Hydrogenation of nitrobenzene to 4-aminophenol in a fully reusable solvent system, by using Pt, Rh, Pd supported on carbon-CF3COOH catalytic system

4-Aminophenol is an important raw material for several products in the field of dyes, photographs and pharmaceutics. For instance, paracetamol (N-acetyl-4-aminophenol) a widely employed analgesic and antipyretic whose production is in continuous growth specially in the far east region. Industrial synthesis of paracetamol is based mainly on 4-aminophenol, which is obtained by three different routes: i) nucleophilic substitution of the Cl of the 4-chloronitrobenzene, ii) reduction of 4-nitro-phenol, iii) selective hydrogenation of nitrobenzene [1]. The selective hydrogenation of nitrobenzene is however, the most convenient from both economical and environmental point of view [1, 2]. The major concern of this process is, however, the presence of H2SO4, which is origin of corrosion, safety, environmental and separation problems. The reaction is typically carried out in CSTR in which the biphasic reaction medium is used to accomplish simultaneously the Pt catalyzed hydrogenation of nitrobenzene and the acid catalyzed Bamberger rearrangement of the intermediate N-phenylhydroxylamine. From environmental point of view, the major drawback of the process is the neutralization of the acidic phase, with the consequent by-production of sulfate salts, which are undesired wastes. Starting from recent results obtained in the Beckmann rearrangement of the cyclohexanone oxime in CH3CN-CF3COOH system [3], here we show some findings on the hydrogenation of nitrobenzene to 4-aminophenol in a single liquid phase CH3CN-H2O-CF3COOH and in the presence a hydrogenation catalyst. The easy of recovery of solvent and catalysts allows to develop a greener process than that based on the biphasic H2SO4-nitrobenzene syste

A matrix isolation and computational study of molecular palladium fluorides : does PdF₆ exist?

Palladium atoms generated by thermal evaporation and laser ablation were reacted with and trapped in F₂ /Ar, F₂ /Ne, and neat F₂ matrices. The products were characterized by electronic absorption and infrared spectroscopy, together with relativistic density functional theory calculations as well as coupled cluster calculations. Vibrational modes at 540 and 617 cm⁻¹ in argon matrices were assigned to molecular PdF and PdF₂ , and a band at 692 cm⁻¹ was assigned to molecular PdF₄ . A band at 624 cm⁻¹ can be assigned to either PdF₃ or PdF₆, with the former preferred from experimental considerations. Although calculations might support the latter assignment, our conclusion is that in these detailed experiments there is no convincing evidence for PdF₆

Directed differentiation of rhesus monkey ES cells into pancreatic cell phenotypes

Embryonic stem cells (ES) can self-replicate and differentiate into all cell types including insulin-producing, beta-like cells and could, therefore, be used to treat diabetes mellitus. To date, results of stem cell differentiation into beta cells have been debated, largely due to difficulties in defining the identity of a beta cell. We have recently differentiated non-human primate (rhesus) embryonic stem (rES) cell lines into insulin producing, beta-like cells with the beta cell growth factor, Exendin-4 and using C-peptide as a phenotype marker. Cell development was characterized at each stage by gene and protein expression. Insulin, NKX6.1 and glucagon mRNA were expressed in stage 4 cells but not in early undifferentiated cells. We concluded that rES cells could be differentiated ex vivo to insulin producing cells. These differentiated rES cells could be used to develop a non-human primate model for evaluating cell therapy to treat diabetes. To facilitate the identification of beta-like cells and to track the cells post-transplantation, we have developed a marker gene construct: fusing the human insulin promoter (HIP) to the green fluorescent protein (GFP) gene. This construct was transfected into stage 3 rES derived cells and subsequent GFP expression was identified in C-peptide positive cells, thereby substantiating endogenous insulin production by rES derived cells. Using this GFP detection system, we will enrich our population of insulin producing rES derived cells and track these cells post-transplantation in the non-human primate model

Observation and Characterization of the Hg-O Diatomic Molecule: A Matrix-Isolation and Quantum-Chemical Investigation

