Structure of magnetically guided nanocarriers of the photodithazine sensitizer from small-angle neutron scattering data

Nanosized complexes of ferromagnetic particles with a photodithazine sensitizer (used in photo-dynamic therapy in oncology) have been synthesized and investigated using small-angle neutron scattering for the first time. The structure of the complexes has been determined, and the influence of the biocompatible polymer Pluronic on their structure has been analyzed. The possibilities of using the complexes for magnetically guided delivery of the photosensitizer to cells and tissues in the treatment of oncological diseases by photodynamic therapy have been discussed.     

Formation of an Equilibrium Complex of Lactate Dehydrogenase with Chlorin e 6

Using spectrophotometric, spectral-luminescent, and polarization methods, we have detected the formation of strong equilibrium complexes of a key glycolytic enzyme — lactate dehydrogenase — with a promising photodynamic sensitizer — chlorin e ₆. It has been established that enzymes serve as the most sensitive targets destroying tumor cells subjected to photodynamic therapy.     

Colour emission tunability in Ho3+–Tm3+–Yb3+ co-doped Y2O3 upconverted phosphor

The frequency upconversion (UC) emission throughout the visible region from the Y₂O₃:Ho³⁺?CTm³⁺?CYb³⁺ co-doped phosphors synthesized by using low temperature combustion process upon excitation with a diode laser operating at 980?nm have been presented. The colour emission tunability in co-doped phosphor has been observed on increasing the pump power and seen by the naked eyes. The tunability in colour emission has also been visualized by CIE chromaticity diagram. The variation in UC emission intensity of the ¹G₄????³H₆ (Tm³⁺) and ⁵F₃????⁵I₈ (Ho³⁺) transitions lying in the blue region has been monitored with increase in the pump power and marked that their ratio can be used to determine the temperature. The developed phosphor has been used to record fingerprints. The observed most intense visible colour emission from the developed material may be used for photodynamic therapy and as an alternative of traditional fluorescent biolabels.     

Synthesis,Spectroscopic and Antimicrobial Studies of Lead (II) Complexes of Schiff Bases Derived From Amino Acids and Isatins

A new series of lead (II) complexes have been synthesized with Schiff bases derived from isatins and amino acids. These ligands act as bidentate species and coordinate to the metal atom through the azomethine nitrogen and carboxylate oxygen atom via deprotonation. The synthesized complexes have been characterized by elemental analysis, conductance measurements, and molecular weight determinations. The mode of bonding of the complexes has been suggested on the basis of infrared, UV-visible, and ¹H- and ¹³C-NMR spectroscopy, and probable structures have been assigned to these complexes. Few representative ligands and metal complexes have also been screened for their antifungal and antibacterial activities. Molecular modeling and analysis for bond lengths and bond angles have also been carried out for one of the representative compound, [Pb(L³)₂], to substantiate the proposed structures.     

Porphyrin effect on the surface morphology of amphiphilic polymers as observed by atomic force microscopy

Complexes of porphyrin photosensitizers (PPS) with triblock copolymers of ethylene- and propylene oxide – Pluronics^® – exhibit markedly increased activity in the generation of singlet oxygen in aqueous media, as compared to pure porphyrins. Pluronics are amphiphilic polymers with surfactant properties suitable for a number of medical applications. PPS–Pluronic systems are considered as promising agents for photodynamic therapy which implies generation of singlet oxygen in the water-based human tissue.Importantly, Pluronics are capable of solubilization of not only water-soluble, but also hydrophobic PPS providing their transfer into the aqueous phase. It has been shown earlier that specific interactions of PPS with Pluronics must play a primary role for the photocatalytic properties of PPS–Pluronic systems. In the process of solubilization of a hydrophobic porphyrin by a Pluronic, both components are dissolved in an organic solvent, which is then removed, and the dry film is re-dissolved in water. Apparently, the initial binding between the porphyrin and the lipophilic part of the polymer takes place already at the stage of the film formation.We applied atomic force microscopy (AFM) to visualize structures formed by Pluronics upon their interactions with meso-tetraphenylporphyrin (TPP). We studied the surface structure of Pluronics^® F87, F108 and F127 crystallized alone or together with TPP on silicon substrates from chloroform solutions. We found Pluronics to form similar dendritic structures independently of their molecular weight and degree of hydrophobicity. In the presence of TPP, though, we observed formation of distinct convex structures on top of the Pluronic dendrites. These structures appeared to consist of multiple flat layers placed on top of each other. Their sizes varied among the three Pluronics. We believe that TPP aggregates interact with the hydrophobic units of Pluronics causing the polymer chains to pack themselves in a distinct manner around those TPP-containing “cores”. These interactions apparently direct formation of complexes between the porphyrin and the polymer upon their dissolution in water, thus resulting in the encapsulation of TPP aggregates inside a Pluronic micelle. A single mechanism for the TPP solubilization by Pluronics is consistent with the same catalytic activity of the three TPP–Pluronic systems observed in the photooxidation of tryptophan.     

