Liquid Crystallinity and Supramolecular Organization of Regioisomeric Isatin Derivatives: An Experimental and Theoretical Study

Spatially organized chromophores can be beneficial for advanced applications like for example, organic solar cells, laser technology or non‐linear optic devices as well as supramolecular photochemistry. Of particular interest are non‐static ordered forms of molecular organization as for example, liquid crystals. With this in mind we synthesised four new regioisomeric isatin derivatives by Suzuki–Miyaura coupling of 4‐dodecyloxyphenylboronic acid with all four possible regioisomers of bromoisatin. Liquid crystalline properties are found for 5‐(4‐dodecyloxyphenyl)isatin, while the other regioisomers do not display a mesomorphic behaviour. The synthesis, physicochemical investigations including polarization microscopy, differential scanning calorimetry and X‐ray investigations are discussed and accompanied with density functional theory calculations with respect to the target molecules and their possible H‐bonded aggregates. Two distinct setups of supramolecular assemblies for such isatin derivatives are discussed and a model for the mesophase is proposed.     

Fluorescence properties of some 2-(4-amino-substituted-3-nitrophenyl)-3-hydroxyquinolin-4(1H)-ones

2-(4-Amino-substituted-3-nitrophenyl)-3-hydroxyquinolin-4(1H)-ones have been studied to evaluate their fluorescence properties and possible use as molecular fluorescent probes. The amino group was substituted with various alkyl moieties possessing a suitable terminal functional group (such as hydroxy or amino group) that could serve to bind a 3-hydroxyquinolin-4(1H)-one (3HQ) fluorescence label to a biomolecule. Besides simple hydrocarbon chains, ligands containing ethylenoxy units as optimal spacers were also tested. The structure-fluorescence properties and theoretical applicability of the studied molecules are discussed.     

Copper(II) and lanthanoid(III) complexes of a new β-diketonate ligand with an appended non-coordinating phenol group

New mononuclear compounds of the ligand 1-(2-hydroxyphenyl)-3-phenylpropane-1,3-dione (H₂L) with Cu(II) and several lanthanoid(III) ions, where Ln(III) = Pr, Nd, Eu, Gd, have been synthesized and characterized by spectroscopic methods and X-ray crystal structure determinations. In all compounds, the ligand coordinates in a bidentate chelating manner, using the diketone function. In the [Cu(HL)₂], the coordination geometry of Cu(II) ion is slightly distorted square-planar; two strong intramolecular (OH?O) hydrogen-bonding interactions are established between the phenolate group and the neighboring ketone function. The lanthanoid(III) compounds have the general formula [Ln(HL)₃(CH₃OH)₂] · CH₃OH · 2H₂O; the lanthanoid(III) ion (Ln) is eight-coordinated and the coordination geometry is based on a distorted square-antiprism. In addition to the intramolecular hydrogen bonding (OH?O), intermolecular hydrogen-bonding interactions are also present between the coordinated methanol molecule and the non-coordinated methanol molecule giving rise to a three-dimensional network.     

Short monolithic columns for purification and fractionation of peptide samples for matrix-assisted laser desorption/ionization time-of-flight/time-of-flight mass spectrometry analysis in proteomics

This study records a novel application of methacrylate-based monolithic columns for MALDI-TOF/TOF MS analyses in proteomics for pre-concentration and separation of peptides derived from protein digestion. Reversed-phase monolithic capillary columns (30 mm × 0.32 mm i.d.) were created inside the fused silica capillary via thermal-initiated free-radical polymerization of ethylene glycol dimethacrylate and lauryl methacrylate monomers in the presence of 1-propanol and 1,4-butandiol as a porogen system. The elution of peptides was achieved using a linear gradient of acetonitrile from 0 to 60% in water with 0.1% trifluoroacetic acid formed in a microsyringe. Individual fractions of separated peptides were collected on the MALDI target spots covered with alpha-cyano-4-hydroxycinnamic acid used as a matrix and then they were analyzed using MALDI-TOF/TOF mass spectrometry. The developed method was tested with a mixture of tryptic peptides from bovine serum albumin and its applicability was also tested for tryptic in-gel digests from barley grain extracts of water soluble proteins separated using SDS gel electrophoresis. The number of detected peptides was approximately three to four times higher compared to the analysis without previous separation. These results show an improved quality of sample information with the higher amount of identified peptides which increased protein sequence coverage and improved sensitivity of mass spectrometry measurements.     

