Synthesis and Pd(II) binding studies of octasubstituted alkyl thio derivatised phthalocyanines

Synthesis and characterization of non-peripherally (4,5) and peripherally (6,7) substituted metal free and Pd octapentylthiophthalocyanine and coordination of palladium ions to these Pcs are reported. The unmetalated complexes (4 and 6) show Pd coordination at the central metal and at the ring. The number of Pd ions bound to complex 4 were found to be five and to complex 6 were three. The equilibrium constant for the binding of Pd to complexes 4 was lower (K = 1.2 × 109 dm3 mol−1) than for complex 6 (K = 5.7 × 1010 dm3 mol−1)

Synthesis and Photophysical Investigation of Tetraazaporphyrin Substituted with Aggregation‐Induced Emission (AIE) Active Moieties

The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields

Synthesis, theoretical calculations and laser flash photolysis studies of selected amphiphilic porphyrin derivatives used as biofilm photodegradative materials

Photodynamic antimicrobial activities of gallium and indium porphyrins as well as their quaternized derivatives have been investigated against S. aureus and E. coli biofilms, as well as on their planktonic (free floating) cells using a light emitting diode lamp at 415 nm. The studied photosensitizers show considerable ability to generate singlet oxygen and the quaternized molecules 2a and 3a are potential photodynamic antimicrobial chemotherapy (PACT) agents with log10 colony forming units >9 for E. coli and S. aureus planktonic cells. The quaternized derivatives are found to have higher ability to significantly suppress the biofilms of both S. aureus and E. coli in vitro. Therefore, this demonstrates that they are potentially suitable photosensitive agents for PACT use. The TD-B3LYP/LanL2DZ calculations were performed to evaluate the singlet excitation energies of quaternized and non-quaternized porphyrins in vacuo. Our study shows excellent agreement between time-dependent density-functional theory (TD-DFT) excited energies and experimental S1 > S0 excitation energies. The small deviation observed between the calculated and experimental spectra arises from the solvent effect. The excitation energies observed in these UV-visible spectra mostly originated from electron promotion between the highest occupied molecular orbital (HOMO) for the less intense band and the HOMO−1 for the most intense band of the ground states to the lower unoccupied molecular orbital (LUMO) of the excited states

Synthesis, theoretical calculations and laser flash photolysis studies of selected amphiphilic porphyrin derivatives used as biofilm photodegradative materials

Photodynamic antimicrobial activities of gallium and indium porphyrins as well as their quaternized derivatives have been investigated against S. aureus and E. coli biofilms, as well as on their planktonic (free floating) cells using a light emitting diode lamp at 415 nm. The studied photosensitizers show considerable ability to generate singlet oxygen and the quaternized molecules 2a and 3a are potential photodynamic antimicrobial chemotherapy (PACT) agents with log10 colony forming units >9 for E. coli and S. aureus planktonic cells. The quaternized derivatives are found to have higher ability to significantly suppress the biofilms of both S. aureus and E. coli in vitro. Therefore, this demonstrates that they are potentially suitable photosensitive agents for PACT use. The TD-B3LYP/LanL2DZ calculations were performed to evaluate the singlet excitation energies of quaternized and non-quaternized porphyrins in vacuo. Our study shows excellent agreement between time-dependent density-functional theory (TD-DFT) excited energies and experimental S1 > S0 excitation energies. The small deviation observed between the calculated and experimental spectra arises from the solvent effect. The excitation energies observed in these UV-visible spectra mostly originated from electron promotion between the highest occupied molecular orbital (HOMO) for the less intense band and the HOMO−1 for the most intense band of the ground states to the lower unoccupied molecular orbital (LUMO) of the excited states

The effect of structure on the electrochemical properties of 14 marine pyrroloquinoline metabolites

The electrochemical properties of 14 structurally related pyrroloquinoline metabolites (compounds 1–14) isolated from marine sponges were studied in pH-varied experiments using cyclic and square wave voltammetry. In general both substitution patterns and pH were observed to influence the reduction potentials of these molecules

Selective adsorption of PVP on the surface of silver nanoparticles

The use of surfactants to affect the shape evolution of silver nanoparticles is explored. This allows one to fine-tune the morphological evolution and the optical properties of the metal nanoparticles. Polyvinyl pyrrolidone (PVP) has been used as a surfactant to control the growth of silver nanoparticles at room temperature. In this paper, molecular dynamics simulations were performed to understand regio-selective adsorption of PVP that leads to the preferential growth of silver nanoparticles in dimethylformamide (DMF). The interaction energies between PVP and Ag(1 1 0), Ag(1 0 0) and Ag(1 1 1) crystal planes were calculated and in addition the length density profile of the surfactant on silver surfaces was also examined. Importantly, it has been demonstrated that the length distribution profiles analysis obtained from the molecular dynamics study fully explained the adsorption of PVP on the surface of silver nanoparticles through the carbonyl group of the PVP ring. The application of molecular dynamics simulation technique is important in understanding the evolution of silver nanoparticles and is vital in choosing the right surfactants

