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Homogeneous copper(II) chelates and heterogeneous Cu(II)-poly(vinylpyridine) complexes as catalysts for 3,5-di-tert-butylcatechol oxidation

Liquid-phase oxidation of 3,5-di-tert-butylcatechol (3,5-DtBC) by molecular oxygen was carried out in the presence of homogeneous Cu(II) chelates or heterogeneous Cu(II)-poly(4-vinylpyridine) (Cu(II)-PVP) catalytic systems. The oxidation product in both cases is 3,5-di-tert-butyl-o-benzoquinone (3,5-DtBQ). The catalytic activity of the oxidation of 3,5-DtBC catalyzed by the homogeneous Cu(II) system was found to be affected by the Cu(II) chelates used as the catalyst, the addition of pyridine derivatives, and their amounts added. The oxidation activity was found to increase with the basicity of the added pyridine derivatives. The kinetic data obtained from the formation rate of 3,5-DtBQ by the homogeneous bis(acetylacetonato)Cu(II)-pyridine catalytic system showed that the rate was independent of the 3,5-DtBC concentration, second order in the concentration of the catalyst, and first order with respect to the partial pressure of oxygen. The homogeneous copper(II) chelate-catalyzed oxidation of 3,5-DtBC confirmed the stoichiometric equation 3,5-DtBC + 1 2O2 = 3,5-DtBQ + H2O. On the basis of these data, possible mechanistic interpretations are discussed, in which a dimeric Cu(II) complex is assumed to be the active species. The kinetics of 3,5-DtBC oxidation by molecular oxygen in the presence of the heterogeneous Cu(II)-PVP catalyst revealed that both the oxygen absorption rate and effectiveness factor decreased with increasing particle size of the Cu(II)-PVP catalyst. The increase of the particle size of the catalyst was found to cause an increase in the fraction of mass transfer resistance in the total (mass transfer + reaction) resistance of the oxidation reaction.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Mechanochemical and solution synthesis, X-ray structure and IR and 31P solid state NMR spectroscopic studies of copper(i) thiocyanate adducts with bulky monodentate tertiary phosphine ligands

A number of adducts of copper(i) thiocyanate with bulky tertiary phosphine ligands, and some nitrogen-base solvates, were synthesized and structurally and spectroscopically characterised. CuSCN:PCy3 (1:2), as crystallized from pyridine, is shown by a single crystal X-ray study to be a one-dimensional polymer.(Cy3P)2CuSCN(Cy3P)2CuSCN. (1) with the four-coordinate copper atoms linked end-on by S-SCN-N bridging thiocyanate groups. A second form (2), obtained from acetonitrile, was also identified and shown by IR and 31P CPMAS NMR spectroscopy to be mononuclear, with the magnitude of the dnuCu parameter measured from the 31P CPMAS and the nu(CN) value from the IR clearly establishing this compound as three-coordinate [(Cy3P) 2CuNCS]. Two further CuSCN/PCy3 compounds CuSCN:PCy 3 (1:1) (3), and CuSCN:PCy3:py (1:1:1) (4) were also characterized spectroscopically, with the dnuCu parameters indicating three- and four-coordinate copper sites, respectively. Attempts to obtain a 1:2 adduct with tri-t-butylphosphine have yielded, from pyridine, the 1:1 adduct as a dimer [(But3P)(SCNNCS)Cu(PBut3)] (5), while similar attempts with tri-o-tolylphosphine (from acetonitrile and pyridine (= L)) resulted in solvated 1:1:1 CuSCN:P(o-tol)3:L forms as dimeric [{(o-tol) 3P}LCu(SCNNCS)CuL{P(o-tol)3}] (6 and 8). The solvent-free 1:1 CuSCN:P(o-tol)3 adduct (7), obtained by desolvation of 6, was characterized spectroscopically and dnuCu measurements from the 31P CPMAS NMR data are consistent with the decrease in coordination number of the copper atom from four (for 6) (P,N(MeCN)Cu,S,N) to three (for 7) (PCuS,N) upon loss of the acetonitrile of solvation. These results are compared with those previously reported for mononuclear and binuclear PPh3 adducts which demonstrate a clear tendency for the copper centre to remain four-coordinate. The IR spectroscopic measurements on these compounds show that bands in the far-IR spectra provide a much more definitive criterion for distinguishing between bridging and terminal bonding than does an often-used empirical rule based on nu(CN) in the mid-IR, which leads to the wrong conclusion in some cases.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Antibacterial susceptibility of new copper(II) N-pyruvoyl anthranilate complexes against marine bacterial strains ? In search of new antibiofouling candidate

Biofouling is a serious problem and very difficult to overcome, since the marine biofilm-producing microorganisms resist the host defense mechanism and antibiotic therapy. Therefore, there is an urgent need to develop potent anti-biofouling agent to effectively eradicate unwanted biofilms. Our work represents antibacterial susceptibility and antibiofilm forming assay of new copper(II) N-pyruvoyl anthranilate architectures (4a?d) against Staphylococcus aureus and Escherichia coli, marine isolates. The preliminary biofilm susceptibility tests revealed that, the most potent staphylococcalcidal (MIC/MBC?=?9.25/10.50?mM) and E. coli-cidal (MIC/MBC?=?13.25/13.50?mM) agent, 4d, exhibits significant biofilm inhibition. Complex 4d can therefore provide an antibiofilm-forming agent candidate to curb the formation of biofilms.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Syntheses, structures, and luminescence properties of two copper(I) thiocyanate coordination polymers with different N-donor ligands