A small molecule discrimination map of the antibiotic resistance kinome

Kinase-mediated resistance to antibiotics is a significant clinical challenge. These enzymes share a common protein fold characteristic of Ser/Thr/Tyr protein kinases. We screened 14 antibiotic resistance kinases against 80 chemically diverse protein kinase inhibitors to map resistance kinase chemical space. The screens identified molecules with both broad and narrow inhibition profiles, proving that protein kinase inhibitors offer privileged chemical matter with the potential to block antibiotic resistance. One example is the flavonol quercetin, which inhibited a number of resistance kinases in vitro and in vivo. This activity was rationalized by determination of the crystal structure of the aminoglycoside kinase APH(2″)-IVa in complex with quercetin and its antibiotic substrate kanamycin. Our data demonstrate that protein kinase inhibitors offer chemical scaffolds that can block antibiotic resistance, providing leads for co-drug design.     

Preparation of flexible and elastic poly(trimethylene carbonate) structures by stereolithography

3D porous and non-porous structures are designed and prepared by stereolithography using resins based on PTMC macromers. Tough, flexible network films prepared in this manner show E moduli of ≈3.8 MPa and high elongations at break >900%; tensile strengths are ≈4.2 MPa. These values increase with increasing PTMC macromer molecular weight. To reach suitable viscosities for processing, up to 45 wt% propylene carbonate is added as non-reactive diluent. The solid specimens have compression moduli of 3.1-4.2 MPa, similar to the values determined in tensile testing. The built porous structures show porosities of 53-66% and average pore sizes of 309-407 μm. The compression moduli of the porous structures are significantly lower than those of the solid structures.     

Vibrational analysis of excited and ground electronic states of all-trans retinal protonated Schiff-bases

We report on vibrational coherence dynamics in excited and ground electronic states of all-trans retinal protonated Schiff-bases (RPSB), investigated by time-resolved Degenerate Four-Wave-Mixing (DFWM). The results show that wave packet dynamics in the excited state of RPSB consist of only low-frequency (<800 cm(-1)) modes. Such low-frequency wave packet motion is observed over a broad range of detection wavelengths ranging from excited state absorption (～500 nm) to stimulated emission (>600 nm). Our results indicate that low-frequency coherences in the excited state are not activated directly by laser excitation but rather by internal vibrational energy redistribution. This is supported by the observation that similar coherence dynamics are not observed in the electronic ground state. Challenging previous experimental results, we show that the formation of low-frequency coherence dynamics in RPSB does not require significant excess vibrational energy deposition in the excited state vibrational manifolds. Concerning ground state wave packet dynamics, we observe a set of high-frequency (>800 cm(-1)) modes, reflecting mainly single and double bond stretching motion in the retinal polyene-chain. Dephasing of these high-frequency coherences is mode-dependent and partially differs from analogous vibrational dephasing of the all-trans retinal chromophore in a protein environment (bacteriorhodopsin).     

The porosity, acidity, and reactivity of dealuminated zeolite ZSM-5 at the single particle level: the influence of the zeolite architecture

A combination of atomic force microscopy (AFM), high‐resolution scanning electron microscopy (HR‐SEM), focused‐ion‐beam scanning electron microscopy (FIB‐SEM), X‐ray photoelectron spectroscopy (XPS), confocal fluorescence microscopy (CFM), and UV/Vis and synchrotron‐based IR microspectroscopy was used to investigate the dealumination processes of zeolite ZSM‐5 at the individual crystal level. It was shown that steaming has a significant impact on the porosity, acidity, and reactivity of the zeolite materials. The catalytic performance, tested by the styrene oligomerization and methanol‐to‐olefin reactions, led to the conclusion that mild steaming conditions resulted in greatly enhanced acidity and reactivity of dealuminated zeolite ZSM‐5. Interestingly, only residual surface mesoporosity was generated in the mildly steamed ZSM‐5 zeolite, leading to rapid crystal coloration and coking upon catalytic testing and indicating an enhanced deactivation of the zeolites. In contrast, harsh steaming conditions generated 5–50 nm mesopores, extensively improving the accessibility of the zeolites. However, severe dealumination decreased the strength of the Brønsted acid sites, causing a depletion of the overall acidity, which resulted in a major drop in catalytic activity.     

Stability studies of clonazepam, diazepam, haloperidol, and doxepin with diverse polarities in an acidic environment

Stability of clonazepam, diazepam, haloperidol, and doxepin was determined in acidic solutions. In addition, determination of the kinetic and thermodynamic properties of this stability was carried out. Reaction rate constants (k), half-life times (t(0.1) and t(0.5)), and activation energy (Ea) were estimated for the drugs, which differed in polarity expressed with log P values. It was observed that estimated Ea values increased from 42.13 to 125.03 kJ/mol with an increase of lipophilicity (log P) beginning from the most hydrophilic drug (clonazepam, 2.70 log P) to the most lipophilic drug (doxepin, 4.10 log P). All degradation products were studied using an HPLC/electrospray ionization-MS technique in the positive ionization mode.