Diacid Species Research Articles

Spectroscopic, X-ray structure, radical scavenging and in vitro antifungal activities and catalytic degradation of methyl orange dye investigation of the Meso-tetrakis(p-tolyl) diprotonated porphyrin

With the aim to fully characterize the diprotonated porphyrin: meso‑tetrakis(p-tolyl)porphyrindi-ium dichloride chloroform trisolvate with the formula [H4TTP]Cl2·3CHCl3 (2) this porphyrinic diacid species was first prepared by protonation of the meso‑tetrakis(p-tolyl)porphyrin (H2TTP, (1)). Compound 2 was studied by UV/Vis, fluorescence, IR, 1H NMR spectroscopy as well as by MALDI-TOF mass spectroscopy. The single crystal X-ray structure of 2 was a very useful technique to show the very important deformation of the porphyrin core of the diprotonated [H4TTP]2+ porphyrinic species (2) which is considered the principal cause of the important redshift of the UV/Vis and fluorescence spectra of compound 2. We used computational studies at B3LYP/6-311+G(d,p) level of theory to investigate the HOMO and LUMO molecular orbitals characteristics and calculate the global reactive parameters of compound 2 such as the electrophilicity index ψ, the chemical potential (μ), the hardness (η) and the chemical softness (S). The diacid porphyrin species (2) was tested as adsorbent of the Methyl Orange dye (MO) and also as catalyst of the degradation of this organic dye in presence of hydrogen peroxide. Biological studies on the H2TTP free base porphyrin (1) and the corresponding [H4TTP]2+ diacid species (2) were carried out in vitro in order to test their inhibitory effect against some fungal strings and the ability of these two porphyrinic compounds to scavenge 1,1-diphenyl-picrylhydrazyl DPPH radical.

Investigation of J-Aggregates of 2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl) Porphyrin in Aqueous Solutions.

The highly distorted water-soluble 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (Br8TPPS44-) is readily protonated under acidic pH, forming the diacid H2Br8TPPS42- and subsequently the zwitterionic H4Br8TPPS4, which eventually evolves into J-aggregates. These latter species exhibit a relevant bathochromic shift with respect to the monomer with a quite sharp band due to motional narrowing. The depolarization ratio measured in resonant light scattering spectra allows estimating a tilt angle of ~20° of the porphyrins in the J-aggregate. The kinetic parameters are obtained by applying a model based on the initial slow nucleation step, leading to a nucleus containing m monomers, followed by fast autocatalytic growth. The kc values for this latter step increase on decreasing the acid concentration and on increasing the porphyrin concentration, with a strong power-law dependence. No spontaneous symmetry breaking or transfer of chirality from chiral inducers is observed. Both Atomic Force Microscopy (AFM) and Dynamic Light Scattering (DLS) point to the presence, in both the solid and solution phases, of globular-shaped aggregates with sizes close to 130 nm. Density functional theory (DFT) calculations performed on simplified models show that (i) upon protonation, the saddled conformation of the porphyrin ring is slightly altered, and a further rotation of the aryl rings occurs, and (ii) the diacid species is more stable than the parent unprotonated porphyrin. Time-dependent DFT analysis allows comparing the UV/Vis spectra for the two species, showing a consistent red shift upon protonation, even if larger than the experimental one. The simulated Raman spectrum agrees with the experimental spectrum acquired on solid samples.

DFT Study of the Formation of Atmospheric Aerosol Precursors from the Interaction between Sulfuric Acid and Benzenedicarboxylic Acid Molecules

Dicarboxylic acids are ubiquitous products of the photooxidation of volatile organic compounds which are believed to play a significant role in the formation of secondary organic aerosols in the atmosphere. In this paper, we report high-level quantum investigations of the clustering properties of sulfuric acid and benzenedicarboxylic acid molecules. Up to four molecules have been considered in the calculations, and the behavior of the three isomers of the organic diacid species have been compared. The most stable geometries have been characterized together with the corresponding thermodynamic data. From an atmospheric point of view, the results of the DFT calculations show that the organic diacid molecules may significantly enhance the nucleation of small atmospheric clusters, at least from an energetic point of view. In this respect, the phthalic acid isomer seems more efficient than the two other isomers of the benzenedicarboxylic acid, in particular because the internal distance between the two carboxyl groups in the organic diacids appears to play an important role in the stabilization of the H-bond network inside the corresponding heterocluster formed with sulfuric acid molecules.

