Electrochemical properties of Au electrodes sequentially modified by self-assembled 1,6 hexanedithiol (1,6HDT) and gold nanorods (AuNRs) are investigated by cyclic voltammetry, square-wave voltammetry, and electrochemical impedance spectroscopy, using [Fe(CN) 6 ] 3-/4-as redox probes. The nanorods stabilized by cetyltrimetylammonium bromide (CTAB) with aspect ratios of 2.20, 2.80, and 3.77 were grown by a seedmediated procedure and chemically bonded to the 1,6HDT-coated electrodes by a place exchange reaction at a 27°C solution temperature. Topographic tapping mode atomic force microscopy measurements revealed an end bonding of the 2.20 aspect ratio rods and a side surface bonding of the 2.80 and 2.77 aspect ratio rods. Analysis of the electrochemical responses as a function of the sizes and surface orientations of the rods revealed that the electron transfer is faster at electrodes modified with smaller and vertically aligned nanorods than those modified with larger and randomly attached nanorods (side surface bonding). A progressive increase in the charge transfer resistance R CT from bilayers composed of 1,6HDT and 2.20 aspect ratio rods to bilayers composed of 1,6HDT and rods of 2.80 or 3.77 aspect ratios was described by a tunneling parameter of ) 1.07 per thiol chain unit. This behavior suggests that the electron transfer kinetics is controlled by coherent electron tunneling across the 1,6HDT monolayer. In addition, the several orders of magnitude changes of the apparent charge transfer resistance upon nanorod adsorption suggest a charging of the rods by the redox probes in solution and electron transfer across them. It is concluded that the electron transfer proceeds via a three-step process: charging of the rods by the redox probes in solution, electron transport across the rods, and electron tunneling across the 1,6HDT-SAM toward the underlying Au substrates.
Intimate partner violence (IPV) is a highly prevalent phenomenon worldwide and is considered a severe violation of human rights. Intimate partner homicide (IPH) and attempted intimate partner homicide (AIPH) although less frequent have a severe direct or indirect impact on victims. Despite the vast literature on IPV and IPH, there is still scarce research on AIPH. Thus, this study aimed to analyze whether perpetrators of IPV, IPH, and AIPH differ from each other, as well as to identify the factors that predict violence in intimacy. For those purposes, we performed a comparative analysis between 50 male individuals convicted of IPH, 27 convicted of AIPH, and 168 convicted of IPV from Portugal. The data were collected using an interview and a set of psychological measures. Results revealed that, although IPV, IPH, and AIPH perpetrators’ share some characteristics, significant differences were found between them. IPV perpetrators were more prone to perpetrate violent behaviors against an intimate partner or ex-partner than IPH or AIPH offenders. The use of weapons and separation from the victim increases the probability of committing IPH or AIPH. Being divorced, having no children, and committing other crimes than domestic violence are predictors of AIPH. These results have some practical implications, in terms of both risk prediction and risk management. Accurate and comprehensive tools should be included as a routine in the primary care services, as well as in the child care services and in victim support services. Prevention and intervention efforts must be comprehensive, involving work with perpetrators and victims.
LMO2 was discovered via chromosomal translocations in T-cell leukaemia and shown normally to be essential for haematopoiesis. LMO2 is made up of two LIM only domains (thus it is a LIM-only protein) and forms a bridge in a multi-protein complex. We have studied the mechanism of formation of this complex using a single domain antibody fragment that inhibits LMO2 by sequestering it in a non-functional form. The crystal structure of LMO2 with this antibody fragment has been solved revealing a conformational difference in the positioning and angle between the two LIM domains compared with its normal binding. This contortion occurs by bending at a central helical region of LMO2. This is a unique mechanism for inhibiting an intracellular protein function and the structural contusion implies a model in which newly synthesized, intrinsically disordered LMO2 binds to a partner protein nucleating further interactions and suggests approaches for therapeutic targeting of LMO2.
This work compares the estimation of the particle size distribution of a pharmaceutical powder using near-infrared spectroscopy (NIRS), powder flowability properties, and components concentration. The estimations were made by considering the former data blocks separately and together using a multi-block approach. The powders were based on a formulation of paracetamol as the pharmaceutical active ingredient. The reference method used to determine particle size distribution was sieving. Partial least squares methods were used to estimate the multivariate regression models, and the results were compared in terms of figures of merit. It was shown that the partial least squares methods gave similar prediction errors. Regarding the data blocks used, the NIRS block was proven the most advantageous to estimate the particle size distribution. The prediction error of the NIRS block was similar to the other data blocks with additional advantages such as less generalization problems and the possibility of its use to predict additional physical and chemical properties with an improvement to analysis time. The multi-block approach produced the worst results but nevertheless allowed a deeper understanding of the individual contributions of the data blocks in the prediction of the particle size distribution.
A novel multilayer film containing a cationic phosphonium-derivatized Ni(salen)-type complex and poly(sodium-4-styrenesulfonate (NaPSS) was assembled onto quartz, mica, and metal surfaces using the layer-by-layer (LbL) technique. Spectroscopic (UV-vis) and gravimetric (QCM) responses for the multilayer films show regular stepwise growth and the signature of strong electrostatic interactions between the component layers. The gravimetric responses indicate the presence of substantial additional (net neutral) material in the PSS layers, which XPS shows is not polyelectrolyte or salt, so charge compensation is intrinsic; we deduce the presence of space-filling solvent. Direct electrostatic interaction of the two-component layers is enhanced by a secondary noncovalent interaction between the delocalized pi-systems of the two components. Permeability of the film to the redox probe [Fe(CN)(6)](3-/4-) was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Qualitatively similar results were obtained in the absence and presence of a precursor PSS/PAH multilayer, but with a general shift in kinetic and diffusional processes to longer time scales (lower frequencies) in the presence of the precursor layer and with increasing numbers of PSS/[Ni(salen)] bilayers. Quantitatively, the EIS data were interpreted using a capillary membrane model (CMM) to yield values of coverage, apparent charge transfer resistance, double-layer capacitance, pore size, and diffusion coefficient. The coverage values were consistent with a model in which there are no preferential growth sites and the surface charge density is independent of the number of bilayers.
The relationship between executive functioning and psychopathy lacks consistent findings. The heterogeneity of the psychopathic personality structure may contribute to the mixed data that emerged from clinical-categorical approaches. Considering the link between antisocial behavior and executive dysfunction from the perspective of the Triarchic Model of Psychopathy, it is suggested that executive impairments in psychopathy are specifically explained by meanness and disinhibition traits, reflecting externalizing vulnerability. In turn, boldness is conceptualized as an adaptive trait. The current study assessed updating (N-back), inhibition (Stroop), and shifting (Trail Making Test) in a forensic (n = 56) and non-forensic sample (n = 48) that completed the Triarchic Psychopathy Measure. A positive association between boldness and inhibition was found, while meanness accounted for the lack of inhibitory control. In addition, disinhibition explained updating dysfunction. These findings provide empirical evidence for dissociable effects of psychopathic traits on executive functioning, in light of the Triarchic Model of Psychopathy.
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