Out-of-plane Distortions Research Articles

Reactivity of inorganic sulfide species towards a pentacoordinated heme model system

The reactivity of inorganic sulfide towards ferric bis(N-acetyl)- microperoxidase 11 in sodium dodecyl sulfate has been explored by means of visible absorption and resonance Raman spectroscopies. The reaction has been previously studied in buffered solutions at neutral pH and in the presence of excess sulfide, revealing the formation of a moderately stable hexacoordinated low spin ferric sulfide complex that yields the ferrous form in the hour's timescale. In the surfactant solution, instead, the ferrous form is rapidly formed. The spectroscopic characterization of the heme structure in the surfactant milieu revealed the stabilization of a major ferric mono-histidyl high spin heme, which may be ascribed to out of plane distortions prompting the detachment of the axially ligated water molecule, thus leading to a differential reactivity. The ferric bis(N-acetyl)- microperoxidase 11 in sodium dodecyl sulfate provides a model for pentacoordinated heme platforms with an imidazole-based ligand.

Electronic and magnetic properties of MoS2 nanoribbons with sulfur line vacancy defects

Motivated by the recent experimental result that single sulfur vacancies in monolayer MoS2 are mobile under the electron beam and easily agglomerate into the sulfur line vacancy defects [Physical Review B 88, 035301(2013)] , the structural, electronic and magnetic properties of one dimensional zigzag (ZZ) and armchair (AC) edge MoS2 nanoribbons with single or double staggered sulfur line vacancy defects (hereafter, abbreviated as SV or DV, respectively), parallel to their edges, have been investigated systematically by density functional theory calculations. It is very interesting to find that the bond strains induced by the sulfur line vacancy defect can cause a much larger out-of plane distortions in the ZZ edge MoS2 nanoribbon than in the AC edge counterpart. Besides, the defective ZZ edge MoS2 nanoribbons with SV or DV are both metals, having their two respective degenerate ground states with the same energy, among which one is ferromagnetic (FM “++”) and the other is antiferromagnetic (AFM “+−”). But the AC edge MoS2 nanoribbons with SV or DV are both nonmagnetic semiconductors, having very different gap values. Finally, the sulfur line vacancy defects would induce some defect states in the electronic structures of the defective MoS2 nanoribbons. All these important results could provide a new route of tuning the electronic properties of MoS2 nanoribbons and its derivatives for their promising applications in nanoelectronics and optoelectronics.

Protonation-deprotonation equilibria in tetrapyrroles Part 4: Mono- and diprotonations of deutero-, hemato-, meso-, and protoporphyrin IX dimethyl esters in methanolic hydrochloric acid

The N-protonations in the deutero, hemato, meso and protoporphyrin IX dimethyl esters (DME) were investigated by spectrophotometric titrations using HCl as the acid and methanol as the solvent. Two spectroscopically different protonated species were observed for each porphyrin DME in addition to the neutral form. These were assigned to the N-protonated monocation and dication. There were no difficulties encountered in observing the monocation formation in the HCl – MeOH system. Very sharp isosbestic points were characteristic of each protonation stage. The p K3 values for the porphyrins in the above order were 3.23, 4.70, 2.93 and 3.37; the p K4 values were 2.48, 2.62, 2.41 and 2.64, respectively. For all porphyrins studied, no further spectral changes were observed after the dication was completely formed. This was interpreted as indicating that the formation of more highly protonated species is not possible in fullydelocalized porphyrins possessing the 18 π-electron [18]diazaannulene delocalization pathway. When the titration was performed on the free dicarboxylic acid porphyrins, aggregation obscured the first protonation step and no clear monocation spectrum could be distinguished. However, also in that case the titration ended up to a UVvis spectrum typical of the dication and the effect of aggregation on the p K4 values was negligible. The UVvis spectrometric parameters are given for the neutral forms and for the protonated species of the porphyrin DMEs. The results are discussed in terms of the NH tautomerization connected to the π-electron delocalization pathway (aromaticity), which tends to hinder outofplane distortions in the porphyrin plane, and in terms of solvation and counterion stabilization of the protonated forms.

Parametric Studies on Effect of Trailing Liquid Nitrogen Heat Sink on TIG Welding of Steels

Welding is an efficient material joining process. But the localised temperature rise up to the melting point in the vicinity of arc causes non uniform expansion and contraction resulting in residual stress and distortions. Post weld, Pre weld and in-process methods have been studied to reduce these unwanted effects of welding. A trailing heat sink is one such method. This consists of a cooling agent traversing at a constant distance behind the weld arc. Introduction of a cooling agent is reported to reduce the distortion. A liquid nitrogen jet is used as the cooling agent in the present study. A finite element model developed using Sysweld is used to study the effect of liquid nitrogen heat sink on weld distortions and residual stresses. The finite element model developed is used to make a parametric study on the effect of cooling jet radius, cooling strength and the distance between the jet and weld arc on out of plane distortions and stresses. Comparative study of the effect of cooling jet is made for mild steel (MS) and stainless steel (SS). It is observed that the out of plane distortions reduce with increasing cooling strength, jet radius. Reduction in distance between the jet and weld arc also causes a reduction in distortions.

A structural and spectroscopic investigation of reduced graphene oxide under high pressure

The effect of high pressure on reduced graphene oxide (RGO) has been investigated using X-ray diffraction (XRD) and infrared (IR) absorption spectroscopy. Our XRD measurements show two-step reversible compression in the inter-layer spacing of RGO whereas intra-layer ordering exhibits a high pressure behavior similar to that of graphite up to 20GPa. The line shape analysis of (100) peak, representing the intra-layer ordering, suggests presence of local out of plane distortions in RGO in the form of puckered regions which progressively straighten out as a function of pressure. IR measurements show reversible changes in spectroscopic features attributed to remnant functional groups in the inter-layer region. These measurements suggest high stability and recovering ability of RGO under pressure cycling.

Structural Distortions in Few-Layer Graphene Creases

Folds and creases are frequently found in graphene grown by chemical vapor deposition (CVD), due to the differing thermal expansion coefficients of graphene from the growth catalyst and the flexibility of the sheet during transfer from the catalyst. The structure of a few-layer graphene (FLG) crease is examined by aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM). A study of 2D fast Fourier transforms (FFTs) taken about the region of the crease allowed for the crystal stacking structure of the system to be elucidated. It was found that strain-induced stacking faults were created in the AB Bernal-stacked FLG bulk around the region proximal to the crease termination; this is of interest as the stacking order of FLG is known to have an effect on its electronic properties and thus should be considered when transferring CVD-grown FLG to alternate substrates for electronic device fabrication. The FFTs, along with analysis of the real space images, were used to determine the configuration of the layers in the crease itself and were corroborated by multislice atomistic TEM simulations. The termination of the crease part way through the FLG sheet is also examined and is found to show strong out of plane distortions in the area about it.