Ion-pairing effects by organic anions on the supramolecular assembling kinetics of sulfonated porphyrins

Camphorsulfonic (CSA) and p-toluenesulfonic (p-TsOH) acids promote the self-assembling process of the diacid meso-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4) into J-aggregates. A general decrease of the rate constants on increasing the acid concentration has been observed for these organic acids. For camphorsulfonic acid the formation of chiral J-aggregates, whose handedness is related to that of the acid, has been revealed by circular dichroism spectra. Changes in the aggregation rates, kinetic profiles and g-factors but no chiral discrimination have been observed for the two different enantiomers, when using different mixing protocols. Moreover, at high acid concentration, aggregation is inhibited and the formation of a new porphyrin species has been detected for both acids. This species has been characterized by steady-state and time-resolved spectroscopic techniques and has been ascribed to an ion pair between the diacid porphyrin and the organic counter-anion. Its role in the aggregation of the initial diacid species has been discussed.

Molecular Distributions of Diacids, Oxoacids, and α‐Dicarbonyls in Summer‐ and Winter‐Time Fine Aerosols From Tianjin, North China: Emissions From Combustion Sources and Aqueous Phase Secondary Formation

AbstractTo understand the characteristics and sources of organic aerosols (OA) in North China, we studied diacids, oxoacids, and α‐dicarbonyls in summer‐ and winter‐time fine aerosols (PM2.5) collected from Tianjin. Oxalic (C2) acid was found to be the most abundant diacid species, followed by succinic (C4), malonic (C3), and sebacic (C8) acids, respectively. Glyoxylic (ωC2) was the most abundant oxoacids followed by pyruvic acid. Concentrations of total diacids, oxoacids, and α‐dicarbonyls in winter were 2–3 times higher than those in summer, but their mass fractions in PM2.5 were exactly the opposite. On average, total diacids carbon accounted for 2.9% in total carbon and 3.3% in organic carbon (OC) in summer and 1.8% and 2.0%, respectively, in winter. Their contributions to water‐soluble OC (WSOC) was almost the same in both seasons (5.5% and 5.3%, respectively). Molecular distributions, mass ratios of selected diacid (C3, C4, M, F, C6, Ph, and C9) species, and the linear relations among the selected species (including ∑C2–C4 and ∑C8–C12) and with inorganic markers (K+ and SO42−) implied that the diacids and related compounds are mainly originated from coal combustion and biomass burning emissions and produced in the atmosphere by both in situ photochemical reactions at local scale and aging during long‐range transport in both summer and winter. This study revealed that diacids and related compounds and WSOC are increased with increasing SO42− and they are produced in the aqueous phase, implying that the reduction in NOx and SO2 emissions could possibly control the water‐soluble OA loading over North China.

Large contribution of fine carbonaceous aerosols from municipal waste burning inferred from distributions of diacids and fatty acids

To investigate the origins, other than fossil fuel combustion and biomass burning, of urban carbonaceosus aerosols, we studied the fine (PM2.5) aerosols collected in Guiyang, Southwest China in winter (December 10–23) 2012 for organic carbon (OC), elemental carbon (EC) and water-soluble diacids, oxoacids, α-dicarbonyls and fatty acids as well as inorganic ions. Oxalic acid (C2) found to be the most abundant diacid species followed by succinic (C4) and terephthalic (t-Ph) acids, respectively. Even-carbon numbered fatty acids showed high abundances with a peak at C16. OC, EC and most of diacids and related compounds, but not inorganic ions, showed a similar temporal pattern with a drastic rise in December 15 day- and night-time samples during the campaign. Based on molecular distributions of diacids and fatty acids, and linear relations of OC and EC with selected marker ions and diacid species, we found that the organics and EC in PM2.5 are mainly derived from higher plant/cooking and municipal waste burning emissions in Guiyang. This study implies that municipal waste burning largely contributes to carbonaceous aerosols and warrants a need of further research on its role in aerosol loading and air quality in the urban atmosphere.

