scholarly journals Controlling J-Aggregates Formation and Chirality Induction through Demetallation of a Zinc(II) Water Soluble Porphyrin

2020 ◽  
Vol 21 (11) ◽  
pp. 4001 ◽  
Author(s):  
Ilaria Giuseppina Occhiuto ◽  
Maria Angela Castriciano ◽  
Mariachiara Trapani ◽  
Roberto Zagami ◽  
Andrea Romeo ◽  
...  
Keyword(s):  
Ionic Strength ◽  
Supramolecular Assembly ◽  
Structural Features ◽  
Cotton Effect ◽  
Resonance Light Scattering ◽  
Water Soluble ◽  
Complete Analysis ◽  
Coupling Mechanism ◽  
Extinction Time ◽  
J Aggregates

Under acidic conditions and at high ionic strength, the zinc cation is removed from its metal complex with 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4) thus leading to the diacid free porphyrin, that subsequently self-organize into J-aggregates. The kinetics of the demetallation step and the successive supramolecular assembly formation have been investigated as a function of pH and ionic strength (controlled by adding ZnSO4). The demetallation kinetics obey to a rate law that is first order in [ZnTPPS4] and second order in [H+], according to literature, with k2 = 5.5 ± 0.4 M−2 s−1 at 298 K (IS = 0.6 M, ZnSO4). The aggregation process has been modeled according to an autocatalytic growth, where after the formation of a starting seed containing m porphyrin units, the rate evolves as a power of time. A complete analysis of the extinction time traces at various wavelengths allows extraction of the relevant kinetic parameters, showing that a trimer or tetramer should be involved in the rate-determining step of the aggregation. The extinction spectra of the J-aggregates evidence quite broad bands, suggesting an electronic coupling mechanism different to the usual Frenkel exciton coupling. Resonance light scattering intensity in the aggregated samples increases with increasing both [H+] and [ZnSO4]. Symmetry breaking occurs in these samples and the J-aggregates show circular dichroism spectra with unusual bands. The asymmetry g-factor decreases in its absolute value with increasing the catalytic rate kc, nulling and eventually switching the Cotton effect from negative to positive. Some inferences on the role exerted by zinc cations on the kinetics and structural features of these nanostructures have been discussed.

scholarly journals Kinetic Investigation on Tetrakis(4-Sulfonatophenyl)Porphyrin J-Aggregates Formation Catalyzed by Cationic Metallo-Porphyrins

Molecules ◽  
2020 ◽  
Vol 25 (23) ◽  
pp. 5742
Author(s):  
Ilaria Giuseppina Occhiuto ◽  
Roberto Zagami ◽  
Mariachiara Trapani ◽  
Maria Angela Castriciano ◽  
Andrea Romeo ◽  
...  
Keyword(s):  
Rate Constants ◽  
Cotton Effect ◽  
Resonance Light Scattering ◽  
Aggregation Kinetics ◽  
Extinction Time ◽  
Negative Cotton Effect ◽  
Metal Derivatives ◽  
J Aggregates ◽  
Derivatives Of

Under mild acidic conditions, various metal derivatives of tetrakis(4-N-methylpyridinium)porphyrin (gold(III), AuT4; cobalt(III), CoT4; manganese(III), MnT4 and zinc(II), ZnT4) catalytically promote the supramolecular assembling process of the diacid 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4) into J-aggregates. The aggregation kinetics have been treated according to a well-established model that involves the initial formation of a critical nucleus containing m porphyrin units, followed by autocatalytic growth, in which the rate evolves as a power of time. An analysis of the extinction time traces allows to obtain the rate constants for the auto-catalyzed pathway, kc, and the number of porphyrins involved in the initial seeding. The aggregation kinetics have been investigated at fixed H2TPPS4 concentration as a function of the added metal derivatives MT4. The derived rate constants, kc, obey a rate law that is first order in [MT4] and depend on the specific nature of the catalyst in the order AuT4 > CoT4 > MnT4 > ZnT4. Both resonance light scattering (RLS) intensity and extinction in the aggregated samples increase on increasing [MT4]. With the exception of AuT4, the final aggregated samples obtained at the highest catalyst concentration exhibit a negative Cotton effect in the J-band region, evidencing the occurrence of spontaneous symmetry breaking. The role of the nature of the metal derivative in terms of overall charge and presence of axial groups will be discussed.

scholarly journals Effects of the Mixing Protocol on the Self-Assembling Process of Water Soluble Porphyrins

