Triazine Group Research Articles

Stepwise co-sensitization as a useful tool for enhancement of power conversion efficiency of dye-sensitized solar cells: The case of an unsymmetrical porphyrin dyad and a metal-free organic dye

A tertiary arylamine compound (DC), which contains a terminal cyano-acetic group in one of its aryl groups, and an unsymmetrical porphyrin dyad of the type Zn[Porph]-L-H2[Porph] (ZnP-H2P), where Zn[Porph] and H2[Porph] are metallated and free-base porphyrin units, respectively, and L is a bridging triazine group functionalized with a glycine moiety, and were synthesized and used for the fabrication of co-sensitized dye-sensitized solar cells (DSSCs). The photophysical and electronic properties of the two compounds revealed spectral absorption features and frontier orbital energy levels that are appropriate for use in DSSCs. Following a stepwise co-sensitization procedure, by immersing the TiO2 electrode in separate solutions of the dyes in different sequence, two co-sensitized solar cells were obtained: devices C (ZnP-H2P/DC) and D (DC/ZnP-H2P).The two solar cells were found to exhibit power conversion efficiencies (PCEs) of 6.16% and 4.80%, respectively. The higher PCE value of device C, which is also higher than that of the individually sensitized devices based on the ZnP-H2P and DC dyes, is attributed to enhanced photovoltaic parameters, i.e. short circuit current (Jsc=11.72mA/cm2), open circuit voltage (Voc=0.72V), fill factor (FF=0.73), as it is revealed by photovoltaic measurements (J–V curves) and by incident photon to current conversion efficiency (IPCE) spectra of the devices, and to a higher total dye loading. The overall performance of device C was further improved up to 7.68% (with Jsc=13.45mA/cm2, Voc=0.76V, and FF=0.75), when a formic acid treated TiO2ZnP-H2P co-sensitized photoanode was employed (device E). The increased PCE value of device E has been attributed to an enhanced Jsc value (=13.45mA/cm2), which resulted from an increased dye loading, and an enhanced Voc value (=0.76V), attributed to an upward shift and increased of electron density in the TiO2 CB. Furthermore, dark current and electrochemical impedance spectra (EIS) of device E revealed an enhanced electron transport rate in the formic acid treated TiO2 photoanode, suppressed electron recombination at the photoanode/dye/electrolyte interface, as well as shorter electron transport time (τd), and longer electron lifetime (τe).

Graphene Quantum Dots as Fluorescence Probes for Turn-off Sensing of Melamine in the Presence of Hg2+

A rapid and sensitive fluorescence sensing system for melamine based on charge transfer quenching of the fluorescence of graphene quantum dots (GQDs) in the presence of Hg(2+) is proposed. The synthesized GQDs were strongly luminescent with predominantly aromatic sp(2) domains. Melamine could coordinate with mercury through nitrogen atoms in both its amine and triazine groups and bring more Hg(2+) to the surface of GQDs through π-π stacking, thus leading to quenching of the GQDs' fluorescence. The quenching mechanism was investigated in detail and ascribed to charge transfer from the GQDs to Hg(2+) with melamine acting as the linkage agent. The melamine demonstrated a linear range 0.15-20 μM and a detection limit of 0.12 μM, which was far below the regulatory level, suggesting the promising practical usage of this sensing system. This sensing system also possessed high selectivity for melamine in the presence of possible interferences. Finally, this novel sensor was successfully applied for melamine detection in raw milk and satisfactory recovery was achieved.

Efficient CO₂ capture by a task-specific porous organic polymer bifunctionalized with carbazole and triazine groups.

A porous triazine and carbazole bifunctionalized task-specific polymer has been synthesized via a facile Friedel-Crafts reaction. The resultant porous framework exhibits excellent CO2 uptake (18.0 wt%, 273 K and 1 bar) and good adsorption selectivity for CO2 over N2.

