Fluorescent Rotary Switches: Four- vs Three-Substituted Phthalimide Boron Difluoride Schiff Base Complexes.

The influence of the substitution pattern in phthalimide boron difluoride Schiff base complexes as fluorescent molecular rotors has been investigated. Due to their ground-state zwitterionic structures, they have exhibited negative solvatochromism in absorption and blue-green emission with moderate to satisfactory photoluminescence quantum yields in solution. Ground-state and excited-state theoretical calculations and time-resolved emission spectroscopy revealed that the excited-state rotation is triggered by planar-induced charge transfer, resulting in switched emission toward the green region. Fluorescence lifetime measurements and species-associated emission spectra exhibited two emitting excited species in equilibrium via a planar transition-state barrier. The substitution pattern models showed different behavior in solid-state mechanochromic switching and were analyzed by subcell unit packing obtained from X-ray structure data. We have attempted to gain in-depth insight into the fluorescence mechanism and photoluminescence properties associated with the substitution pattern of the phthalimide motif in order to understand the structure-property-function relationship.

Haloalkalitolerant Fungi from Sediments of the Big Tambukan Saline Lake (Northern Caucasus): Diversity and Antimicrobial Potential.

We have performed a characterization of cultivated haloalkalitolerant fungi from the sediments of Big Tambukan Lake in order to assess their biodiversity and antimicrobial activity. This saline, slightly alkaline lake is known as a source of therapeutic sulfide mud used in sanatoria of the Caucasian Mineral Waters, Russia. Though data on bacteria and algae observed in this lake are available in the literature, data on fungi adapted to the conditions of the lake are lacking. The diversity of haloalkalitolerant fungi was low and represented by ascomycetes of the genera Acremonium, Alternaria, Aspergillus, Chordomyces, Emericellopsis, Fusarium, Gibellulopsis, Myriodontium, Penicillium, and Pseudeurotium. Most of the fungi were characterized by moderate alkaline resistance, and they tolerated NaCl concentrations up to 10% w/v. The analysis of the antimicrobial activity of fungi showed that 87.5% of all strains were active against Bacillus subtilis, and 39.6% were also determined to be effective against Escherichia coli. The majority of the strains were also active against Aspergillus niger and Candida albicans, about 66.7% and 62.5%, respectively. These studies indicate, for the first time, the presence of polyextremotolerant fungi in the sediments of Big Tambukan Lake, which probably reflects their involvement in the formation of therapeutic muds.

Solvent-Triggered Long-Range Proton Transport in 7-Hydroxyquinoline Using a Sulfonamide Transporter Group.

The ability of long-range proton transport by substitution of 7-hydroxyquinoline at the eighth position with sulfonamide and sulfonylhydrazone rotor units to act as a crane-arm has been studied. Different proton transport pathways triggered by different stimuli have been established depending on the structure of the crane-arms. Solvent-driven proton switching from OH to the quinoline nitrogen (Nquin) site, facilitated by a sulfonamide transporter group in polar protic and aprotic solvents, has been confirmed by optical (absorption and fluorescence) and NMR spectroscopies as well as by single-crystal X-ray structure analysis. Photoinduced long-range proton transport to the Nquin site upon 340 nm UV light irradiation has been estimated in sulfonylhydrazone, which is not sensitive to solvent-driven switching. Both compounds have exhibited acid-triggered switching by trifluoroacetic acid due to the formation of a stable six-membered intramolecular hydrogen bonding interaction between the protonated Nquin and crane-arm. The structures of acid-switched form were confirmed by NMR spectroscopy and single-crystal X-ray structure analysis. The behavior of the compounds suggests a big step forward in the advanced proton pump-switching architecture because they cover three distinct driving forces in the switching process: solvent, light, and acid.

Complex Activity and Sensor Potential toward Metal Ions in Environmental Water Samples of N-Phthalimide Azo-Azomethine Dyes.