2021 ◽  
Vol 22 (2) ◽  
pp. 797
Author(s):  
Maria Angela Castriciano ◽  
Sergio Cardillo ◽  
Roberto Zagami ◽  
Mariachiara Trapani ◽  
Andrea Romeo ◽  
...  
Keyword(s):  
Alternative Pathway ◽  
Ion Pairs ◽  
Resonance Light Scattering ◽  
Water Soluble ◽  
Self Assembling ◽  
Vis Spectroscopy ◽  
Acidic Conditions ◽  
J Aggregates ◽  
Kinetics Of ◽  
Tartrate Anion

The hierarchical self-assembling kinetics of the porphyrin 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS44−) into J-aggregates at high ionic strength under acidic conditions and eventually in the presence of an added chiral templating agent (tartrate) were investigated through UV/Vis spectroscopy, resonance light scattering, and circular dichroism (CD). The effect of changing the mixing order of the various components in the solution on the kinetic parameters and the expression of chirality on the final J-aggregates was evaluated. In this latter case, only when the chiral tartrate anion is premixed with the porphyrin, the resulting nano-architectures exhibit CD spectra that reflect the handedness of the chiral inducer. We discuss a general mechanistic scheme, with the involvement of ion pairs or dimers that offer an alternative pathway to the aggregation process.

THE WATER-SOLUBLE POLYSACCHARIDES OF DERMATOPHYTES: IV. GALACTOMANNANS I FROM TRICHOPHYTON GRANULOSUM, TRICHOPHYTON INTERDIGITALE, MICROSPORUM QUINCKEANUM, TRICHOPHYTON RUBRUM, AND TRICHOPHYTON SCHÖNLEINII

1965 ◽  
Vol 43 (1) ◽  
pp. 30-39 ◽  
Author(s):  
C. T. Bishop ◽  
M. B. Perry ◽  
F. Blank ◽  
F. P. Cooper
Keyword(s):  
Aqueous Solutions ◽  
Copper Complexes ◽  
Trichophyton Rubrum ◽  
Periodate Oxidation ◽  
Structural Features ◽  
Water Soluble ◽  
Major Constituent ◽  
Branch Points ◽  
Terminal Units ◽  
Hydrolysis Of

A group of polysaccharides, called galactomannans I, were precipitated as their insoluble copper complexes from aqueous solutions of the crude polysaccharides obtained from each of the organisms designated in the title. The five galactomannans I were homogeneous under conditions of electrophoresis and ultracentrifugation and had high positive specific rotations. The major constituent monosaccharide was D-mannose; amounts of D-galactose ranged from nil for the polysaccharide from T. rubrum to 13% for that from T. schönleinii. Methylation and hydrolysis of the five galactomannans I yielded varying amounts of the following: 2,3,5,6-tetra-O-methyl-D-galactose (not present in the products from T. rubrum), 2,3,4,6-tetra-O-methyl-D-mannose, 2,3,4-tri-O-methyl-D-mannose, 2,4,6-tri-O-methyl-D-mannose, 3,4-di-O-methyl-D-mannose, and 3,5-di-O-methyl-D-mannose. Periodate oxidation results agreed with the methylation studies. The gross structural features of each galactomannan I appear to be the same, namely, a basic chain of 1 → 6 linked α-D-mannopyranose units for approximately every 22 of which there is a 1 → 3 linked α-D-mannopyranose residue. Branch points occur along the 1 → 6 linked chain at the C2 positions of the D-mannopyranose units and once in every 45 units at the C2 position of a 1 → 6 linked D-mannofuranose residue. The D-galactose in the polysaccharides is present exclusively as non-reducing terminal furanose units; non-reducing terminal units of D-mannopyranose are also present. The variations in the identities and relative amounts of the non-reducing terminal units were the only apparent differences in the gross structural features within this group of polysaccharides.

scholarly journals A Labile Metallo-Porphyrin as Tool to Control J-Aggregates Chiroptical Properties

2020 ◽  
Author(s):  
Luigi Monsù Scolaro ◽  
Ilaria Occhiuto ◽  
Mariachiara Trapani ◽  
ROBERTO ZAGAMI ◽  
Andrea Romeo ◽  
...  
Keyword(s):  
Dipolar Coupling ◽  
Initial Conditions ◽  
Coupling Mechanism ◽  
Precise Control ◽  
Rate Determining Step ◽  
Initial Nucleus ◽  
Acidic Conditions ◽  
J Aggregates ◽  
Kinetics Of ◽  
Autocatalytic Growth

