Organometallic complexes with biological molecules

Novel triorganotin(IV) complexes of two beta-lactamic antibiotics, 6-[D-(-)-beta-amino-p-hydroxyphenyl-acetamido]penicillin (=amoxicillin) and 6-[D-(-)-alpha-aminobenzyl]penicillin (=ampicillin), have been synthesized and investigated both in solid and solution states. The complexes corresponded to the general formula R(3)Sn(IV)antib*H(2)O (R=Me, n-Bu, Ph; antib=amox=amoxicillinate or amp=ampicillinate). Structural investigations about configuration in the solid state have been carried out by interpreting experimental IR and 119Sn Mossbauer data. In particular, IR results suggested polymeric structures both for R(3)Sn(IV)amox.H(2)O and R(3)Sn(IV)amp*H(2)O. Moreover, both antibiotics appear …

Fluorescent Boron Oxide Nanodisks as Biocompatible Multi-messenger Sensors for Ultrasensitive Ni$^{2+}$ Detection

Boron-based nanocomposites are very promising for a wide range of technological applications, spanning from microelectronics to nanomedicine. A large variety of B-based nanomaterials has been already observed, such as borospherene, B nanotubes and nanoparticles, and boron nitride nanoparticles. However, their fabrication usually involves toxic precursors or leads to very low yields or small boron atom concentration. In this work, we report the synthesis of nanometric B$_{2}$O$_{3}$ nanodisks, a family of nanomaterials with a quasi-2D morphology capable of intense fluorescence in the visible range. Such as boron-based nanomaterial, which we synthesized by pulsed laser ablation of a boron tar…

Improved Photocatalytic Activity of Polysiloxane TiO2 Composites by Thermally Induced Nanoparticle Bulk Clustering and Dye Adsorption

Fine control of nanoparticle clustering within polymeric matrices can be tuned to enhance the physicochemical properties of the resulting composites, which are governed by the interplay of nanoparticle surface segregation and bulk clustering. To this aim, out-of-equilibrium strategies can be leveraged to program the multiscale organization of such systems. Here, we present experimental results indicating that bulk assembly of highly photoactive clusters of titanium dioxide nanoparticles within an in situ synthesized polysiloxane matrix can be thermally tuned. Remarkably, the controlled nanoparticle clustering results in improved degradation photocatalytic performances of the material under …

Organotin IV-Quinilone Antibiotic Derivatives: Solid State Investigations

Structural characterization of triorganotin(IV) complexes with sodium fusidate and DFT calculations

Abstract Three new complexes of the steroid sodium fusidate (sodium 2-[(1 S ,2 S ,5 R ,6 S ,7 S ,10 S ,11 S ,13 S , 14 Z ,15 R ,17 R )-13-(acetyloxy)-5,17-dihydroxy-2,6,10,11-tetramethyl tetracyclo[8.7.0.0 2,7 .0 11,15 ] heptadecan-14-ylidene]-6-methylhept-5-enoate = (NaFusidate, Na FA )]), with triorganotin(IV) moieties have been prepared and investigated by conventional techniques as FTIR, Mossbauer, ESI-MS and NMR spectroscopy. The isolated compounds showed stoichiometries organotin(IV)/fusidate 1/1, R 3 Sn(IV) FA (R = Me, FA1 ; Bu, FA2 ; Ph, FA3 ). The ligand coordination sites were determined by FTIR spectroscopic measurements. In the complexes, the carboxylate group of the fusidate li…

Equilibria involved in the diorganotin(IV) and triorganotin(IV) phosphomycin interaction in aqueous solution

Four new diorganotin(IV), (R = Me, Bu), and triorganotin(IV), (R = Me, Ph), derivatives of the phosphomycin disodium salt antibiotic[(1R,2S)-1,2-epoxypropylphosphonate]Na2 have been synthesized and their solid state configuration studied by X-ray crystallography, FT-IR, Mossbauer, UV–Vis spectroscopies. The X-ray diffraction investigation, performed on the bis[trimethyltin(IV)]- phosphomycin, showed that the coordination geometry at all the Sn atoms is trigonal bipyramidal. The structure of the complex forms an unusual polymeric zig-zag planar network. The FT-IR and the 119Sn Mo¨ssbauer studies supported the formation of trigonal bipyramidal (Tbp) molecular structures, both in the diorganot…

Amperometric Biosensor and Front-End Electronics for Remote Glucose Monitoring by Crosslinked PEDOT-Glucose Oxidase

Focusing on the interplay between interface chemistry, electrochemistry, and integrated electronics, we show a novel low-cost and flexible biosensing platform for continuous glucose monitoring. The amperometric biosensing system features a planar three-electrode structure on a plastic substrate, and a wireless near-field communication-powered electronic system performing sensor analog front-end, A/D conversion, digital control, and display tasks. The working electrode is made of electropolymerized poly (3,4-ethylenedioxythiophene) film onto a polyethylene terephthalate/gold electrode followed by immobilization of cross-linked glucose oxidase by glutaraldehyde. The advantages offered by such…

Substrate and atmosphere influence on oxygen p-doped graphene

Abstract The mechanisms responsible for p-type doping of substrate supported monolayer graphene (Gr) by thermal treatments in oxygen ambient have been investigated by micro-Raman spectroscopy, atomic force microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS), considering commonly employed dielectric substrates, such as SiO 2 and Al 2 O 3 thin films grown on Si. While a high p-type doping (∼10 13  cm −2 ) is observed for Gr on SiO 2 , no significant doping is found for Gr samples on the Al 2 O 3 substrate, suggesting a key role of the Gr/SiO 2 interface states in the trapping of oxygen responsible for the Gr p-type doping. Furthermore, we investigated the doping stability of Gr on SiO…

Lead(II) ions adsorption onto amyloid particulates: An in depth study

The production of new cost-effective biocompatible sorbent sustainable materials, with natural origins, able to remove heavy metals from water resources is nowadays highly desirable in order to reduce pollution and increase clean water availability. In this context, self-assembled protein materials with amyloid structures seem to have a great potential as natural platform for a broader development of highly-tunable structures. In this work we show how protein particulates, a generic form of protein aggregates, with spherical micro sized shape can be used as adsorbents of Pb2+ ions from aqueous solution. The effect of pH, ionic medium, ionic strength and temperature of the metal ion solution…

Preparation and XAFS studies of organotin(IV) complexes with adenosine and related compounds and calf thymus DNA

Complexes of adenosine and related compounds (adenosine-5’-monophosphate, adenosine-5’-triphosphate and pyridoxal-5-phosphate) with Bu2SnO and/or BuSnCl2 were prepared in the solid state. The compositions of the complexes were determined by standard analytical methods. It was found that the complexes contain the organotin(IV) moiety and the ligand in a ratio of 1:1. The FT-IR spectra demonstrated that Bu2SnO reacts with the D-ribose moiety of the ligands, while Bu2SnCl2 is coordinated to the deprotonated phosphate group. The basic part of the ligands does not participate directly in complex formation. Comparison of the experimental Mossbauer Δ (quadrupole splitting) values with those calcul…

3D MICROSIZED PROTEIN AMYLOID PARTICULATES AS EFFECTIVE BIOADSORBERS FOR Pb2+ IONS

The production of new cost-effective biocompatible sorbent sustainable materials, with natural origins, able to remove heavy metals from water resources is nowadays highly desirable in order to reduce pollution and increase clean water availability. In this context, self-assembled protein materials with highly ordered amyloid structures, stabilised by H-bonds, seems to have a great potential as natural platform for a broader development of highly-tunable structures. By suitably varying solution conditions it is possible to tune aggregate size, surface area and morphologies as well as their physicochemical (hydrophobicity, hydrophilicity, swelling/deswelling properties) and mechanical proper…

Mössbauer Spectroscopy and Organotin Polymers

Mössbauer spectroscopy allows the structural analysis of certain metal atoms situated in complex structures. Briefly, Mössbauer spectroscopy is a resonant absorption spectroscopy that is observed best in isotopes having long lived, low-lying excited nuclear energy states. The largest recoil-free resonant cross-section is found for 57Fe. Currently, Mössbauer spectroscopy is being used on Mars to identify iron compounds that are present in the Martian landscape. There are over 20,000 entries in SciFinder for Mössbauer spectroscopy, of which the two largest entries are for iron and tin containing compounds. There are only about 100 entries for organotin compounds, with only a handful related t…

New Ruthenium complexes with antitumoral activity

Synthesis, Structural characterization and Exafs investigations of new ruthenium(III) complexes.