Sources and Formation Processes of Short-Chain Saturated Diacids (C2–C4) in Inhalable Particles (PM10) from Huangshi City, Central China

PM10 samples were collected from Huangshi (HS) city, Central China during April 2012 to March 2013, and were analyzed for short-chain saturated dicarboxylic acids (diacids) using a capillary gas chromatograph (GC). We found that oxalic acid (C2, 318 ± 104 ng·m−3) was the most abundant diacid species, followed by malonic acid (C3, 25.4 ± 9.11 ng·m−3) and succinic acid (C4, 2.09 ± 0.52 ng·m−3). The concentrations of C2 and C4 diacids were highest in winter, followed by summer and spring, and lowest in autumn. C3 diacid was decreased in the order of summer > winter > autumn > spring. Further, the seasonal variations of WSOC (water-soluble organic carbon)- and OC (organic carbon)-normalized diacid concentrations were similar to those of diacid concentrations, suggesting that both primary emission and secondary production are important sources for diacids in Huangshi (HS) aerosols. Strong correlations were found among C2 diacid and the three ions SO42−, NO3−, and NH4+ in summer and winter, suggesting that the species could undergo a similar secondary oxidation processing. C2 had good correlation with K+ in summer and autumn, which indicates an enhanced contribution of combustion sources for C2 diacid. Moreover, according to the ratio of C2/K+, we can conclude that C2 diacid should be formed by a secondary reaction of biomass combustion in HS aerosols, especially in summer and autumn. The ratios of C2/C4 and C3/C4 were compared with those reported in other sites, and the results suggest that HS aerosols should be more photochemically aged than at other urban areas. Principal component analysis of diacids and selected water-soluble inorganic ions over four seasons suggests that HS aerosols are influenced not only from primary emission, but also from secondary reaction. According to the linear relation between C2 and C3 diacids, the results indicate that C2 diacid is formed from the oxidation of hydrocarbon compounds in spring, while it is from the oxidation of C3 and C4 diacids in summer, autumn, and winter.

Springtime influences of Asian outflow and photochemistry on the distributions of diacids, oxoacids and α-dicarbonyls in the aerosols from the western North Pacific Rim

Total suspended particle (TSP) samples were collected at Cape Hedo, Okinawa on a basis of 24, 12 and 3 h intervals in March to April 2007, when the Asian outflow is enhanced. The filter samples were analysed for dicarboxylic acids, oxoacids, benzoic acid and α-dicarbonyls to better understand the sources, chemical composition and photochemical ageing of organic aerosols during long-range transport. Their molecular distributions showed a predominance of oxalic acid (C2) followed by malonic (C3) and succinic (C4) acids. Day/night samples did not show clear diurnal variations, suggesting that local anthropogenic influence is not important. The highest concentrations of C2 and other diacid species were observed in April 10 when air masses were delivered from north China. Higher concentrations were observed when air masses arrived from East Asia and coastal China. The 3 h samples showed higher concentrations of oxalic acid at 16:30 or at 13:30 during April 14 and 16, whereas higher relative abundance of C2 in total diacids and higher concentration ratios (C2/C3, C2/C4, C3/C4, C2/Gly, and C2/ωC2) were observed at 7:30 during April 14–16. These results suggest that aerosols were accumulated in the atmosphere during night and photochemically modified early in the morning. Oxalic acid–C/OC did not show a prominent peak in 3-h samples. Temporal variations in the concentrations of diacids, oxoacids and α-dicarbonyls, relative abundances and diacid–C/OC ratios together with 5 day back trajectory analyses show that the aerosols from Cape Hedo are strongly influenced by long-range atmospheric transport from East Asia, especially in China. Strong correlations of C2 with nss-SO42− and NO3− in night-time suggest a secondary formation of water-soluble diacids via heterogeneous aqueous phase oxidation during long-range transport.