Two coordination polymers, [Cu(SCN)(3-ptz)]n(1) and [Cu(SCN)(btmb)]n¡¤nCH3CN (2) (3-ptz = 5-(3-pyridyl)tetrazole, btmb = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene), were synthesized and characterized by EA, IR, PXRD and thermogravimetry. Complex 1 is a 2-D coordination polymer constructed from bidentate 3-ptz and 1,3-thiocyanate ligands. Complex 2 is a 2-D wave-like coordination polymer assembled by bidentate btmb and 1,3-thiocyanate ligands. Acetonitrile guest molecule is perched in the tunnel. Complexes 1 and 2 remain stable up to 240C and 280C, respectively. Complex 1 emits strong orange luminescence at 590 nm, and complex 2 emits blue luminescence at 468 nm.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Integration of phenylammoniumiodide (PAI) as a surface coating molecule towards ambient stable MAPbI3 perovskite for solar cell application

In the present work, different hybrid perovskites were synthesized by gradual concentration variation of larger cation of phenylammoniumiodide (PAI) and methylammoniumiodide (MAI) in PbI2 solution with the aim of improving the stability of MAPbI3 film and photovoltaic efficiency. To understand the properties of perovskite like structural, optical, thermal, morphological and chemical state, extensive characterizations such as XRD, UV?visible spectroscopy, FE-SEM, SEM, EDX and XPS were performed. The role of PAI was investigated further with the use of DFT studies. The DFT results confirmed that the PAI was passivated on the surface of MAPbI3 with most stable arrangement. The stable arrangement revealed the formation of ?-? interactions within the phenyl rings, which shielded the MAI crystals and thereby resulted in enhanced stability of the perovskites. Highly protected perovskite consequently yielded high- performance solar cell device with enhanced stability under 60% humidity, high temperature exposure and longer time stability even when directly exposed to normal room temperature. The new investigation of capping techniques with the use of bigger organic molecules, high performance solar cell with low device costs could emerge. This could lead to unprecedented rapid progress on power conversion efficiency (PCE). Thus, more stable organic-inorganic hybrid perovskites could be developed for future applications.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Tubulin binding ligands and corresponding prodrug constructs

A diverse set of tubulin binding ligands have been discovered which are structurally characterized, in a general sense, by a semi-rigid molecular framework capable of maintaining aryl-aryl, pseudo pi stacking distances appropriate for molecular recognition of tubulin. In phenolic or amino form, these ligands may be further functionalized to prepare phosphate esters, phosphate salts, and phosphoramidates capable of demonstrating selective targeting and destruction of tumor cell vasculature.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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SUBSTITUTED INDOLINE DERIVATIVES AS DENGUE VIRAL REPLICATION INHIBITORS

The present invention concerns substituted indoline derivatives, methods to prevent or treat dengue viral infections by using said compounds and also relates to said compounds for use as a medicine, more preferably for use as a medicine to treat or prevent dengue viral infections. The present invention furthermore relates to pharmaceutical compositions or combination preparations of the compounds, to the compositions or preparations for use as a medicine, more preferably for the prevention or treatment of dengue viral infections. The invention also relates to processes for preparation of the compounds.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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COPPER MEDIATED REACTIONS IN NUCLEOSIDE SYNTHESIS

The regiospecific functionalization of the base moiety of purine nucleosides through copper-mediated nucleophilic reactions is described.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Top Picks: new discover of Cuprous thiocyanate

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Electron and hole transport layers optimization by numerical simulation of a perovskite solar cell

In this paper an n-i-p perovskite solar cell was studied using SCAPS simulator. The primary solar cell’s structure is FTO/ITO/Perovskite/PEDOT:PSS/Au which has achieved a power conversion efficiency of eta ? 13.94%. In order to enhance its performance, several materials were suggested as electron and hole transport layers (ETL and HTL). Among the proposed ETL materials it was found that Zinc oxide (ZnO) and titanium dioxide (TiO2) are the most adequate materials. For the HTL materials, among the proposed materials Copper (I) thiocyanate (CuSCN) forms the appropriate one. Also, the solar cell performance was improved by optimizing the absorber thickness which was found to be 1 mum. With these considerations the power conversion efficiency reached 25.02%. In addition, the detrimental effect of defects at the perovskite/TiO2 interface on the solar cell performance is also presented.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Synthesis, Crystal Structures and Thermal Properties of the New Copper(I) Pseudohalide Coordination Polymers Catena[(mu2-thiocyanato-N,S)-(1- ethyl-2-methylpyrazine-N)]copper(I) and Poly[(di-mu2-tniocyanato-N, S)-(mu2-1-ethyl-2-methylpyrazine-N,N?)]dicopper(I)

Reaction of copper(I) thiocyanate with 1-ethyl-2-methyl-pyrazine in acetonitrile yields the two new coordination polymers catena[(mu 2-thiocyanato-N,S)-(1-ethyl-2-methylpyrazine-N)] copper(I)(I) and poly[(di-mu2-thiocyanato-N,S)-(mu2-1-ethyl-2-methyl- pyrazine-N,N?)] di-copper(I) (II). The crystal structure of I is composed of CuSCN double chains in which each copper atom is connected to two thiocyanate anions and two 1-ethyl-2-methyl-pyrazine ligands. In this compound only one nitrogen atom of the 1-ethyl-2-methyl-pyrazine ligand is involved in copper coordination. The crystal structure of II is composed of CuSCN layers that are connected by the N-donor ligands via mu-N,N? coordination into a three-dimensional coordination network. On heating the amine rich compound I loses half of the ligands and transforms into the amine-poorer compound II which occurs as an intermediate. Compound II decomposes on further heating to CuSCN. This reaction was investigated using simultaneous differential thermoanalysis and thermogravimetry coupled with mass spectroscopy and temperature dependent X-ray powder diffraction.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”