Immobilisation of Phenanthroline-Bis Triazine (C1-BTPhen) on Magnetic Nanoparticles for Co-Extraction of Americium(III) and Europium(III)

The present work reports a convenient route for the immobilisation of a phenanthroline-bis triazine (C1-BTPhen) group on the surface of zirconia-coated maghemite (γ-Fe2O3) magnetic nanoparticles. The magnetic nanoparticles functionalized with C1-BTPhen were able to co-extract Am(III) and Eu(III) from nitric acid (HNO3). The extraction efficiency of these C1-BTPhen-functionalized magnetic nanoparticles for both Am(III) and Eu(III) was 20% at 4M HNO3. The interaction between C1-BTPhen and metal cations is reversible. These functionalized magnetic nanoparticles can be used for the co-extraction of traces of Am(III) and Eu(III).

New solution processed bulk-heterojunction organic solar cells based on a triazine-bridged porphyrin dyad as electron donor

An unsymmetrical porphyrin dyad (ZnP)-[triazine-Npip]-(ZnPCOOH) consisting of two zinc-porphyrin units covalently linked to a peridine-containing triazine group has been used with PC71BM as electron donor and acceptor, respectively, for the active layer of solution-processed BHJ organic solar cells.

Hydrophobic shape memory poly(oxazolidone-triazine) cyclomatrix networks with high transition temperatures

Shape memory cyclomatrix network polymers comprising oxazolidone and triazine groups linked by a shape memory segment of polycaprolactone are synthesised by co-reacting a cyanate ester with an epoxy monomer in the presence of a polycaprolactone diol (PCLD). These systems possess transition temperatures (Ttrans) between 127 and 180 °C and are tunable by the PCLD concentration. The cross-linked polymers exhibit 100% shape fixity and near complete shape recovery in a short span of time. The high Ttrans and low propensity for moisture absorption provide a stable fixed shape. Water repellency is reflected in the contact angles of 82–86°, which are higher than that for typical epoxy systems.

Investigating the Gas Sorption Mechanism in an rht-Metal–Organic Framework through Computational Studies

Grand canonical Monte Carlo (GCMC) simulations were performed to investigate CO2 and H2 sorption in an rht-metal–organic framework (MOF) that was synthesized with a ligand having a nitrogen-rich trigonal core through trisubstituted triazine groups and amine functional groups. This MOF was synthesized by two different groups, each reporting their own distinct gas sorption measurements and crystal structure. Electronic structure calculations demonstrated that the small differences in the atomic positions between each group’s crystal structure resulted in different electrostatic parameters about the Cu2+ ions for the respective unit cells. Simulations of CO2 sorption were performed with and without many-body polarization effects and using our recently developed CO2 potentials, in addition to a well-known bulk CO2 model, in both crystallographic unit cells. Simulated CO2 sorption isotherms and calculated isosteric heats of adsorption, Qst, values were in excellent agreement with the results reported previousl...

Synthesis and photophysical studies of triazine-linked porphyrin–perylene bisimide dyad with long-lived perylene triplet state

Abstract Porphyrin–perylene bisimide dyad containing a triazine group as the linker was synthesized and characterized. The absorption spectra reveal that there is no appreciable interaction between the ground-state porphyrin and ground-state perylene. The fluorescence spectra illustrate that photoinduced energy transfer takes place from the excited perylene to ground-state porphyrin moiety when excited at 491 nm, while enhanced photoinduced electron transfer occurs from the porphyrin singlets to ground-state perylene moiety in the case of excitation at 423 nm. The kinetic analysis indicates that a long-lived perylene triplet state (146 μs) forms via triplet–triplet energy transfer from the porphyrin to perylene moiety, showing potential applications in the photodynamic therapy. These photochemical events are explained with an energy-level diagram.

