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Population aging, reduced economic capacity, and neglecting the treatments for oral pathologies, are the main causal factors for about 3 billion individuals who are suffering from partial/total edentulism or alveolar bone resorption: thus, the demand for dental implants is increasingly growing. To achieve a good prognosis for implant-supported restorations, adequate peri-implant bone volume is mandatory. The Guided Bone Regeneration (GBR) technique is one of the most applied methods for alveolar bone reconstruction and treatment of peri-implant bone deficiencies. This technique involves the use of different types of membranes in association with some bone substitutes (autologous, homologous, or heterologous). However, time for bone regeneration is often too long and the bone quality is not simply predictable. This study aims at engineering and evaluating the efficacy of modified barrier membranes, enhancing their bioactivity for improved alveolar bone tissue regeneration. We investigated membranes functionalized with chitosan (CS) and chitosan combined with the peptide GBMP1α (CS + GBMP1α), to improve bone growth. OsseoGuard® membranes, derived from bovine Achilles tendon type I collagen crosslinked with formaldehyde, were modified using CS and CS + GBMP1α. The functionalization, carried out with 1-ethyl-3-(3 dimethylaminopropyl)carbodiimide and sulfo-N-Hydroxysuccinimide (EDC/sulfo-NHS), was assessed through FT-IR and XPS analyses. Biological assays were performed by directly seeding human osteoblasts onto the materials to assess cell proliferation, mineralization, gene expression of Secreted Phosphoprotein 1 (SPP1) and Runt-Related Transcription Factor 2 (Runx2), and antibacterial properties. Both CS and CS + GBMP1α functionalizations significantly enhanced human osteoblast proliferation, mineralization, gene expression, and antibacterial activity compared to commercial membranes. The CS + GBMP1α functionalization exhibited superior outcomes in all biological assays. Mechanical tests showed no significant alterations of membrane biomechanical properties post-functionalization. The engineered membranes, especially those functionalized with CS + GBMP1α, are suitable for GBR applications thanks to their ability to enhance osteoblast activity and promote bone tissue regeneration. These findings suggest a potential advancement in the treatment of oral cavity problems requiring bone regeneration., (© 2024 Wiley Periodicals LLC.)

We have investigated the local structure of the iron-based CaKFe 4 As 4 superconductor featuring distinct aliovalent substitutions at the Ca and K sites, that is CaKFe 4 As 4 , CaK 0.9 Sr 0.1 Fe 4 As 4 , CaK 0.9 Ba 0.1 Fe 4 As 4 and Ca 0.9 Na 0.1 K 0.9 Ba 0.1 Fe 4 As 4 . Temperature-dependent Fe K-edge extended x-ray absorption fine structure (EXAFS) measurements are used to determine the near-neighbors bondlengths and their stiffness. The EXAFS analysis reveals that the Fe-As bondlength undergoes negligible changes by substitution, however, the Fe-Fe bondlength and the As height are affected by the Sr substitution. The superconducting transition temperatures of CaK 0.9 Sr 0.1 Fe 4 As 4 and CaK 0.9 Ba 0.1 Fe 4 As 4 are very similar even if the mean As heights are significantly different suggesting that the anion height may not be a unique parameter to describe the superconductivity in CaKFe 4 As 4 . The mean As heights show a peculiar temperature dependence characteristic of CaKFe 4 As 4 system. Furthermore, the temperature-dependent mean square relative displacements reveal similar Fe-Fe bond stiffness in all samples, instead the Fe-As bond is substantially stiffer in case of CaK 0.9 Sr 0.1 Fe 4 As 4 . The local structure results are discussed in relation to the differing transport properties of aliovalent substituted 1144 superconductor., (Creative Commons Attribution license.)

We have investigated the in-plane local structure of the Ba 0.6 K 0.4 Fe 2 As 2 superconductor by polarized Fe K-edge extended X-ray absorption fine structure (EXAFS) measurements with temperature. The near neighbor bond distances and their stiffness, measured by polarized EXAFS in two orthogonal directions, are different suggesting in-plane anisotropy of the atomic displacements and local orthorhombicity in the title system. The X-ray absorption near edge structure (XANES) spectra reveal anisotropy of valence electronic structure that changes anomalously below ∼100 K. The local iron magnetic moment, measured by Fe Kβ X-ray emission spectroscopy (XES), increases below the anomalous temperature and shows a decrease in the vicinity of the superconducting transition temperature ( T c ∼ 36 K). The results provide a clear evidence of coupled local lattice, electronic and magnetic degrees of freedom to induce possible nematic fluctuations in an optimally hole doped iron-based superconductor.

Nuclear-grade graphite is a high-efficiency material, widely used for vacuum applications in nuclear reactors and accelerators as targets facing particle beams. In these contexts, graphite is often exposed to extreme thermal stresses altering its physical and chemical properties. The thermal-induced release of volatile contaminants from targets and the damage of structural components are critical issues that can affect the safety and operation efficiency of beamline facilities. Here, we provide for the first time a detailed picture of the chemical and morphological changes occurring in a nuclear-grade graphite target, obtained through Electrical Discharge Machining (EDM), when exposed in vacuum to high temperatures. The radial temperature gradient induced by the impact of a pulsed energetic (MeV- GeV range) focused particle beams was reproduced by cyclically heating, in the 1300-1800 K temperature range, a disc-shaped graphite target in a vacuum setup. An accurate surface and in-depth chemical analysis of the graphite target was obtained thanks to the high sensitivity (ppm/ppb) of the Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) technique. The chemical maps clearly show the presence of several metal oxides and impurities in the surface and subsurface regions of the untreated sample. Such contaminants were removed because of the thermal treatment in vacuum more or less efficiently, as demonstrated by Thermogravimetric analysis (TGA), X-ray Photoelectron Spectroscopy (XPS), and ToF-SIMS. However, Raman spectroscopy and SEM-EDS revealed that the high-temperature treatment induces a decrease in the crystallite size of the graphite as well as changes in the target surface porosity with the appearance of microvoids, leading the graphite target to be more prone to the breakage., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