Herein, the spectral and electrochemical characterizations of three different substituted N-phthalimide azo-azomethine (NAA) dyes (L) containing an o-hydroxy group and their NAA-M(II) chelates [M(II): Cu, Ni, Co, Pb] were reported by using UV-Vis and fluorescence spectroscopy and potentiometric and voltamperometric techniques. The pK value of the dyes as well as the stoichiometry and stability of the NAA-metal chelates were studied, and the stoichiometry was found to be mostly 1:2 (ML2) with high complex stability constant values. The sensor activity of N-phthalimide azo-azomethine derivatives toward pH and metal ions has been also investigated and tested for indicator application in acid-base analysis and detection of Cu(II) ions in real samples of surface river water using voltamperometric detection. The results showed that one of the ligands possesses the highest electrochemical response upon binding to copper ions and could be successfully used in the analysis of copper in water at a concentration range of the analyte from 3.7 × 10-7 to 5.0 × 10-6 mol L-1, with analytical characteristics of the method being Sr = 1.5%, LOD = 3.58 µg L-1 and LOQ =11.9 µg L-1.

Conservative and Atypical Ferritins of Sponges.

Ferritins comprise a conservative family of proteins found in all species and play an essential role in resistance to redox stress, immune response, and cell differentiation. Sponges (Porifera) are the oldest Metazoa that show unique plasticity and regenerative potential. Here, we characterize the ferritins of two cold-water sponges using proteomics, spectral microscopy, and bioinformatic analysis. The recently duplicated conservative HdF1a/b and atypical HdF2 genes were found in the Halisarca dujardini genome. Multiple related transcripts of HpF1 were identified in the Halichondria panicea transcriptome. Expression of HdF1a/b was much higher than that of HdF2 in all annual seasons and regulated differently during the sponge dissociation/reaggregation. The presence of the MRE and HRE motifs in the HdF1 and HdF2 promotor regions and the IRE motif in mRNAs of HdF1 and HpF indicates that sponge ferritins expression depends on the cellular iron and oxygen levels. The gel electrophoresis combined with specific staining and mass spectrometry confirmed the presence of ferric ions and ferritins in multi-subunit complexes. The 3D modeling predicts the iron-binding capacity of HdF1 and HpF1 at the ferroxidase center and the absence of iron-binding in atypical HdF2. Interestingly, atypical ferritins lacking iron-binding capacity were found in genomes of many invertebrate species. Their function deserves further research.

Acylhydrazone Subunits as a Proton Cargo Delivery System in 7-Hydroxyquinoline.

The reimagined concept of long-range tautomeric proton transfer using crane subunits is shown by designing and synthesising two new acylhydrazones containing a 7-hydroxyquinoline (7-OHQ) platform. The acylhydrazone subunits attached to the 7-OHQ at the 8th position act as crane arms for delivering proton cargo to the quinoline nitrogen. Light-induced tautomerization to their keto forms leads to Z/E isomerization of the C=C axle bond, followed by proton delivery to the quinoline nitrogen by the formation of covalent or hydrogen bonds. The axle's being either an imine or ketimine bond is the structural difference between the studied compounds. The -CH3 group in the latter provides steric strain, resulting in different proton transport pathways. Both compounds show long thermal stability in the switched state, which creates a tuneable action of bidirectional proton cargo transport by using different wavelengths of irradiation. Upon the addition of acid, the quinoline nitrogen is protonated; this results in E/Z configuration switching of the acylhydrazone subunits. This was proven by single-crystal X-ray structure analysis and NMR spectroscopy.

A single isomer rotary switch demonstrating anti-Kasha behaviour: Does acidity function matter?

A novel rotary switch, overcoming the disadvantages of hydrazone based switches with competitive proton acceptor sub-rotors, has been designed. The new compound contains a pyridyl ring and a COOH group as sub-rotors, which provides engagement of the pyridyl nitrogen atom and leads to the existence of a single isomer in the ground state. The availability of acidic functionality in the rotor creates conditions for excited state intramolecular proton transfer (ESIPT), which exhibits anti-Kasha behavior.

Tautomeric influence on the photoinduced birefringence of 4-substituted phthalimide 2-hydroxy Schiff bases in PMMA matrix.

The photoinduced birefringence of two 4-substituted phthalimide 2-hydroxy Schiff bases, containing salicylic (4) and 2-hydroxy-1-naphthyl (5) moieties has been investigated in PMMA matrix. Their optical behaviour as nanocomposite films was revealed by combined use of DFT quantum chemical calculations (in ground and excited state) and experimental optical spectroscopy (UV-Vis and fluorescence). The results have shown that solid-state reversible switching takes place by enol/keto tautomerization and Z/E isomerization. Birefringence study was performed in the PMMA nanocomposite films using pump lasers at λrec = 355 nm and λrec = 442 nm. Fast response time and high stability of anisotropy up to 58% for (4) and 95% for (5) after turning off the excitation laser, was observed, which makes these materials appropriate candidates for cutting-edge optical information technology materials. The possibility for multiple cycles of recording, reading and optical erasure of the photoinduced birefringence at λrec = 442 nm in 5 has been demonstrated. The obtained results have shown that the maximum value of the measured birefringence is close to the anisotropic characteristics of the most frequently used azo materials.