Efficient Sensitization of Dye-Sensitized Solar Cells by Novel Triazine-Bridged Porphyrin–Porphyrin Dyads

Two novel porphyrin-porphyrin dyads, the symmetrical Zn[Porph]-Zn[Porph] (2) and unsymmetrical Zn[Porph]-H2[Porph] (4), where Zn[Porph] and H2[Porph] are the metalated and free-base forms of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin, respectively, in which two porphyrin units are covalently bridged by 1,3,5-triazine, have been synthesized via the stepwise amination of cyanuric chloride. The dyads are also functionalized by a terminal carboxylic acid group of a glycine moiety attached to the triazine group. Photophysical measurements of 2 and 4 showed broaden and strengthened absorptions in their visible spectra, while electrochemistry experiments and density functional theory calculations revealed negligible interaction between the two porphyrin units in their ground states but appropriate frontier orbital energy levels for use in dye-sensitized solar cells (DSSCs). The 2- and 4-based solar cells have been fabricated and found to exhibit power conversion efficiencies (PCEs) of 3.61% and 4.46%, respectively (under an illumination intensity of 100 mW/cm(2) with TiO2 films of 10 μm thickness). The higher PCE value of the 4-based DSSC, as revealed by photovoltaic measurements (J-V curves) and incident photon-to-current conversion efficiency (IPCE) spectra of the two cells, is attributed to its enhanced short-circuit current (J(sc)) under illumination, high open-circuit voltage (V(oc)), and fill factor (FF) values. Electrochemical impedance spectra demonstrated shorter electron-transport time (τd), longer electron lifetime (τe), and high charge recombination resistance for the 4-based cell, as well as larger dye loading onto TiO2.

Selectivity of the Highly Preorganized Tetradentate Ligand 2,9-Di(pyrid-2-yl)-1,10-phenanthroline for Metal Ions in Aqueous Solution, Including Lanthanide(III) Ions and the Uranyl(VI) Cation

Some metal ion complexing properties of DPP (2,9-Di(pyrid-2-yl)-1,10-phenanthroline) are reported with a variety of Ln(III) (Lanthanide(III)) ions and alkali earth metal ions, as well as the uranyl(VI) cation. The intense π-π* transitions in the absorption spectra of aqueous solutions of 10(-5) M DPP were monitored as a function of pH and metal ion concentration to determine formation constants of the alkali-earth metal ions and Ln(III) (Ln = lanthanide) ions. It was found that log K(1)(DPP) for the Ln(III) ions has a peak at Ln(III) = Sm(III) in a plot of log K(1) versus 1/r(+) (r(+) = ionic radius for 8-coordination). For Ln(III) ions larger than Sm(III), there is a steady rise in log K(1) from La(III) to Sm(III), while for Ln(III) ions smaller than Sm(III), log K(1) decreases slightly to the smallest Ln(III) ion, Lu(III). This pattern of variation of log K(1) with varying size of Ln(III) ion was analyzed using MM (molecular mechanics) and DFT (density functional theory) calculations. Values of strain energy (∑U) were calculated for the [Ln(DPP)(H(2)O)(5)](3+) and [Ln(qpy)(H(2)O)(5)](3+) (qpy = quaterpyrdine) complexes of all the Ln(III) ions. The ideal M-N bond lengths used for the Ln(III) ions were the average of those found in the CSD (Cambridge Structural Database) for the complexes of each of the Ln(III) ions with polypyridyl ligands. Similarly, the ideal M-O bond lengths were those for complexes of the Ln(III) ions with coordinated aqua ligands in the CSD. The MM calculations suggested that in a plot of ∑U versus ideal M-N length, a minimum in ∑U occurred at Pm(III), adjacent in the series to Sm(III). The significance of this result is that (1) MM calculations suggest that a similar metal ion size preference will occur for all polypyridyl-type ligands, including those containing triazine groups, that are being developed as solvent extractants in the separation of Am(III) and Ln(III) ions in the treatment of nuclear waste, and (2) Am(III) is very close in M-N bond lengths to Pm(III), so that an important aspect of the selectivity of polypyridyl type ligands for Am(III) will depend on the above metal ion size-based selectivity. The selectivity patterns of DPP with the alkali-earth metal ions shows a similar preference for Ca(II), which has the most appropriate M-N lengths. The structures of DPP complexes of Zn(II) and Bi(III), as representative of a small and of a large metal ion respectively, are reported. [Zn(DPP)(2)](ClO(4))(2) (triclinic, P1, R = 0.0507) has a six-coordinate Zn(II), with each of the two DPP ligands having one noncoordinated pyridyl group appearing to be π-stacked on the central aromatic ring of the other DPP ligand. [Bi(DPP)(H(2)O)(2)(ClO(4))(2)](ClO(4)) (triclinic, P1, R = 0.0709) has an eight-coordinate Bi, with the coordination sphere composed of the four N donors of the DPP ligand, two coordinated water molecules, and the O donors of two unidentate perchlorates. As is usually the case with Bi(III), there is a gap in the coordination sphere that appears to be the position of a lone pair of electrons on the other side of the Bi from the DPP ligand. The Bi-L bonds become relatively longer as one moves from the side of the Bi containg the DPP to the side where the lone pair is thought to be situated. A DFT analysis of [Ln(tpy)(H(2)O)(n)](3+) and [Ln(DPP)(H(2)O)(5)](3+) complexes is reported. The structures predicted by DFT are shown to match very well with the literature crystal structures for the [Ln(tpy)(H(2)O)(n)](3+) with Ln = La and n = 6, and Ln = Lu with n = 5. This then gives one confidence that the structures for the DPP complexes generated by DFT are accurate. The structures generated by DFT for the [Ln(DPP)(H(2)O)(5)](3+) complexes are shown to agree very well with those generated by MM, giving one confidence in the accuracy of the latter. An analysis of the DFT and MM structures shows the decreasing O--O nonbonded distances as one progresses from La to Lu, with these distances being much less than the sum of the van der Waals radii for the smaller Ln(III) ions. The effect that such short O--O nonbonded distances has on thermodynamic complex stability and coordination number is then discussed.