Complex phenomena characterize the intercalation of ions inside stratified crystals. Their comprehension is crucial in view of exploiting the intercalation mechanism to change the transport properties of the crystal or obtaining a fine control of crystal delamination. In particular, the relationship between the concentration and nature of intercalated ions and surface structural modifications of the host stratified crystal is still under debate. Here, we discuss a theoretical effort to provide a rationale for some structural changes observed on the highly oriented pyrolytic graphite (HOPG) surface after electrochemical treatment in perchloric and sulphuric acid solutions. The formation of the so-called nano-protrusions on the basal plane of intercalated graphite was previously observed with scanning tunneling microscopy (STM). In this work, we employed both STM and density functional theory (DFT) simulations to elucidate the physical and chemical mechanisms driving the emergence of these nano-protrusions. The DFT results show that, in a bilayer graphene system, the presence of a single ion can generate a nano-protrusion with 2.49 Å height and 21.27 Å width. In the deformed area, the C-C bond length is stretched by about 2.5% more than the normal graphene bond. These values are of the same dimensional scale as those reported in previous STM experimental results. 25 However, the simulated STM images obtained by increasing the amount of intercalated ions per area suggest that the presence of more than one ion is needed for the deformation of the uppermost graphite layer during the early stages of intercalation. In contrast, in a multilayer graphene system, no significant surface deformation is detected when ions are intercalated between the third and fourth layers. Charge analysis indicates an altered distribution of the charges as a consequence of the intercalation. The charge transfer from graphene layers to the intercalated ions results in a surface layer more prone to oxidation.

Chicago's lead problem has been shown to disproportionately affect populations of color and lower socioeconomic status (SES). The disproportionate effects on low-income areas and communities of color can be traced back to several key decisions in Chicago's history. A search of the National Library of Medicine's MEDLINE/PubMed as well as Google, and Google Scholar was performed to find all articles relating to lead poisoning in Chicago, lead utilization, Chicago's municipal and political history, and lead physiology between May 2020 and May 2023. Additionally, several studies and textbooks were reviewed regarding the latest advancements in lead poisoning. The study identified several key political moves over the course of Chicago's history that have resulted in disproportionate toxicity in minority populations and those of lower SES. Lead is more readily absorbed in the pediatric population. Additionally, prior regulations had published acceptable blood lead levels (BLLs) in children, but more recent evidence indicates a myriad of detrimental effects in BLLs below that cutoff. There is substantial evidence to suggest that there is no acceptable BLL. Lead toxicity is generally improving nationally but there still exists a considerable need for improvement. Programs should be expanded to ensure that individuals living in communities most at risk of lead exposure have the means to both, replace lead-contaminated infrastructure, and to be able to supply these communities with affordable housing. From a physician and clinician standpoint, knowing the increased risk of lead poisoning in these populations should prompt earlier testing., Competing Interests: The authors have declared that no competing interests exist., (Copyright © 2024, Goodwin et al.)

We have investigated the effect of the Ni substitution on the local structure and the valence electronic states of the SrFe2-xNixAs2 (x = 0.00, 0.16, and 0.23) superconductor with a multi-edge extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy. The As K-edge and Fe K-edge EXAFS measurements in the two polarizations (E‖ab and E‖c) show a clear change in the local structure with Ni concentration. The near-neighbor bondlengths and the related mean-square relative displacements (MSRDs) decrease as the Ni content increases. The polarized XANES spectra at the As, Fe and Ni K edges reveal a systematic change in the anisotropy of the valence electronic structure. The results suggest that the quasi 2D electronic structure of this system tends to become more isotropic as the Ni content increases. The local structure and the valence electronic states are discussed in the frame of the evolving electronic transport of the SrFe2-xNixAs2 system.

The advent and growing popularity of generative artificial intelligence (GenAI) holds the potential to revolutionise AI applications in forensic psychiatry and criminal justice, which traditionally relied on discriminative AI algorithms. Generative AI models mark a significant shift from the previously prevailing paradigm through their ability to generate seemingly new realistic data and analyse and integrate a vast amount of unstructured content from different data formats. This potential extends beyond reshaping conventional practices, like risk assessment, diagnostic support, and treatment and rehabilitation plans, to creating new opportunities in previously underexplored areas, such as training and education. This paper examines the transformative impact of generative artificial intelligence on AI applications in forensic psychiatry and criminal justice. First, it introduces generative AI and its prevalent models. Following this, it reviews the current applications of discriminative AI in forensic psychiatry. Subsequently, it presents a thorough exploration of the potential of generative AI to transform established practices and introduce novel applications through multimodal generative models, data generation and data augmentation. Finally, it provides a comprehensive overview of ethical and legal issues associated with deploying generative AI models, focusing on their impact on individuals as well as their broader societal implications. In conclusion, this paper aims to contribute to the ongoing discourse concerning the dynamic challenges of generative AI applications in forensic contexts, highlighting potential opportunities, risks, and challenges. It advocates for interdisciplinary collaboration and emphasises the necessity for thorough, responsible evaluations of generative AI models before widespread adoption into domains where decisions with substantial life-altering consequences are routinely made., Competing Interests: The author declares that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Tortora.)

The study explores the application of natural biocides (oregano essential oil and eugenol, directly applied in solutions or encapsulated within silica nanocapsules) for safeguarding stone cultural heritage from biodeterioration, using green algae ( Chlorococcum sp.) and cyanobacteria ( Leptolyngbya sp.) as common pioneer biodeteriogens. Core-shell nanocontainers were built for a controlled release of microbicidal agents, a safe application of chemicals and a prolonged efficacy. The qualitative and quantitative evaluations of biocide efficiency at different doses were periodically performed in vitro, after six scheduled intervals of time (until 100 days). The release kinetics of composite biocide-embedding silica nanocapsules were characterized by the UV-Vis spectroscopy technique. Data showed both promising potential and some limitations. The comparative tests of different biocidal systems shed light on their variable efficacy against microorganisms, highlighting how encapsulation influences the release dynamics and the overall effectiveness. Both the essential oils showed a potential efficacy in protective antifouling coatings for stone artifacts. Ensuring compatibility with materials, understanding their differences in biocidal activity and their release rates becomes essential in tailoring gel, microemulsion or coating products for direct on-site application.

The present review places emphasis on a comprehensive survey of experimental techniques to probe the structural and morphological features at the nanoscale range in thin magnetic films, incorporating those available at in-house laboratories as well as those at state-of-the-art synchrotron radiation facilities. This elucidating the range of available techniques, and the information they can yield represents a step for advancing the understanding of and for unlocking new possibilities in the design and optimization of thin magnetic films across a wide range of applications.