Two new complexs of Ru(III) with glucosaminic acid and 1-Methyluracil, [RuCl2(Glun-N,O)2]H (I), (Glun-= glucosaminate); [RuCl4(1-MeU-N3)(DMSO)]H2.H2O (II), (1-MeU-= 1-Methyluracilate) were prepared from the same Ru(III) precursors, RuCl3•3H2O and [(DMSO)2H][trans-RuCl4(DMSO)2]. The characterization of the complexes have been carried out by elemental analysis, FT-IR, ES-MS, NMR and EXAFS.

Preparation and structural studies on the tBu2Sn(IV) complexes with aromatic mono- and dicarboxylic acids containing hetero {N} donor atom

Nine complexes of 'Bu2Sn(IV)(2+) were obtained in the solid state with ligands containing -COOH group(s) and aromatic (N) donor atom. The binding sites of the ligands were identified by FT-IR spectroscopic measurements. It was found that in most cases the -COO- groups are co-ordinated in monodentate manner. Nevertheless, in some of our complexes, the -COO- group forms bridges between two central {Sn} atoms resulting in the formation of an oligomeric structure, a motif that is characteristic only to the nicotinate compound. These pieces of information and the rationalisation of the experimental Sn-119 Mossbauer nuclear quadrupole splittings, Delta, - according to the point charge model forma…

119Sn NMR Ccomputational study of Dimethyltin(IV) - D-ribonic Acid and Dimethyltin(IV) - N-Acetylneuraminic acid complexes

Vibrational Assignments for Organotin Dihalides and the Organotin Polyester Amines Containing Ciprofloxacin

Scientific studies for the restoration of a wood painting of the Galleria Interdisciplinare Regionale della Sicilia—Palazzo Mirto di Palermo

Abstract The Ritratto muliebre, referring to Venus, is a panel painting, oil on wood, attributed to unknown artist and probably dated to the second half of 16th century, today conserved in the Galleria Interdisciplinare Regionale della Sicilia—Palazzo Mirto of Palermo. The aim of this research was to assess the techniques used to decorate the wooden painting and to verify the state of conservation of the artwork's materials but also to identify the previous treatments. This study was the essential condition to plane and perform the correct restoration. For this reason, an integrated analytical approach based on the use of non-invasive and micro-invasive techniques was used, with the aim to …

Point-Of-Care Plastic Biosensor Devices using a PEDOT-modified Electrochemical Glucose Sensing Platform

There is an emerging global epidemic of diabetes that can be related to rapid increases in overweight, including obesity and physical inactivity. According to World Healthcare Organization, diabetes is a leading cause of blindness, amputation and kidney failure, while total deaths from diabetes are projected to rise by more than 50% in the next 10 years. To prevent life threatening and debilitating complications associated with diabetes, researchers are continuously involved in developing glucose biosensors. Hence, it is essential to develop a biosensor that can determine glucose levels having fast-response, high sensitivity and selectivity. Depending upon the transduction technique, a numb…

Organotin(IV) derivatives of fatty acids: Solid state and solution phase investigations

How organotin(IV)(sulfonatophenyl) porphynate may activate the apoptotic pathways in melanoma cells?

Bu2Sn(N-acetyl-L-cysteinate) antitumor activity on HepG2 cells

Gamma rays induced synthesis of graphene oxide/gold nanoparticle composites: structural and photothermal study

Gamma irradiation provides an alternative pathway to conventional gold nanoparticle synthesis because it is simple, fast, and economical. Here, we employed gamma irradiation at low doses (1–20 kGy) to obtain gold nanoparticles (Au NPs) anchored onto graphene oxide (GO) sheets. GO was selected as a suitable platform for the nucleation and growth of Au NPs because of its large surface area and good dispersibility in water due to the presence of polar oxygen-containing functional groups in its structure. Gamma irradiation at all the applied doses led to the reduction of chloroauric acid and the formation of evenly distributed Au NPs at the GO surface, simultaneously causing the reduction of GO…

Diorganotin(IV) N-acetyl-L-cysteinate complexes: synthesis, solid state, solution phase, DFT and biological investigations.

Diorganotin(IV) complexes of N-acetyl-L-cysteine (H(2)NAC; (R)-2-acetamido-3-sulfanylpropanoic acid) have been synthesized and their solid and solution-phase structural configurations investigated by FTIR, Mössbauer, (1)H, (13)C and (119)Sn NMR spectroscopy. FTIR results suggested that in R(2)Sn(IV)NAC (R = Me, Bu, Ph) complexes NAC(2-) behaves as dianionic tridentate ligand coordinating the tin(IV) atom, through ester-type carboxylate, acetate carbonyl oxygen atom and the deprotonated thiolate group. From (119)Sn Mössbauer spectroscopy it could be inferred that the tin atom is pentacoordinated, with equatorial R(2)Sn(IV) trigonal bipyramidal configuration. In DMSO-d(6) solution, NMR spectr…

Synthesis, characterization of diorganotin(IV) complexes of N-(2-hydroxyarylidene)aminoacetic acid and antitumour screening in vivo in ehrlich ascites carcinoma cells

Some new diorganotin(IV) complexes have been prepared by reacting potassium N-(2-hydroxyarylidene)aminoacetate with R2SnCl2(R = Me,nBu,Ph). The complexes have been characterized by 1H,13C,119Sn NMR, IR and 119mSn Mössbauer spectroscopic techniques in combination with elemental analysis. In the solid state, the complexes possess penta- and hexa-coordinated tin centres. The hexa-coordinated tin complexes were found to dissociate in solution, giving rise to penta-coordinated species as revealed by 119Sn NMR spectroscopy. Antitumour screening in vivo of the complexes L4snPh2,L4SnPh2· Ph3SnCl and L4SntBU2·t Bu2SnCl2 (L4 = N-(2-hydroxyacetophenone)aminoacetate) is also reported. Copyright © 2001 …

Dibutyltin(IV) complexes containing arylazobenzoate ligands: chemistry, in vitro cytotoxic effects on human tumor cell lines and mode of interaction with some enzymes.

Dibutyltin(IV) complexes of composition Bu2Sn (LH)2, where LH is a carboxylate residue derived from 2-[(E)- (5-tert-butyl-2- hydroxyphenyl)diazenyl]benzoate (L1H) with water molecule (1), 4-[(E)-(5-tert-butyl-2-hydroxyphenyl) diazenyl]benzoate (L2H) (2) and 4-[(E)-(4-hydroxy-5- methylphenyl)diazenyl]benzoate (L3H) (3), were synthesized and characterized by spectroscopic (1H, 13C and 119Sn NMR, IR, 119Sn Mössbauer) techniques. A full characterization was accomplished from the crystal structure of complex 1. The molecular structures and geometries of the complexes (1a i.e. 1 without water molecule and 3) were fully optimized using the quantum mechanical method (PM6). Complexes 1 and 3 were fo…

Organometallic complexes with biological molecules. XVIII. Alkyltin(IV) cephalexinate complexes: synthesis, solid state and solution phase investigations

Abstract Dialkyltin(IV) and trialkyltin(IV) complexes of the deacetoxycephalo-sporin-antibiotic cephalexin [7-( d -2-amino-2-phenylacetamido)-3-methyl-3-cephem-4-carboxylic acid] (Hceph) have been synthesized and investigated both in solid and solution phase. Analytical and thermogravimetric data supported the general formula Alk 2 SnOHceph · H 2 O and Alk 3 Snceph · H 2 O (Alk=Me, n -Bu), while structural information has been gained by FT-IR, 119 Sn Mossbauer and 1 H, 13 C, 119 Sn NMR data. In particular, IR results suggested polymeric structures both for Alk 2 SnOHceph · H 2 O and Alk 3 Snceph · H 2 O. Moreover, cephalexin appears to behave as monoanionic tridentate ligand coordinating th…

