Synthesis, NMR spectral and single crystal X-ray structural studies on Ni(II) dithiocarbamates. Fabrication of nickel sulfide nanospheres by the solvothermal method

Abstract Three dithiocarbamatonickel(II) complexes, [Ni(bzbudtc)2] (1), [Ni(bzbudtc)(PPh3)(NCS)] (2) and [Ni(bzbudtc)(PPh3)(CN)] (3) (where, bzbudtc = the N-benzyl-N-butyldithiocarbamato anion and PPh3 = triphenylphosphine), were prepared. All three complexes were analyzed by UV–Vis, IR and NMR (1H, 13C and 31P) spectra. The 13C NMR spectra of complexes 1–3 show the most crucial thioureide signal at around 200 ppm. A significant deshielding observed for the 31P signals in 2 and 3 reveals the effective bonding of phosphorus to the metal center. Single crystal X-ray analysis of crystals of 1–3 show that all the described complexes exhibit a distorted square planar coordination geometry in the…

Phase selective synthesis of ZnS nanoparticles from structurally new dithiocarbamate precursor

Abstract A phase selective solvothermal synthesis of ZnS (wurzite) nanoparticles with a flower-like morphology using a dithiocarbamate precursor, [Zn(4-dpmpzdtc)2(dpmpz)] (1) (where, dpmpz=(diphenylmethyl)piperazine), is described. The nanoparticles were identified as ZnS (wurzite) with the particle size of about 3 to 10 nm by scanning and transmission electron microscopy as well as powder X-ray diffraction (XRD). In addition, the precursor complex 1 was characterized using single crystal X-ray diffraction.

Synthesis and structural studies on Ni(II) dithiocarbamates : Exploring intramolecular Ni···H-C interactions

Five new Ni(II) dithiocarbamates with NiS4, NiS2PN and NiS2PCl coordination spheres, viz. [Ni(bupmbzdtc)2] (1), [Ni(bupmbzdtc)(PPh3)(NCS)] (2), [Ni(bupmbzdtc)(PPh3)Cl] (3), [Ni(4-dpmpzdtc)(PPh3)Cl] (4) and [Ni(pbbzbudtc)(PPh3)(NCS)] (5), where bupmbzdtc = N-butyl(p-methylbenzyl)dithiocarbamato anion, 4-dpmpzdtc = 4-(diphenylmethyl)piperazinecarbodithioato anion, pbbzbudtc = N-(p-bromobenzyl)butyl-dithiocarbamato anion and PPh3 = triphenylphosphine, were synthesized and characterized by UV, IR, NMR and single crystal X-ray diffraction methods. Spectral results suggest a square planar geometry around the Ni(II) metal center for all the synthesized complexes. Single crystal X-ray structural an…

Complete1H,13C{1H}, and31P NMR spectral parameters of some pyrophosphates

The 1 H, 13 C{1 H}, and 31 P NMR spectral parameters of some pyrophosphates were determined in CDCl3 . The most complicated 1 H spectrum can be solved fully only as (A3 MN)R6 XX'R6 '(MNA3 )', where R6 (= -N(CH3 )2 ) is coupled only to phosphorus (X). Second-order coupling between phosphorus was found and solved with iterative analysis. A signal shape of one of the carbon resonance cannot be explained only with couplings. Explanation for exceptional shape was searched from molecular modeling results. Copyright © 2017 John Wiley & Sons, Ltd.

Synthesis, NMR spectral and structural studies on mixed ligand complexes of Pd(II) dithiocarbamates: First structural report on palladium(II) dithiocarbamate with SCN-ligand

Abstract Three new mixed ligand complexes of palladium(II) dithiocarbamates; [Pd(4-dpmpzdtc)(PPh3)(SCN)] (1), [Pd(4-dpmpzdtc)(PPh3)Cl] (2) and [Pd(bzbudtc)(PPh3)Cl] (3), (where, 4-dpmpzdtc = 4-(diphenylmethyl)piperazinecarbodithioato anion, bzbudtc = N-benzyl-N-butyldithiocarbamato anion and PPh3 = triphenylphosphine) have been synthesized from their respective parent dithiocarbamates by ligand exchange reactions and characterized by IR and NMR (1H, 13C and 31P) spectroscopy. IR and NMR spectral data support the isobidentate coordination of the dithiocarbamate ligands in all complexes (1–3) in solid and in solution, respectively. Single crystal diffraction analysis of complexes 1–3 evidence…

