Nanomaterials Based on 2,7,12,17-Tetra-tert-butyl-5,10,15,20-tetraaza-21H,23H-porphine Exhibiting Bifunctional Sensitivity for Monitoring Chloramphenicol and Co2.

Monitoring antibiotic retention in human body fluids after treatment and controlling heavy metal content in water are important requirements for a healthy society. Therefore, the approach proposed in this study is based on developing new optical sensors using porphyrin or its bifunctional hybrid materials made with AuNPs to accomplish the accurate detection of chloramphenicol and cobalt. To produce the new optical chloramphenicol sensors, 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraaza-21H,23H-porphine (TBAP) was used, both alone in an acid medium and as a hybrid material with AuNPs in a water-DMSO acidified environment. The same hybrid material in the unchanged water-DMSO medium was the sensing material used for Co2+ monitoring. The best results of the hybrid materials were explained by the synergistic effects between the TBAP azaporphyrin and AuNPs. Chloramphenicol was accurately detected in the range of concentrations between 3.58 × 10-6 M and 3.37 × 10-5 M, and the same hybrid material quantified Co2+ in the concentration range of 8.92 × 10-5 M-1.77 × 10-4 M. In addition, we proved that AuNPs can be used for the detection of azaporphyrin (from 2.66 × 10-5 M to 3.29 × 10-4 M), making them a useful tool to monitor porphyrin retention after cancer imaging procedures or in porphyria disease. In conclusion, we harnessed the multifunctionality of this azaporphyrin and of its newly obtained AuNP plasmonic hybrids to detect chloramphenicol and Co2+ quickly, simply, and with high precision.

The Influence of the Nature of the Polymer Incorporating the Same A3B Multifunctional Porphyrin on the Optical or Electrical Capacity to Recognize Procaine.

The multifunctionality of an A3B mixed-substituted porphyrin, namely 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl)porphyrin (5-COOH-3MPP), was proven due to its capacity to detect procaine by different methods, depending on the polymer matrix in which it is incorporated. The hybrid nanomaterial containing k-carrageenan and AuNPs (5-COOH-3MPP-k-carrageenan-AuNPs) was able to optically detect procaine in the concentration range from 5.76 × 10-6 M to 2.75 × 10-7 M, with a limit of detection (LOD) of 1.33 × 10-7 M. This method for the detection of procaine gave complementary results to the potentiometric one, which uses 5-COOH-3MPP as an electroactive material incorporated in a polyvinylchloride (PVC) membrane plasticized with o-NPOE. The detected concentration range by this ion-selective membrane electrode is wider (enlarged in the field of higher concentrations from 10-2 to 10-6 M), linearly dependent with a 53.88 mV/decade slope, possesses a detection limit of 7 × 10-7 M, a response time of 60 s, and has a certified stability for a working period of six weeks.

Nanomaterials Based on Collaboration with Multiple Partners: Zn3Nb2O8 Doped with Eu3+ and/or Amino Substituted Porphyrin Incorporated in Silica Matrices for the Discoloration of Methyl Red.

Designing appropriate materials destined for the removal of dyes from waste waters represents a great challenge for achieving a sustainable society. Three partnerships were set up to obtain novel adsorbents with tailored optoelectronic properties using silica matrices, Zn3Nb2O8 oxide doped with Eu3+, and a symmetrical amino-substituted porphyrin. The pseudo-binary oxide with the formula Zn3Nb2O8 was obtained by the solid-state method. The doping of Zn3Nb2O8 with Eu3+ ions was intended in order to amplify the optical properties of the mixed oxide that are highly influenced by the coordination environment of Eu3+ ions, as confirmed by density functional theory (DFT) calculations. The first proposed silica material, based solely on tetraethyl orthosilicate (TEOS) with high specific surface areas of 518-726 m2/g, offered better performance as an adsorbent than the second one, which also contained 3-aminopropyltrimethoxysilane (APTMOS). The contribution of amino-substituted porphyrin incorporated into silica matrices resides both in providing anchoring groups for the methyl red dye and in increasing the optical properties of the whole nanomaterial. Two different types of methyl red adsorption mechanisms can be reported: one based on surface absorbance and one based on the dye entering the pores of the adsorbents due to their open groove shape network.