Synthesis of a novel flame retardant containing phosphorus-nitrogen and its comparison for cotton fabric

A new charring agent, a derivative of cyanuric chloride, mono-substituted, dimethyl (4,6-dichloro-1,3,5-triazin-2- yloxy)methylphosphonate (CN), was synthesized in good yield and characterized. Its flame retardant and thermogravimetric properties were compared to those of the di-substituted compound, tetramethyl (6-chloro-1,3,5-triazine-2,4-diyl)bis(oxy)bis (methylene)diphosphonate (CN-1), which was prepared in previous work. All untreated fabric showed limiting oxygen index (LOI) values of about 18 vol% oxygen in nitrogen. Fabrics treated with CN at 5-21 wt% add-ons had high LOI values of 30- 40 vol%, while fabrics treated with CN-1 at 5-19 wt% add-ons had low to high LOI value of 20-36 vol%. In 45 o angle flammability tests, all treated fabrics with CN and CN-1 were passed and some fabrics were not igniting at all. Thermal degradation revealed that onset of degradation and the char yield of CN compound is higher than that of CN-1. Treated fabric with CN, 21 wt% add-on, had an onset of degradation of 240 oC, while fabric treated with CN-1, 19 wt% add-on displayed an onset of degradation of 230 o C. Despite the differences in onset temperature, the two samples provided almost the same char yield at 600 o C, 35 and 36 %. With Fourier transform infrared (FTIR), samples of treated/unburned and treated/burned of CN and CN-1 showed the same functional groups and revealed the disappearance of triazine group and P-O-methyl after burning. Additionally, scanning electron microscopy (SEM) showed that both CN and CN-1 acted as flame retardants by the same mechanism and characterized the surface morphology of the flame retardant treated twill fabrics.