2-Acylamino- and 2,4-bis(acylamino)pyrimidines as supramolecular synthons analysed by multiple non-covalent interactions. DFT, X-ray diffraction, and NMR spectral studies

Intermolecular interactions of ten 2-acylamino and 2,4-bis(acylamino)pyrimidines (7 of which are previously unknown) have been investigated by X-ray structural, quantum chemical (DFT), and NMR spectral methods. Especially the concentration dependencies of the (1)H NMR chemical shifts and titrations with other molecules capable of multiple hydrogen bonding provided useful information regarding their association via triple or quadruple hydrogen bonding, which is controlled by the conformational preferences of 2-acylamino- and 2,4-bis(acylamino)pyrimidines. On comparison of the properties of 2-acylamino- and 2,4-bis(acylamino)pyrimidines with the corresponding pyridines, an additional nitrogen…

Discovery of a Pederin Family Compound in a Nonsymbiotic Bloom-Forming Cyanobacterium

The pederin family includes a number of bioactive compounds isolated from symbiotic organisms of diverse evolutionary origin. Pederin is linked to beetle-induced dermatitis in humans, and pederin family members possess potent antitumor activity caused by selective inhibition of the eukaryotic ribosome. Their biosynthesis is accomplished by a polyketide/nonribosomal peptide synthetase machinery employing an unusual trans-acyltransferase mechanism. Here, we report a novel pederin type compound, cusperin, from the free-living cyanobacterium Cuspidothrix issatschenkoi (earlier Aphanizomenon). The chemical structure of cusperin is similar to that of nosperin recently isolated from the lichen cya…

Effect of different co-solvents on biodiesel production from various low-cost feedstocks using Sr–Al double oxides

The main objective of the present paper comprises the investigation of biodiesel production from low-cost feedstock such as lard oil and waste cooking oil (WCO) using Sr-Al double oxides. Nanocatalyst was characterised FTIR, XRD, SEM, TEM, BET and XPS. The Sr:Al with 3:1 molar ratio showed the best catalytic activity in the conversion of both oils to fatty acid methyl ester. The effect of acetone and tetrahydrofuran (THF) as a co-solvent for transesterification were compared and the best result was obtained with 5 % THF. The mutual effect of the nanocatalyst and co-solvent on biodiesel production was investigated. The characterisation of biodiesel synthesised from lard oil and WCO was perfo…

Chloride ligands on DNA-stabilized silver nanoclusters

DNA-stabilized silver nanoclusters (AgN-DNAs) are known to have one or two DNA oligomer ligands per nanocluster. Here, we present the first evidence that AgN-DNA species can possess additional chloride ligands that lead to increased stability in biologically relevant concentrations of chloride. Mass spectrometry of five chromatographically isolated near-infrared (NIR)-emissive AgN-DNA species with previously reported X-ray crystal structures determines their molecular formulas to be (DNA)2[Ag16Cl2]8+. Chloride ligands can be exchanged for bromides, which red-shift the optical spectra of these emitters. Density functional theory (DFT) calculations of the 6-electron nanocluster show that the …

Alternative Biosynthetic Starter Units Enhance the Structural Diversity of Cyanobacterial Lipopeptides

Puwainaphycins (PUWs) and minutissamides (MINs) are structurally analogous cyclic lipopeptides possessing cytotoxic activity. Both types of compound exhibit high structural variability, particularly in the fatty acid (FA) moiety. Although a biosynthetic gene cluster responsible for synthesis of several PUW variants has been proposed in a cyanobacterial strain, the genetic background for MINs remains unexplored. Herein, we report PUW/MIN biosynthetic gene clusters and structural variants from six cyanobacterial strains. Comparison of biosynthetic gene clusters indicates a common origin of the PUW/MIN hybrid nonribosomal peptide synthetase and polyketide synthase. Surprisingly, the biosynthet…