Mercuric oxide is a well-known and stable solid, but the diatomic molecule Hg-O is very fragile and do not survive detection in the gas phase. However, laser ablation of Hg atoms from a dental amalgam target into argon or neon containing about 0.3% of 16 O 2 or of 18 O 2 during their condensation into a cryogenic matrix at 4 K allows the formation of O atoms which react on annealing to make ozone and new IR absorptions in solid argon at 521.2 cm –1 for Hg- 16 O or at 496.4 cm –1 for Hg- 18 O with the oxygen isotopic frequency ratio 521.2/496.4 = 1.0500. Solid neon gives a 529.0 cm –1 absorption with a small 7.8 blue shift. CCSD(T) calculations found 594 cm –1 for Hg 16 O and 562 cm –1 for Hg 18 O (frequency ratio = 1.0569). Such calculations usually produce harmonic frequencies that are slightly higher than the anharmonic (observed) values, which supports their relationship. These observed frequencies have the isotopic shift predicted for Hg-O and are within the range of recent high-level frequency calculations for the Hg-O molecule. Spectra for the related mercury superoxide and ozonide species are also observed for the first time

Dementia Knowledge Assessment Tool Version Two: Development of a tool to inform preparation for care planning and delivery in families and care staff

Care for the person with dementia requires understanding of the person’s perspective and preferences, integrated with knowledge of dementia’s trajectory and appropriate care. Version One of the Dementia Knowledge Assessment Tool addressed such knowledge in care workers; Version Two is for families as well as staff. Content validity was established during development. Revisions addressed clarity, time for completion, and reliability. When 671 staff completed Version One before an education intervention, internal consistency reliability estimates exceeded 0.70. Validity was supported by higher scores in professional versus nonprofessional staff and following the education. Version Two was used with 34 family carers and 70 staff members. Internal consistency reliability (Cronbach’s alpha coefficient) was promising (0.79, both groups). Completion was within 15 minutes. Median correct responses (from 21) were 14 for families (range 4–20) and 16 for the staff (range 3–21). Eighteen staff members (26%) and two family carers (6%) reported substantive dementia education. Inclusion of the person with dementia in care planning is often limited because of a late diagnosis and the progressive impacts of the condition. Establishing a shared staff–family understanding of the dementia trajectory and care strategies likely to be helpful is therefore critical to embarking upon the development and implementation of collaborative long term and end-of-life care plans. Version Two can help establish needs for, and outcomes of, education programs and informational resources in a way that is feasible, minimises burden, and facilitates comparisons across family and staff carer groups

Identifying acne treatment uncertainties via a James Lind Alliance Priority Setting Partnership

Objectives: The Acne Priority Setting Partnership (PSP) was set up to identify and rank treatment uncertainties by bringing together people with acne, and professionals providing care within and beyond the National Health Service (NHS). Setting: The UK with international participation. Participants: Teenagers and adults with acne, parents, partners, nurses, clinicians, pharmacists, private practitioners. Methods: Treatment uncertainties were collected via separate online harvesting surveys, embedded within the PSP website, for patients and professionals. A wide variety of approaches were used to promote the surveys to stakeholder groups with a particular emphasis on teenagers and young adults. Survey submissions were collated using keywords and verified as uncertainties by appraising existing evidence. The 30 most popular themes were ranked via weighted scores from an online vote. At a priority setting workshop, patients and professionals discussed the 18 highest-scoring questions from the vote, and reached consensus on the top 10. Results: In the harvesting survey, 2310 people, including 652 professionals and 1456 patients (58% aged 24 y or younger), made submissions containing at least one research question. After checking for relevance and rephrasing, a total of 6255 questions were collated into themes. Valid votes ranking the 30 most common themes were obtained from 2807 participants. The top 10 uncertainties prioritised at the workshop were largely focused on management strategies, optimum use of common prescription medications and the role of nondrug based interventions. More female than male patients took part in the harvesting surveys and vote. A wider range of uncertainties were provided by patients compared to professionals. Conclusions: Engaging teenagers and young adults in priority setting is achievable using a variety of promotional methods. The top 10 uncertainties reveal an extensive knowledge gap about widely used interventions and the relative merits of drug versus non-drug based treatments in acne management

Symptomology Associated with in Utero Exposures to Polysubstance in an Appalachian Population.