8-(Pyridin-2-yl)quinolin-7-ol as a Platform for Conjugated Proton Cranes: A DFT Structural Design.

Theoretical design of conjugated proton cranes, based on 7-hydroxyquinoline as a tautomeric sub-unit, has been attempted by using ground and excited state density functional theory (DFT) calculations in various environments. The proton crane action request existence of a single enol tautomer in ground state, which under excitation goes to the excited keto tautomer through a series of consecutive excited-state intramolecular proton transfer (ESIPT) steps with the participation of the crane sub-unit. A series of substituted pyridines was used as crane sub-units and the corresponding donor-acceptor interactions were evaluated. The results suggest that the introduction of strong electron donor substituents in the pyridine ring creates optimal conditions for 8-(pyridin-2-yl)quinolin-7-ols to act as proton cranes.

Indirect solvent assisted tautomerism in 4-substituted phthalimide 2-hydroxy-Schiff bases.

The paper presents the synthesis and characterization of two 4-substituted phthalimide 2-hydroxy-Schiff bases containing salicylic (4) and 2-hydroxy-1-naphthyl (5) moieties. The structural differences of 2-hydroxyaryl substituents, resulting in different enol/keto tautomeric behaviour, depending on the solvent environment were studied by absorption UV-Vis spectroscopy. Compound 5 is characterized by a solvent-dependent tautomeric equilibrium (KT in toluene = 0.12, acetonitrile = 0.22 and MeOH = 0.63) while no tautomerism is observed in 4. Ground state theoretical DFT calculations by using continuum solvation in MeOH indicate an energy barrier between enol/keto tautomer 5.6 kcal mol-1 of 4 and 0.63 kcal mol-1 of 5, which confirms the experimentally observed impossibility of the tautomeric equilibrium in the former. The experimentally observed specific solvent effect in methanol is modeled via explicit solvation. The excited state intramolecular proton transfer (ESIPT) was investigated by steady state fluorescence spectroscopy. Both compounds show a high rate of photoconversion to keto tautomers hence keto emissions with large Stokes shifts in five alcohols (MeOH, EtOH, 1-propanol, 1-butanol, and 1-pentanol) and various aprotic solvents (toluene, dichlormethane, acetone, AcCN). According to the excited state TDDFT calculations using implicit solvation in MeOH, it was found that enol tautomers of 4 and 5 are higher in energy compared to the keto ones, which explains the origin of the experimentally observed keto form emission.

Correction: Iron metabolic pathways in the processes of sponge plasticity.

[This corrects the article DOI: 10.1371/journal.pone.0228722.].

Iron metabolic pathways in the processes of sponge plasticity.

The ability to regulate oxygen consumption evolved in ancestral animals and is intrinsically linked to iron metabolism. The iron pathways have been intensively studied in mammals, whereas data on distant invertebrates are limited. Sea sponges represent the oldest animal phylum and have unique structural plasticity and capacity to reaggregate after complete dissociation. We studied iron metabolic factors and their expression during reaggregation in the White Sea cold-water sponges Halichondria panicea and Halisarca dujardini. De novo transcriptomes were assembled using RNA-Seq data, and evolutionary trends were analyzed with bioinformatic tools. Differential expression during reaggregation was studied for H. dujardini. Enzymes of the heme biosynthesis pathway and transport globins, neuroglobin (NGB) and androglobin (ADGB), were identified in sponges. The globins mutate at higher evolutionary rates than the heme synthesis enzymes. Highly conserved iron-regulatory protein 1 (IRP1) presumably interacts with the iron-responsive elements (IREs) found in mRNAs of ferritin (FTH1) and a putative transferrin receptor NAALAD2. The reaggregation process is accompanied by increased expression of IRP1, the antiapoptotic factor BCL2, the inflammation factor NFκB (p65), FTH1 and NGB, as well as by an increase in mitochondrial density. Our data indicate a complex mechanism of iron regulation in sponge structural plasticity and help to better understand general mechanisms of morphogenetic processes in multicellular species.