Mesoporous silica nanoparticles (MSNPs) are currently used in different fields like catalysis, nanomedicine, and conservation science, taking advantage of their high surface area. Here, we synthesized and functionalized mesoporous dendritic fibrous nanoparticles to realize a smart delivery system of protective agents for metals. Different MSNPs were obtained via the microemulsion method followed by a hydrothermal or refluxing treatment at different w/o ratios, times, and temperatures. Dendritic spherical silica nanoparticles with specific features such as an appropriate size (450 nm), a very large surface area (600 m 2 g -1 ), and a high yield synthesis (86%) were selected for surface modification. The fiber surface of the selected MSNPs was functionalized with 3-aminopropyl triethoxysilane (3-APTES). 3-APTES works as a pH-driven "nanogate", suppressing the immediate leakage of the total guest molecule load and modulating the release as a function of pH conditions. Surface-modified MSNPs were tested as a reservoir of the most diffused corrosion inhibitors: Mercaptobenzothiazole (MBT) and 1H-Benzotriazole (BTA); their release properties were studied in solutions with pH = 4 and 7. Functionalized and non-functionalized MSNPs showed a good loading efficiency of guest molecules (34-64%) and a pH-dependent release of the corrosion inhibitors on a timescale of several hours.

We have combined the extended X-ray absorption fine structure (EXAFS) and X-ray emission spectroscopy (XES) to investigate the local structure and the local iron magnetic moments of (Li 1- x Fe x )OHFeSe ( x ∼0.2) superconductors. The local structure, studied by Fe K-edge EXAFS measurements, is found to be inhomogeneous that is characterized by different Fe-Se bond lengths. The inhomogeneous phase exhibits a peculiar temperature dependence with lattice anomalies in the local structural parameters at the critical temperature T c (36 K) and at the spin density wave (SDW) transition temperature T N (130 K). Fe Kβ XES shows iron to be in a low spin state with the local Fe magnetic moment evolving anomalously as a function of temperature. Apart from a quantitative measurement of the local structure of (Li 1- x Fe x )OHFeSe, providing direct evidence of nanoscale inhomogeneity, the results provide further evidence of the vital role that the coupled electronic, lattice and magnetic degrees of freedom play in the iron-based superconductors.

The local structure of the filled tetragonal tungsten bronze (TTB) niobate Ba3Nb5-xTixO15 ( x = 0, 0.1, 0.7, 1.0), showing a metal-insulator transition with Ti substitution, has been studied by Nb K-edge extended X-ray absorption fine structure (EXAFS) measurements as a function of temperature. The Ti substitution has been found to have a substantial effect on the local structure, that remains largely temperature independent in the studied temperature range of 80-400 K. The Nb-O bonds distribution shows an increased octahedral distortion induced by Ti substitution, while Nb-Ba distances are marginally affected. The Nb-O bonds are stiffer in the Ti substituted samples, which is revealed by the temperature dependent mean square relative displacements (MSRDs). Furthermore, there is an overall increase in the configurational disorder while the system with Nb 4 d electrons turns insulating. The results underline a clear relationship between the local structure and the electronic transport properties suggesting that the metal-insulator transition and possible thermoelectric properties of TTB structured niobates can be tuned by disorder.

Introduction: While the opioid crisis has claimed the lives of nearly 500,000 in the U.S. over the past two decades, and pediatric cases of opioid intoxications are increasing, only sparse data exist regarding risk factors for severe outcome in children following an opioid intoxication. We explore predictors of severe outcome (i.e., intensive care unit [ICU] admission or in-hospital death) in children who presented to the Emergency Department with an opioid intoxication., Methods: In this prospective cohort study we collected data on all children (0-18 years) who presented with an opioid intoxication to the 50 medical centers in the US and two international centers affiliated with the Toxicology Investigators Consortium (ToxIC) of the American College of Medical Toxicology, from August 2017 through June 2020, and who received a bedside consultation by a medical toxicologist. We collected relevant demographic, clinical, management, disposition, and outcome data, and we conducted a multivariable logistic regression analysis to explore predictors of severe outcome. The primary outcome was a composite severe outcome endpoint, defined as ICU admission or in-hospital death. Covariates included sociodemographic, exposure and clinical characteristics., Results: Of the 165 (87 females, 52.7%) children with an opioid intoxication, 89 (53.9%) were admitted to ICU or died during hospitalization, and 76 did not meet these criteria. Seventy-four (44.8%) children were exposed to opioids prescribed to family members. Fentanyl exposure (adjusted OR [aOR] = 3.6, 95% CI: 1.0-11.6; p  = 0.03) and age ≥10 years (aOR = 2.5, 95% CI: 1.2-4.8; p  = 0.01) were independent predictors of severe outcome., Conclusions: Children with an opioid toxicity that have been exposed to fentanyl and those aged ≥10 years had 3.6 and 2.5 higher odds of ICU admission or death, respectively, than those without these characteristics. Prevention efforts should target these risk factors to mitigate poor outcomes in children with an opioid intoxication.

In the forensic field, most studies employing virtual reality (VR) interventions have focused on offenders. The validity and safety of VR applications for victims of crime are still unclear. Following PRISMA guidelines, a systematic review on VR interventions for crime victims was performed to assess the efficacy, acceptability by patients, and cost-effectiveness of these interventions compared to in-person care. We identified 34 potentially eligible studies from 188 records obtained from database searches (Medline/Pubmed, CINAHL, PsycINFO, Web of Science, and Scopus); four additional articles were identified via alternative sources. In total, nine articles were included for the qualitative synthesis. Patient satisfaction with VR interventions was found to be equivalent to face-to-face interventions. Both VR exposure and control groups found relief from posttraumatic symptoms, with differences either statistically insignificant or in favor of VR. Despite the increased costs linked to the technology required, VR appears to be a promising alternative to in vivo exposure, but further research is needed. Limitations of the review include the varied experimental protocols, which did not allow us to conduct a quantitative analysis and comparison of findings across different studies, and the generally poor quality of the studies included. Further research, preferably in larger groups, is needed to shed more light on the effectiveness of VR interventions for traumatized victims of crime., (© 2022 The Authors. Journal of Traumatic Stress published by Wiley Periodicals LLC on behalf of International Society for Traumatic Stress Studies.)

