CP/MAS spectroscopy in the determination of the tautomeric forms of gossypol, its Schiff bases and hydrazones in the solid state

New Schiff bases and new hydrazones were synthesized and studied by (13)C and (15)N CP/MAS spectroscopy and by (1)H--(1)H COSY, (1)H--(13)C HMBC, (1)H--(13)C HSQC, (1)H--(15)N HMQC and (1)H--(15)N HSQC correlations. The CP/MAS investigation of gossypol has demonstrated that in the solid state it exists exclusively in the aldehyde-aldehyde tautomeric form. In contrast, CP/MAS studies of hydrazones and Schiff bases reveal that these compounds occur in the solid state in the N-imine-N-imine and enamine-enamine tautomeric forms, respectively. It is shown that the (13)C resonances of C-6, C-7 and C-11 carbon atoms are suitable for distinguishing between the tautomeric forms of aza-derivatives of gossypol in the solid state. Furthermore, we have proved that the (15)N CP/MAS spectra can be used to identify these tautomeric forms.     

X-ray,FT-IR,ESI MS and PM5 studies of Schiff base of gossypol with allylamine and its complexes with alkali metal cations and perchlorate anion

Crystals of the Schiff base derivative of gossypol with allylamine (GSBAL) were grown and subsequently examined by X-ray diffraction and FT-IR methods. The crystal space group is C2/c with a = 16.057(1) Å, b = 14.112(1) Å, c = 27.185(2) Å, β = 99.371(5)? and Z  = 8. In the crystal, GSBAL exists in the enamine–enamine tautomeric form. The FT-IR spectral features of the crystals are in agreement with the X-ray data indicating that both parts of the molecule are similarly intramolecular hydrogen-bonded but different intermolecular hydrogen-bonded, although the molecule is symmetrically substituted. On the basis of the electrospray ionization mass spectrometry (ESI MS) experiments, it has been shown for the first time that Schiff base of gossypol forms complexes with the perchlorate anion and metal cations simultaneously. The ESI MS spectra of the 1:1:1 mixtures of GSBAL:GOS:M⁺, in the positive and negative ion detection mode, have indicated the preferential formation of the 1:1 complexes of GSBAL with M⁺ (Li, Na or K) and ClO₄ ^? over the respective complexes forming between GOS and the metal cation or the anion. The PM5 semiempirical calculations have allowed visualization of the most energetically favourable structures of these two types of GSBAL complexes.     

New ferroelectric and antiferroelectric liquid crystals studied by complementary methods

Four new synthesised liquid crystalline compounds belonging to the homologous series of fluorinated biphenyl benzoate esters have been studied to compare their dielectric and electrooptic properties. Three of the studied compounds exhibited ferro- and antiferroelectric phases while one of them exhibited only one liquid crystalline phase – ferroelectric SmC*. No paraelectric phase was detected and straight transition between isotropic liquid and ferroelectric phases was observed for all studied compounds. Tilt angle for all of the studied compounds was equal to ca. 45? in the liquid crystalline phases, except temperature range close to the isotropic liquid–ferroelectric smectic phase transition. Temperature dependences of helical pitch, spontaneous polarisation and switching time have been determined. Based on XRD results, temperature dependence of the layer thickness has also been found. Only one relaxation process has been revealed in the ferroelectric as well as antiferroelectric phases, even the bias field up to 8 V/µm was applied. The dielectric and electrooptic data are discussed based on the mean-field theory predictions.     

Recognition of Chiral Carboxylates by Synthetic Receptors

Recognition of anionic species plays a fundamental role in many essential chemical, biological, and environmental processes. Numerous monographs and review papers on molecular recognition of anions by synthetic receptors reflect the continuing and growing interest in this area of supramolecular chemistry. However, despite the enormous progress made over the last 20 years in the design of these molecules, the design of receptors for chiral anions is much less developed. Chiral recognition is one of the most subtle types of selectivity, and it requires very precise spatial organization of the receptor framework. At the same time, this phenomenon commonly occurs in many processes present in nature, often being their fundamental step. For these reasons, research directed toward understanding the chiral anion recognition phenomenon may lead to the identification of structural patterns that enable increasingly efficient receptor design. In this review, we present the recent progress made in the area of synthetic receptors for biologically relevant chiral carboxylates.     

Crystal structure of 3-diethylaminomethyl-2,2′-biphenol

Crystals of 3-diethylaminomethyl-2,2′-biphenol were examined using X-ray diffraction and FT-IR spectroscopy. Their space group is P2₁/c with a=7.305(1), b=13.816(2), c=29.232(4) Å, β=92.411(3)° and Z=8. The unit cell contains two symmetry-independent zwitterions. The hydrogen atom of the protonated diethylaminomethyl group is linked to the negatively charged phenolate oxygen atom, which in turn is linked to the hydroxyl group by a short hydrogen bond (molecule a: NO=2.604(3), OO=2.512(3) Å; molecule b: NO=2.593(4), OO=2.489(4) Å). The OHO⁻H⁺N bifurcated intramolecular hydrogen bonds are crystallographically asymmetric. The IR spectrum of the crystals confirms very well the results obtained by the X-ray study. Instead of continuous absorption, only broad bands are found indicating relatively low proton polarisability in the two types of intramolecular hydrogen bonds.     