Novel Functionality of Lithium-Impregnated Titania as Nanocatalyst

The present work incorporates the synthesis of a multifunctional catalyst for the transesterification of waste cooking oil (WCO) to biodiesel and recovery of rare earth elements (REEs). For this purpose, TiO2 nanoparticles and TiO2 doped with lithium ions were prepared. The influence of lithium ions on the catalytic performance of TiO2 was attained by impregnation of the different molar ratios of lithium hydroxide to bare TiO2. Then each catalyst was screened for catalytic conversion of WCO to fatty acid methyl ester (FAME) and also for REEs recovery. All synthesized materials were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), Transmission electron microsc…

Effect of lithium ions on the catalytic efficiency of calcium oxide as a nanocatalyst for the transesterification of lard oil

The present work encompasses the effect of Li+ ions on CaO nanoparticles for the transesterification of lard oil. The modification of CaO nanoparticles was achieved by the impregnation of different molar ratios of lithium hydroxide. Later, each catalyst was screened for the catalytic conversion of lard oil to a fatty acid methyl ester (FAME). The nanocatalyst CaO–0.5LiOH (1 : 0.5 molar ratio) showed the best conversion rate for FAME. The synthesized nanocatalyst was characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) analysis, and Hammett indicato…

Production of High Amounts of Hepatotoxin Nodularin and New Protease Inhibitors Pseudospumigins by the Brazilian Benthic Nostoc sp. CENA543

Nostoc is a cyanobacterial genus, common in soils and a prolific producer of natural products. This research project aimed to explore and characterize Brazilian cyanobacteria for new bioactive compounds. Here we report the production of hepatotoxins and new protease inhibitors from benthic Nostoc sp. CENA543 isolated from a small, shallow, saline-alkaline lake in the Nhecolandia, Pantanal wetland area in Brazil. Nostoc sp. CENA543 produces exceptionally high amounts of nodularin-R. This is the first free-living Nostoc that produces nodularin at comparable levels as the toxic, bloom-forming, Nodularia spumigena. We also characterized pseudospumigins A-F, which are a novel family of linear te…

Spectral and structural studies on Ni(II) dithiocarbamates: Nickel sulfide nanoparticles from a dithiocarbamate precursor

Abstract Three new planar Ni(II) dithiocarbamate complexes; [Ni(4-dpmpzdtc)2] (1), [Ni(4-dpmpzdtc)(PPh3)(NCS)] (2) and [Ni(bupcbzdtc)(PPh3)(NCS)] (3) (where, 4-dpmpzdtc = 4-(diphenylmethyl)piperazinecarbodithioato anion, bupcbzdtc = N-butyl-N-(4-chlorobenzyl))dithiocarbamato anion and PPh3 = triphenylphosphine) with “NiS4” and “NiS2PN” chromophore units were synthesized and characterized by single crystal X-ray structural analysis as well as UV–Vis, IR and NMR (1H, 13C and 31P) spectroscopy. For 2, 1H–1H COSY spectrum was also recorded. Single crystal X-ray structural analysis of 1–3, reveals a slightly distorted square planar geometry in all three complexes wherein the steric and electroni…

Application of Potassium Ion Impregnated Titanium Dioxide as Nanocatalyst for Transesterification of Linseed Oil

The current work comprises the investigation of biodiesel production from linseed oil using TiO2 and a potassium L-tartrate monobasic (C4H5KO6)-modified TiO2 nanocatalyst. Different amounts of C4H5KO6 were considered for TiO2 modification. The nanocatalyst TiO2–0.5C4H5KO6 (1:0.5 molar ratio) showed the best conversion rate for biodiesel production. The nanocatalyst was characterized by FTIR, XRD, TEM, BET, and XPS, and the Hammett indicator–benzenecarboxylic acid titration method was used for basicity measurement. The biodiesel was characterized by GC-MS and 1H and 13C NMR. Furthermore, the optimum reaction parameters for transesterification reaction were analyzed, and the yield was determi…

Substituent Effect in 2-Benzoylmethylenequinoline Difluoroborates Exhibiting Through-Space Couplings. Multinuclear Magnetic Resonance, X-ray Diffraction, and Computational Study

The series of nine 2-benzoylmethylenequinoline difluoroborates have been synthesized and characterized by multinuclear magnetic resonance, X-ray diffraction (XRD), and computational methods. The through-space spin-spin couplings between (19)F and (1)H/(13)C nuclei have been observed in solution. The NMR chemical shifts have been correlated to the Hammett substituent constants. The crystal structures of six compounds have been solved by XRD. For two derivatives the X-ray wave function refinement was performed to evaluate the character of bonds in the NBF(2)O moiety by topological and integrated bond descriptors.