We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (Zn II ) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential., (© 2021 The Authors. Published by Wiley-VCH GmbH.)

Hybrid biomaterials allow for the improvement of the biological properties of materials and have been successfully used for implantology in medical applications. The covalent and selective functionalization of materials with bioactive peptides provides favorable results in tissue engineering by supporting cell attachment to the biomaterial through biochemical cues and interaction with membrane receptors. Since the functionalization with bioactive peptides may alter the chemical and physical properties of the biomaterials, in this study we characterized the biological responses of differently functionalized chitosan analogs. Chitosan analogs were produced through the reaction of GRGDSPK (RGD) or FRHRNRKGY (HVP) sequences, both carrying an aldehyde-terminal group, to chitosan. The bio-functionalized polysaccharides, pure or "diluted" with chitosan, were chemically characterized in depth and evaluated for their antimicrobial activities and biocompatibility toward human primary osteoblast cells. The results obtained indicate that the bio-functionalization of chitosan increases human-osteoblast adhesion ( p < 0.005) and proliferation ( p < 0.005) as compared with chitosan. Overall, the 1:1 mixture of HVP functionalized-chitosan:chitosan is the best compromise between preserving the antibacterial properties of the material and supporting osteoblast differentiation and calcium deposition ( p < 0.005 vs. RGD). In conclusion, our results reported that a selected concentration of HVP supported the biomimetic potential of functionalized chitosan better than RGD and preserved the antibacterial properties of chitosan.

In this work, an innovative analytical approach focused on the use of advanced imaging techniques for the chemical mapping of degradation and/or restoration products is proposed. A representative cross-section showing a very complex stratigraphy from the Saint Wilgefortis Triptych (Hieronymus Bosch), exhibited in the Galleria dell'Accademia di Venezia, was investigated. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) experiments were performed using a time-of-flight detector operating in the so-called delayed extraction mode. The time delay applied during the extraction of the secondary ions permitted mass spectra to be obtained with an excellent mass resolution and chemical maps with nanometer scale spatial resolution. The painting's cross-section was also analysed at the micrometer scale by micro-Fourier transform infrared spectroscopy (micro-FTIR). The combined analytical approaches highlighted the colocalization of lead chloride, oxychloride, and hydroxychloride ions, suggesting the transformation of lead white ((PbCO 3 ) 2 Pb(OH) 2 ) into laurionite (PbClOH). Furthermore, chlorine appears evenly diffused in the cinnabar (HgS) layer, inducing the alteration of its more external part into calomel (Hg 2 Cl 2 ). In fact, from the chemical maps the presence in the sample of an unaltered portion of the cinnabar layer is evident. Such degradation products were probably due to the exposure of the painting to a chloride-rich atmosphere for a long time. This led to a global blackening of the painting. To protect the painting from aggressive chemical species, siloxane compounds were probably used as a modern restorative treatment. ToF-SIMS chemical maps revealed permeation of the silicon-based consolidants within the sample's cracks and no interaction products with the other constitutive materials of the painting were found. Finally, the presence of different lead soaps was detected in correspondence with the lead white layer.

A modular X-ray scanning system was developed, to fill in the gap between portable instruments (with a limited analytical area) and mobile instruments (with large analytical areas, and sometimes bulky and difficult to transport). The scanner has been compared to a commercial tabletop instrument, by analysing a Portuguese tile ( azulejo ) from the 17th century. Complementary techniques were used to achieve a throughout characterisation of the sample in a complete non-destructive approach. The complexity of the acquired X-ray fluorescence (XRF) spectra, due to inherent sample stratigraphy, has been resolved using Monte Carlo simulations, and Raman spectroscopy, as the most suitable technique to complement the analysis of azulejos colours, yielding satisfactory results. The colouring agents were identified as cobalt blue and a Zn-modified Naples-yellow. The stratigraphy of the area under study was partially modelled with Monte Carlo simulations. The scanners performance has been compared by evaluating the images outputs and the global spectrum.

Hydroxyapatite (HAP) coatings can improve the biocompatibility and bioactivity of titanium alloys, such as Ti6Al4V, commonly used as material for orthopedic prostheses. In this framework, we have studied the surface of HAP coatings enriched with Mg and either Si or Ti deposited by RF magnetron sputtering on Ti6Al4V. HAP coatings have been furtherly functionalized by adsorption of a self-assembling peptide (SAP) on the HAP surface, with the aim of increasing the material bioactivity. The selected SAP (peptide sequence AbuEAbuEAbuKAbuKAbuEAbuEAbuKAbuK) is a self-complementary oligopeptide able to generate extended ordered structures by self-assembling in watery solutions. Samples were prepared by incubation of the HAP coatings in SAP solutions and subsequently analyzed by X-Ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FTIR) and Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopies, in order to determine the amount of adsorbed peptide, the peptide stability and the structure of the peptide overlayer on the HAP coatings as a function of the HAP substrate and of the pH of the mother SAP solution. Experimental data yielded evidence of SAP adsorption on the HAP surface, and peptide overlayers showed ordered structure and molecular orientation. The thickness of the SAP overlayer depends on the composition of the HAP coating., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

The aim of this study was to develop smart materials with stimuli-responsive properties for the long-term protection of steel. The idea was to obtain a tailored and controlled release of protective agents in response to the environment stimuli. First, the protective efficacy of three inhibitors containing a carboxylic moiety, such as p -aminobenzoic (pAB), succinic (SA), and caffeic (CA) acids, was investigated in alkaline chloride solutions. The results revealed that pAB is the most effective protective agent, significantly better than SA and CA. It is surprising that the steel surface in the pAB solution remains unchanged even after 5 months of corrosion treatment, whereas the formation of degradation products in the SA and CA solutions was observed after only 6 days. Based on these findings, pAB was selected and used for the functionalization of silica nanoparticles and layered double hydroxides (LDHs) that can act as delivery vehicles and as an inhibitor reservoir. Specifically, pAB was chemisorbed on silica amino groups via an amide bond, and this makes possible a gradual inhibitor release induced by an alkaline environment. The intercalation of pAB in its anionic form into the LDHs structure is responsible for a completely different behavior since the release is induced by chloride ions and occurs by an anionic exchange reaction. Thus, these materials play a dual role by acting as an inhibitor reservoir and by capturing chlorides. These findings reveal that it is possible to create a reservoir of corrosion inhibitors gradually released on demand based on the chemical environment. The stimuli-responsive properties and the complementary protective action of inhibitor-loaded silica and LDHs make them attractive for the long-term protection of steel and open the way for innovative solutions in the preservation of concrete cultural heritage., (Copyright © 2020 Giuliani, Messina, Staccioli, Pascucci, Riccucci, Liotta, Tortora, Ingo and Di Carlo.)