Synthesis, density functional theory, molecular dynamics and electrochemical studies of 3-thiopheneacetic acid-capped gold nanoparticles

Gold nanoparticles capped with a bifunctional ligand, 3-thiopheneacetic acid (3-TAA) were synthesised by borohydride reduction at room temperature. The transmission electron microscopy (TEM) analysis showed that the particle aggregates and had semi-linear partial linkages that could be attributed to multi-modal binding of the ligand with various gold nanoparticles through the terminal thiolether (–S–) group and oxygen of the carboxylic (–COOH) group. This bimodal interaction led to limited stability of the resultant nanoparticles when tested using highly electrolytic media. To investigate further, density functional theory (DFT) quantum chemical and molecular dynamic calculations were conducted. The energetically favorable binding modes of the ligand to gold nanoparticle surfaces using the Gaussian program were studied. The DFT results showed kinetic stability of Au–3-TAA–Au interactions leading to inter-particle coupling or aggregation. Electrochemical analysis of the resultant nature of the capping agent revealed that 3-thiopheneacetic acid did not form a polymer during the preparation of Au–3-TAA. The cyclic voltammograms of Au–3-TAA nanoparticles coated glassy carbon electrode showed a typical gold character with the oxidation and reduction peaks at 1.4 V and 0.9 V, respectively

Introducing chemistry students to the “real world” of chemistry

A majority of chemistry graduates seek employment in a rapidly changing chemical industry. Our attempts to provide the graduates with skills in entrepreneurship and the ability to understand and communicate with their chemical engineering colleagues, in addition to their fundamental knowledge of chemistry, are described. This is done at second-year level with practical projects in which student teams formulate and prepare relatively simple chemical products for marketing, followed a year later by a more advanced study of the feasibility of producing and marketing a fine chemical on a commercial scale

Electrode modification using nanocomposites of electropolymerised cobalt phthalocyanines supported on multiwalled carbon nanotubes

A polymer of tetra(4)-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II) (CoPyPc) has been deposited over a multiwalled carbon nanotube (MWCNT) platform and its electrocatalytic properties investigated side by side with polymerized cobalt tetraamino phthalocyanine (CoTAPc). X-ray photoelectron spectroscopy, scanning electron microscopy and cyclic voltammetry studies were used for characterization of the prepared polymers of cobalt phthalocyanine derivatives and their nanocomposites. L-Cysteine was used as a test analyte for the electrocatalytic activity of the nanocomposites of polymerized cobalt phthalocyanines and multiwalled carbon nanotubes. The electrocatalytic activity of both polymerized cobalt phthalocyanines was found to be superior when polymerization was done on top of MWCNTs compared to bare glassy carbon electrode. A higher sensitivity for L-cysteine detection was obtained on CoTAPc compared to CoPyPc

Magnetic and Photoluminescent Sensors Based on Metal-Organic Frameworks Built up from 2-aminoisonicotinate

Red Guipuzcoana de Ciencia, Tecnologia e Innovacion OF218/2018 University of Basque Country GIU 17/13 Basque Government IT1005-16 IT1291-19 IT1310-19 Junta de Andalucia FQM-394 Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) PGC2018-102052-A-C22 PGC2018-102052-B-C21 MAT2016-75883-C2-1-P European Union (EU) ESFIn this work, three isostructural metal-organic frameworks based on frst row transition metal ions and 2-aminoisonicotinate (2ain) ligands, namely, {[M(μ-2ain)2]·DMF}n [MII=Co (1), Ni (2), Zn (3)], are evaluated for their sensing capacity of various solvents and metal ions by monitoring the modulation of their magnetic and photoluminescence properties. The crystal structure consists of an open diamond-like topological 3D framework that leaves huge voids, which allows crystallizing two-fold interpenetrated architecture that still retains large porosity. Magnetic measurements performed on 1 reveal the occurrence of feld-induced spin-glass behaviour characterized by a frequency-independent relaxation. Solvent-exchange experiments lead successfully to the replacement of lattice molecules by DMSO and MeOH, which, on its part, show dominating SIM behaviour with low blocking temperatures but substantially high energy barriers for the reversal of the magnetization. Photoluminescence studied at variable temperature on compound 3 show its capacity to provide bright blue emission under UV excitation, which proceeds through a ligand-centred charge transfer mechanism as confrmed by timedependent DFT calculations. Turn-of and/or shift of the emission is observed for suspensions of 3 in diferent solvents and aqueous solutions containing metal ions