Solid State Analysis of Metal-Containing Polymers Employing Mossbauer Spectroscopy, Solid State NMR and F EI TOF MALDI MS

Polymers in general and metal-containing polymers in particular are often sparingly soluble or insoluble, in contrast to small molecules. Thus, special significance is attached to characterization techniques that can be applied to the materials as solids. Here, three techniques are discussed that give structural information gained from the solid material. Mossbauer spectroscopy is a powerful technique that may give information on the structure about the metal-containing moiety for about 44 different nuclei. Its use in describing the structure of the product obtained from organotin dichlorides and the unsymmetrical ciprofloxacin is presented along with the reaction implications of the result…

Thermodynamic and spectroscopic study of the binding of dimethyltin(IV) by citrate at 25°C

Thermodynamic (potentiometric and calorimetric) and spectroscopic ( 1 H NMR, 119 Sn Mossbauer) studies were performed in aqueous solution in order to characterize the interaction of dimethyltin(IV) cation with citrate ligand. Six species {(CH 3 ) 2 Sn(cit) - ; [(CH 3 ) 2 Sn] 2 (cit) 2 2- ; (CH 3 ) 2 Sn(cit)H 0 ; (CH 3 ) 2 Sn(cit)OH 2- ; [(CH 3 ) 2 Sn] 2 (cit)OH 0 ; [(CH 3 ) 2 Sn] 2 (cit)(OH) 2 - } were found. All the species formed in this system are quite stable and formation percentages are fairly high. For example, at pH = 7.5 and C (CH3)2Sn = C cit = 10 mmol l -1 , E% for [(CH 3 ) 2 Sn] 2 (cit)(OH) 2 - and (CH 3 ) 2 Sn(cit)OH 2- species reaches 65%. Overall thermodynamic parameters obta…

Erratum to “Cerium effect on the phase structure, phase stability and redox properties of Ce-doped strontium ferrates”

Organotin(IV) and simple fatty acids: preliminary assessments

Our group has a long researching tradition in the field of organotin(IV) complexes, usually proposed and tested as potential anti-tumor drugs. The leitmotif has usually been the modulation of the intrinsic toxicity/cytotoxicity of the organometallic moiety and a modulation of the toxic effect by means of biologically related molecules (synthetic or natural). Such a modulation is usually achieved by two (often overlapping) routes: dampen the damaging effects of the metal core, and serving as a carrier for specific tissue districts. Since a too tight binding on the organotin moiety is not always desirable – a too much stable complex could be a non-active one – carboxylates have always played …

Inkjet Printing Quasi-Miscible Droplets for Pseudo-Planar Organic Heterojunctions

Aqueous Processed Biopolymer Interfaces for Single-Cell Microarrays

Single-cell microarrays are emerging tools to unravel intrinsic diversity within complex cell populations, opening up new approaches for the in-depth understanding of highly relevant diseases. However, most of the current methods for their fabrication are based on cumbersome patterning approaches, employing organic solvents and/or expensive materials. Here, we demonstrate an unprecedented green-chemistry strategy to produce single-cell capture biochips onto glass surfaces by all-aqueous inkjet printing. At first, a chitosan film is easily inkjet printed and immobilized onto hydroxyl-rich glass surfaces by electrostatic immobilization. In turn, poly(ethylene glycol) diglycidyl ether is graft…

Organotin(IV)(sulfonatophenyl)porphynate effects on survival and apoptotic signalling pathways in melanoma cells

Effects of sublethal levels of tributyltin chloride on a new toxicity test organism,Liza saliens (osteichthyes, mugilidae): a histological study

The histopathological effects of 10−7 and 10−9M tributyltin(IV)chloride,TBTCl, solutions on different Liza saliens organs have been studied by light microscope. The fish were sacrificed after 3–4 h incubation in 10−7M TBTCl solution or after 15 days incubation in 10−9M solution. The observed histopathological changes were dose- and time-dependent. The 10−7M TBTCl concentration resulted in major damage to the gill epithelium, indicating that TBTCl primarily interfered with the respiration, osmoregulation, acid balance and nitrogenous waste excretion processes. After incubation in 10−9M TBTCl solution the fish lived 20 or more days, but many of the organs were altered. Thymus atrophy, reduced…

Structural investigations on diorgano- and triorganotin(IV) derivatives of [meso-tetra(4-sulfonatophenyl)porphine]metal chlorides.

Abstract Several new complexes of organotin(IV) moieties with MCln[meso-tetra(4-sulfonatophenyl)porphine], (R2Sn)2MCln[meso-tetra(4-sulfonatophenyl)-porphinate]s and (R3Sn)4MCln [meso-tetra(4-sulfonatophenyl)porphinate]s, [M = Fe(III), Mn(III): n = 1, R = Me, n-Bu; Ph; M = Sn(IV): n = 2, R = Me, n-Bu] have been synthesized and their solid state configuration investigated by infrared (IR) and Mossbauer spectroscopy, and by 1H and 13C NMR in D2O. The electron density on the metal ion coordinated inside the porphyrin ring is not influenced by the organotin(IV) moieties bonded to the oxygen atoms of the side chain sulfonatophenyl groups, as it has been inferred on the basis of Mossbauer spectro…

X‐Ray Photoelectron Spectroscopy

X-ray photoelectron spectroscopy (XPS) is a spectroscopic technique in the family of electron spectroscopies, that is, those methods whose probe consists of electrons instead of photons. In the case of XPS, a soft, usually monochromatic X-ray causes the emission of electrons by means of the photoelectric effect. Differences in chemical potential and/or polarizability of the molecules can cause an alteration of the binding energy; in addition to photoelectrons, an ordinary XPS spectrum may also contain Auger electrons. In an XPS system, an electron gun is used to deliver a low-energy electron flux with a low current over the illuminated spot. In an XPS instrument, an ion gun may be used with…

Improved performance in flexible organic solar cells by using copolymeric phase-separation modulators

One of the main problems related to the low performance of the organic solar cells (OSCs), concerns the low mobility of the materials constituting the heterojunction. Indeed, the poor charge transport in the active layer is the principal cause of a competition between separation and recombination of the photogenerated carriers. In this regard, a major obstacle to enhance OSCs efficiency is developing strategies to optimize the exciton dissociation and, consequently, the charge collection at the electrodes. Donor and acceptor systems must be well mixed on the length scale of 5 – 20 nm (exciton diffusion length) to meet the criteria for efficient exciton dissociation. In addition, the network…

Ciprofloxacin Polymers Derived from Diallyltin and Divinyltin Dihalides

The initial synthesis of condensation polymers from newly available divinyltin dichloride and diallyltin dichloride and ciprofloxacin is accomplished employing a modified interfacial polycondensation process. The polymeric (DP are about 2,000) products are rapidly (less than 15 seconds) formed in good yield. Infrared spectroscopy shows the formation of Sn-O and Sn-N bonds as predicted from the proposed structure. F-MALDI MS also shows ion fragments containing organotin in the predicted isotopic abundances as well as ion fragments containing both organotin and ciprofloxacin. The polymers exhibit low toxicity towards healthy WI-38 cells with variable toxicities towards a variety of cancer cel…

Lipid and fatty acid variations inCiona intestinalis ovary after tri-n-butyltin(IV)chloride exposure

Reduction of total lipids (TL) content and significant variations of triglyceride (TG) and phospholipid (PL) fractions were observed as a consequence of exposure of Ciona intestinalis ovaries to tributyltin chloride (TBTCL) solutions. In particular, an evident TG decrease and a PL increase were observed, which probably provoked an increment in membrane fluidity, because of the high concentration of long chain fatty acids and, as a consequence, PL. This could be a cell adaptive standing mechanism towards the pollutants, as observed in Saccharomyces cerevisiae. Also the increase in the content of the polyunsaturated fatty acids (PUFA), important in the synthesis of compounds such as prostagla…