Advances in the use of neuroimaging in combination with A.I., and specifically the use of machine learning techniques, have led to the development of brain-reading technologies which, in the nearby future, could have many applications, such as lie detection, neuromarketing or brain-computer interfaces. Some of these could, in principle, also be used in forensic psychiatry. The application of these methods in forensic psychiatry could, for instance, be helpful to increase the accuracy of risk assessment and to identify possible interventions. This technique could be referred to as 'A.I. neuroprediction,' and involves identifying potential neurocognitive markers for the prediction of recidivism. However, the future implications of this technique and the role of neuroscience and A.I. in violence risk assessment remain to be established. In this paper, we review and analyze the literature concerning the use of brain-reading A.I. for neuroprediction of violence and rearrest to identify possibilities and challenges in the future use of these techniques in the fields of forensic psychiatry and criminal justice, considering legal implications and ethical issues. The analysis suggests that additional research is required on A.I. neuroprediction techniques, and there is still a great need to understand how they can be implemented in risk assessment in the field of forensic psychiatry. Besides the alluring potential of A.I. neuroprediction, we argue that its use in criminal justice and forensic psychiatry should be subjected to thorough harms/benefits analyses not only when these technologies will be fully available, but also while they are being researched and developed., (Copyright © 2020 Tortora, Meynen, Bijlsma, Tronci and Ferracuti.)

When investigating gilded artifacts or works of art, the determination of the gilding thickness plays a significant role in establishing restoration protocols or conservation strategies. Unfortunately, this is done by cross-sectioning the object, a destructive approach not always feasible. A non-destructive alternative, based on the differential attenuation of fluorescence radiation from the sample, has been developed in the past years, but due to the intrinsic random nature of X-rays, the study of single or few spots of an objects surface may yield biased information. Furthermore, considering the effects of both porosity and sample inhomogeneities is a practice commonly overlooked, which may introduce systematic errors. In order to overcome these matters, here we propose the extrapolation of the differential-attenuation method from single-spot X-ray fluorescence (XRF) measurements to macro-XRF (MA-XRF) scanning. In this work, an innovative algorithm was developed for evaluating the large amount of data coming from MA-XRF datasets and evaluate the thickness of a given overlapping layer over an area. This approach was adopted to study a gilded copper-based buckle from the sixteenth to seventeenth century found in Rome. The gilded object under investigation was also studied by other analytical techniques including scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS). Previous results obtained from SEM-EDS were used to confront the data obtained with the proposed methodology and validate it. MA-XRF elemental distribution maps were fundamental in identifying and choosing sampling areas to calculate the thickness of the gilding layer, avoiding lead islands present in the sample that could negatively influence the results. Albeit the large relative standard deviation, the mean thickness values fell within those found in literature and those obtained from previous studies with SEM-EDS. Surface fissure has been found to deeply affect the results obtained, an aspect that is often disregarded., (Copyright © 2020 Barcellos Lins, Ridolfi, Gigante, Cesareo, Albini, Riccucci, di Carlo, Fabbri, Branchini and Tortora.)

Molecular self-assembly consists of the spontaneous aggregation of molecules into a well-defined structure guided by noncovalent bonds. The self-assembly strategy is ubiquitous in nature and recently has been proposed as a nature-mimetic strategy in polymer science and biomaterial engineering. In this context, we aim at designing and testing innovative but simple chemical strategies to efficiently modify surfaces by exploiting minor modifications in the bioactive molecule functionalities, for example, introducing cysteine (Cys) as a terminal residue in self-assembling peptides (SAPs). In this work, we report the attenuated total reflection-Fourier transform infrared spectroscopy, synchrotron radiation-induced X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and time-of-flight secondary ion mass spectrometry investigation of self-assembled layers of oligopeptides anchored onto gold surfaces through cysteine residues, opportunely inserted in an SAP (EAK16-II) main chain in three different positions: at the amine end group, at the carboxyl end group, and at both terminal groups (i.e., a bidentate SAP). This study, which allowed us to individuate in the bidentate SAP the best candidate for the controlled production of ordered SAP layers on the gold substrate surface, is envisaged to open wide perspectives for efficient chemical modification of surfaces with biomolecules, leading to obtaining innovative bioactive materials for applications in the field of tissue engineering.

In this work, hydrophilic silver nanoparticles (AgNPs), bifunctionalized with citrate (Cit) and L-cysteine (L-cys), were synthesized. The typical local surface plasmon resonance (LSPR) at λ max = 400 nm together with Dynamic Light Scattering (DLS) measurements (<2R H > = 8 ± 1 nm) and TEM studies (Ø = 5 ± 2 nm) confirmed the system nanodimension and the stability in water. Molecular and electronic structures of AgNPs were investigated by FTIR, SR-XPS, and NEXAFS techniques. We tested the system as plasmonic sensor in water with 16 different metal ions, finding sensitivity to Hg 2+ in the range 1-10 ppm. After this first screening, the molecular and electronic structure of the AgNPs-Hg 2+ conjugated system was deeply investigated by SR-XPS. Moreover, in view of AgNPs application as sensors in real water systems, environmental safety assessment (ecosafety) was performed by using standardized ecotoxicity bioassay as algal growth inhibition tests (OECD 201, ISO 10253:2006), coupled with determination of Ag + release from the nanoparticles in fresh and marine aqueous exposure media, by means of ICP-MS. These latest studies confirmed low toxicity and low Ag + release. Therefore, these ecosafe AgNPs demonstrate a great potential in selective detection of environmental Hg 2+ , which may attract a great interest for several biological research fields.