Synthesis and Antitumor,Antioxidant Effects Studies of N-Ethylpiperazine Substitute Thiourea Ligands and Their Copper(II) Complexes

A series of N-ethylpiperazine substitute thioureas [C₆N₂H₁₃NHCSNHR], where R = -C₃H₅ (L ₁ ), -C₁₀H₇ (L ₂ ), and -C₇H₇ (L ₃ ), and their copper (II) complexes have been synthesized. These ligands and complexes have been characterized by elemental analyses, IR, ¹H and ¹³C-NMR spectra, UV-Vis, magnetic susceptibility, thermogravimetrical analyses, and MALDI-TOF MS. In vitro antitumor activity of ligands and their complexes has been screened toward several tumor cell lines. The effects on these complexes of the growth of L1210 and MCF7 were studied comparatively with that of free ligands. Antioxidant and radical scavenging activities of synthesized compounds were determined by various in vitro assays including 1,1-diphenyl-2-picryl-hydrazyl free radicals (DPPH), 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid radicals (ABTS+), and ferrous ion (Fe²⁺) chelating activities. Moreover, these activities were compared to synthetic and standard antioxidant trolox. The results showed that the synthesized compounds had effective antioxidant power.     

Spectral-Fluorescent Properties of Supramolecular Systems Based on Chlorin e<Subscript>6</Subscript>

The spectral-fluorescent properties of various supramolecular systems based on chlorin e₆ (Ce₆) are determined to facilitate the development of new medicines for photodynamic therapy and diagnostics. The effect of various excipients, such as poly-N-vinylpyrrolidone (PVP), polyethylene glycol (PEG), bovine serum albumin (BSA), chitosan, Triton X-100 (TX-100), sodium hexametaphosphate (SHMP), and poly(dimethyldiallylammonium chloride) chloride (PDDAC), on the optical absorption and fluorescence of Ce₆ is demonstrated. In the Ce₆?PVP, Ce₆?PEG, Ce₆?BSA, Ce₆?TX-100, Ce₆?SHMP, and Ce₆?PDDAC systems, Ce₆ molecules are disaggregated and complexes thereof with excipients are formed. The quantum yield of Ce₆ fluorescence in supramolecular systems is close to that of the free-form photosensitizer, in the absence of excipients. The results suggest that supramolecular complexes of Ce₆ are promising for the development of medicines with controllable photodynamic activity.     

Design, synthesis and characterization of a linear hydrogen bonded homologous series

A linear hydrogen bonded liquid crystalline homologous series has been synthesized and characterized. Hydrogen bond is formed between p-n-dodecyloxy benzoic acid and various p-n-alkyl benzoic acids whose alkyl chain vary from octyl to ethyl. Synthesized complexes are characterized by FTIR, ¹H NMR and ¹³C NMR studies for inferring the formation of hydrogen bonds. Polarizing Optical Microscopy (POM) and DSC studies reveal various mesophases and their corresponding transition temperatures along with respective enthalpy values. All the seven synthesized complexes exhibit rich liquid crystalline mesomorphism. A new phase namely smectic X has been observed in five of the complexes with a narrow thermal range. This phase has been characterized by optical textural, DSC, tilt angle and helicoidal pitch studies. Smectic X is sandwiched between traditional smectic C and re-entrant smectic C (designated as C_R) phases. Homeotropic transition in nematic phase is observed in all the mesogens and thus these materials can be used as thermally controlled optical shutters. Tilt angle in smectic C, smectic X and smectic C_R phases have been experimentally elucidated for all the mesogens.     

Synthesis,characterization and mesomorphic behaviour of lanthanide (III) 4-alkoxybenzoates

The lanthanide (III) 4-alkoxybenzoates [Ln(C_nH_2n?+?1OC₆H₄CO₂)₃, Ln?=?La (III), Pr (III), Nd (III), Eu (III), Gd (III), Tb (III) and Dy (III) and n?=?6, 8, 10, 12 and 16] have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, and IR and electronic spectroscopy. Hot-stage polarizing optical microscopy and differential scanning calorimetry have been used to investigate the mesomorphic behaviour. The chain length influences the structure and hence the thermal behaviour of these compounds. All the lanthanide complexes except decyloxy derivatives exhibit smectic A mesophase. The decyloxy-containing complexes are non-mesomorphic. The differential scanning calorimeter traces do not display the exothermic peak for all the compounds except for the hexadecyloxy derivatives, which exhibit enantiotropic smectic A phase. The influence of the lanthanide ions on the phase transition has also been clearly demonstrated.     