Unusual Stepwise Protonation and J‐Aggregation of meso‐Tetrakis(N‐methylpyridinium‐4‐yl)porphine on Binding Poly(sodium vinylsulfonate)

The binding of a tetracationic porphyrin to a highly charged polymer like poly(sodium vinylsulfonate) has been investigated over a wide pH range and under various experimental conditions. We present evidence that, depending on the pH, the high electrostatic field exerted by the polymer stabilizes the diprotonated form of the free base porphyrin at unusual pH values or otherwise causes the formation of H-type aggregates. In particular, at a low polymer concentration, lowering the pH at first allows the formation of the diacid species then it determines its reorganization in close-packed J-type aggregates. The employment of various metallo-derivatives of the title porphyrin enables a better insight into the nature of all the detected species.

Molecular composition of dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls and fatty acids in atmospheric aerosols from Tanzania, East Africa during wet and dry seasons

Abstract. Atmospheric aerosol samples of PM2.5 and PM10 were collected during the wet and dry seasons in 2011 from a rural site in Tanzania and analysed for water-soluble dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, and fatty acids using a gas chromatography/flame ionization detector (GC/FID) and GC/mass spectrometry. Here we report the molecular composition and sources of diacids and related compounds for wet and dry seasons. Oxalic acid (C2) was found as the most abundant diacid species followed by succinic and/or malonic acids whereas glyoxylic acid and glyoxal were the dominant ketoacid and α-dicarbonyl, respectively in both seasons in PM2.5 and PM10. Mean concentration of C2 in PM2.5 (121 ± 47 ng m−3) was lower in wet season than dry season (258 ± 69 ng m−3). Similarly, PM10 samples showed lower concentration of C2 (169 ± 42 ng m−3) in wet season than dry season (292 ± 165 ng m−3). Relative abundances of C2 in total diacids were 65% and 67% in PM2.5 and 65% and 64% in PM10 in the wet and dry seasons, respectively. Total concentrations of diacids (289–362 ng m−3), ketoacids (37.8–53.7 ng m−3), and α-dicarbonyls (5.7–7.8 ng m−3) in Tanzania are higher than those reported at a rural background site in Nylsvley (South Africa) but comparable or lower than those reported from sites in Asia and Europe. Diacids and ketoacids were found to be present mainly in PM2.5 in both seasons (total α-dicarbonyls in the dry season), suggesting a production of organic acids from pyrogenic sources and photochemical oxidations. Averaged contributions of total diacids to aerosol total carbon were 1.4% in PM2.5 and 2.1% in PM10 during wet season and 3.3% in PM2.5 and 3.9% in PM10 during dry season whereas those to water-soluble organic carbon were 2.2% and 4.7% in PM2.5 during wet season and 3.1% and 5.8% in PM10 during dry season. The higher ratios in dry season suggest an enhanced photochemical oxidation of organic precursors probably via heterogeneous reactions on aerosols under strong solar radiation. Strong positive correlations were found among diacids and related compounds as well as good relations to source tracers in both seasons, suggesting a mixed source from natural biogenic emissions, biomass burning, biofuel combustion, and photochemical production.

Time-resolved variations in the distributions of inorganic ions, carbonaceous components, dicarboxylic acids and related compounds in atmospheric aerosols from Sapporo, northern Japan during summertime

To better understand time-resolved variations of water-soluble organic aerosols in the atmosphere, we collected atmospheric particles (TSP) every 3 h during summertime (8–10 August, 2005) in Sapporo, northern Japan. We measured inorganic ions, carbonaceous components, dicarboxylic acids, ketoacids and α-dicarbonyls in TSP. SO42− was found as the most abundant ionic species (57 ± 9% of total ions determined) followed by NH4+ and NO3−. However, none of the ionic species showed any diurnal trend throughout the campaign. Organic carbon (OC) ranged from 2.1 to 12.1 μg m−3 whereas elemental carbon (EC) was negligible in most of the samples (0.31 ± 0.56 μg m−3). Oxalic (C2) acid was the most abundant diacid species, followed by malonic (C3) and succinic (C4) acids. Water-soluble OC (WSOC), water-insoluble OC (WIOC) and OC as well as dominant diacids (C2–C4), total diacids, ketoacids and α-dicarbonyls did not show diurnal trend on 8 August, but they showed clear diurnal distributions during 9–10 August following the changes in ambient temperature (and radiation). Detailed analyses of time-resolved aerosols demonstrate that diurnal variations of organic aerosol compositions are caused by local in situ photochemical production, but are significantly superimposed by long-range atmospheric transport of aerosols, particularly when the air masses are enriched with emissions from higher plants and/or biomass burning, and their photochemical processing during the transport.