The zinc(II) metal derivative of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4) is quite labile and readily demetallates under acidic conditions, affording the parent diacid porphyrin in a monomeric form. The rate of this process is first order on [ZnTPPS4] and second order on [H+], allowing a precise control of the monomer release in solution. Under high ionic strength, this latter species is able to self-assemble into J-aggregates, whose kinetics of growth are largely modulated by pH. The aggregation kinetics have been treated according to a well-established model, in which the formation of an initial nucleus is the rate determining step preceding the autocatalytic growth of the whole assembly. The extinction spectra of the aggregates suggest the occurrence of a dipolar coupling mechanism very similar to that operating in metal nanoparticles. Spontaneous symmetry breaking takes place in these aggregates as evidenced by unusual circular dichroism spectra. The intensity and sign of the effect is controlled by the aggregation rate and therefore can be tuned through a proper choice of initial conditions.

scholarly journals Novel Nanohybrids Based on Supramolecular Assemblies of Meso-tetrakis-(4-sulfonatophenyl) Porphyrin J-aggregates and Amine-Functionalized Carbon Nanotubes

Nanomaterials ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 669 ◽  
Author(s):  
Mariachiara Trapani ◽  
Antonino Mazzaglia ◽  
Anna Piperno ◽  
Annalaura Cordaro ◽  
Roberto Zagami ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Carbon Nanotubes ◽  
Transmission Electron Microscopy ◽  
Fluorescence Emission ◽  
Resonance Light Scattering ◽  
Therapeutic Window ◽  
Multiwalled Carbon ◽  
Experimental Conditions ◽  
Transmission Electron ◽  
J Aggregates

The ability of multiwalled carbon nanotubes (MWCNTs) covalently functionalized with polyamine chains of different length (ethylenediamine, EDA and tetraethylenepentamine, EPA) to induce the J-aggregation of meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) was investigated in different experimental conditions. Under mild acidic conditions, protonated amino groups allow for the assembly by electrostatic interaction with the diacid form of TPPS, leading to hybrid nanomaterials. The presence of only one pendant amino group for a chain in EDA does not lead to any aggregation, whereas EPA (with four amine groups for chain) is effective in inducing J-aggregation using different mixing protocols. These nanohybrids have been characterized through UV/Vis extinction, fluorescence emission, resonance light scattering and circular dichroism spectroscopy. Their morphology and chemical composition have been elucidated through transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). TEM and STEM analysis evidence single or bundles of MWCNTs in contact with TPPS J-aggregates nanotubes. The nanohybrids are quite stable for days, even in aqueous solutions mimicking physiological medium (NaCl 0.15 M). This property, together with their peculiar optical features in the therapeutic window of visible spectrum, make them potentially useful for biomedical applications.

Water-soluble p-carboxybenzylated beechwood 4-O-methylglucuronoxylan: structural features and properties

2000 ◽  
Vol 42 (2) ◽  
pp. 123-131 ◽  
Author(s):  
A. Ebringerová ◽  
J. Alföldi ◽  
Z. Hromádková ◽  
G.M. Pavlov ◽  
S.E. Harding
Keyword(s):  
Structural Features ◽  
Water Soluble ◽  
Water Soluble P ◽  
Soluble P

Aggregation of meso-tetrakis(4-sulfonatophenyl)porphyrin on polyethyleneimine in aqueous solutions and on a glass surface

2002 ◽  
Vol 06 (06) ◽  
pp. 431-438 ◽  
Author(s):  
Maria Angela Castriciano ◽  
Andrea Romeo ◽  
Luigi Monsù Scolaro
Keyword(s):  
Aqueous Solutions ◽  
Fluorescence Emission ◽  
Resonance Light Scattering ◽  
Glass Substrates ◽  
Vis Spectroscopy ◽  
The Matrix ◽  
J Aggregates ◽  
Matrix Concentration ◽  
Glass Surfaces ◽  
Neutral Conditions

The aggregation behavior of meso-tetrakis(4-sulfonatophenyl)porphyrin, [ H 2( TPPS 4)]4-, in the presence of hydrated polyethyleneimine ( PEI ) in aqueous solutions (1.6 < pH < 7.6) has been investigated. The interaction leads to the formation of a variety of pH dependent species, which have been attributed to porphyrin dimers or small oligomers under neutral conditions and J-aggregates on lowering the pH. The aggregation process follows kinetics typical of self-similar systems whose rates increase steeply on increasing the matrix concentration. This finding could be explained on the basis of an increased availability of binding sites for the growing aggregates. The charged polymer has been used to electrostatically adsorb the porphyrin onto glass substrates affording multilayered films. Our results point to the presence of fully protonated species in the solid state, which rearrange into J-aggregates as a function of pH and water content. The systems in solution and on glass surfaces have been investigated through a combination of UV-vis spectroscopy, fluorescence emission and resonance light scattering techniques.