Synthesis, characterization and anticonvulsant activity of new azobenzene-containing VV-hemorphin-5 bio photoswitch.

A novel analog of VV-hemorphin-5 containing azobenzene moiety has been synthesized and investigated for anticonvulsant activity in relation to its E → Z photophysical properties activated by long wavelength light at 365 nm. The synthesis was achieved by a modified SPPS by Fmoc-dimerization strategy. The electrochemical behavior before and after UV illumination was investigated using different voltammetric modes. The number of electrons transferred, heterogenic rate constant and diffusion coefficient for E- and Z-isomers were also evaluated. Revealing the governing principles involved in signaling and nerve pulse propagation requires the detailed characterization of the electrical properties of cell membranes. For probing the effect of synthesized azo-peptide on the membrane electrical properties, we measured the specific capacitance of lipid bilayers, representing a basic physical model of biomembranes with their simple reproducibility in laboratory conditions at controlled membrane composition and physicochemical parameters of the surrounding aqueous medium. Our results have shown reduced membrane capacitance in the presence of the azo-peptide, thus providing evidences for possible alterations in the dielectric permittivity of the bilayer. The (Val-Val-Tyr-Pro-Trp-Thr-Gln)2Azo peptide was explored also in vivo for preliminary anticonvulsant activity by using the 6-Hz seizure test and pentylenetetrazol (PTZ) seizure test in mice. The Z-isomer has exhibited higher potency compared to E-isomer most pronouncedly in the 6 Hz test for psychomotor seizures where the compound had activity at all three tested doses. It was found that the Z-isomer decrease the latency for onset of clonic seizures induced by PTZ. These results demonstrate that the Z-isomer deserves further evaluation in other screening tests for anticonvulsant activity.

Synthesis and photochromic properties of some N-phthalimide azo-azomethine dyes. A DFT quantum mechanical calculations on imine-enamine tautomerism and trans-cis photoisomerization.

This paper presents synthesis, photophysical characterization and quantum mechanical calculations of some N-phthalimide azo-azomethine dyes. The dyes were synthesized via azo coupling reaction between 2,4-substituted aromatic anilines and salicylic aldehyde followed by condensation reactions between azo dyes and N-aminophtalimide. Quantum chemical calculations to optimise the molecular geometry and to determine the electron densities of the trans (E) imine ⇌ enamine and the cis (Z) imine ⇌ enamine isomers and their vibrational frequencies have been computed by using DFT at B3LYP/6-31 + G(d,p) level of theory in vacuo. The effect of the used DMF solvent on the molecular structure and bond energies has been determined by using the IEFPCM model. Thermodynamic parameters such as total electronic energy E(RB3LYP), enthalpy H298 (sum of electronic and thermal enthalpies), free Gibbs energy G298 (sum of electronic and thermal free Gibbs energies) and dipole moment µ were computed in order to estimate the ΔE, Δµ, ΔH, ΔG and ΔS values. The NBO analysis was performed in order to understand the intramolecular charge transfer and the energy of resonance stabilization. After molecular geometry optimization, the electronic spectra were obtained by TD-DFT calculations at the above mentioned basis set using the IEFPCM model of DMF as a solvent. The solvatochromic effect of the dyes in four solvents with different polarity has been studied by UV-VIS spectroscopy and compared with the theoretically predicted. The coincidence between measured and calculated spectra is satisfactory. The dynamic photoisomerization experiments were performed in DMF under irradiation with UV light at λ = 365 nm (mostly E → Z) and with VIS light at λ = 400-800 nm (mostly Z → E). The spectra were recorded in the spectral region from 300 to 800 nm at identical sample concentrations of the three dyes and illumination times in order to investigate the photodynamical E → Z → E conversion of the NN chromophore group of the dyes as well as the imine ⇌ enamine tautomerization.

Synthesis, spectroscopic and TD-DFT quantum mechanical study of azo-azomethine dyes. A laser induced trans-cis-trans photoisomerization cycle.