Synthesis, characterization and in vitro antimicrobial activity of triorganotin(IV)fusidate complexes

Synthesis, structural investigations on organotin(IV) chlorin-e6 complexes, their effect on sea urchin embryonic development and induced apoptotic changes

Semitransparent Design of Planar n-i-p Perovskite Solar Cells using a Cost-Effective, Perovskite-Compatible DMD Structure as the Top Electrode

In recent years, a significant emphasis has been placed on developing multi-functional solar cells that integrate new features such as color and transparency, thereby opening up the possibility of unconventional photovoltaic (PV) applications, including building-integrated PV (BIPV) systems, tandem solar cells, and wearable electronics. In particular, the integration of semitransparent (ST) solar cells into buildings as power-generating windows, facades or other aesthetic architectural elements constitutes one of the most intriguing perspectives [1]. Since silicon-based panels are generally opaque and unaesthetic, there has been a growing research interest in emerging thin-film solar cells …

Preparation and structural characterization of organotin(IV) complexes with ligands containing a hetero {N} atom and a hydroxy group or hydroxy and carboxyl groups

AbstractTwenty-two n-butyltin(IV) and t-butyltin(IV) complexes of ligands containing an –OH (–C@O) group or –OH and –COOHgroups and an aromatic {N} donor atom were prepared by metathetical reactions. On the basis of the FT-IR and Mo¨ssbauer spec-troscopic data, molecular structures were assigned to these compounds. The binding sites of the ligands were identified by means ofFT-IR spectroscopic measurements, and it was found that in most cases the organotin(IV) moiety reacts with the phenolic form ofthese ligands. In the complexes with –OH and –COOH functions, the –COOH group is coordinated to the organotin(IV) centres in amonodentate manner. The 119 Sn Mo¨ssbauer and the FT-IR studies suppor…

Triphenyltin(IV) 2-[(E)-2-(aryl)-1-diazenyl]benzoates as anticancer drugs: Synthesis, structural characterization, in vitro cytotoxicity and study of its influence towards the mechanistic role of some key enzymes

Summary: Triphenyltin(IV) complexes of composition [Ph3SnL 1H]n (1) and [Ph3SnL2H]n (2) (where L1H=2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1-diazenyl] benzoate and L2H = 2-[(E)-2-(4-Hydroxy-5-methylphenyl)-1-diazenyl] benzoate) were synthesized and characterized by spectroscopic (1H, 13C and 119Sn NMR, IR, 119Sn Mössbauer) techniques in combination with elemental analysis. The molecular structures and geometries of the complexes (1 and 2) were fully optimized using the quantum mechanical method (PM3). Complexes (1 and 2) were found to exhibit stronger cytotoxic activity in vitro across a panel of human tumour cell lines viz., A498, EVSA-T, H226, IGROV, M19 MEL, MCF-7 and WIDR. The test compound…

Diphenyltiv(VI) complexes with substituted 5-azoxines: synthesis, structural characterization and assessment of in vitro cytotoxicity.

Nonprecious Copper‐Based Transparent Top Electrode via Seed Layer–Assisted Thermal Evaporation for High‐Performance Semitransparent n‐i‐p Perovskite Solar Cells

Semitransparent perovskite solar cells (ST‐PSCs) are highly attractive for applications in building‐integrated photovoltaics as well as in multijunction tandem devices. To fabricate high‐performance ST‐PSCs, suitable transparent top electrodes are strongly needed. Dielectric/metal/dielectric (DMD) multilayer structures have been shown to be promising candidates, though generally based on high‐value metals such as gold or silver, the latter causing also stability issues by reacting with perovskite. Here, a novel DMD transparent electrode based on nonprecious, less‐reactive copper is developed via thermal evaporation and used as a top anode in the fabrication of high‐performance semitranspare…

Effects of tributyltin(IV) chloride on the gametes and fertilization ofAscidia malaca (Ascidiacea: Tunicata)

Ascidia malaca gametes before fertilization incubated in 10-5 or 10-7 M solutions of tributyltin(IV) chloride, TBTCl, for 3 h appear highly damaged under transmission electron microscopy observation. Also, the fertilization process is affected by the compound: the damaged spermatozoa are present in the vitelline coat and the egg does not cleave. An increase of microbodies, structurally similar to peroxisomes, have been detected in the egg peripheral cytoplasm, probably in relation to their role in alleviating damage to some cellular components. The results have shown that the reproduction of ascidians under unfavourable environmental conditions is prevented. Copyright © 2003 John Wiley &amp…

Synthesis and Characterization of organotin (IV) derivates of nalidixic acid

Effects of sublethal levels of tributyltin chloride on a new toxicity test organism, Liza saliens (Osteichthyes, Mugilidae)

The histopathological effects of 10−7 and 10−9 M tributyltin(IV)chloride,TBTCl, solutions on different Liza saliens organs have been studied by light microscope. The fish were sacrificed after 3–4 h incubation in 10−7 M TBTCl solution or after 15 days incubation in 10−9 M solution. The observed histopathological changes were dose- and time-dependent. The 10−7 M TBTCl concentration resulted in major damage to the gill epithelium, indicating that TBTCl primarily interferedwith the respiration, osmoregulation, acid balance and nitrogenous waste excretion processes. After incubation in 10−9 M TBTCl solution the fish lived 20 or more days, but many of the organs were altered. Thymus atrophy, red…

Self-Cleaning ZnO Nanosheets for Piezoelectric Sensors

The design of wearable sensors coupling versatile analytical detection to self-cleaning is a highly desired combination, tackling the need of smart devices in response to the recent virus pandemics. To this aim, this work shows ZnO nanostructures obtained by a mild wet-chemistry approach onto ITO/PET flexible supports, resulting in wearable piezoelectric sensors exhibiting photocatalytic activity. ITO surfaces are treated with 0.5 mM KMnO4 aqueous solution (20 minutes, 90°C); ZnO growth is subsequently carried out by a previously shown wet-chemistry method [1]. SEM analysis shows the presence of a good surface coverage of ZnO nanosheets (NSs) (about 1.5 NSs/μm2) in the case of treated ITO, …

Dynamics of cell membrane passive depolarization: A phase portrait.

Effects of organotin(IV)(metal-sulfonatophenyl)porphinates on the growth of A375 human melanoma cells

Piezoresistive semi-transparent flexible sensors by bithiophene fulleropyrrolidine thin films

Piezoresistive sensors are considered among the fundamental components of the future wearable electronic devices, given their potential applications in artificial skin, motion capture and personalized medicine.[1-5] Here, we present a cost-effective, viable fabrication approach to realize piezoresistive sensors using a novel polymeric biotiophene fulleropyrrolidine system (bis-C60Bi) synthesized on flexible ITO/PET supports by electrochemical chronoamperometry. By applying an anodic potential (1.5 V) to a solution containing the monomer, it is possible to obtain a homogeneous semi-transparent thin film on the ITO/PET surface (see Figure). AFM, XPS, UV-vis have been employed to characterize …

Influence of Calcium Carbonate Nanoparticles on the Soil Burial Degradation of Polybutyleneadipate-Co-Butylenetherephthalate Films.

A polybutyleneadipate-co-butylenetherephthalate (PBAT) sample, commercially known as Ecoflex®, was processed via melt extrusion with CaCO3 nanoparticles coated with a hydrophobic coating. Blown films of PBAT and two composites with nanofiller (2% and 5%wt) were prepared and degradation tests in soil at 30 °C up to 180 days were carried out with weight loss measurements. Furthermore, biodegradation test according to ISO 14851 was carried out at 30 °C. The effect of CaCO3 on soil burial degradation was assessed by surface wettability and SEM. ATR-FTIR and XPS analyses highlighted chemical modifications induced by soil degradation. CaCO3 nanoparticles decreased surface wettability …

Carbocysteine degradation catalyzed by organotin(IV) compounds.

