Synthesis and spectral studies on Ni(II) complexes involving N-furfuryl-N-substituted benzyldithiocarbamates and PPh3: Anagostic and C–H…π(chelate) interactions in (N-furfuryl-N-(4-fluorobenzyl)dithiocarbamato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Twelve new nickel(II) complexes of functionalized dithiocarabamates [Ni(S₂CNRR')₂](1-6) and [Ni(S₂CNRR')(NCS)(PPh₃)](7-12) [where R=furfuryl; R'=2-hydroxy benzyl (1,7), 3-hydroxy benzyl (2,8), 4-hydroxy benzyl (3,9), 4-methoxy benzyl (4,10), 4-fluoro benzyl (5,11), 4-chloro benzyl (6,12)] have been prepared and characterized by elemental analysis, IR, UV-Vis and NMR (¹H and ¹³C) spectroscopy. IR spectra of the complexes support the bidentate coordination of dithiocarbamate ligands. Electronic spectral studies on complexes 1-12 indicate square planar geometry around the nickel(II) central atom. In the ¹³C NMR spectra, the upfield shift of NCS₂ carbon signal for heteroleptic complex (7-12) compared to homoleptic complexes (1-6) is due to the effect of PPh₃ on the mesomeric drift of electron density toward nickel through thioureide C-N bond. Single crystal X-ray structural analysis of complex 11 confirms that the coordination geometry about the Ni(II) is distorted square planar. A rare intramolecular anagostic interaction C–H^…Ni [Ni???H=2.804 Å] is observed. The packing of complex 11 is stabilized by non-conventional C–H^…S, C–H?F and C–H?π(chelate, NiS₂C) bonding interactions.     

Rapid Classification and Recognition Method of the Species and Chemotypes of Essential Oils by ATR-FTIR Spectroscopy Coupled with Chemometrics

In the present work, the applicability of attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, coupled with chemometric tools in recognizing essential oils (EOs) for routine control, was evaluated. EOs belonging to Mentha, Cymbopogon, and Lavandula families and to S. rosmarinus and T. vulgaris species were analyzed, and the performance of several untargeted approaches, based on the synergistic combination of ATR-FTIR and Partial Least Squares Discriminant Analysis (PLS-DA), was tested to classify the species and chemotypes. Different spectra pre-processing methods were employed, and the robustness of the built models was tested by means of a Receiver Operating Characteristic (ROC) curve and random permutations test. The application of these approaches revealed fruitful results in terms of sensitivity and specificity, highlighting the potentiality of ATR-FTIR and chemometrics techniques to be used as a sensitive, cost-effective, and rapid tool to differentiate EO samples according to their species and chemotype.     

Synthesis of nickel sulfide and nickel–iron sulfide nanoparticles from nickel dithiocarbamate complexes and their photocatalytic activities

[ Ni(dtc)₂] (dtc = N-(pyrrole-2-ylmethyl)-N-thiophenemethyldithiocarbamate ( 1 ), N-methylferrocenyl-N-(2-phenylethyl)dithiocarbamate ( 2 ), N-furfuryl-N-methylferrocenyldithiocarbamate ( 3 ), and (N-[pyrrole-2-ylmethyl]-N-thiophenemethyldithiocarbamato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II) ( 4 ) complexes were prepared and characterized by elemental analysis, infrared, ultraviolet–visible, and nuclear magnetic resonance (¹H and ¹³C) spectroscopies. The data were consistent with the formation of square planar nickel(II) complexes, which was confirmed by single-crystal X-ray diffraction studies on 2 and 4 . Fe···Fe interactions exhibited by complex 2 led to supramolecular aggregation. The structure of 4 reveals intermolecular and intramolecular C-H···Ni anagostic interactions. The anion-sensing properties of 2 were studied with halide ions by cyclic voltammetry. It was observed that 2 acts as sensor for bromide. Complexes 1 , 2 , and 3 , were utilized to prepare nickel sulfide, nickel–iron sulfide-1, and nickel–iron sulfide-2, respectively. The composition, structure, morphology, and optical properties of nickel sulfide and nickel–iron sulfides were examined using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, ultraviolet–visible, fluorescence, and infrared spectroscopy. Powder X-ray diffraction patterns of nickel sulfide, nickel–iron sulfide-1, and nickel–iron sulfide-2 indicate the formation of orthorhombic Ni₉S₈, cubic NiFeS₂, and cubic Ni₂FeS₄, respectively. The photocatalytic activities of as-prepared nickel sulfide and nickel–iron sulfide-1 nanoparticles were investigated for photodegradation of methylene blue and rhodamine-B under ultraviolet irradiation. Nickel–iron sulfide-1 nanoparticles show slightly higher photodegradation efficiency compared with the nickel sulfide nanoparticles.     

Adsorption and electrically stimulated desorption of the triblock copolymer poly(propylene sulfide-bl-ethylene glycol) (PPS-PEG) from indium tin oxide (ITO) surfaces

Protein-resistant triblock copolymers, poly(propylene sulfide-bl-ethylene glycol) (PPS-PEG) have been previously demonstrated to chemisorb onto gold surfaces forming monolayers that resist non-specific protein adsorption and are stable against oxidation. In this paper, we report on the adsorption of PPS-PEG onto a transparent and electrically conductive substrate, indium tin oxide (ITO). In addition, we demonstrate the controlled desorption of PPS-PEG by applying an electrical stimulus. We have used three complementary surface characterization techniques: variable angle spectroscopic ellipsometry (VASE), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to analyze the adsorption and electro-desorption of PPS-PEG from an ITO surface. All three methods confirmed the formation of PPS-PEG adlayers on the ITO surfaces. Based on our experimental XPS and ToF-SIMS results as well as former publications, we postulate that the chemisorption of the PPS-PEG on ITO involves direct sulfide-indium (or tin) interactions. When an ascending anodic electrical stimulus was applied to the surface of the modified samples, a gradual and steady polymer removal was observed, with complete loss of the polymeric monolayer at a potential of 2000 mV (referenced to Ag electrode). Anodic polarization did not result in oxidation of the thioether function of the PPS-PEG adlayers, indicating excellent oxidation resistance of PPS-PEG on ITO surfaces. This work is focused on exploiting electrical stimuli for the in situ surface modification under dynamic control.     

Spectroscopic evidence for polarons in poly(3-methylthiophene)

We present the results of an in-situ spectroscopic study of poly(3-methylthiopene) electrochemically doped with BF₄^?. It is concluded that polarons are the primary elementary excitations in the dilute doping regime.