This paper describes the synthesis, spectroscopic characterization and quantum mechanical calculations of three azo-azomethine dyes. The dyes were synthesized via condensation reaction between 4-(dimethylamino)benzaldehyde and three different 4-aminobenzene azo dyes. Quantum chemical calculations on the optimized molecular geometry and electron densities of the trans (E) and cis (Z) isomers and their vibrational frequencies have been computed by using DFT/B3LYP density-functional theory with 6-311++G(d,p) basis set in vacuo. The thermodynamic parameters such as total electronic energy E (RB3LYP), enthalpy H298 (sum of electronic and thermal enthalpies), free Gibbs energy G298 (sum of electronic and thermal free Gibbs energies) and dipole moment µ were computed for trans (E) and cis (Z) isomers in order to estimate the ΔEtrans→cis, Δµtrans→cis,ΔHtrans→cis, ΔGtrans→cis and ΔStrans→cis values. After molecular geometry optimization the electronic spectra have been obtained by TD-DFT calculations at same basis set and correlated with the spectra of vapour deposited nanosized films of the dyes. The NBO analysis was performed in order to understand the intramolecular charge transfer and energy of resonance stabilization. Solvatochromism was investigated by UV-VIS spectroscopy in five different organic solvents with increasing polarity. The dynamic photoisomerization experiments have been performed in DMF by pump lasers λ=355nm (mostly E→Z) and λ=491nm (mostly Z→E) in spectral region 300nm - 800nm at equal concentrations and times of illumination in order to investigate the photodynamical trans-cis-trans properties of the CHN and NN chromophore groups of the dyes.

Synthesis, structure, spectral properties and DFT quantum chemical calculations of 4-aminoazobenzene dyes. Effect of intramolecular hydrogen bonding on photoisomerization.

In this paper three different "push-pull" 4-aminoazobenzene dyes have been synthesized in order to characterize their photochromic behavior in different solvents. The molecular geometry was optimized by DFT/B3LYP functional combined with the standard 6-31+G(d,p) basis set for trans (E) and cis (Z) isomers and the energy levels of HOMO and LUMO frontier orbitals were computed using IEFPCM solvation in CHCl3 and DMF. The calculated results were compared to the experimental optical band gap and HOMO values of cyclic voltammetry. The intramolecular six-membered hydrogen bond was formed in both isomers of the synthesized dyes. The thermodynamic parameters such as total electronic energy E (RB3LYP), enthalpy H298 (sum of electronic and thermal enthalpies), free Gibbs energy G298 (sum of electronic and thermal free Gibbs energies) and dipole moment µ were computed for trans (E) and cis (Z) isomers in order to estimate the ΔEtrans→cis, Δµtrans→cis, ΔHtrans→cis, ΔGtrans→cis and ΔStrans→cis values. The NBO analysis was performed in order to understand the intramolecular charge transfer and energy of resonance stabilization. The solvatochromic shift was evaluated by UV-VIS spectroscopy in CHCl3 (nonpolar), EtOH (polar protic) and DMF (polar aprotic) solvents to determine the electron withdrawing and donating properties of the substituents on electron transitions energy. Through the increasing solvent polarity a strong bathochromic shift is observed. The photoisomerization experiments have been performed in two solvents CHCl3 (nonpolar) and DMF (polar aprotic) by UV light irradiation with λ=365nm at equal concentrations and time of illuminations. The electronic spectra were computed by TD-DFT after geometry optimization using IEFPCM solvation in CHCl3 and DMF. The degree of photoisomerization was calculated for the three azo chromophores in both solvents. By using first derivative of the UV-VIS spectra it was possible to resolve the overlapped electron transitions absorption bands. The existing intramolecular hydrogen bond in the azo chromophores was discussed in relation to the isomerization mechanisms and relative stability of the cis (Z) isomers.

Spectroscopic investigation of different concentrations of the vapour deposited copper phthalocyanine as a "guest" in polyimide matrix.

Nanocomposite layers 250 nm copper phthalocyanine/polyimide prepared by simultaneous vapour deposition of three different sources were studied. Different concentrations of copper phthalocyanine as a "guest" in polyimide matrix as a function of conditions of the preparation have been determined by FTIR (Fourier Transform Infrared) and UV-VIS (Ultraviolet-Visible) spectroscopies. The aim was to estimate the possibility of the spectroscopic methods for quantitative determination of the "guest" and compare with the quality of the polyimide thin films in relation to the "guest" concentration. The band at 1334 cm(-1) has been used for quantitative estimation of "guest" in polyimide matrix. The concentrations of the copper phthalocyanine less than 20% require curve fitting techniques with Fourier self deconvolution. The relationship between "guest" concentrations and degree of imidization, as well as the electronic UV-VIS spectra are discussed in relation to the composition, imidization degree and the two crystallographic modification of the embedded chromophore.