Complete 1H, 13C{1H}, and 31P NMR Spectral Parameters of Some Pyrophosphates

The 1H, 13C{1H}, and 31P NMR spectral parameters of some pyrophosphates were determined in CDCl3. The most complicated 1H spectrum can be solved fully only as (A3MN)R6XX′R6′(MNA3)′, where R6 (= ―N(CH3)2) is coupled only to phosphorus (X). Second-order coupling between phosphorus was found and solved with iterative analysis. A signal shape of one of the carbon resonance cannot be explained only with couplings. Explanation for exceptional shape was searched from molecular modeling results. peerReviewed

Nano-magnetic potassium impregnated ceria as catalyst for the biodiesel production

Abstract The main objective of this work comprises the investigation of biodiesel production from rapeseed oil using potassium impregnated Fe3O4-CeO2 nanocatalyst. The various concentration of potassium impregnated Fe3O4-CeO2 was screened for catalytic conversion of rapeseed oil to triglyceride methyl ester. The 25 wt % potassium impregnated Fe3O4-CeO2 nanocatalyst showed best biodiesel production. Nanocatalyst was characterized by FTIR, XRD, SEM, TEM, BET and Hammett indicator for basicity test. The characterization of biodiesel was performed with GC-MS, 1H and 13C NMR. Moreover, the optimum reaction parameters such as catalyst amount (wt %), oil to methanol ratio, reaction time and reacti…

DUAL APPLICATION OF DIVALENT ION-ANCHORED CATALYST: BIODIESEL SYNTHESIS AND PHOTOCATALYTIC DEGRADATION OF CARBAMAZEPINE

Synthesis and structural studies on Ni(II) dithiocarbamates : Exploring intramolecular Ni···H-C interactions

Abstract Five new Ni(II) dithiocarbamates with NiS4, NiS2PN and NiS2PCl coordination spheres, viz. [Ni(bupmbzdtc)2] (1), [Ni(bupmbzdtc)(PPh3)(NCS)] (2), [Ni(bupmbzdtc)(PPh3)Cl] (3), [Ni(4-dpmpzdtc)(PPh3)Cl] (4) and [Ni(pbbzbudtc)(PPh3)(NCS)] (5), where bupmbzdtc = N-butyl(p-methylbenzyl)dithiocarbamato anion, 4-dpmpzdtc = 4-(diphenylmethyl)piperazinecarbodithioato anion, pbbzbudtc = N-(p-bromobenzyl)butyl-dithiocarbamato anion and PPh3 = triphenylphosphine, were synthesized and characterized by UV, IR, NMR and single crystal X-ray diffraction methods. Spectral results suggest a square planar geometry around the Ni(II) metal center for all the synthesized complexes. Single crystal X-ray stru…

CCDC 1429013: Experimental Crystal Structure Determination

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CCDC 901286: Experimental Crystal Structure Determination

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CCDC 990215: Experimental Crystal Structure Determination

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CCDC 1007104: Experimental Crystal Structure Determination

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CCDC 1014209: Experimental Crystal Structure Determination

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CCDC 841777: Experimental Crystal Structure Determination

Related Article: Borys Ośmiałowski , Erkki Kolehmainen , Satu Ikonen , Arto Valkonen , Adam Kwiatkowski , Izabela Grela , and Esa Haapaniemi|2012|J.Org.Chem.|77|9609|doi:10.1021/jo301643z

CCDC 996586: Experimental Crystal Structure Determination

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CCDC 990214: Experimental Crystal Structure Determination

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CCDC 996587: Experimental Crystal Structure Determination

Related Article: Balasubramaniam Arul Prakasam, Manu Lahtinen, Anssi Peuronen, Manickavachagam Muruganandham, Erkki Kolehmainen, Esa Haapaniemi, Mika Sillanpaa|2014|Polyhedron|81|588|doi:10.1016/j.poly.2014.06.059

CCDC 1027704: Experimental Crystal Structure Determination

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CCDC 841780: Experimental Crystal Structure Determination