Topographical and Optical Characteristics of Thermoplastic Dental Appliances Materials Related to Water Sorption.

Clear thermoplastic materials have increased in popularity in the dental field due to their various applications, combination of excellent aesthetics, and good biomechanical behavior, but they may be influenced by different environmental conditions. The purpose of the present study was to assess the topographical and optical characteristics of thermoplastic dental appliances materials relative to water sorption. PET-G polyester thermoplastic materials were evaluated in this study. Related to water uptake and desiccation stages, surface roughness was analyzed, and three-dimensional AFM profiles were generated for nano-roughness measurements. Optical CIE L*a*b* coordinates were recorded and parameters like translucency (TP), contrast ratio for the opacity (CR), and opalescence (OP) were derived. Levels of color changes were achieved. Statistical analyses were performed. Water uptake significantly increases the specific weight of the materials, and after desiccation, the mass decreases. Roughness increased after water immersion as well. Regression coefficients indicated a positive correlation between TP and a* and between OP and b*. Studied PET-G materials have a different behavior to water exposure, but for all their specific weight, they increased significantly within the first 12 h. It is accompanied by an increase in the roughness values, even if they continue to be kept below the critical mean surface roughness. On nano-level, 3D images show an increase in inhomogeneity in the network structure of particles. Slight color changes were registered.

One A3B Porphyrin Structure-Three Successful Applications.

Porphyrins are versatile structures capable of acting in multiple ways. A mixed substituted A3B porphyrin, 5-(3-hydroxy-phenyl)-10,15,20-tris-(3-methoxy-phenyl)-porphyrin and its Pt(II) complex, were synthesised and fully characterised by 1H- and 13C-NMR, TLC, UV-Vis, FT-IR, fluorescence, AFM, TEM and SEM with EDX microscopy, both in organic solvents and in acidic mediums. The pure compounds were used, firstly, as sensitive materials for sensitive and selective optical and fluorescence detection of hydroquinone with the best results in the range 0.039-6.71 µM and a detection limit of 0.013 µM and, secondly, as corrosion inhibitors for carbon-steel (OL) in an acid medium giving a best performance of 88% in the case of coverings with Pt-porphyrin. Finally, the electrocatalytic activity for the hydrogen and oxygen evolution reactions (HER and OER) of the free-base and Pt-metalated A3B porphyrins was evaluated in strong alkaline and acidic electrolyte solutions. The best results were obtained for the electrode modified with the metalated porphyrin, drop-casted on a graphite substrate from an N,N-dimethylformamide solution. In the strong acidic medium, the electrode displayed an HER overpotential of 108 mV, at i = -10 mA/cm2 and a Tafel slope value of 205 mV/dec.

Surface Characteristics and Color Stability of Dental PEEK Related to Water Saturation and Thermal Cycling.

(1) Background: The study was undertaken to evaluate the surface characteristics, microhardness, and color stability of PEEK materials related to water saturation and in vitro aging. (2) Methods: Custom specimens of unmodified and modified PEEK CAD/CAM materials were investigated: BioHPP, a ceramic reinforced PEEK, and Finoframe PEEK and Juvora medical PEEK, 100% PEEK materials. Forty-eight plates were sectioned in rectangular slices. The specimens were immersed in distilled water at 37 °C for a period of 28 days, and then subjected to aging by thermal cycling (10,000 cycles). Surface roughness was measured with a contact profilometer; nanosurface topographic characterization was made by Atomic Force Microscopy; Vickers hardness measurements were performed with a micro-hardness tester; color changes were calculated. All registrations were made before immersion in water and then subsequently once a week for 4 weeks, and after thermocycling. (3) Results: The studied reinforced and unfilled PEEK materials reached water saturation after the first week of immersion, without significant differences between them. The most affected from this point of view was the reinforced PEEK material. Thermocycling induces a significant increase inmicroroughness, without significant differences between the studied materials. In relation to the nanosurface topography and roughness, the reinforced PEEK material was the least modified by aging. The color changes after 4 weeks of water immersion and one year of simulated in vitro aging ranged from extremely slight to slight, for all materials. (4) Conclusions: Water absorption was associated with a decrease in microhardness. Surface characteristics are affected by water immersion and thermocycling. Perceivable or marked color changes of the materials were not detected during the study.

