Browse
Submit Data
Databases
API
Help

Dataset Information

15 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Lipophilic Re(CO)₃pyca complexes for Mid-IR imaging applications.

ABSTRACT: Several Re(i)pyca conjugates incorporating long aliphatic amines have been synthesized through a one-pot methodology. The compounds have been fully characterized, and seven compounds have been structurally elucidated by single crystal X-ray diffraction. The C14 variant was probed as a potential organometallic IR dye. Large unilamellar vesicles were generated with DOPC and the C14 compound and we observed incorporation of the rhenium complex as observed by FTIR microscopy.

SUBMITTER: Schrage BR

PROVIDER: S-EPMC7932017 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Systematic investigation of CO2 : NH3 ice mixtures using mid-IR and VUV spectroscopy - part 1: thermal processing.

Project description:The adjustment of experimental parameters in interstellar ice analogues can have profound effects on molecular synthesis within an ice system. We demonstrated this by systematically investigating the stoichiometric mixing ratios of CO2 : NH3 ices as a function of thermal processing using mid-IR and VUV spectroscopy. We observed that the type of CO2 bonding environment was dependent on the different stoichiometric mixing ratios and that this pre-determined the NH3 crystallite structure after phase change. The thermal reactivity of the ices was linked to the different chemical and physical properties of the stoichiometric ratios. Our results provide new details into the chemical and physical properties of the different stoichiometric CO2 : NH3 ices enhancing our understanding of the thermally induced molecular synthesis within this ice system.

| S-EPMC9057146 | biostudies-literature

Di-Zinc-Aryl Complexes: CO2 Insertions and Applications in Polymerisation Catalysis.

Project description:Two new di-zinc-aryl complexes, [LZn2 Ph2 ] and [LZn2 (C6 F5 )2 ], coordinated by a diphenol tetraamine macrocyclic ligand have been prepared and fully characterised, including by single-crystal X-ray diffraction experiments. The complexes' reactivities with monomers including carbon dioxide, cyclohexene oxide, phthalic anhydride, isopropanol and phenol were investigated using both experimental studies and density functional theory calculations. In particular, [LZn2 Ph2 ] readily inserts carbon dioxide to form a carboxylate, at 1 bar pressure, whereas [LZn2 (C6 F5 )2 ] does not react. Under these conditions [LZn2 Ph2 ] shows moderate activity in the ring-opening copolymerisation of cyclohexene oxide/carbon dioxide (TOF=20 h-1 ), cyclohexene oxide/phthalic anhydride (TOF=33 h-1 ) and the ring-opening polymerisations of rac-lactide (TOF=99 h-1 ) and ϵ-caprolactone (TOF=5280 h-1 ).

| S-EPMC5488170 | biostudies-literature

In vivo O2 imaging in hepatic tissues by phosphorescence lifetime imaging microscopy using Ir(III) complexes as intracellular probes.

Project description:Phosphorescence lifetime imaging microscopy (PLIM) combined with an oxygen (O2)-sensitive luminescent probe allows for high-resolution O2 imaging of living tissues. Herein, we present phosphorescent Ir(III) complexes, (btp)2Ir(acac-DM) (Ir-1) and (btp-OH)3Ir (Ir-2), as useful O2 probes for PLIM measurement. These small-molecule probes were efficiently taken up into cultured cells and accumulated in specific organelles. Their excellent cell-permeable properties allowed for efficient staining of three-dimensional cell spheroids, and thereby phosphorescence lifetime measurements enabled the evaluation of the O2 level and distribution in spheroids, including the detection of alterations in O2 levels by metabolic stimulation with an effector. We took PLIM images of hepatic tissues of living mice by intravenously administrating these probes. The PLIM images clearly visualized the O2 gradient in hepatic lobules with cellular-level resolution, and the O2 levels were derived based on calibration using cultured cells; the phosphorescence lifetime of Ir-1 gave reasonable O2 levels, whereas Ir-2 exhibited much lower O2 levels. Intravenous administration of NH4Cl to mice caused the hepatic tissues to experience hypoxia, presumably due to O2 consumption to produce ATP required for ammonia detoxification, suggesting that the metabolism of the probe molecule might affect liver O2 levels.

| S-EPMC7713648 | biostudies-literature

Pyridylbenzimidazole based Re(i)(CO)3 complexes: antimicrobial activity, spectroscopic and density functional theory calculations.