Toxic Effects of Organometallic Compounds towards Marine Biota

Organometallic derivatives are compounds containing a direct σ or π carbon metal linkage. Furthermore, the concept of the metallic atom must be extended to all the elements that are less negative than the carbon atom. As a consequence, taking into account all elements that are less negative than carbon and the number of existing organic compounds, it is possible to synthesize millions of organometallic derivatives. Several of these are extensively used in organic syntheses; others may find application in agriculture and in many other fields as pesticides, fire retardants, wood preservatives, antifouling agents, etc. In general, the organic derivatives of the metals are more toxic than the p…

Piezoresistive Sensors from Bithiophene-fulleropyrrolidine Bisadducts Thin-Films

The phenomenon of piezoresistivity in materials is based on the separation of conductive domains triggered by mechanical strains, resulting in a variation of the electrical resistance.1 This property is at the core of sensors for wearable electronics, e-skins, human motion detectors and machine learning devices.2 Fundamental requirements include lightness, good transparency, high flexibility and sensitivity to tiny deformations. However, the fabrication of a system integrating all these features is challenging. Herein, we show a semitransparent piezoresistive sensor realized by an electropolymerized bithiophene‐fulleropyrrolidine bisadduct onto ITO/PET3 (see Figure 1a). The good outcome of …

Novel metallic and organometallic based antiproliferative complexes: Integrated methodologies of evaluation

Synthesis, photophysical properties and structures of organotin-Schiff bases utilizing aromatic amino acid from the chiral pool and evaluation of the biological perspective of a triphenyltin compound

Abstract Five new organotin(IV) complexes of compositions [Me 2 SnL 1 ] ( 1 ), [Me 2 SnL 2 ] n ( 2 ), [Me 2 SnL 3 ] ( 3 ), [Ph 3 SnL 1 H] n ( 4 ) and [Ph 3 SnL 3 H] ( 5 ) (where L 1  = (2 S )-2-(( E )-(( Z )-4-hydroxypent-3-en-2-ylidene)amino)-3-(1 H -indol-3-yl)propanoate, L 2  = (2 S )-( E )-2-((2-hydroxybenzylidene)amino)-3-(1 H -indol-3-yl)propanoate and L 3  = (2 S )-( E )-2-((1-(2-hydroxyphenyl)ethylidene)amino)-3-(1 H -indol-3-yl)propanoate were synthesized and spectroscopically characterized. The crystal structures of 1 – 4 were determined. For the dimethyltin derivative 2 , a polymeric chain structure was observed as a result of a long Sn∙∙∙O contact involving the exocyclic carbony…

Potential use of organotin(IV)-tripetide complexes as stopper in tumor cells growth.

Gamma irradiation of graphene quantum dots with ethylenediamine: Antioxidant for ion sensing

Due to the low consumption of chemicals, the absence of toxic residual side products, the procedure simplicity and time-saving aspects, gamma irradiation offers advantages over the classical chemical protocols. We successfully employed gamma irradiation in order to introduce N-atoms in Graphene Quantum Dots (GQDs). By irradiating GQDs water dispersions in the presence of isopropyl alcohol and ethylenediamine, at doses of 25, 50 and 200 kGy, we attached amino groups onto GQDs in a single synthetic step. At the same time, a chemical reduction is achieved, too. Selected conditions induced incorporation of N-atoms within GDQs atomic lattice (around 3 at%), at all applied doses. Additionally, th…

Donor–Acceptor Interfaces by Engineered Nanoparticles Assemblies for Enhanced Efficiency in Plastic Planar Heterojunction Solar Cells

Precisely positioning functionalized gold nanoparticles assemblies at planar donor-acceptor interfaces results in 14-fold enhancement of power conversion efficiency in P3HT/PCBM organic solar cells on plastic (ITO/PET) substrates. This result has been achieved by employing naphthalenethiol-capped gold nanoparticles (NT-Au-NPs) produced by laser ablation in liquid and size varied in the 10-30 nm range. Upon surface functionalization with the aromatic thiol, these particles self-assemble in submicrometer aggregates, which give increased light scattering. When these aggregates are deposited in the planar heterojunction between the donor and the acceptor systems, the localized scattering leads …

Synthesis and structural investigations on R2Sn(IV)-D-aldonic acid complexes (R = methyl; butyl). Their effect on a new toxicity test organism,Liza saliens(Osteichthyes, Mugilidae): a histological study

Eight R2Sn(IV)-D-aldonate complexes [(R = Me, Bu; D-aldonate = D-galactonate2− (Galn), D-Gluconate2− (Glun), D-Gulonate2− (Guln), D-Ribonate2− (Ribn)], five of which are new derivatives, have been synthesized and structurally characterized both in solid and solution state by IR, 119Sn Mossbauer and 1H, 13C, 119Sn NMR spectroscopies, showing that ligands act as dianonic chelating agents. In solution phase, NMR data suggest that the bidentate chelation is attained by the O1 carboxylate and the vicinal O2 alkoxide atoms, which can be dynamically extended to a third binding site (O4) competing with O2. In Me2Sn(IV)-D-gluconate complex the occurrence of a self-association process leading to a di…

Ambipolar MoS2 Transistors by Nanoscale Tailoring of Schottky Barrier Using Oxygen Plasma Functionalization

One of the main challenges to exploit molybdenum disulfide (MoS2) potentialities for the next-generation complementary metal oxide semiconductor (CMOS) technology is the realization of p-type or ambipolar field-effect transistors (FETs). Hole transport in MoS2 FETs is typically hampered by the high Schottky barrier height (SBH) for holes at source/drain contacts, due to the Fermi level pinning close to the conduction band. In this work, we show that the SBH of multilayer MoS2 surface can be tailored at nanoscale using soft O-2 plasma treatments. The morphological, chemical, and electrical modifications of MoS2 surface under different plasma conditions were investigated by several microscopi…

ATTIVITÀ CITOTOSSICA DEI COMPLESSI DIORGANOSTAGNO(IV)-N-ACETILCISTEINA SU CELLULE DI MELANOMA A-375.

Effects of tributyltin(IV) chloride on fertilization ofStyela plicata(Ascidiacea: Tunicata): II. Scanning and transmission electron microscopy studies

The morphological aspects of Styela plicata fertilization after treatment with tributyltin(IV) chloride are described by means of scanning and transmission electron microscopy investigations. Alterations have been shown both on female and male gametes; spermatozoa, all the egg envelopes and the mitochondria of the egg cortical cytoplasm are modified in relation to incubation time. As a consequence, the damage to gametes blocks sperm–egg interaction and fertilization does not occur. Copyright © 2003 John Wiley & Sons, Ltd.

Structural investigations on diorganotin and triorganotin(IV) phosphomycin derivatives.

Abstract Four new diorganotin(IV), (R = Me, Bu), and triorganotin(IV), (R = Me, Ph), derivatives of the phosphomycin disodium salt antibiotic[(1R,2S)-1,2-epoxypropylphosphonate]Na2 have been synthesized and their solid state configuration studied by X-ray crystallography, FT-IR, Mossbauer, UV–Vis spectroscopies. The X-ray diffraction investigation, performed on the bis[trimethyltin(IV)]phosphomycin, showed that the coordination geometry at all the Sn atoms is trigonal bipyramidal. The structure of the complex forms an unusual polymeric zig-zag planar network. The FT-IR and the 119Sn Mossbauer studies supported the formation of trigonal bipyramidal (Tbp) molecular structures, both in the dio…

Preparation and structural studies on diorganotin(IV) complexes of N-nitroso-N-phenylhydroxylaminates