Surface Characteristics of High Translucent Multilayered Dental Zirconia Related to Aging.

(1) Background: The purpose of this study was to evaluate the differences in terms of surface characteristics (roughness, topography, microhardness) among layers for multi-layered high translucent and super-high translucent zirconia and the influence of finishing and aging on surface characteristics and microstructure. (2) Methods: Three types of translucent multilayer zirconia were evaluated: STML (4Y-TZP); IPS e.maxZirCAD CEREC/in Lab MT Multi (4Y-TZP + 5Y-TZP); CeramillZolidfx ML (5Y-TZP). Ninety-six plate-shaped samples (32 for a material), 16 mm × 14 mm × 1 mm size, were cut with a precision disc, polished on both sides with sand papers and sintered respecting the manufacturer's protocol. Half of the specimens (16) were finished by polishing and the other half by glazing and then equally divided into one control group and one group subject to aging by autoclaving (1 h, 134 °C, 0.2 MPa), resulting in four groups of eight samples, for each zirconia. The specimens were evaluated in three areas: cervical, medium, incisal-of each glazed or polished surface, before and after aging. Tests were performed to determine the surface roughness using a profilometer; the surface topography by an atomic force microscope (AFM) and a scanning electron microscope (SEM). Microhardness was recorded using a microhardness tester. Statistical analyses were performed using two-way ANOVA test, unpaired sample t-Test, paired sample t-Test (α = 0.05) and Pearson's correlation. (3) Results: Before and after autoclaving, for glazed samples significance (p < 0.05) higher surface roughness, respectively lower microhardness in comparison with the polished group was assessed. No significant differences (p > 0.05) were reported between the three areas, on glazed or polished surfaces of a material. Although, after aging an increase in surface roughness was observed both on glazed and polished samples, statistical differences were found for STML (p < 0.05). No significant differences (p> 0.05) concerning microhardness among the same areas, on glazed and polished surfaces, recorded before and after aging, except CeramillZolidfx ML glazed samples. (4) Conclusions: For tested zirconia materials no significant differences among layers were registered regarding surface characteristics. Surface treatment (glazing or polishing) has a significant impact on surface roughness and microhardness. Both before and after aging, the surface roughness values for the glazed samples were higher than for those polished. The super translucent 4Y-TZP material was more affected by aging compared to the super-high translucent 5Y-TZP material. The combined material revealed similarities for each layer corresponding to the microstructure.

Efficient Decrease in Corrosion of Steel in 0.1 M HCl Medium Realized by a Coating with Thin Layers of MnTa2O6 and Porphyrins Using Suitable Laser-Type Approaches.

The purpose of this research is to meet current technical and ecological challenges by developing novel steel coating systems specifically designed for mechanical equipment used in aggressive acid conditions. Homogeneous sandwich-type layered films on the surface of steel electrodes were realized using a pseudo-binary oxide, MnTa2O6, and two different substituted porphyrin derivatives, namely: 5-(4-carboxy-phenyl)-10,15,20-tris (4-methyl-phenyl)-porphyrin and 5-(4-methyl-benzoate)-10,15,20-tris (4-methyl-phenyl)-porphyrin, which are novel investigated compound pairs. Two suitable laser strategies, pulsed laser deposition (PLD) and matrix-assisted pulsed laser evaporation (MAPLE), were applied in order to prevent porphyrin decomposition and to create smooth layers with low porosity that are extremely adherent to the surface of steel. The electrochemical measurements of corrosion-resistant coating performance revealed that in all cases in which the steel electrodes were protected, a significant value of corrosion inhibition efficiency was found, ranging from 65.6 to 83.7%, depending on the nature of the porphyrin and its position in the sandwich layer. The highest value (83.7%) was obtained for the MAPLE/PLD laser deposition of 5-(4-carboxy-phenyl)-10,15,20-tris (4-methyl-phenyl)-porphyrin/MnTa2O6(h), meaning that the inhibitors adsorbed and blocked the access of the acid to the active sites of the steel electrodes.