Neonatal abstinence syndrome (NAS) is seen as a very high rate at our institution in Huntington, West Virginia, and the majority of exposures are polysubstance in nature. Polysubstance can have different meaning for each region. At our institution, polysubstance is any combination of opioids, gabapentin, methamphetamine, cocaine, marijuana, benzodiazepines, nicotine or other neuroactive substances with 3-4 substances being the norm. Rapidly changing combinations of drug use and the lack of literature create a difficult situation for clinicians who are often reliant on treatment recommendations that lack references or conclusive data supporting the clinical approaches. Elucidating withdrawal symptoms consistent with in utero exposures to particular drug combinations is difficult. Many substances induce similar withdrawal symptoms in neonates and the vast majority of cases present as polysubstance exposure. Standard methodology often leads to a research approach which isolates populations and substance of exposure to determine the individual effects on the neonate. In some drug combinations, like opioid and gabapentin exposure, the substances in concert create symptoms and complications that are not observed with either drug alone. The history of responses to substance use epidemics has been to handle each drug as a separate disease process, this is no longer a viable option. The following is a review of the literature available discussing individual substance withdrawal characteristics in neonates combined with the clinical insight gained at our hospital from treating such high rates of complex polysubstance exposure

(Noble Gas)n-NC+ Molecular Ions in Noble Gas Matrices: Matrix Infrared Spectra and Electronic Structure Calculations

An investigation of pulsed-laser-ablated Zn, Cd and Hg metal atom reactions with HCN under excess argon during co-deposition with laser-ablated Hg atoms from a dental amalgam target also provided Hg emissions capable of photoionization of the CN photo-dissociation product. A new band at 1933.4 cm−1 in the region of the CN and CN+ gas-phase fundamental absorptions that appeared upon annealing the matrix to 20 K after sample deposition, and disappeared upon UV photolysis is assigned to (Ar)nCN+, our key finding. It is not possible to determine the n coefficient exactly, but structure calculations suggest that one, two, three or four argon atoms can solvate the CN+ cation in an argon matrix with C−N absorptions calculated (B3LYP) to be between 2317.2 and 2319.8 cm−1. Similar bands were observed in solid krypton at 1920.5, in solid xenon at 1935.4 and in solid neon at 1947.8 cm−1. H13CN reagent gave an 1892.3 absorption with shift instead, and a 12/13 isotopic frequency ratio–nearly the same as found for 13CN+ itself in the gas phase and in the argon matrix. The CN+ molecular ion serves as a useful infrared probe to examine Ng clusters. The following ion reactions are believed to occur here: the first step upon sample deposition is assisted by a focused pulsed YAG laser, and the second step occurs on sample annealing: (Ar)2++CN→Ar+CN+→(Ar)nCN+

EQUIPT: protocol of a comparative effectiveness research study evaluating cross-context transferability of economic evidence on tobacco control

This is an Open Access article distributed in accordance with the Creative Commons Attribution Non Commercial (CC BY-NC 4.0) license, which permits others to distribute, remix, adapt, build upon this work non-commercially, and license their derivative works on different terms, provided the original work is properly cited and the use is non-commercial.This article has been made available through the Brunel Open Access Publishing Fund.Tobacco smoking claims 700 000 lives every year in Europe and the cost of tobacco smoking in the EU is estimated between €98 and €130 billion annually; direct medical care costs and indirect costs such as workday losses each represent half of this amount. Policymakers all across Europe are in need of bespoke information on the economic and wider returns of investing in evidence-based tobacco control, including smoking cessation agendas. EQUIPT is designed to test the transferability of one such economic evidence base-the English Tobacco Return on Investment (ROI) tool-to other EU member states