Synthesis and Characterization of New Fluorene-Based Singlet Oxygen Sensitizers

The synthesis, photophysical characterization, and determination of singlet oxygen quantum yields (Φ_Δ) for a class of fluorene derivatives with potential application in two-photon photodynamic therapy (PDT) is reported. It has been demonstrated that these compounds possess the ability to generate singlet oxygen (¹O₂) upon excitation. A photochemical method, using 1,3-diphenylisobenzofuran (DPBF) as ¹O₂ chemical quencher, was employed to determine the singlet oxygen quantum yields (Φ_Δ) of the fluorene-based photosensitizers in ethanol. Φ_Δ values ranged from 0.35 to 0.75. These derivatives may have potential application as two-photon photosensitizers when pumped via two-photon excitation in the near-IR spectral region.     

Deep-Red Phosphorescent Iridium(III) Complexes Containing 1-(Benzo[b] Thiophen-2-yl) Isoquinoline Ligand: Synthesis,Photophysical and Electrochemical Properties and DFT Calculations

Four new bis-cyclometalated iridium(III) complexes, [Ir(btq) ₂phen] [PF₆] (3a), [Ir(btq) ₂bpy] [PF₆] (3b), [Ir(btq) ₂dtbipy] [PF₆] (3c) and [Ir(btq) ₂pic] (3d) (btq?=?1-(benzo[b] thiophen-2-yl) isoquinoline, phen?=?1,10-phenanthroline, bpy?=?2,2′-bipyridine, dtbipy?=?4,4′-di-tert-butyl-2,2′-bipyridine, pic?=?picolinic acid) have been synthesized and fully characterized. The crystal structure of 3a has been determined by X-ray analysis. The photophysical and electrochemical properties of these new complexes 3a???3d have been studied. The photoluminescence spectra of all Ir(III) complexes exhibit deep-red emission maxima at 682, 682, 683 and 698 nm, respectively. The most representative molecular orbital energy-level diagrams and the lowest energy electronic transitions of 3a???3d have been calculated with density functional theory (DFT) and time-dependent DFT (TD???DFT). The results show that the pic ancillary ligand of complex 3d influences the absorption and emission energies with a further red-shift relative to other three complexes 3a???3c.     

Use of X-ray photoelectron and Mössbauer spectroscopies in the study of iron pentacyanide complexes

A number of iron pentacyanide complexes of the Na_itn [Fe(CN)₅X] type have been synthesized. The compounds have been examined by X-ray photoelectron (ESCA) and Mössbauer spectroscopies. The influence of the nature of ligand X upon the properties of iron- (II) pentacyanide complexes has been studied. The donor properties of dinitrogen as a ligand have been compared with those of other nitrogen-containing ligands. A correlation has been established between the ESCA and Mössbauer data.     

Theoretical studies and antibacterial activity for Schiff base complexes

New ligand 4‐((2‐Hydroxy1‐naphthyl) methylene amino)‐1.5‐dimethyl‐2‐phenyl‐1H‐pyrazol‐3(2H)‐one (HL) was synthesized from the reaction of 2‐hydroxy‐1‐naphthaldehyde and 4‐aminophenaz one. A complexes of this ligand [VO(II)(HL)(SO₄)], [Pt(IV)(L)Cl₃], [Re(V)(L)Cl₃]Cl, and [M(II)(L)Cl] (M═Pd(II), Ni(II), Cu(II)) were synthesized. The resulted compounds were characterized by IR, NMR (¹H and ¹³C), mass spectrometry, element analysis, and UV‐Vis spectroscopy. Additionally, the spectroscopic studies revealed octahedral geometries for the Re(V), Pt(IV) complexes, and square pyramidal for VO(II), square planar for Pd(II) complex, and tetrahedral for the Ni(II) and Cu(II) complexes. Thermodynamic parameters (ΔE^*, ΔH^*, ΔS^*, ΔG^*, and K) were calculated using from the TGA curve Coats‐Red fern method. Therefore, hyper Chem‐8 program has been used to predict structural geometries of compounds in the gas phase. Finally, the synthesized Schiff base and its metal complexes were screened for their biological activity against bacterial species, 2 Gram‐positive bacteria (Bacillus subtilis and Staphylococcus aureus) and 2 Gram‐negative bacteria (Escherichia coli and Pseudomonas aeruginosa).     