Surface Characterisation of Dental Resin Composites Related to Conditioning and Finishing.

Due to the little information related to surface processing and conditioning of resin matrix ceramic materials previous glazing, the main purpose of this in vitro study was to investigate the effect of different surface treatments on the surface morphology of different resin composite materials. Five types of resin composite CAD-CAM materials: a resin composite ceramic Vita Enamic (E) and four types of nanoparticle-filled resins, like Lava Ultimate (L), Cerasmart (C), Shofu HC (S), Hyramic (H) were taken into consideration. Specimens received the following surface treatment protocols: conventional polishing [p], polishing and glazing [pg], conditioning with CoJet [c], conditioning with CoJet and glazing [cg], sandblasting [s], sandblasting and glazing [sg], etching [e], etching and glazing [eg]. Surface roughness was analyzed for all samples and nanosurface topographic characterization was made by Atomic Force Microscopy. The highest roughness was registered for sandblasted surfaces [s], followed by tribochemical silica airborne particle abrasion [c], and etching [e]. A very strong correlated conditioning behavior of resin nanoceramic materials, like L, C and S samples was found. The microroughness decreased thus [s] > [c] > [e]. These are moderate correlated with H, and are moderate negative correlated to E, where e is more efficient. Three-dimensional images indicated visible grain boundaries after conditioning, for all materials. After polishing and glazing, surfaces became smoother. For all tested conditioning and finishing methods, surface roughness values were within clinically acceptable limits. Finishing by polishing was proved to be a good choice for all materials taken into consideration, polishing and glazing likewise, excepting Hyramic. For Enamic and Shofu HC sandblasting or tribochemical conditioning and glazing and for Hyramic polishing and glazing are not the best options, related to nanoroughness values. Referring to the nanosurface topography, for Enamic, Cerasmart and Hyramic, glazing would be the method of choice, associated with the adequate conditioning method for each material.

Hybrid Silica Materials Applied for Fuchsine B Color Removal from Wastewaters.

Hybrid materials, with applications in fuchsine B color removal from wastewaters, were obtained by in situ incorporation of platinum nanoparticles and/or Pt-porphyrin derivatives into silica matrices. The inorganic silica matrices were synthesized by the sol-gel method, conducted in acid-base catalysis in two steps and further characterized by Nitrogen porosimetry, Small Angle Neutron Scattering (SANS), Scanning electron microscopy, Atomic force microscopy and UV-vis spectroscopy. All of the investigated silica hybrid materials were 100% efficient in removing fuchsine B if concentrations were lower than 1 × 10-5 M. For higher concentrations, the silica matrices containing platinum, either modified with Pt-metalloporphyrin or with platinum nanoparticles (PtNPs), are the most efficient materials for fuchsine B adsorption from wastewaters. It can be concluded that the presence of the platinum facilitates chemical interactions with the dye molecule through its amine functional groups. An excellent performance of 197.28 mg fuchsine B/g adsorbent material, in good agreement with the best values mentioned in literature, was achieved by PtNPs-silica material, capable of removing the dye from solutions of 5 × 10-4 M, even in still conditions.

Selective Laser Sintering versus Selective Laser Melting and Computer Aided Design - Computer Aided Manufacturing in Double Crowns Retention.