Uniaxial order parameters of the nematic and columnar mesophases in the lyotropic chromonic liquid crystal Sunset Yellow FCF have been determined from deuteron nuclear magnetic resonance, where random confinement of the system by the dispersion of aerosil nanoparticles has been performed to help obtain the angular dependent spectra. The long-time evolution study of the order parameters shows that the system requires tens of hours to stabilize after a deep change in temperature, in contrast with the very fast assembly process of the aggregates. Finally, the degree of order of the water molecules, forced by the uniaxial environment, has been determined.

Introduction: Use of synthetic cannabinoids (SC) has recently emerged as a new drug epidemic. Our emergency departments (EDs) received a surge of SC users presenting with lethargy and bradycardia, contrasting prior reports of SC-induced tachycardia and agitation. Our goal was to describe these novel presentations and characterize the compounds., Methods: We present a case series of patients with SC intoxication who presented to our toxicology service covering two tertiary care EDs between 2/11/2015 and 6/23/2015. A retrospective chart review recorded initial vital signs, chief complaint and clinical course. Urine, blood and xenobiotic samples were analyzed using either liquid chromatography/mass spectrometry or gas chromatography/mass spectrometry. We compared resulting spectra against databases containing numerous SCs or metabolites and scored based on a reference comparison., Results: Between 2/11/2015 and 6/23/2015, we identified 141 visits. Males comprised 139 visits (age range 21-68 years; median 35, interquartile range 20). Sixty-eight percent presented with lethargy or loss of consciousness. Hypotension (SBP <90 mmHg) and bradycardia (HR<60 bpm) were seen in 10% and 24% of visits, respectively. While most patients were discharged after observation, three were admitted to the intensive care unit and seven to telemetry. Admissions were for vital sign instability, bradycardia requiring pacing, prolonged sedation and respiratory failure requiring mechanical ventilation.Laboratory analysis revealed SC in the XLR-11 family in 18/36 drug, 9/12 blood, and 23/31 urine samples. Carboxamide indazole derivative (CID) family compounds were detected in 13/36 drug samples, 21/31 urine samples, but no blood samples; 11/31 drug samples contained both XLR-11 and CID. Other compounds detected included PB-22 and nicotine. No JWH compounds, opiates, imidazoline receptor agonists, benzodiazepines or other sedative-hypnotics were detected., Conclusion: Unlike their predecessors, novel SC may be associated with significant central nervous system depression and bradycardia. While prior reports indicated that SC mostly contained JWH compounds, none were detected in these samples. The most commonly identified compounds in this series were CID and alkyl SC derivatives, such as INACA compounds and XLR-11. These tend to be full agonists at the cannabinoid receptor and are presumably more potent. The lack of other depressants suggests that the clinical findings are due to the combination of these compounds and not coingestants or adulterants. SC intoxication should be considered for patients with undifferentiated psychomotor depression and bradycardia., Competing Interests: Conflicts of Interest: By the WestJEM article submission agreement, all authors are required to disclose all affiliations, funding sources and financial or management relationships that could be perceived as potential sources of bias. Matthew Stripp, MD was previously employed by American Forensic Toxicology Services (AFTS Labs) from June 2010 to August 2010. AFTS Labs is now Cordant Health Solutions. We worked with Cordant Health Solutions for the testing of toxicology drug, urine and blood samples for research purposes only.

Here, time of flight secondary ion mass spectrometry (ToF-SIMS) and multivariate analysis were combined to study the role of ulcerative colitis (UC), a type of inflammatory bowel disease (IBD), in the colon cancer progression. ToF-SIMS was used to obtain mass spectra and chemical maps from the mucosal surface of human normal (NC), inflamed (IC), and dysplastic (DC) colon tissues. Chemical mapping with a lateral resolution of ≈ 1 μm allowed to evaluate zonation of fatty acids and amino acids as well as the morphological condition of the intestinal glands. High mass resolution ToF-SIMS spectra showed chemical differences in lipid and amino acid composition as a function of pathological state. In positive ion mode, mono- (MAG), di- (DAG), and triacylglycerol (TAG) signals were detected in NC tissues, while in IC and DC tissues, the only cholesterol was present as lipid class representative. Signals from fatty acids, collected in negative ion mode, were subjected to principal component analysis (PCA). PCA showed a strict correlation between IC and DC samples, due to an increase of stearic, arachidonic, and linoleic acid. In the same way, differences in the amino acid composition were highlighted through multivariate analysis. PCA revealed that glutamic acid, leucine/isoleucine, and valine fragments are related to IC tissues. On the other hand, tyrosine, methionine, and tryptophan peaks contributed highly to the separation of DC tissues. Finally, a classification of NC, IC, and DC patients was also achieved through hierarchical cluster analysis of amino acid fragments. In this case, human colonic inflammation showed a stronger relationship with normal than dysplastic condition. Graphical Abstract ᅟ.

Functionalization of poly(ε-caprolactone) (PCL) was performed via hydrolysis and subsequent grafting of lactose-modified chitosan (chitlac) at two different degrees of derivatization (9% and 64%). Time of flight secondary ion mass spectrometry (ToF-SIMS) and multivariate analysis (principal component analysis) were successfully applied to the characterization of PCL surface chemistry, evidencing changes in the biopolymer surface following base-catalyzed hydrolysis treatment. ToF-SIMS analysis also confirmed positive EDC/NHS-catalyzed (EDC: N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide; NHS: N-hydroxysuccinimide) immobilization of chitlac onto activated PCL surface, with formation of amide bonds between PCL surface carboxyl groups and amine residues of chitlac. Yield of grafting reaction was also shown to be dependent upon the lactosilation degree of chitlac.

Phosphorus complexes of corrole have recently attracted increasing interest since these compounds can be easily prepared in good yields, are stable, and show unusual optical properties. For these reasons, phosphorus corroles represent a class of interesting compounds to be exploited in the field of material science or for biomedical investigations and the definition of synthetic pathways for their functionalization is an important step to optimize their properties for various applications. We report here the reactivity of the phosphorus complex of 5,10,15-tritolylcorrole in the nitration or bromination reaction. Both these attempts were successful, allowing the preparation of substituted phosphorus corroles, which can be used as intermediates of more complex architectures endowed with useful properties. Furthermore, the crystallographic characterization of both complexes shows that they have an unusual ruffled geometry of the corrole core, a conformation that has not been considered possible for such a macrocycle., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The synthesis and the characterization of three new naproxen decorated polymers are described. A versatile and general approach is employed to link the drug to polymers, affording the derivatives with a very high degree of purity. The release of the drug from the conjugates proved to be exceptionally slow, even in acidic aqueous media, and the kinetic of the process seems to be triggered by their solubility in water. On the other hand, the interesting outcome of the first ex vivo drug release experiments on human blood samples makes this preliminary study valuable for future investigations on the use of these polymeric prodrugs in in vivo treatment of inflammatory states.