Abstract Diorganotin(IV)-complexes of the N -nitroso- N -phenylhydroxylaminates (hereinafter cupf), Et 2 Sn(cupf) 2 ( 1 ), Bu 2 Sn(cupf) 2 ( 2 ), {[Bu 2 Sn(cupf)] 2 O} 2 ( 3 ), t -Bu 2 Sn(cupf) 2 ( 4 ) and Oc 2 Sn(cupf) 2 ( 5 , 6 ) were prepared and characterised by FT-IR and Mossbauer spectroscopic measurements. The binding modes of the ligand were identified by FT-IR spectroscopy, and it was found that the ligand is coordinated in chelating or bridging mode to the organotin(IV) center. The 119 Sn Mossbauer and FT-IR studies support the formation of trans -O h ( 1 – 6 ) structures. The X-ray diffraction analysis of 4 revealed that the tin centre is in a skew-trapezoidal geometry defined by…

Equilibrium, Structural and Biological Activity Studies on [Organotin(IV)]n+ Complexes

Organotin(IV) compounds are characterized by the presence of at least one covalent C–Sn bond. The compounds contain tetravalent {Sn} centers and are classified as mono-, di-, tri-, and tetraorganotin(IV), depending on the number of alkyl (R) or aryl (Ar) moieties bound. The anions are usually Cl, F, O2, OH,–COO, or –S. It seems that the nature of the anionic group has only secondary importance in biological activity. The rapid rise in the industrial (catalyst in PVC and foam production), agricultural (fungicides and acaricides), and biological applications (wood, stone, and glass preservatives) of organotin(IV) compounds during the last few decades has led to their accumulation in the envir…

Interference of tributyltin(IV)chloride on the vascular plant cells

In the recent past years, interest in the environmental impact of organotin(IV) compounds has risen markedly. Considering that most data in the scientific literature refers to the animal kingdom and not to higher plants cells, we tested the effects of organotin compounds on vascular plant cells, by studying the interaction of tributyltin chloride (TBTCl) with Allium cepa, Solanun tuberosum and Solanum melongena, vascular plants that are directly involved in the human food chain. The TBTCl effects on mitotic metaphase plates, on pollen grains and on both microtubers and adult tuber parenchymatic cells were investigated and the concentrations of TBTCl inside the treated parenchymatic cells we…

Characterization of complexes formed between [Me2Sn(IV)]2+ and carboxymethylcelluloses.

Complexes formed between carboxymethylcellulose (CMC) and the [Me(2)Sn(IV)]2+ cation have been prepared in the solid state and characterized by FTIR and Mossbauer spectroscopy. The complexes contained CMC with varying molar weight and degree of carboxylation, and the complexes were isolated both from acidic and from neutral solutions at varying metal-to-ligand ratios. The characteristic vibration bands of the ligands were identified from their pH-dependent FTIR spectra. In the organotin(IV) complexes obtained at pH approximately 2, the -COO- moieties were found to be coordinated in a monodentate manner, and the band characteristic of the protonated (unbound) -COO- group(s) was also identifi…

Thiophene pyrenyl derivatives for the supramolecular processability of single-walled carbon nanotubes in thin film heterojunction

Abstract A major problem for the use of single-wall carbon nanotubes (SWCNTs) in electronic devices relates to their poor processability. Chemical modification inevitably introduces defects in the nanotube lattice, resulting in a loss of electronic properties. In this contest, we report on a supramolecular approach with the aim of increasing the dispersion of SWCNTs in solution and in organic semiconductor matrices by ensuring the optoelectronic properties. In particular, new pyrenyl derivatives of thiophene have been synthesized and used to improve the solubility of SWCNTs for electron transfer in thin film heterojunction with poly(3-hexylthiophene) (P3HT) as donor system. Photoinduced ele…

Blue light activated photodegradation of biomacromolecules by N-doped titanium dioxide in a chitosan hydrogel matrix

The use of photocatalysis activated by titanium dioxide nanostructured materials is a promising solution for many biomedical applications ranging from drug-free antibacterial to anticancer therapies, as well as for innovative hydrogel-supported phototherapies. This makes the effects of photocatalysis on the structure of biomolecules of a great relevance in order to define the applicability of photocatalytic materials in the biomedical fields. In this work, the effects of nitrogen-doped titanium dioxide (N-TiO2) dispersed in a biocompatible chitosan/PEG hydrogel on myoglobin and bovine serum albumin as target model proteins were investigated. The efficiency of this composite biocompatible ma…

Bending Sensors Based on Thin Films of Semitransparent Bithiophene-Fulleropyrrolidine Bisadducts

In this study, a novel bithiophene‐fulleropyrrolidine bisadducts system (bis‐Th2PC 60 ) was synthesized and electropolymerized by chronoamperometry onto flexible ITO/PET substrates. The resulting semitransparent thin film was characterized by XPS, FT‐IR, cyclic voltammetry and optical techniques, confirming the good outcome of the electropolymerization process. AFM investigations permitted to highlight an inherent disordered granular morphology, in which the grain‐to‐grain separation depends upon the application of bending. The electrical resistance of the thin film was characterized as function of bending (in the range 0°‐90°), showing promising responsivity to low bending angles (10°‐30°)…

Self-Cleaning Bending Sensors Based on Semitransparent ZnO Nanostructured Films

The design of multifunctional nanostructured materials is the key to the development of smart wearable devices. For instance, nanostructures endowed with both piezoelectric and photocatalytic activities could well be the workhorse for solar-light-driven self-cleaning wearable sensors. In this work, a simple strategy for the assembly of a flexible, semitransparent piezophotocatalytic system is demonstrated by leveraging rational wet chemistry synthesis of ZnO-based nanosheets/nanoflowers (NSs/NFs) under basic pH conditions onto flexible ITO/PET supports. A KMnO4 pretreatment before the ZnO synthesis (seeded ZnO) allows for the control of the density, size, and orientation of the NSs/NFs syst…

Synthesis, Structural Analysis, Fiber Formation and Preliminary Anticancer Characterization of the Organotin Polyether from Dibutyltin Dichloride and 2,5-Dimethyl-3-hexyne-2,5-diol

The organotin polyether derived from reaction of dibutyltin dichloride and 2,5-dimethyl-3-hexyne-2,5-diol was rapidly synthesized employing classical interfacial polymerization in 65% yield and a chain length of 360 units. IR results are consistent with the polyether structure. Bands characteristic of the formation of the Sn-O are present and bands characteristic of the Sn-Cl are absent. F MALDI MS results in the low mass range gives ion fragment clusters to five units. Isotopic abundance matches for tin are consistent with its presence in these ion fragment clusters. In the high mass range ion fragment clusters to greater than 300 units are found. The products offer outstanding inhibition …

Az N-nitrozo-N-fenil-hidroxil-amin (kupferron) ón(IV)organikus komplexeinek előállítása és szerkezetvizsgálata

Blue luminescent amino-functionalized graphene quantum dots as a responsive material for potential detection of metal ions and malathion

Large amounts of hazardous and toxic substances in the environment require non-toxic, cheap, easy, rapid, and sensitive methods for their detection. Blue luminescent graphene quantum dots (GQDs) were produced by electrochemical cleavage of graphite electrodes followed by gamma irradiation in the presence of ethylenediamine (EDA). Modified dots were able to detect metal ions (Co2+, Pd2+, Fe3+) due to photoluminescence quenching. The highest sensitivity was detected for the sample irradiated at a dose of 25 kGy. The limits of detection (LODs) were 1.79, 2.55, and 0.66 μmol L−1 for Co2+, Fe3+, and Pd2+, respectively. It was observed that GQDs irradiated at 200 kGy act as an ultra-sensitive tur…

Synthesis and characterization of diorganotin(IV)complexes with Phenothiazine class Drugs. Biological and Theoretical studies on cytotoxic activity

Preparation and structural characterization of Ph3Sn(IV)+ complexes with pyridinecarboxylic acids or hydroxypyridene, -pyrimidine and –quinoline.