Purpose This in vitro study aimed at ascertaining the retention forces for telescopic crowns fabricated with Selective Laser Manufacturing (SLM) and Selective Laser Sintering (SLS) additive technologies, and Computer Aided Design - Computer Aided Manufacturing (CAD-CAM) subtractive technology, by using suitable materials for each.Materials and Methods Full-factorial design was employed for experimental testing, considering the following three factors: (a) inner crown material ‒ technology (zirconia ‒ CAD-CAM; metal-alloy ‒ SLS; metal-alloy ‒ SLM); (b) tooth type (canine or molar); (c) wet vs. dry conditions (i.e. either with or without artificial saliva). The roughness of the inner crowns was analyzed through atomic force microscopy. Three-way analysis of variance (ANOVA) was applied for statistical analysis, followed by Tukey's post-hoc comparisons between the crown types.Results The retention force mean values were between 3.8 N (dry, SLM) and 14.8 N (artificial saliva, SLS), with statistically significant (p<0.001) differences between the three types of inner crowns and interaction with the tooth type. No significant interaction was found between crown or tooth types and the wet vs. dry testing conditions. The zirconia crowns' retention force was significantly (p<0.001) higher compared to similar SLM crowns, with 95% CI (3.62; 5.55) N for the differences. Zirconia was significantly (p<0.001) less retentive compared to similar SLS crowns, with 95% CI (-5.99; -4.06) N for the differences. The roughness decrease and subsequent loss of retention force was the largest in zirconia.Conclusions The SLS inner crowns showed the best retention, followed by zirconia and SLM inner crows.

Surface Quality Evaluation of Removable Thermoplastic Dental Appliances Related to Staining Beverages and Cleaning Agents.

(1) Background: Thermoplastic materials are not inert and subject to changes in the oral environment, which affect their surface quality. Color stability and topographic characteristics of clear thermoplastic appliances are critical considerations. The study aimed to evaluate the optical changes and surface topography of different thermoplastic materials related to staining beverages and cleaning agents. (2) Methods: Thermoplastic polyethylene terephthalate glycol (PET-G) material specimens were selected for the study: S (Duran, Scheu-Dental GmbH, Iserlohn, Germany), D (Biolon, Dreve Dentamid GmbH, Unna, Germany), and B (Crystal, Bio Art Dental Equipment, Sao Carlos, Brazil). Four different media were involved for immersion: coffee (C) and black tea (T) at 55 °C, Coca-Cola (K) at 5 °C, and distilled water (W) at 22 °C. As for cleaning, chemical options and mechanical brushing were selected (P-powder, T-tablets, and X-brushing). Color changes, and mean surface roughness were measured at 24 h, 48 h, and after 7 days. Statistical analysis was performed. After the testing period, atomic force microscopy (AFM) analyses and SEM images were registered in order to characterize the surface topography. (3) Results: Quantitative color change evaluations revealed a slight change in color after 24 h and an extremely marked change after 48 h, respective 7 days. Mean roughness values are kept below the clinically acceptable limit of 0.20 µm for all samples. Related to mean nanoroughness values Sa, and 3D evaluations of the surface quality, Biolon samples have demonstrated the most constant behavior, while Crystal samples are visibly influenced by water immersion. Related to the cleaning method, the topography of Duran samples was influenced by mechanical brushing. (4) Conclusions: Nanoscale investigations provided high accuracy and more realistic surface quality examinations of the examined samples compared to profilometry. Both SEM and AFM should be used for a more detailed description of the surface topography.

Surface Characterization and Optical Properties of Reinforced Dental Glass-Ceramics Related to Artificial Aging.