Synthesis, DNA-binding, Cytotoxicity, Photo Cleavage, Antimicrobial and Docking Studies of Ru(II) Polypyridyl Complexes

Three Ruthenium(II) polypyridine complexes, [Ru(phen)₂(mipc)]²⁺(1), [Ru(bpy)₂(mipc)]²⁺ (2) and [Ru(dmb)₂(mipc)]²⁺(3) [mipc?=?2-(6-methyl-3-(1H-imidazo[4, 5-f][1,10]-phenanthroline-2-yl)-4H-chromene-4-one, phen?=?1,10-phenanthroline,bpy?=?2, 2′bipyridine,dmb?=?4, 4′-dimethyl-2, 2′-bipyridine] have been synthesized and characterized by elemental analysis, IR, UV–Vis, ¹H& ¹³C NMR and mass spectra. The DNA-binding properties of the Ruthenium(II) complexes were investigated by spectrophotometric methods, viscosity measurements and light switch studies. These three complexes have been focused on photo activated cleavage studies with pBR-322 and antimicrobial studies. Experimental results indicate that the three complexes intercalate into DNA base pairs and follows the order of 1?>?2?>?3 respectively. Molecular docking studies also support the DNA interactions with complexes through hydrogen bonding and vander Waal’s interactions. Cytotoxicity studies with Hela cell lines has been revealing about anti tumor activity of these complexes.     

Carbon-13 NMR Spectra of Some Group VIIB Transition Metal Thiocarbonyl and Selenocarbonyl Complexes

Recently, we reported the discovery of the first examples of transition metal selenocarbonyl complexes, (n⁵-C₅H₅) Mn (CO)₂ (CSe) and (n⁶-C₆H₅CO₂CH₂(CO)₂ (CSe).¹ These complexes are particularly interesting because, unlike CO and CS, the diatomic CSe molecule has so far eluded isolation even at very low temperatures,² and so these complexes represent the stabilization of a chemically unstable species through coordination to a metal (cf. metal carbene complexes). We have also synthesized several thiocarbonyl complexes of the same type,^3,4 as well as the analogous rhenium selenocarbonyl complexes.⁴ While many detailed studies of the ¹³C nmr spectra of transition metal carbonyls have appeared in the literature over the past few years, there have been no such studies for the closely related thiocarbonyls and selenocarbonyls, although a few isolated data have been reported recently for metal thiocarbonyls.^5,6 In this communication, we report the ¹³C nmr spectra of the isoelectronic series of complexes, (n⁵-C₅H₄R) M(COI)₂ (CX) (M = Mn, R = H, CH₃; M = Re, R = H; X = O,S, Se).     

Comparison of the ht Ultraviolet-Visible Spectra of the Copper(Ii) Complexes of Bidentate Schiff Base Ligands

Abstract

The bis(salicylaldiminato)copper(II) complexes of the ligand series of salicylaldimines derived from the condensation of n-alkyl or n-alkyloxy substituted aromatic amines with 2,4-dihydroxybenzaldehyde were synthesized. a series of Schiff base ligands with the general formula 4-X-N-(2,4-dihydroxybenzylidene)-aniline and differing only in substituents were synthesized. Some of these compounds have already been reported in literature. X=OCH₃[1],OC₂H₅[2],C₄H₉[1]. the copper(II) complexes of these ligands having the general formula, copper, bis[o-[N-(p-X-phenyl) formimidoyl]-4-hydroxyphenolato] were also synthesized. the ligands and their complexes, a total of 24 in number, are studied systematically with ultraviolet-visible spectroscopy to examine the effect of various n-alkyl- and n-alkyloxy substituents on the ligands and on their complexes. in the electronic spectrum of these compounds, the bands observed in the 200-450 run region which involve charge transfer π-π? transition were interpreted.     