Surfactant-like Behavior of Short-Chain Alcohols in Porphyrin Aggregation

UV/vis absorption and time-resolved fluorescence measurements on alcoholic solutions of meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS(4)) in neutral and acid form have been performed as a function of the alcohol polarity. These solutions show a peculiar behavior that mimics porphyrin in confined water solutions. In alcohols, TPPS(4) exhibits a metastable phase showing the formation of new species in analogy with the confined water environment of AOT microemulsions. Various species have been detected at different pH values and on aging the solutions. Under neutral pH conditions, the porphyrin is present as free base monomer (S415) with a small amount of H-dimeric species (S400). On aging, the S415 leads to the formation of a new species (S423), which has been assigned as a J-type dimer of the neutral porphyrin. The species S400 and S423 are not present in bulk water solution but are typical of TPPS(4) in confined water. On decreasing pH, the S415 almost immediately converts into the diacid form (S438), which evolves toward red-shifted J-aggregates (S490) and blue-shifted H-aggregates (S420). On decreasing alcohol polarity, the kinetic evolution from fresh to aged solution and from the monomeric diacid species to H- and J-aggregates speeds up. Exploiting the amphiphilic character of short chain alcohols and widely varying their polarity, we were able to enhance in bulk conditions the peculiar behavior observed in close proximity to the microemulsion wall.

Resonance Raman and electronic absorption study of free‐base tetraphenylporphine diacid dispersed in polymethylcyanoacrylate

AbstractWe report a resonance Raman study on free‐base tetraphenylporphine (H2TPP) and its chemically prepared diacid dispersed in polymethylcyanoacrylate (PMCA). Photoexcitation of the neutral porphine by laser light leads irreversibly to the formation of the diacid, with the π‐cation radical as intermediate species. Resonance Raman (RR) spectra of the diacid dispersed in the polymer obtained with 441.6 nm in the wavenumber region of 100–1650 cm−1 are recorded. Wavenumbers with other excitation lines are also reported for the diacid species. Some bands assigned to out‐of‐plane vibrational modes and forbidden under ideal D2h symmetry are also observed in the resonance Raman spectra of the diacid. These bands arise from the out‐of‐plane distortions, which reduce the symmetry of the molecule. These findings are supported by the electronic absorption studies of the diacid in the polymer. Copyright © 2007 John Wiley & Sons, Ltd.

Spectroscopic Studies of Water‐Soluble Porphyrins with Protein Encapsulated in Bis(2‐ethylhexyl)sulfosuccinate (AOT) Reverse Micelles: Aggregation versus Complexation

We have investigated the interaction of two water-soluble free-base porphyrins (negatively charged meso-tetrakis(p-sulfonatophenyl)porphyrin sodium salt (TSPP) and positively charged meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMpyP)) with two drug-carrier proteins (human serum albumin (HSA) and beta-lactoglobulin (betaLG)) in bis(2-ethylhexyl)sulfosuccinate (AOT)/isooctane/water reverse micelles (RM) by using steady-state and transient-state fluorescence spectroscopy. TSPP exhibited a complex pattern of aggregation on varying the RM size and pH in the absence of the protein: at low omega0 (the ratio of water concentration to AOT concentration, the emission of H-aggregates prevails under acidic or neutral "pH(ext)" conditions. Upon formation of the water-pool, J-aggregates and monomeric diacid species dominate at low "pH(ext)" but only monomer is detected at neutral "pH(ext)". The aggregation number increases with omega0 and the presence of the protein does not seem to contribute to further growth of the aggregate. The presence of protein leads to H-deaggregation but promotes J-aggregation up to a certain protein/porphyrin ratio above which, complexation with the monomer bound to a hydrophobic site of the protein prevails. The effective complex binding constants are smaller than in free aqueous solution; this indicates a weaker binding in these RM probably due to some conformational changes imposed by encapsulation. Only a weak quenching of TMpyP fluorescence is detected due to the presence of protein in contrast to the negative porphyrin.