The development of various dental glass-ceramic materials and the evolution of novel processing technologies lead to an essential change in the clinical and technical workflow. The long-term success of a dental restoration treatment is defined by its durability, which is directly influenced by the oral environment. This study's purpose was to evaluate the artificial aging behavior of nanostructured, respective microstructured ceramics related to surface topography, roughness, and optical properties. Six monolithic restoration materials were selected: milled lithium disilicate glass-ceramic (LDS-M) MT (medium translucency), hot-pressed lithium disilicate glass-ceramic (LDS-P) MT and HT (high translucency), milled zirconia-reinforced lithium silicate ceramic (ZLS-M) MT and hot-pressed zirconia-reinforced lithium silicate ceramic (ZLS-P) MT and HT, resulting n = 96 surfaces. All the samples were artificially aged by thermal cycling, and all investigations were made before and after thermal cycling. In terms of optical properties, differences recorded between ZLS and LDS ceramics are not significant. Thermal cycling increases the translucency of ZLS and LDS glass-ceramic materials significantly, with the most harmful effect on the pressed and polished samples. Micro- and nano roughness are significantly influenced by in vitro aging and a negative correlation was recorded. Glazed samples are characterized by significant rougher surfaces for all types of materials. On nanolevel, ZLS materials are significantly smoothed by thermal cycling.

Hybrid Materials Based on Silica Matrices Impregnated with Pt-Porphyrin or PtNPs Destined for CO2 Gas Detection or for Wastewaters Color Removal.

Multifunctional hybrid materials with applications in gas sensing or dye removal from wastewaters were obtained by incorporation into silica matrices of either Pt(II)-5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (PtTAOPP) or platinum nanoparticles (PtNPs) alone or accompanied by 5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (TAOPP). The tetraethylorthosilicate (TEOS)-based silica matrices were obtained by using the sol-gel method performed in two step acid-base catalysis. Optical, structural and morphological properties of the hybrid materials were determined and compared by UV-vis, fluorescence and FT-IR spectroscopy techniques, by atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM) and by Brunauer-Emmett-Teller (BET) analysis. PtTAOPP-silica hybrid was the most efficient material both for CO2 adsorption (0.025 mol/g) and for methylene blue adsorption (7.26 mg/g) from wastewaters. These results were expected due to both the ink-bottle mesopores having large necks that exist in this hybrid material and to the presence of the porphyrin moiety that facilitates chemical interactions with either CO2 gas or the dye molecule. Kinetic studies concerning the mechanism of dye adsorption demonstrated a second order kinetic model, thus it might be attributed to both physical and chemical processes.

Effect of Thermocycling, Surface Treatments and Microstructure on the Optical Properties and Roughness of CAD-CAM and Heat-Pressed Glass Ceramics.

Dental ceramic restorations are widely spread nowadays due to their aesthetics and biocompatibility. In time, the colour and structure of these ceramic materials can be altered by aging processes. How does artificial aging affect the optical and surface roughness of ceramics? This study aims to assess the effect of thermocycling, surface treatments and microstructure upon translucency, opalescence and surface roughness on CAD-CAM and heat-pressed glass-ceramic. Forty-eight samples (1.5 mm thickness) were fabricated from six types of A2 MT ceramic: heat-pressed and milled glass-ceramic (feldspathic, lithium disilicate and zirconia reinforced lithium silicate). The samples were obtained respecting the manufacturer's instructions. The resulted surfaces (n = 96) were half glazed and half polished. The samples were subjected to thermocycling (10,000 cycles) and roughness values (Ra and Rz), colour coordinates (L*, a*, b*) and microstructural analyses were assessed before and after thermocycling. Translucency (TP) and opalescence (OP) were calculated. Values were statistically analysed using ANOVA test (one way). TP and OP values were significantly different between heat-pressed and milled ceramics before and also after thermocycling (p < 0.001). Surface treatments (glazing and polishing) had a significant effect on TP and OP and surface roughness (p < 0.05). The heat-pressed and milled zirconia reinforced lithium silicate glass-ceramic experienced a loss in TP and OP. Ra and Rz increased for the glazed samples, TP and OP decreased for all the samples after thermocycling. Microstructural analyse revealed that glazed surfaces were more affected by the thermocycling and especially for the zirconia reinforced lithium silicate ceramic. Optical properties and surface roughness of the chosen ceramic materials were affected by thermocycling, surface treatments and microstructural differences. The least affected of the ceramics was the lithium disilicate ceramic heat-pressed polished and glazed.