Related Article: Borys Ośmiałowski , Erkki Kolehmainen , Satu Ikonen , Arto Valkonen , Adam Kwiatkowski , Izabela Grela , and Esa Haapaniemi|2012|J.Org.Chem.|77|9609|doi:10.1021/jo301643z

CCDC 1014211: Experimental Crystal Structure Determination

Related Article: Anna Zakrzewska, Erkki Kolehmainen, Arto Valkonen, Esa Haapaniemi, Kari Rissanen, Lilianna Chęcińska, and Borys Ośmiałowski|2013|J.Phys.Chem.A|117|252|doi:10.1021/jp311072q

CCDC 996588: Experimental Crystal Structure Determination

Related Article: Balasubramaniam Arul Prakasam, Manu Lahtinen, Anssi Peuronen, Manickavachagam Muruganandham, Erkki Kolehmainen, Esa Haapaniemi, Mika Sillanpaa|2014|Polyhedron|81|588|doi:10.1016/j.poly.2014.06.059

CCDC 1429012: Experimental Crystal Structure Determination

Related Article: Balasubramaniam Arul Prakasam, Anssi Peuronen, Manu Lahtinen, Manickavachagam Muruganandham, Erkki Kolehmainen, Esa Haapaniemi, Mika Sillanpää|2017|Polyhedron|123|453|doi:10.1016/j.poly.2016.11.027

CCDC 901285: Experimental Crystal Structure Determination

Related Article: Anna Zakrzewska, Erkki Kolehmainen, Arto Valkonen, Esa Haapaniemi, Kari Rissanen, Lilianna Chęcińska, and Borys Ośmiałowski|2013|J.Phys.Chem.A|117|252|doi:10.1021/jp311072q

CCDC 1429016: Experimental Crystal Structure Determination

Related Article: Balasubramaniam Arul Prakasam, Anssi Peuronen, Manu Lahtinen, Manickavachagam Muruganandham, Erkki Kolehmainen, Esa Haapaniemi, Mika Sillanpää|2017|Polyhedron|123|453|doi:10.1016/j.poly.2016.11.027

CCDC 1027705: Experimental Crystal Structure Determination

Related Article: Balasubramaniam Arul Prakasam, Manu Lahtinen, Anssi Peuronen, Manickavachagam Muruganandham, Erkki Kolehmainen, Esa Haapaniemi, Mika Sillanpää|2016|J.Mol.Struct.|1108|195|doi:10.1016/j.molstruc.2015.11.076

CCDC 1014210: Experimental Crystal Structure Determination

Related Article: Anna Zakrzewska, Erkki Kolehmainen, Arto Valkonen, Esa Haapaniemi, Kari Rissanen, Lilianna Chęcińska, and Borys Ośmiałowski|2013|J.Phys.Chem.A|117|252|doi:10.1021/jp311072q

CCDC 1429014: Experimental Crystal Structure Determination

Related Article: Balasubramaniam Arul Prakasam, Anssi Peuronen, Manu Lahtinen, Manickavachagam Muruganandham, Erkki Kolehmainen, Esa Haapaniemi, Mika Sillanpää|2017|Polyhedron|123|453|doi:10.1016/j.poly.2016.11.027

CCDC 1027703: Experimental Crystal Structure Determination

Related Article: Balasubramaniam Arul Prakasam, Manu Lahtinen, Anssi Peuronen, Manickavachagam Muruganandham, Erkki Kolehmainen, Esa Haapaniemi, Mika Sillanpää|2016|J.Mol.Struct.|1108|195|doi:10.1016/j.molstruc.2015.11.076

CCDC 1429015: Experimental Crystal Structure Determination

Related Article: Balasubramaniam Arul Prakasam, Anssi Peuronen, Manu Lahtinen, Manickavachagam Muruganandham, Erkki Kolehmainen, Esa Haapaniemi, Mika Sillanpää|2017|Polyhedron|123|453|doi:10.1016/j.poly.2016.11.027

CCDC 1014212: Experimental Crystal Structure Determination

Related Article: Anna Zakrzewska, Erkki Kolehmainen, Arto Valkonen, Esa Haapaniemi, Kari Rissanen, Lilianna Chęcińska, and Borys Ośmiałowski|2013|J.Phys.Chem.A|117|252|doi:10.1021/jp311072q