Preparation and properties of fumed silica/cyanate ester nanocomposites

Fumed silica/bisphenol A dicyanate ester (BADCy) nanocomposites were prepared by introducing different contents of nano-sized fumed SiO2 into the BADCy matrix. Two different average primary particle diameters of 12 and 40 nm were chosen. Dibutyltindilaurate (DBTDL) catalyst was chosen to catalyze the cyanate ester group into triazine group via cyclotrimerization reaction. The SEM micrographs indicated that the fumed SiO2 particles were homogeneously dispersed in the poly(bisphenol A dicyanate) matrix by means of ultrasonic treatment and the addition of a coupling agent. The FTIR spectroscopy shows that, not only DBTDL catalyzes the polymerization reaction but also -OH groups of the SiO2 particles surface help the catalyst for the complete polymerization of BADCy monomer. The thermal stability of the cured BADCy can be improved by adequate addition of fumed SiO2. A slight increase in the dielectric constant and dielectric loss values were identified by testing the dielectric properties of the prepared nanocomposite samples. By increasing the SiO2 content, there was a slight increasing in the thermal conductivity values of the tested samples. The obtained results proved that the fumed silica/BADCy nanocomposites had good thermal and dielectrical properties and can be used in many applications such as in the thermal insulation field.

Characterization of 4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine

Abstract4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine (DANT) was prepared with a 35 % yield from cyanuric chloride in a three step process. DANT was characterized by IR and NMR spectroscopy (1H, 13C, 15N), single‐crystal X‐ray diffraction, and DTA. The crystal density of DANT is 1.849 g cm−3. The cyclization of one azido group and one nitrogen atom of the triazine group giving tetrazole was observed for DANT in a dimethyl sulfoxide solution using NMR spectroscopy. An equilibrium exists between the original DANT molecule and its cyclic form at a ratio of 7 : 3. The sensitivity of DANT to impact is between that for PETN and RDX, sensitivity to friction is between that for lead azide and PETN, and sensitivity to electric discharge is about the same as for PETN. DANT′s heat of combustion is 2060 kJ mol−1.

The effects of metribuzin on early life stages of common carp (Cyprinus carpio)

Metribuzin belongs to the triazine group of herbicides, which are frequently used in agriculture. The aim of this study was to assess the impact of metribuzin on growth and development of early life stages of fish. Subchronic toxic effects of metribuzin at concentrations of 0.9, 4, 14, and 32mg/L on embryos and larvae of common carp (Cyprinus carpio) were investigated during a 30day toxicity test under experimental conditions. Exposure to metribuzin at 32mg/L was associated with increased mortality. Negative effects on total body length, weight, and inhibition of specific growth rate were induced by all experimental concentrations. Length and weight parameters were the most sensitive. The negative impact of metribuzin was observed in the highest tested concentration beginning on day 6 of exposure. Retardation of early ontogeny was associated with concentrations ⩾4mg/L. Histological examination revealed changes in liver and caudal kidney after 30days exposure to 32mg/L. Based on growth parameters, development, and histological examination, the Lowest Observed Effect Concentration (LOEC) value was 0.9mg/L.

Photodegradation of commercial dye, CI Reactive Blue 160 using ZnO nanopowder: Degradation pathway and identification of intermediates by GC/MS

The ZnO-mediated photocatalysis process has been successfully applied to degradation of commercial dye, CI Reactive Blue 160 (RB 160). Eleven reaction intermediates were separated, identified and characterized by the GC–MS techniques, giving insight into mechanistic details of the ZnO-mediated catalysis process under UV irradiation and the pathways of degradation process. The degradation process take place through competitive reactions such as destruction of chromophoric group, hydroxylation of the aromatic ring, substitution on aromatic ring, desulphonation, decarboxylation and further ring opening to give aliphatic compounds. Smaller aliphatic compounds formed during the process were identified by IC, while the triazine group and naphthalene group containing compounds remains intact even after decolorization for a prolonged time due to high resistance to oxidation. The probable degradation pathways were proposed and discussed.