Photochemical production and loss of organic acids in high Arctic aerosols during long-range transport and polar sunrise ozone depletion events

Abstract Unique daily measurements of water-soluble organics in fine ( 2 μm) aerosols were conducted at Alert in the Canadian Arctic in winter to spring of 1992. They yield insight into photochemical production and loss of organics during long-range transport and ozone depletion events following polar sunrise. Comprehensive analyses of α, ω-dicarboxylic acids (C2–C12), ω-oxocarboxylic acids (C2–C9) and α-dicarbonyls (C2, C3) as well as pyruvic acid and aromatic (phthalic) diacid were conducted using GC and GC/MS techniques. Oxalic (C2) acid was generally the dominant diacid species in both fine and coarse fractions, followed by malonic (C3) and succinic (C4) acids. Concentrations of total diacids in the fine aerosol fraction (0.2–64 ng m−3) were 5–60 times higher than those in the coarse fraction (0.01–3 ng m−3). After polar sunrise in early-March, the total concentration of fine aerosol diacids increased by a factor of 3–5 while the coarse mode did not change significantly. From dark winter to sunlit spring, temporal changes in correlations and ratios of these water-soluble organics to vanadium and sulfate measured simultaneously suggest that atmospheric diacids and related organic compounds are largely controlled by long-range atmospheric transport of polluted air during winter, but they are significantly affected by photochemical production. The latter can occur in sunlight either during transport to the Arctic or during photochemical events associated with surface ozone depletion and bromine chemistry near Alert in spring. Conversion of gaseous precursors to particulate matter via photochemical oxidation was intensified at polar sunrise, resulting in a peak in the ratio of total diacids to V. During ozone depletion events, complex patterns are indicated in photochemical production and loss depending on the diacid compound. Unsaturated (maleic and phthalic) diacids were inversely correlated with particulate Br whereas saturated diacids (C2–C4) positively correlated with particulate Br. These results suggest that Br chemistry associated with ozone depletion leads to degradation of unsaturated diacids and to the production of smaller saturated diacids.

Fine and coarse modes of dicarboxylic acids in the Arctic aerosols collected during the Polar Sunrise Experiment 1997

Fine (<1 μm) and coarse (>1 μm) aerosol particles were collected at Alert, Canada (82°27′N, 62°30′W), during the Arctic spring as part of the Polar Sunrise Experiment 1997 and were analyzed for low molecular weight dicarboxylic acids (C2–C11) using gas chromatography with flame ionization detector (GC‐FID) and GC/mass spectrometry (GC/MS). More than 80% of total diacids were detected in the fine fraction, suggesting the production by gas‐to‐particle conversion in the Arctic. In both fractions, oxalic acid was the dominant diacid species followed by succinic and malonic acids. Shorter chain diacids (C2–C5) showed the concentration maximum on 5–7 April; however, longer chain diacids (<C6) did not show a clear peak in the same periods. A significant depletion of ozone was observed during the experiment, where an anticorrelation was found between the concentrations of ozone and shorter chain diacids (C2–C5) in both fine and coarse aerosols. During this event, we also observed the enhanced concentration of filterable bromine in both modes. Peaks of dicarboxylic acids in both coarse and fine aerosols during ozone depletion events indicate that heterogeneous reactions are occurring on coarse particle and possibly on fine particles as well. Dicarboxylic acids may be produced by the oxidation of precursor compounds such as glyoxal and glyoxylic and other ω‐oxocarboxylic acids that contain aldehyde (hydrated form) group, being involved with ozone and halogen chemistry in the Arctic marine boundary layer.