A number of [Ph3Sn(IV)](+) complexes formed with ligands containing -OH (-C=O), or -COOH group(s) and aromatic IN) donor atom have been prepared. The binding sites of the ligands were identified by FT-IR spectroscopic measurements. In the complexes containing hydroxy and carboxylate functions, the carboxylato group is coordinated to the organotin(IV) centres in monodentate or bridging bidentate manner. It was also found that in the hydroxypyridine and -pyrimidine complexes the [Ph3Sn(IV)]+ moiety in most cases reacts with the phenolic form of the ligands. The rationalisation of the experimental Sn-119 Mossbauer nuclear quadrupole splittings, vertical bar Delta(exp)vertical bar - according t…

Gamma-Ray-Induced Structural Transformation of GQDs towards the Improvement of Their Optical Properties, Monitoring of Selected Toxic Compounds, and Photo-Induced Effects on Bacterial Strains.

Structural modification of different carbon-based nanomaterials is often necessary to improve their morphology and optical properties, particularly the incorporation of N-atoms in graphene quantum dots (GQDs). Here, a clean, simple, one-step, and eco-friendly method for N-doping of GQDs using gamma irradiation is reported. GQDs were irradiated in the presence of the different ethylenediamine (EDA) amounts (1 g, 5 g, and 10 g) and the highest % of N was detected in the presence of 10 g. N-doped GQDs emitted strong, blue photoluminescence (PL). Photoluminescence quantum yield was increased from 1.45, as obtained for non-irradiated dots, to 7.24% for those irradiated in the presence of 1 g of …

Diorganotin(IV) complexes with aldonic acids. Synthesis and structural study in solid state and in solution phase and biological activity

Computational studies of new metallic ions complexes of antioxidant dipeptides

Cerium effect on the phase structure, phase stability and redox properties of Ce-doped strontium ferrates

Nanostructured perovskite-type Sr1−aCeaFeO3−x, (0⩽a<0.15) powders have been prepared by citrate–nitrate smoldering auto-combustion. Their phase structure and stability, surface and morphological properties, reduction behavior and interaction with oxygen have been investigated by X-ray Powder Diffraction combined with Rietveld Analysis, 57Fe Mossbauer and X-ray Photoelectron Spectroscopies, N2-adsorption method, Temperature Programmed Reduction and Oxidation experiments. Our results reveal that citrate–nitrate auto-combustion method is effective in obtaining single phase Sr1−aCeaFeO3−x. The Sr1−aCeaFeO3−x structure is cubic only for a⩾0.06, while for a<0.06 remains tetragonal. Moreover, for …

Diorganotin(IV) complexes ofD-galacturonic acid: solid-state and solution-phase structural study

Three diorganotin(IV) complexes of D-galacturonic acid (H2GalA; R = Me, n-Bu, Ph), two of which are new derivatives (R = Me, Ph), have been synthesized and their solid-state and solution-phase investigated by IR, Mossbauer, 1H, 13C and 119Sn NMR spectroscopy. The FTIR data suggest that H2GalA, in the dialkyltin derivatives, behaves as a dianionic ligand, coordinating the tin(IV) atom through an ester-type carboxylate and deprotonated alcoholic hydroxo groups, whereas a bridging carboxylate occurs in the diphenyltin(IV) complex. Octahedral and trigonal bipyramidal local geometries on tin(IV) atoms are proposed for dialkyltin(IV)GalA and diphenyltin(IV)GalA complexes respectively on the basis…

Computational study of dimethyl- and trimethyl-tin(IV) complexes of porphyrin derivatives

The molecular geometry, energetics and electronic charge distribution of diorgano- and triorgano-tin(IV) complexes of [protoporphyrin-IX] and [meso-tetra(4-carboxyphenyl)porphine] derivatives were determined at semi-empirical and ab initio levels. To study the molecular details of the complexes, simpler molecule models were calculated by the ab initio pseudo-potential method. The molecular properties of these complexes are essentially independent of the presence of the peripheral tin atoms. Agreement was always found among the results of the different computational approaches, as well as between the theoretical and the experimental findings on the molecular geometry of the hypothesized comp…

Organotin(IV)derivatives neurotoxicity and their modulation by Baclofen

Several new diorganotin(IV) and triorganotin(IV) complexes with 4-amino-3- (4-chloro phenyl)]-butanoic acid ( = Baclofen) have been synthesized and their structure investigated both in the solid state and in solution phase through spectroscopic methods (FT-IR, Mössbauer, 1H and 13C NMR). According to experimental analytical data, the stoichiometry of the complexes has been proposed as R2SnBac2 and R3SnBac, respectively for diorganotin(IV) and triorganotin(IV) baclofen complexes. (Baclofen = HBac; R = Me, Bu, Ph).

Molecular basis of the interaction of novel tributyltin(IV) 2/4-[(E)-2-(aryl)-1-diazenyl] benzoates endowed with an improved cytotoxic profile: Synthesis, structure, biological efficacy and QSAR studies

A series of tributyltin(IV) complexes based on 2/4-[(E)-2-(aryl)-1-diazenyl]benzoate ligands was synthesized, wherein the position of the carboxylate and aryl substituents (methyl, tert-butyl and hydroxyl) varies. The complexes, Bu(3)SnL(1-4)H (1-4), have been structurally characterized by elemental analysis and IR, NMR ((1)H, (13)C, and (119)Sn) and (119)Sn Mossbauer spectroscopy. All have a tetrahedral geometry in solution and a trigonal bipyramidal geometry in the solid-state, except for Bu(3)SnL(4)H (4) that was ascertained to have tetrahedral coordination by X-ray crystallography. Cytotoxicity studies were carried out on human tumor cell lines A498 (renal cancer), EVSA-T (mammary cance…

Enhanced power-conversion efficiency in organic solar cells incorporating copolymeric phase-separation modulators

A new class of copolymers containing oligothiophene moieties with different lengths and fullerene units have been designed and prepared by an easy and inexpensive one-step synthetic approach. The incorporation of small quantities of these copolymers into bulk heterojunction (BHJ) solar cells with donor regioregular polythiophene (P3HT) and an acceptor fullerene derivate (PCBM) results in good control of the phase separation process without further affecting the BHJ optoelectronic properties. Indeed, under thermal annealing these copolymers allow the modulation of the growth of domains whose size depends on the length of the copolymer repetitive units. Domain size on the same length scale as…

Pseudo-Planar Organic Heterojunctions by Sequential Printing of Quasi-Miscible Inks

This work deals with the interfacial mixing mechanism of picoliter (pL)-scale droplets produced by sequential inkjet printing of organic-based inks onto ITO/PET surfaces at a moderately high Weber number (~101). Differently from solution dispensing processes at a high Bond number such as spin coating, the deposition by inkjet printing is strictly controlled by droplet velocity, ink viscosity, and surface tension. In particular, this study considers the interfacial mixing of droplets containing the most investigated donor/acceptor couple for organic solar cells, i.e., poly(3-hexylthiophene) (P3HT) and (6,6)-phenyl-C61-butyric acid methyl ester (PCBM), showing how low-viscosity and low-surfac…

SUPERHYDROPHOBIC TIO2-FLUORINATED POLYSILOXANE NANOCOMPOSITES WITH PHOTOCATALYTIC CLEANING ACTIVITY FOR CULTURAL HERITAGE APPLICATIONS

Synergies and compromises between charge and energy transfers in three-component organic solar cells

In this paper, we developed different three-component organic heterojunction structures supported by PET/ITO substrates with the aim to study the possible synergies and/or compromises between charge transfer (CT) and energy transfer (ET) processes in organic solar cells (OSCs). As components, we employed poly(3-hexylthiophene-2,5-diyl) (P3HT; donor), [6,6]-phenyl-C61-butyric acid methyl ester (PCBM; acceptor) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) that is known to give good ET to P3HT. At first, we observed that in a planar heterojunction (PHJ) solar cell, F8BT has to be properly located in between P3HT and PCBM to get a cascade energy level configuration allowing for a b…

Synthesis, chemical characterization and biological activity of new histone acetylation/deacetylation specific inhibitors: a novel and potential approach to cancer therapy

Three new triorganotin(IV) complexes of valproic acid (vp1, Me3Sn-valproate; vp2, Bu3Sn-valproate; vp3, Ph3Sn-valproate) have been synthesized and investigated by spectroscopic and biological methods. An anionic, monodentate valproate ligand was observed, ester-like coordinating the tin atom on a tetra-coordinated, monomeric environment. The structures, though, can distort towards a penta-coordination, as a consequence of a long range O center dot center dot center dot Sn interaction. Crystallographic and NMR findings confirm this situation both in solid state and solution. Biological finding evidenced a clear cytotoxic action of the complexes in hepatocellular carcinoma cell cultures: one …

Synthesis, structural investigation and biological activity of new diorganotin(IV) N-acetylcysteine Complexes.