The purpose of this study was to determine the diagnostic test characteristics of serum neuregulin-1β (NRG-1β) for the detection of acute coronary syndrome (ACS). We recruited emergency department patients presenting with signs and symptoms prompting an evaluation for ACS. Serum troponin and neuregulin-1β levels were compared between those who had a final discharge diagnosis of myocardial infarction (STEMI and NSTEMI) and those who did not, as well as those who more broadly had a final discharge diagnosis of ACS (STEMI, NSTEMI, and unstable angina). Of 319 study participants, 11% had evidence of myocardial infarction, and 19.7% had a final diagnosis of ACS. Patients with MI had median neuregulin levels of 0.16 ng/mL (IQR [0.16-24.54]). Compared to the median of those without MI, 1.46 ng/mL (IQR [0.16-15.02]), there was no significant difference in the distribution of results (P = 0.63). Median neuregulin levels for patients with ACS were 0.65 ng/mL (IQR [0.16-24.54]). There was no statistical significance compared to those without ACS who had a median of 1.40 ng/mL (IQR [0.16-14.19]) (P = 0.95). Neuregulin did not perform successfully as a biomarker for acute MI or ACS in the emergency department.

Post-mastectomy breast reconstruction with expanders and implants is recognized as an integral part of breast cancer treatment. Its main complication is represented by capsular contracture, which leads to poor expansion, breast deformation, and pain, often requiring additional surgery. In such a scenario, the debate continues as to whether the second stage of breast reconstruction should be performed before or after post-mastectomy radiation therapy, in light of potential alterations induced by irradiation to silicone biomaterial. This work provides a novel, multi-technique approach to unveil the role of radiotherapy in biomaterial alterations, with potential involvement in capsular contracture. Following irradiation, implant shells underwent mechanical, chemical, and microstructural evaluation by means of tensile testing, Attenuated Total Reflectance Fourier Transform InfraRed spectroscopy (ATR/FTIR), Scanning Electron Microscopy (SEM), high resolution stylus profilometry, and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS). Our findings are consistent with radiation-induced modifications of silicone that, although not detectable at the microscale, can be evidenced by more sophisticated nanoscale surface analyses. In light of these results, biomaterial irradiation cannot be ruled out as one of the possible co-factors underlying capsular contracture., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A gas sensor array based on peptide modified gold nanoparticles deposited onto 20MHz quartz crystal microbalances has been realized. Glutathione and its constituting aminoacids and dipeptides have been used as ligands. A great increase in sensitivity (2 orders of magnitude) was achieved using gold nanoparticles versus monolayer modified QCMs. The sensors have been characterised in terms of sensitivity for hexane, water, trimethylammine and ethanol. Highest sensitivity was found for water. The ability to discriminate typical food aromas as cis-3-hexenol, isopentylacetate, ethylacetate, and terpinen-4-ol dissolved in different solvents was studied using a gas sensor array constituted by gold nanoparticles modified with the glutathione peptides, thioglycolic acid and an heptapeptide. The array was found able to discriminate the food aromas, the response being dependent on the polarity of the solvent used. Tests on real olive oil samples gave a satisfactory separation among samples having defects versus non defected samples demonstrating that this approach has high potential for the development of gas sensor arrays to be used in real samples., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Using a magnetic Frederiks transition technique, we measure the temperature and concentration dependences of splay K1, twist K2, and bend K3 elastic constants for the lyotropic chromonic liquid crystal sunset yellow formed through noncovalent reversible aggregation of organic molecules in water. K1 and K3 are comparable to each other and are an order of magnitude higher than K2. At higher concentrations and lower temperatures, K1 and the ratios K1/K3 and K1/K2 increase, which is attributed to elongation of self-assembled lyotropic chromonic liquid crystal aggregates, a feature not found in conventional thermotropic and lyotropic liquid crystals formed by covalently bound units of a fixed length.

Functionalization of the β-pyrrolic positions of the corrole macrocycle with -NO(2) groups is limited at present to metallocorrolates due to the instability exhibited by corrole free bases under oxidizing conditions. A careful choice of the oxidant can limit the transformation of corroles into decomposition products or isocorrole species, preserving the corrole aromaticity, and thus allowing the insertion of nitro groups onto the corrole framework. Here we report results obtained by reacting 5,10,15-tritolylcorrole (TTCorrH(3)) with the AgNO(2)/NaNO(2) system, to give mono- and dinitrocorrole derivatives when stoichiometry is carefully controlled. Reactions were found to be regioselective, affording the 3-NO(2)TTCorrH(3) and 3,17-(NO(2))(2)TTCorrH(3) isomers as the main products in the case of mono- and disubstitution, in 53 and 20% yields, respectively. In both cases, traces of other mono- and disubstituted isomers were detected, which were structurally characterized by X-ray crystallography. The influence of the β-nitro substituents on the corrole properties is studied in detail by UV-visible, electrochemical, and spectroelectrochemical characterization of these functionalized corroles. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations of the ground and excited state properties of these β-nitrocorrole derivatives also afforded significant information, closely matching the experimental observations. It is found that the β-NO(2) substituents conjugate with the π-aromatic system of the macrocycle, which initiates significant changes in both the spectroscopic and redox properties of the so functionalized corroles. This effect is more pronounced when the nitro group is introduced at the 2-position, because in this case the conjugation is, for steric reasons, more efficient than in the 3-nitro isomer.

