crossed polarizers in the polarizing microscope, whereas they become anisotropic (i.e., nematic hydrogels) upon increasing the dimer salt concentration or under physical stirring. The parallel arrangement of nanofibers from randomly directed fibrous networks may be responsible for the formation of such nematic hydrogels.

Metal ion binding by laterally non-symmetric macrobicyclic oxa-aza cryptands.

Macrobicyclic cryptands incorporating amine groups along with oxygen donors that are laterally non-symmetric constitute an important class of organic compounds. These molecules can form inclusion complexes with different transition and main group metal ions. It is also possible to modify the binding characteristics of these compounds through attachment of different groups. Some of these metal complexes can be useful homogeneous catalysts in different organic transformations. If there are chiral centers present in the cryptands, they can be useful in asymmetric syntheses. The three secondary amine groups present in the bridges can be partially or completely derivatized with different fluorophores for fluorescence signaling of transition, inner-transition and heavy metal ions. It is also possible to sequentially attach different fluorophores to study single- as well as multi-step Förster resonance energy transfer. Different donor/acceptor groups can be attached to study second and third order optical nonlinearity. The present article describes several aspects of the chemistry of laterally non-symmetric cryptands and provides future directions for research in this area.

Synthesis and Structural Evaluation of 5-Methyl-6-acetyl Substituted Indole and Gramine.

The synthesis and crystal structures of 1-(5-methyl-1H-indol-6-yl)ethan-1-one (7), C11H11NO, and 1-3-[(dimethylamino) methyl]-5-methyl-1H-indol-6-ylethan-1-one (8), C14H18N2O, are reported. The synthesis is based on the Diels-Alder cycloaddition of a substituted 2H-pyran-2-one derivative, followed by an acid-catalyzed cyclization and concomitant deprotection (the last two steps were carried out as a one-pot domino process) yielding substituted indole 7, which was further derivatized via Mannich reaction to the gramine derivative 8. Both structures 7 and 8 were determined on the basis of IR, 1H NMR and mass spectroscopy, as well as by the elemental analysis and melting point determination. According to the single-crystal X-Ray diffraction analysis, the structure 7 has a single unique molecule in the asymmetric unit whereas the structure 8 contains four unique molecules in the asymmetric unit. Molecules 7 are linked via N-H···O hydrogen bonds between the secondary amine group and carbonyl moiety of the acetyl group of adjacent molecules, whereas molecules 8 are linked via N-H···N hydrogen bonds between the secondary and tertiary amine groups of adjacent molecules. Both structures are further stabilized by weak C-H···O, C-H···π and π···π interactions.