HYBRID NANOMATERIALS CONTAINING PAMAM, POLYROTAXANE AND QUANTUM DOT BLOCKS

Pseudopolyrotaxanes, Ps-PR, consisting of α-cyclodextrin rings, polyethylene glycol axes and end triazine groups were prepared and then were capped by amino-functionalized quantum dots, NH2 -QDs, to achieve polyrotaxanes. The amino-functionalized QDs stoppers of polyrotaxanes were used as core to synthesize polyamidoamine, PAMAM, dendrons divergently and hybrid nanomaterials were obtained. Synthesized hybrid nanomaterials were characterized by different spectroscopy, microscopy and thermal analysis methods. They were freely soluble in water and their aqueous solutions were stable at room temperature over several months. Due to their biocompatible backbone, high functionality and water solubility synthesized hybrid nanomaterials are promising carriers and probes in cancer diagnosis and therapy.

Quantum dot-pseudopolyrotaxane supramolecules as anticancer drug delivery systems

Pseudopolyrotaxanes (Ps-PR) consisting of α-cyclodextrin rings, polyethylene glycol axes and end triazine groups were synthesized and characterized. Dissociation of the α-cyclodextrin rings from the polyethylene glycol axes was avoided by the host–guest relationship between its end triazine groups and β-cyclodextrins conjugated onto the surface of quantum dots ( β-CD- graft-QDs), leading to a new type of the dynamic polyrotaxanes in which QDs play the role of stoppers noncovalently. Stability of the synthesized supramolecules was depended on the efficiency of the host–guest relationships between the end triazine groups of Ps-PR and β-CD- graft-QDs through which release of α-cyclodextrin rings from the polyethylene glycol axes was controlled. To prove the efficacy of the synthesized supramolecules as drug delivery systems (DDSs) cisplatin (Cis-Diamminedichloroplatinum (CDDP) a platinum-based chemotherapy drug) and folic acid as a tumor-recognition module were conjugated to their stoppers and they were subjected to the receptor-mediated endocytosis and release inside the cancer cells, murine colon adenocarcinoma tumor C26. Then, it was proved that these tumor-targeting DDSs are promising systems for future cancer therapy. Rate of the release of the drugs, conjugated to the functional groups of stoppers was also investigated.

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.

Headspace solid phase microextraction method for determination of triazine and organophosphorus pesticides in soil

A headspace solid phase microextraction method (HS-SPME) for simultaneous determination of five pesticides belonging to triazine and organophosphorus pesticide groups in soil samples was developed. Microextraction conditions, such as temperature, extraction time and sodium chloride (NaCl) content were investigated and optimized using 100 μ m polydimethyl-siloxane (PDMS) fiber. Detection and quantification were done by gas chromatography-mass spectrometry (GC-MS). Relative standard deviation (RSD) and recovery values for multiple analysis of soil samples fortified at 30 μ g kg− 1 of each pesticide were below 13 % and higher than 70 %, respectively. Limits of detection (LOD) for all the compounds studied were less than 3.2 μ g kg− 1. The proposed method was applied in the analysis of some agricultural soil samples.

Molecular characterization of accessions of crabgrass (Digitaria nuda) and response to ametryn

Digitaria species are sugar cane crop weeds in Brazil and are being controlled with herbicides, although there are some reports of control failure, notably to the triazine group. Molecular techniques are recommended to analyze the genetic variability in weeds. RAPD (Random Amplified Polymorphic DNA), PCR-RFLP (Polymerase Chain Reaction - Restriction Fragment Length Polymorphism) and, in combination with sequencing, allow the localization of resistance genes, as well as possible mutations related to the onset of resistant individuals in some species. Thus, the objective of this work was to characterize ten accessions of Digitaria spp. by RAPD and PCR-RFLP markers, to sequence a conserved region of the psbA gene and evaluate the accessions response to ametryn. As showed by molecular analysis there was high genetic similarity among the accessions, all of them presented similar genetics profiles and were susceptible to ametryn.