Two different methods for the regioselective nitration of different meso-triarylcorroles leading to the corresponding β-substituted nitrocorrole iron complexes have been developed. A two-step procedure affords three Fe(III) nitrosyl products-the unsubstituted corrole, the 3-nitrocorrole, and the 3,17-dinitrocorrole. In contrast, a one-pot synthetic approach drives the reaction almost exclusively to formation of the iron nitrosyl 3,17-dinitrocorrole. Electron-releasing substituents on the meso-aryl groups of the triarylcorroles induce higher yields and longer reaction times than what is observed for the synthesis of similar triarylcorroles with electron-withdrawing functionalities, and these results can be confidently attributed to the facile formation and stabilization of an intermediate iron corrole π-cation radical. Electron-withdrawing substituents on the meso-aryl groups of triarylcorrole also seem to labilize the axial nitrosyl group which, in the case of the pentafluorophenylcorrole derivative, results in the direct formation of a disubstituted iron μ-oxo dimer complex. The influence of meso-aryl substituents on the progress and products of the nitration reaction was investigated. In addition, to elucidate the most important factors which influence the redox reactivity of these different iron nitrosyl complexes, selected compounds were examined by cyclic voltammetry and thin-layer UV-visible or FTIR spectroelectrochemistry in CH(2)Cl(2)., (© 2012 American Chemical Society)

Mono- and di-substituted β-nitro derivatives have been obtained from the reaction of ttcorrFeCl with sodium nitrite in refluxing DMF. This result is unprecedented for iron corrolates and further evidences the non-innocent character of the corrole ligand.

Bromination of 3-nitro-5,10,15-triarylcorrole selectively provides two regioisomers, depending on the reaction pathway. An isocorrole species is the key intermediate to drive the reaction towards the 2-Br-17-nitro regioisomer.

We use optical and fluorescence microscopy, densitometry, cryo-transmission electron microscopy (cryo-TEM), spectroscopy, and synchrotron X-ray scattering to study the phase behavior of the reversible self-assembled chromonic aggregates of an anionic dye Sunset Yellow (SSY) in aqueous solutions crowded with an electrically neutral polymer polyethylene glycol (PEG) and doped with the salt NaCl. PEG causes the isotropic SSY solutions to condense into a liquid-crystalline region with a high concentration of SSY aggregates, coexisting with a PEG-rich isotropic (I) region. PEG added to the homogeneous nematic (N) phase causes separation into the coexisting N and I domains; the SSY concentration in the N domains is higher than the original concentration of PEG-free N phase. Finally, addition of PEG to the highly concentrated homogeneous N phase causes separation into the coexisting columnar hexagonal (C) phase and I phase. This behavior can be qualitatively explained by the depletion (excluded volume) effects that act at two different levels: at the level of aggregate assembly from monomers and short aggregates and at the level of interaggregate packing. We also show a strong effect of a monovalent salt NaCl on phase diagrams that is different for high and low concentrations of SSY. Upon the addition of salt, dilute I solutions of SSY show appearance of the condensed N domains, but the highly concentrated C phase transforms into a coexisting I and N domains. We suggest that the salt-induced screening of electric charges at the surface of chromonic aggregates leads to two different effects: (a) increase of the scission energy and the contour length of aggregates and (b) decrease of the persistence length of SSY aggregates.

In many colloidal systems, an orientationally ordered nematic (N) phase emerges from the isotropic (I) melt in the form of spindle-like birefringent tactoids. In cases studied so far, the tactoids always reveal a mirror-symmetric nonchiral structure, sometimes even when the building units are chiral. We report on chiral symmetry breaking in the nematic tactoids formed in molecularly nonchiral polymer-crowded aqueous solutions of low-molecular weight disodium cromoglycate. The parity is broken by twisted packing of self-assembled molecular aggregates within the tactoids as manifested by the observed optical activity. Fluorescent confocal microscopy reveals that the chiral N tactoids are located at the boundaries of cells. We explain the chirality induction as a replacement of energetically costly splay packing of the aggregates within the curved bipolar tactoidal shape with twisted packing. The effect represents a simple pathway of macroscopic chirality induction in an organic system with no molecular chirality, as the only requirements are orientational order and curved shape of confinement.

In modern transformation optics, one explores metamaterials with properties that vary from point to point in space and time, suitable for application in devices such as an "optical invisibility cloak" and an "optical black hole". We propose an approach to construct spatially varying and switchable metamaterials that are based on colloidal dispersions of metal nano-rods (NRs) in dielectric fluids, in which dielectrophoretic forces, originating in the electric field gradients, create spatially varying configurations of aligned NRs. The electric field controls orientation and concentration of NRs and thus modulates the optical properties of the medium. Using gold (Au) NRs dispersed in toluene, we demonstrate electrically induced change in refractive index on the order of 0.1.

The surface alignment of lyotropic chromonic liquid crystals can not only be planar (tangential) but also homeotropic, with self-assembled aggregates perpendicular to the substrate, as demonstrated by mapping optical retardation and by three-dimensional imaging of the director field. With time, the homeotropic nematic undergoes a transition into a tangential state. The anchoring transition is discontinuous and can be described by a double-well anchoring potential with two minima corresponding to tangential and homeotropic orientation.

Lyotropic chromonic liquid crystals (LCLCs) are formed by molecules with ionic groups at the periphery that associate into stacks through noncovalent self-assembly while in water. The very existence of the nematic (N) phase in the typical LCLC, the dye Sunset Yellow (SSY) is a puzzle, as the correlation length associated with the stacking, as measured in the X-ray experiments, is too short to explain the orientational order by the Onsager model. We propose that the aggregates can be more complex than simple rods and contain "stacking faults" such as junctions with a shift of neighboring molecules, 3-fold junctions, etc. We study how ionic additives, such as salts of different valency and pH-altering agents, alter the N phase of SSY purified by recrystallization. The additives induce two general trends: (a) stabilization of the N phase, caused by the mono and divalent salts (such as NaCl), and evidenced by the increase of the N-to-I transition temperature and the correlation length; (b) suppression of the N phase manifested in the decrease of the N-to-I transition temperature and in separation of the N phase into a more densely packed N phase or the columnar (C) phase, coexisting with a less condensed I phase. The scenario (b) can be triggered by simply increasing pH (adding NaOH). The effects produced by tetravalent spermine fall mostly into the category (b), but the detail depends on whether this additive is in its salt form or a free base form. The base form causes changes through changes in pH and possible excluded volume effects whereas the salt form might disrupt the structure of SSY aggregates.