Project description:fac-[ReBr(CO)3(L1,2)] L1 = 1-ethyl-2-(pyridin-2-yl)benzimidazole (1) and L2 = 1-[(pyridin-2-yl) benzimidazole]-propyl-sulfonic acid (2), fac-[Re2Br2(CO)6L3] (3) L3 = 1,1'-(hexane-1,6-diyl)bis[2-(pyridin-2-yl)1H-benzimidazole] and fac-[ReBr(CO)3(L4,5-κ2N1N2)] (L4 = 2,6-bis(benzimidazol-2'-yl)pyridine (4) and L5 = 2,6-bis(1-ethyl-benzimidazol-2'-yl)pyridine (5) were synthesized and fully characterized using different spectrocopic and analytical tools. The spectrocopic data showed coordination of L1-3 to fac-ReBr(CO)3 via the benzimidazole and pyridine N-atoms. For 4 and 5, the absence of a two-fold axis of symmetry for L4,5 in the 1H NMR spectra reflect the κ2N1,N2 mode of coordination. The electronic properties of 1-5 were investigated by time-dependent density functional theory calculations in the singlet and triplet states. The ligands and their Re(i) complexes were assessed for their potential antimicrobial activity. Compound 5 was screened against non-malignant cell line (noncancerous human embryonic kidney cell line (HEK293)) as well as evaluated for its blood compatibility.

| S-EPMC9064247 | biostudies-literature

CO2 capture by Mn(i) and Re(i) complexes with a deprotonated triethanolamine ligand.

Project description:CO2 capture at low concentration by catalysts is potentially useful for developing photocatalytic and electrocatalytic CO2 reduction systems. We investigated the CO2-capturing abilities of two complexes, fac-Mn(X2bpy)(CO)3(OCH2CH2NR2) and fac-Re(X2bpy)(CO)3(OCH2CH2NR2) (X2bpy = 4,4'-X2-2,2-bipyridine and R = -CH2CH2OH), which work as efficient catalysts for CO2 reduction. Both complexes could efficiently capture CO2 even from Ar gas containing only low concentration of CO2 such as 1% to be converted into fac-M(X2bpy)(CO)3(OC(O)OCH2CH2NR2) (M = Mn and Re). These CO2-capturing reactions proceeded reversibly and their equilibrium constants were >1000. The substituents of X2bpy strongly affected the CO2-capturing abilities of both Mn and Re complexes. The density functional theory (DFT) calculation could be used to estimate the CO2-capturing abilities of the metal complexes in the presence of triethanolamine.

| S-EPMC6429607 | biostudies-literature

Electronic Effects of Substituents on fac-M(bpy-R)(CO)3 (M = Mn, Re) Complexes for Homogeneous CO2 Electroreduction.

Project description:Synthesis and characterization of 14 new 2,2'-bipyridine metal complexes fac-M(bpy-R)(CO)3X (where M = Mn, X = Br or M = Re, X = Cl and R = -CF3, -CN, -Ph, -PhOH, -NMe2) are reported. The complexes have been characterized by NMR, IR spectroscopy and elemental analysis. Single crystal X-Ray diffraction structures have been solved for Re(dpbpy)(CO)3Cl (dpbpy = 4,6-diphenyl-2,2'-bipyridine) and Re(hpbpy)(CO)3Cl (hpbpy = 4-(2-hydroxy-phenyl)-6-phenyl-2,2'-bipyridine). Electrochemical behaviors of the complexes in acetonitrile under Ar and their catalytic performances for CO2 reduction with added water and MeOH have been investigated by cyclic voltammetry and controlled potential electrolysis. The role of the substituents on the electrochemical properties and the related over potentials required for CO2 transformation have been analyzed. The complexes carrying only electron withdrawing groups like -CF3, -CN totally lose their catalytic activities toward CO2 reduction, whereas the symmetric -NMe2 substituted and push-pull systems (containing both -NMe2 and -CF3) still display electrocatalytic current enhancement under CO2 atmosphere. The complexes carrying a phenyl or a phenol group in position 4 show catalytic behaviors similar to those of simple M-bpy systems. The only detected reduction product by GC analysis is CO: for example, fac-Re (bpy-4,4'-NMe2)(CO)3Cl gives CO with high faradic efficiency and a TON of 18 and 31, in absence of external proton source and with 5% MeOH, respectively. DFT calculations were carried out to highlight the electronic properties of the complexes; results are in agreement with experimental electrochemical data.

| S-EPMC6561311 | biostudies-literature

Fluoro Nitrenoid Complexes FN=MF2 (M=Co, Rh, Ir): Electronic Structure Dichotomy and Formation of Nitrido Fluorides N?MF3.