Boosting the Performance of One-Step Solution-Processed Perovskite Solar Cells Using a Natural Monoterpene Alcohol as a Green Solvent Additive

The perovskite film is the core of a perovskite solar cell (PSC), and its quality is crucial for the performance of such devices. The morphology, crystallinity, and surface coverage of the perovskite layer greatly affect the power conversion efficiency (PCE), hysteresis, and long-term stability of PSCs. The incorporation of appropriate solvent additives in the perovskite precursor solution is an effective strategy to control the film morphology and reduce the defects and grain boundaries. However, the commonly used solvent additives are environmentally harmful and highly toxic. In this work, α-terpineol (a nontoxic, eco-friendly, and low-cost monoterpene alcohol) is employed for the first t…

Synthesis, Characterization and in vitro antimicrobial activity of dialkyltin(IV)bis(fusidate) complexes.

The complexation of one steroid antibiotic of the fusidane family, sodium fusidate [sodium 2-16-acetyloxy-3,11-dihydroxy-4,8,10,14-tetramethyl-2,3,4,5,6,7,9,11,12, 13,15,16-dodeca hydro-1H-cyclopenta[a]phenanthren-7-ylidene)-6-methyl-hept-5-enoate = (Nafus)], by dialkyltin(IV) has been studied by conventional technique as FT-IR, Mössbauer and NMR spectroscopies. Analytical data supported the general formula Alk2Sn(IV)fus2 (Alk = Me, Bu). Infrared spectral data of the complexes imply the presence of both uni- and bidentate, ester-type and bridging carboxylate group, respectively. On the basis of FT-IR and 119Sn Mössbauer spectroscopy, in both Me2Sn(IV)fus2 and Bu2Sn(IV)fus2, trigonal bipyram…

Speciation of tin(II) in aqueous solution: thermodynamic and spectroscopic study of simple and mixed hydroxocarboxylate complexes

This contribution reports the results of potentiometric and Mossbauer investigations on the formation, stability, and structure of binary and ternary mono- and binuclear complexes of Sn2+ with three hydroxocarboxylic ligands (namely L = tartrate, malate, and citrate) and chloride at T = 298.15 K in different ionic media and ionic strengths (0.15 and 1.00 mol dm−3 in NaCl(aq) and 1.00 mol dm−3 in NaNO3(aq)). The stability constants of various simple Sn i H j L (2+−) and mixed Sn i H j L k Cl (2+−−) species obtained in the different experimental conditions are reported, and various speciation diagrams of the simple and mixed systems are shown in different conditions. The sequestering ability …

Mössbauer Investigation on Organotin Polyester Amines Containing Ciprofloxacin.

An in vitro comparative assessment with a series of new triphenyltin(IV) 2-/4-[(E)-2-(aryl)-1-diazenyl]benzoates endowed with anticancer activities: Structural modifications, analysis of efficacy and cytotoxicity involving human tumor cell lines

Four new triphenyltin(IV) complexes of composition Ph 3SnLH (where LH = 2-/4-[(E)-2-(aryl)-1-diazenyl]benzoate) (1-4) were synthesized and characterized by spectroscopic ( 1H, 13C and 119Sn NMR, IR, 119Sn Mössbauer) techniques in combination with elemental analysis. The 119Sn NMR spectroscopic data indicate a tetrahedral coordination geometry in non-coordinating solvents. The crystal structures of three complexes, Ph 3SnL 1H (1), Ph 3SnL 3H (3), Ph 3SnL 4H (4), were determined. All display an essentially tetrahedral geometry with angles ranging from 93.50(8) to 124.5(2)°; 119Sn Mössbauer spectral data support this assignment. The cytotoxicity studies were performed with complexes 1-4, along…

New histone acetylation/deacetylation specific inhibitors: a novel and potential approach to cancer therapy

The acetylation status of histones is regulated in eukaryotes by two kinds of enzymes, histone acetyltransferases (HATs) and histone deacetylases (HDACs), which are responsible for acetylation and deacetylation of lysines residues in N-terminal tails of histone.[1] Thus acetylation, together with phosphorylation and methylation of N-terminal tail of histones, are involved in regulating fundamental processes, such as proliferation and cell death.[2-3] Sodium butyrate, which belongs together with valproic acid to the class of short chain fatty acids, was the first HDAC inhibitor (HDACI) to be identified.[1] Organotin compounds have various influences on physical function including the hormone…

Low angle bending detection semi-transparent piezoresistive sensor

We designed, fabricated, and validated a piezoresistive bending sensor, a fundamental component of wearable electronic devices for monitoring human motion. The most diffused opaque carbon-based resistance flex sensors suffer from low detection for small bending angles. The sensor we here present is based on a semi-transparent active material (fulleropyrrolidine bisadducts polymer) and has the remarkable advantage of good electrical properties for low bending angles. The fabrication steps are effective since a pre-patterned ITO/PET surface is functionalized by chronoamperometric deposition, and the silver electrical contacts are inkjet printed. We propose a fitting function of the measured t…

Organometallic Complexes with Biological Molecules. Structural investigation of cis-diammineplatinum(II)-Porphyrin derivatives.

CCDC 1431712: Experimental Crystal Structure Determination

Related Article: Tushar S. Basu Baul, Pelesakuo Kehie, Andrew Duthie, Nikhil Guchhait, Nune Raviprakash, Raveendra B. Mokhamatam, Sunil K. Manna, Nerina Armata, Michelangelo Scopelliti, f, Ruimin Wang, Ulli Englert|2017|J.Inorg.Biochem.|168|76|doi:10.1016/j.jinorgbio.2016.12.001

CCDC 1431713: Experimental Crystal Structure Determination

Related Article: Tushar S. Basu Baul, Pelesakuo Kehie, Andrew Duthie, Nikhil Guchhait, Nune Raviprakash, Raveendra B. Mokhamatam, Sunil K. Manna, Nerina Armata, Michelangelo Scopelliti, f, Ruimin Wang, Ulli Englert|2017|J.Inorg.Biochem.|168|76|doi:10.1016/j.jinorgbio.2016.12.001

CCDC 830010: Experimental Crystal Structure Determination

Related Article: Ornella Pellerito, Cristina Prinzivalli, Elisabetta Foresti, Piera Sabatino, Michele Abbate, Girolamo Casella, Tiziana Fiore, Michelangelo Scopelliti, Claudia Pellerito, Michela Giuliano, Giulia Grasso, Lorenzo Pellerito|2013|J.Inorg.Biochem.|125|16|doi:10.1016/j.jinorgbio.2013.04.008

CCDC 1431715: Experimental Crystal Structure Determination

Related Article: Tushar S. Basu Baul, Pelesakuo Kehie, Andrew Duthie, Nikhil Guchhait, Nune Raviprakash, Raveendra B. Mokhamatam, Sunil K. Manna, Nerina Armata, Michelangelo Scopelliti, f, Ruimin Wang, Ulli Englert|2017|J.Inorg.Biochem.|168|76|doi:10.1016/j.jinorgbio.2016.12.001

CCDC 1431714: Experimental Crystal Structure Determination

Related Article: Tushar S. Basu Baul, Pelesakuo Kehie, Andrew Duthie, Nikhil Guchhait, Nune Raviprakash, Raveendra B. Mokhamatam, Sunil K. Manna, Nerina Armata, Michelangelo Scopelliti, f, Ruimin Wang, Ulli Englert|2017|J.Inorg.Biochem.|168|76|doi:10.1016/j.jinorgbio.2016.12.001