Fluoroscent properties of 22,24-diprotonated 5,10,15,20-tetrakis (4-sulfonatophenyl)porphyrin interacting with a β-sheet structure of a zwitterionic polypeptide

The fluorescent properties of 22,24-Diprotonated 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin interacting with the β-sheet structure of a zwitterionic Poly(Glu-Val-Lys-Val) were investigated under various conditions. The TPPS diacid species formed four types of aggregated species by the addition of the polypeptide and/or NaCl. The fluorescent bands were observed for the monomeric and their three aggregated species. The fluorescent intensity changes and maximum wavelength shifts indicated that the monomeric and their aggregated species bound to the polypeptide by electrostatic interaction. The poly(Glu-Val-Lys-Val)/TPPS diacid species system may be provided a good model for studying the porphyrin assembly binding to specific protein domains with definite orientations and alignments.

Interaction of porphyrin derivatives with a β-sheet structure of a zwitterionic polypeptide in aqueous solution

Complex formation of porphyrin derivatives with zwitterionic poly(Glu-Leu-Lys-Leu) was investigated as a protein-porphyrin complex model. The β-sheet structure of poly(Glu-Leu-Lys-Leu) interacted with a 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (TPPS) diacid form which has positive charge in the porphyrin center. On the other hand, no interaction of 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin (TMPyP) or a TPPS free form with the polypeptide was observed. The positive charge in the porphyrin center for the diacid species may play an important role in the complex formation. The TPPS diacid species was aggregated by the addition of the polypeptide and/or NaCl; at least three kinds of TPPS aggregates were observed.

Effect of fatty acid positional distribution and triacylglycerol composition on lipid by‐products formation during heat treatment: I. polymer formation

AbstractEffects of the fatty acid positional distribution and of the triacylglycerol (TG) composition on polymerization of TG during heat treatment were studied. Diacid TG molecules, acylated only with linoleic acid or linolenic acid along with palmitic acid, and positioned either in the central position (PLP and PLnP, respectively) or in one of the two outer positions (PPL and PPLn, respectively) were synthesized. Monoacid TG, i.e., trilinolein and trilinolenin, were also synthesized and mixed with tripalmitin in a 1:2 ratio. These model TG were also compared to TG models that consisted of a canola oil and its randomized counterpart, whose fatty acid positional distribution and TG composition were determined by means of high‐performance liquid chromatography (HPLC). After heating, the polymer content and composition were evaluated by HPLC‐size exclusion chromatography. Both pure TG and the canola oil models showed that acylation of polyunsaturated acids in the central position was protective against polymerization, although the effect was mainly observed with linolenic acid. The synthetic‐TG study showed that the monoacid TG species exhibited higher sensitivity toward polymerization than the diacid species. The slight differences in the TG species between both canola oils did not allow observation of such a relationship with regard to TG composition.

Effect of fatty acid positional distribution and triacylglycerol composition on lipid by‐products formation during heat treatment: I. Polymer formation

AbstractEffects of the fatty acid positional distribution and of the triacylglycerol (TG) composition on polymerization of TG during heat treatment were studied. Diacid TG molecules, acylated only with linoleic acid or linolenic acid along with palmitic acid, and positioned either in the central position (PLP and PLnP, respectively) or in one of the two outer positions (PPL and PPLn, respectively) were synthesized. Monoacid TG, i.e., trilinolein and trilinolenin, were also synthesized and mixed with tripalmitin in a 1:2 ratio. These model TG were also compared to TG models that consisted of a canola oil and its randomized counterpart, whose fatty acid positional distribution and TG composition were determined by means of high‐performance liquid chromatography (HPLC). After heating, the polymer content and composition were evaluated by HPLC‐size exclusion chromatography. Both pure TG and the canola oil models showed that acylation of polyunsaturated acids in the central position was protective against polymerization, although the effect was mainly observed with linolenic acid. The synthetic‐TG study showed that the monoacid TG species exhibited higher sensitivity toward polymerization than the diacid species. The slight differences in the TG species between both canola oils did not allow observation of such a relationship with regard to TG composition.