Project description:The fluoronitrenoid metal complexes FNCoF2 and FNRhF2 as well as the first ternary RhVI and IrVI complexes NIrF3 and NRhF3 are described. They were obtained by the reaction of excited Group-9 metal atoms with NF3 and their IR spectra, isolated in solid rare gases (neon and argon), were recorded. Aided by the observed 14/15 N isotope shifts and quantum-chemical predictions, all four stretching fundamentals of the novel complexes were safely assigned. The F-N stretching frequencies of the fluoronitrenoid complexes FNCoF2 (1056.8?cm-1 ) and FNRhF2 (872.6?cm-1 ) are very different and their N-M bonds vary greatly. In FNCoF2 , the FN ligand is singly bonded to Co and bears considerable iminyl/nitrene radical character, while the N-Rh bond in FNRhF2 is a strong double bond with comparatively strong ?- and ?-bonds. The anticipated rearrangement of FNCoF2 to the nitrido CoVI complex is predicted to be endothermic and was not observed.

| S-EPMC7756499 | biostudies-literature

Time lapse synchrotron IR chemical imaging for observing the acclimation of a single algal cell to CO2 treatment.

Project description:Algae are the main primary producers in aquatic environments and therefore of fundamental importance for the global ecosystem. Mid-infrared (IR) microspectroscopy is a non-invasive tool that allows in principle studying chemical composition on a single-cell level. For a long time, however, mid-infrared (IR) imaging of living algal cells in an aqueous environment has been a challenge due to the strong IR absorption of water. In this study, we employed multi-beam synchrotron radiation to measure time-resolved IR hyperspectral images of individual Thalassiosira weissflogii cells in water in the course of acclimation to an abrupt change of CO2 availability (from 390 to 5000 ppm and vice versa) over 75 min. We used a previously developed algorithm to correct sinusoidal interference fringes from IR hyperspectral imaging data. After preprocessing and fringe correction of the hyperspectral data, principal component analysis (PCA) was performed to assess the spatial distribution of organic pools within the algal cells. Through the analysis of 200,000 spectra, we were able to identify compositional modifications associated with CO2 treatment. PCA revealed changes in the carbohydrate pool (1200-950 cm[Formula: see text]), lipids (1740, 2852, 2922 cm[Formula: see text]), and nucleic acid (1160 and 1201 cm[Formula: see text]) as the major response of exposure to elevated CO2 concentrations. Our results show a local metabolism response to this external perturbation.

| S-EPMC8225881 | biostudies-literature

Biocompatible Ir(III) Complexes as Oxygen Sensors for Phosphorescence Lifetime Imaging.

Project description:Synthesis of biocompatible near infrared phosphorescent complexes and their application in bioimaging as triplet oxygen sensors in live systems are still challenging areas of organometallic chemistry. We have designed and synthetized four novel iridium [Ir(N^C)2(N^N)]+ complexes (N^C-benzothienyl-phenanthridine based cyclometalated ligand; N^N-pyridin-phenanthroimidazol diimine chelate), decorated with oligo(ethylene glycol) groups to impart these emitters' solubility in aqueous media, biocompatibility, and to shield them from interaction with bio-environment. These substances were fully characterized using NMR spectroscopy and ESI mass-spectrometry. The complexes exhibited excitation close to the biological "window of transparency", NIR emission at 730 nm, and quantum yields up to 12% in water. The compounds with higher degree of the chromophore shielding possess low toxicity, bleaching stability, absence of sensitivity to variations of pH, serum, and complex concentrations. The properties of these probes as oxygen sensors for biological systems have been studied by using phosphorescence lifetime imaging experiments in different cell cultures. The results showed essential lifetime response onto variations in oxygen concentration (2.0-2.3 μs under normoxia and 2.8-3.0 μs under hypoxia conditions) in complete agreement with the calibration curves obtained "in cuvette". The data obtained indicate that these emitters can be used as semi-quantitative oxygen sensors in biological systems.

| S-EPMC8153025 | biostudies-literature

GeS2-In2S3-CsI Chalcogenide Glasses Doped with Rare Earth Ions for Near- and Mid-IR Luminescence.

Project description:Chalcogenide glass has been considered as a promising host for the potential laser gain and amplifier media operating in near- and mid-IR spectral region. In this work, the IR luminescence spectra of rare earth ions (Tm3+, Er3+, and Dy3+) doped 65GeS2-25In2S3-10CsI chalcogenide glasses were measured under the excitation of an 808?nm laser diode. To the best of our knowledge, it firstly provides the luminescence spectra of a full near- and mid-IR spectral range from 1 to 4??m in rare earth ions doped chalcogenide glasses. The results of absorption spectra, luminescence spectra, and fluorescence decay curves were obtained in these samples with singly-, co- and triply-doping behaviors of Tm3+, Er3+, and Dy3+ ions. In order to search possible efficient IR emissions, the luminescence behavior was investigated specifically with the variation of doping behaviors and dopant ions, especially in the samples co- and triply-doped active ions. The results suggest that favorable near- and mid-IR luminescence of rare earth ions can be further modified in chalcogenide glasses through an elaborated design of doping behavior and optically active ions.

| S-EPMC5116617 | biostudies-literature