Synthesis and characterization of blue phosphorescent cyclometalated Ir(III) complexes containing 2-(imidazol-2-yl)pyridine as ancillary ligand

Four new blue phosphorescent iridium complexes containing 2-(fluoro substituted phenyl)pyridine as the cyclometalated ligands and 2-(imidazol-2-yl)pyridine as an ancillary ligand have been synthesized and characterized. The complexes have the general structure (C^N)₂Ir(pym), where C^N are cyclometalating ligands (e.g., 2-(2,4-difluorophenyl)pyridine (24f₂ppyH), 2-(3,4-difluorophenyl)pyridine (34f₂ppyH), 2-(3,5-difluorophenyl)pyridine (35f₂ppyH), and 2-(3,4,5-trifluorophenyl)pyridine (345f₃ppyH)), pym is 2-(imidazol-2-yl)pyridine (pymH). The absorption, emission, and cyclic voltammetry of the complexes were systematically investigated. The (46f₂ppy)₂Ir(pym) has been characterized using X-ray crystallography and the electronic ground state calculated using B3LYP density functional theory. The highest occupied molecular orbital (HOMO) consists of a mixture of pym ligand (83.7%) and Ir orbitals (12.1%), while the lowest occupied molecular orbital (LUMO) is mostly on f₂ppy ligands (93.4%). By replacing the ancillary ligand pic with pym can finely tune emission of the iridium complexes, showing blue luminescence at a wavelength of 467-491 nm at room temperature in CH₂Cl₂.     

Synthesis and photophysics of a new deep red soluble phosphorescent iridium(III) complex based on chlorine-methyl-substituted 2,4 diphenyl quinoline

A new iridium complex with a chlorine-methyl-substituted 2,4 diphenyl quinoline, (Cl-MDPQ) ligand has been synthesized. The synthesized iridium metal complex, Ir(Cl-MDPQ)₂(acac) where Cl-MDPQ=chlorine-methyl substituted, 2,4 diphenyl quinoline, acac=acetyl acetone is characterized by employing different techniques such as mass spectrometry, ¹H NMR, DTA/TGA, XRD, and FTIR. The molecular structures of Cl-MDPQ and Ir(Cl-MDPQ)₂(acac) complexes are confirmed by the FTIR spectra. Strong singlet metal-to-ligand charge-transfer (¹MLCT) and triplet metal-to-ligand charge-transfer (³MLCT) absorption peaks at 353 and 437 nm in tetrahydrofuran (THF) are reported in the synthesized complex, respectively. A deep red emitting Ir(Cl-MDPQ)₂(acac) complex at 662 nm is promising for flexible organic devices.     

Synthesis,Characterization Luminiscence Studies and Microbial Activity of Ethylenediamine Ruthenium (II) Complexes with Dipyridophenazine Ligands

Three symmetric ligands 7-methyl dipyrido-[3,2-a;2′,3′-c]phenazine (dppz-CH₃), 7-nitro dipyrido-[3,2-a;2′,3′-c]phenazine (dppz-NO₂) and benzo[i]dipyrido-[3,2-a;2′,3′-c]phenazine (dppn) and their ruthenium(II) complexes [Ru(en)₂(L)][ClO₄]₂ (en= ethylenediamine), L= dppz-CH₃, dppz-NO₂ and dppn have been synthesized and characterized by IR, ¹H, ¹³C NMR and Mass spectra. The interactions of these complexes with calf thymus DNA have been investigated by spectrophotometric, spectrofluorimetric, circular dichroism, viscosity and thermal denaturation studies. As the planar extension of the intercalative ligand increases, the interaction of the complex with DNA increases, indicating that the size and shape of the intercalalative ligand has a marked effect on the strength of interaction. The plot of log K versus log [Na⁺] yield a slope of -1.26, -1.53, -1.60 for the complexes 1, 2 and 3 respectively. These three complexes have been found to promote the cleavage of plasmid pBR 322 DNA upon irradiation.     

Synthesis and Fluorescence Properties of Lanthanide (III) Perchlorate Complexes with Bis(benzoylmethyl) Sulfoxide

A ligand with two carbonyl groups and one sulfinyl group has been synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹H NMR and UV spectra. The results indicated that the composition of these complexes is REL₅(ClO₄)₃·3H₂O (RE = La(III), Pr(III), Eu(III), Tb(III), Yb(III), L = C₆H₅COCH₂SOCH₂COC₆H₅). The fluorescent spectra illustrate that both the Tb (III) and Eu (III) complexes display characteristic metal-centered fluorescence in solid state, indicating the ligand favors energy transfer to the excitation state energy level of them. However, the Tb (III) complex displays more effective luminescence than the Eu (III) complex, which is attributed to especial effectively in transferring energy from the average triplet energy level of the ligands (T) onto the excited state (⁵D₄) of Tb (III) than that (⁵D₀) of Eu (III), showing a good antenna effect for Tb(III) luminescence. The phosphorescence spectra and the relationship between fluorescence lifetimes and fluorescence intensities were also discussed.