[OHO] and [NHO] hydrogen bonds in the 2:1 adduct of pentachlorophenol with 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene [(PCP)2·MTBD]

The results of X-ray diffraction and IR spectroscopic studies for 2:1 pentachlorophenol-7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene [(PCP)₂·MTBD] adduct are reported. The geometry of MTBD cations reflects the equal distribution of the positive charge among three nitrogen atoms. Short asymmetric [OHO]⁻ hydrogen bonds with OO distance of 2.508(2) Å and NH⁺O⁻ hydrogen bonds with NO distance of 2.802(2) Å are formed showing broad IR absorption with two maxima located at 1200 and 2400 cm⁻¹. The second maximum is interpreted as due to the 0→2 transition between split levels in an asymmetric double minimum potential. One of the oxygen atoms forms an additional OH–N⁺ hydrogen bonding with an MTBD cation. The situation is somewhat different in acetonitrile solution whose IR spectrum shows continuous absorption extended over whole the IR region. In acetonitrile, dissociation to free OHO⁻ and ⁺NH ions takes place and the OHO⁻ bridges become dynamically symmetric. The broadening is interpreted in terms of a stochastic distribution of the geometry and the Zundel polarizability theory.     

Synthesis and Structural Characterization of Pyridine-2,6-dicarboxamide and Furan-2,5-dicarboxamide Derivatives

Derivatives based on pyridine-2-6- and furan-2,5-dicarboxamide scaffolds reveal numerous chemical properties and biological activities. This fact makes them an exciting research topic in supramolecular and coordination chemistry and in discovering new pharmacologically-active compounds. This work aimed to obtain a series of symmetrical pyridine-2-6- and furan-2,5-dicarboxamides through a condensation reaction of the appropriate acyl chlorides and aromatic amides. Successful syntheses were confirmed with NMR spectroscopy. We solved their crystal structures for seven compounds; two pyridine and five furan derivatives. Based on our crystallographic studies, we were able to indicate supramolecular features of the crystals under investigation. Additionally, Hirshfeld surface analysis allowed us to calculate a distribution of intermolecular contacts in the dicarboxamide crystals.     

H-Bond Mediated Phase-Transfer Catalysis: Enantioselective Generating of Quaternary Stereogenic Centers in β-Keto Esters

In this work, we would like to present the development of a highly optimized method for generating the quaternary stereogenic centers in β-keto esters. This enantioselective phase-transfer alkylation catalyzed by hybrid Cinchona catalysts allows for the efficient generation of the optically active products with excellent enantioselectivity, using only 1 mol% of the catalyst. The vast majority of phase-transfer catalysts in asymmetric synthesis work by creating ionic pairs with the nucleophile-attacking anionic substrate. Therefore, it is a sensible approach to search for new methodologies capable of introducing functional groups into the precursor’s structure, maintaining high yields and enantiomeric purity.     

Influence of Nanocellulose Structure on Paper Reinforcement

This article describes how crystalline or fibrous nanocellulose influences the mechanical properties of paper substrate. In this context, we used commercially available cellulose nanocrystals, mechanically prepared cellulose nanofibers dispersed in water or ethanol, and carboxy cellulose nanofibers. Selective reinforcement of the paper treated with the nanocellulose samples mentioned above was observed. The change in the fibre structure was assessed using scanning electron microscopy, roentgenography, and spectroscopy techniques. In addition, the effect of nanocellulose coating on physical properties was evaluated, specifically tensile index, elongation coefficient, Elmendorf tear resistance, Bendtsen surface roughness, Bendtsen air permeability, and bending strength. It can be concluded that the observed decrease in the strength properties of the paper after applying some NC compositions is due to the loss of potential disturbances in hydrogen bonds between the nanocellulose dispersed in ethanol and the paper substrate. On the other hand, significantly increased strength was observed in the case of paper reinforced with nanocellulose functionalized with carboxyl groups.     

Controlling the fluorescence quantum yields of benzothiazole-difluoroborates by optimal substitution

Precise tuning of the fluorescence quantum yield, vital for countless applications of fluorophores, remains exceptionally challenging due to numerous factors affecting energy dissipation phenomena often leading to its counterintuitive behavior. In contrast to the absorption and emission wavelength which can be precisely shifted to the desired range by simple structural changes, no general strategy exists for controllable modification of the fluorescence quantum yield. The rigidification of the molecular skeleton is known to usually enhance the emission and can be practically realized via the limiting molecular vibrations by aggregation. However, the subtle balance between the abundant possible radiative and non-radiative decay pathways makes the final picture exceptionally sophisticated. In the present study, a series of nine fluorophores obtained by peripheral substitution with two relatively mild electron donating and electron withdrawing groups are reported. The obtained fluorescence quantum yields range from dark to ultra-bright and the extreme values are obtained for the isomeric molecules. These severe changes in emission efficiency have been shown to arise from the complex relationship between the Franck–Condon excited state and conical intersection position. The experimental findings are rationalized by the advanced quantum chemical calculations delivering good correlation between the measured emission parameters and theoretical radiative and internal conversion rate constants. Therefore, the described substituent exchange provides a method to rigorously adjust the properties of molecular probes structurally similar to thioflavin T.

A full palette of FQY (form ca. 0 to 98%) was covered by exchanging two groups in a series of nine compounds. The darkest (OMe/CF₃) and brightest (CF₃/OMe) are isomers. All experimental data are supported by TD-DFT calculations.