X-ray Structure Elucidation of a Pt-Metalloporphyrin and Its Application for Obtaining Sensitive AuNPs-Plasmonic Hybrids Capable of Detecting Triiodide Anions.

The development of UV⁻vis spectrophotometric methods based on metalloporphyrins for fast, highly sensitive and selective anion detection, which avoids several of the practical challenges associated with other detection methods, is of tremendous importance in analytical chemistry. In this study, we focused on achieving a selective optical sensor for triiodide ion detection in traces based on a novel hybrid material comprised of Pt(II) 5,10,15,20-tetra(4-methoxy-phenyl)-porphyrin (PtTMeOPP) and gold nanoparticles (AuNPs). This sensor has high relevance in medical physiological tests. The structure of PtTMeOPP was investigated by single crystal X-ray diffraction in order to understand the metal surroundings and the molecule conformation and to assess if it qualifies as a potential sensitive material. It was proven that the Pt-porphyrin generated 1D H-bond supramolecular chains due to the weak C-H···O intermolecular hydrogen bonding. The presence of ordered voids in the crystal encouraged us to use PtTMeOPP as the sensing material for triiodide ion and to enhance its potential in a novel AuNPs/PtTMeOPP hybrid by the synergistic effects provided by the plasmonic gold nanoparticles. The spectrophotometric sensor is characterized by a detection limit of 1.5 × 10-9 M triiodide ion concentration and a remarkable confidence coefficient of 99.98%.

Trace Oxygen Sensitive Material Based on Two Porphyrin Derivatives in a Heterodimeric Complex.

The successful preparation of a novel dimer complex formed between 5,10,15,20-tetrakis(3,4-dimethoxyphenyl)-porphyrin Fe(III) chloride and (5,10,15,20-tetraphenylporphinato) dichlorophosphorus(V) chloride using the well-known reactivity of the P-X bond is reported. The obtained complex was characterized by UV-vis, Fourier transform infrared spectroscopy (FT-IR), fluorescence, ¹H-NMR, 13C-NMR, and 31P-NMR spectroscopic techniques and also by additional Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple Bond Correlation (HMBC) experiments in order to correctly assign the NMR signals. Scanning electron microscopy (SEM) and EDX quantifications completed the characterizations. This novel porphyrin dimer complex demonstrated fluorescence sensing of H2O2 in water for low oxygen concentrations in the range of 40-90 µM proving medical relevance for early diagnosis of diseases such as Alzheimer's, Parkinson's, Huntington's, and even cancer because higher concentrations of H2O2 than 50 µM are consideredcytotoxic for life. Due to its optical properties, this novel metalloporphyrin-porphyrin based complex is expected to show PDT and bactericidal activity under visible-light irradiation.

A sensitive A3B porphyrin nanomaterial for CO2 detection.

The present report deals with the tailoring, preparation and characterization of novel nanomaterials sensitive to CO2 for use in detection of this gas during space habitation missions. A new nanostructured material based on mixed substituted asymmetrical A3B porphyrin: 5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)-porphyrin (PyTDMeOPP) was synthesized and characterized by 1H-NMR, FT-IR, UV-vis, fluorescence, MS, HPLC and AFM. Introducing one pyridyl substituent in the 5-meso-position of porphyrin macrocycle confers some degree of hydrophilicity, which may cause self-assembly properties and a better response to increased acidity. The influence of pH and nature of the solvent upon H and J aggregates of the porphyrin are discussed. Porphyrin aggregation at the air-THF interface gave a triangular type morphology, randomly distributed but uniformly oriented. When deposition was made by multiple drop-casting operations, a network of triangles of uniform size was created and a porous structure was obtained, being reorganized finally in rings. When the deposition was made from CHCl3, ring structures ranging in internal diameter from 300 nm to 1 µm, but with the same width of the corona circular of approx. 200 nm were obtained. This porphyrin-based material, capable of generating ring aggregates in both THF and CHCl3, has been proven to be sensitive to CO2 detection. The dependence between the intensity of porphyrin UV-vis absorption and the concentration of CO2 has a good correlation of 98.4%.