Identification and tissue expression profiling of candidate UDP-glycosyltransferase genes expressed in Holotrichia parallela motschulsky antennae

2018 ◽  
Vol 108 (6) ◽  
pp. 807-816 ◽  
Author(s):  
S. Wang ◽  
Y. Liu ◽  
J.-J. Zhou ◽  
J.-K. Yi ◽  
Y. Pan ◽  
...  
Keyword(s):  
Tissue Expression ◽  
Gene Signature ◽  
Structural Features ◽  
Water Soluble ◽  
Economic Losses ◽  
Uridine Diphosphate ◽  
Produce Water ◽  
Holotrichia Parallela ◽  
A Genome ◽  
Olfactory Tissue

AbstractIt is difficult to control Holotrichia parallela Motschulsky with chemical insecticides due to the larvae's soil-living habit, thus the pest has caused great economic losses in agriculture. In addition, uridine diphosphate-glycosyltransferases (UGTs) catalyze the glycosylation process of a variety of small lipophilic molecules with sugars to produce water-soluble glycosides, and play multiple roles in detoxification, endobiotic modulation, and sequestration in an insect. Some UGTs were found specifically expressed in antennae of Drosophila melanogaster and Spodoptera littoralis, and glucurono-conjugated odorants could not elicit any olfactory signals, suggesting that the UGTs may play roles in odorant inactivation by biotransformation. In the current study, we performed a genome-wide analysis of the candidate UGT family in the dark black chafer, H. parallela. Based on a UGT gene signature and the similarity of these genes to UGT homologs from other organisms, 20 putative H. parallela UGT genes were identified. Bioinformatics analysis was used to predict sequence and structural features of H. parallela UGT proteins, and revealed important domains and residues involved in sugar donor binding and catalysis by comparison with human UGT2B7. Phylogenetic analysis of these 20 UGT protein sequences revealed eight major groups, including both order-specific and conserved groups, which are common to more than one order. Of these 20 UGT genes, HparUGT1265-1, HparUGT3119, and HparUGT8312 were highly (>100-fold change) expressed in antennae, suggesting a possible role in olfactory tissue, and most likely in odorant inactivation and olfactory processing. The remaining UGT genes were expressed in all tissues (head, thorax, abdomen, leg, and wing), indicating that these UGTs likely have different biological functions. This study provides the fundamental basis for determining the function of UGTs in a highly specialized olfactory organ, the H. parallela antenna.

scholarly journals Water-Soluble O-, S- and Se-Functionalized Cyclic Acetyl-triaza-phosphines. Synthesis, Characterization and Application in Catalytic Azide-alkyne Cycloaddition

Molecules ◽  
2020 ◽  
Vol 25 (22) ◽  
pp. 5479
Author(s):  
Abdallah Mahmoud ◽  
Piotr Smoleński ◽  
M. Guedes da Silva ◽  
Armando Pombeiro
Keyword(s):  
Cycloaddition Reaction ◽  
Structural Features ◽  
Water Soluble ◽  
31P Nmr Spectroscopy ◽  
The Novel ◽  
X Ray Diffraction ◽  
One Pot ◽  
Hirshfeld Surfaces ◽  
The One ◽  
High Yields

The 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) derivatives, viz. the already reported 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane 5-oxide (DAPTA=O, 1), the novel 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane-5-sulfide (DAPTA=S, 2), and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane-5-selenide (DAPTA=Se, 3), have been synthesized under mild conditions. They are soluble in water and most common organic solvents and have been characterized using 1H and 31P NMR spectroscopy and, for 2 and 3, also by single crystal X-ray diffraction. The effect of O, S, or Se at the phosphorus atom on the structural features of the compounds has been investigated, also through the analyses of Hirshfeld surfaces. The presence of 1–3 enhances the activity of copper for the catalytic azide-alkyne cycloaddition reaction in an aqueous medium. The combination of cheaply available copper (II) acetate and compound 1 has been used as a catalyst for the one-pot and 1,4-regioselective procedure to obtain 1,2,3-triazoles with high yields and according to ‘click rules’.

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