Carbon-sulfur bond strength in methanesulfinate and benzenesulfinate ligands directs decomposition of Np(v) and Pu(v) coordination complexes.

Gas-phase coordination complexes of actinyl(v) cations, AnO2+, provide a basis to assess fundamental aspects of actinide chemistry. Electrospray ionization of solutions containing an actinyl cation and sulfonate anion CH3SO2- or C6H5SO2- generated complexes [(AnVO2)(CH3SO2)2]- or [(AnVO2)(C6H5SO2)2]- where An = Np or Pu. Collision induced dissociation resulted in C-S bond cleavage for methanesulfinate to yield [(AnVO2)(CH3SO2)(SO2)]-, whereas hydrolytic ligand elimination occurred for benzenesulfinate to yield [(AnVO2)(C6H5SO2)(OH)]-. These different fragmentation pathways are attributed to a stronger C6H5-SO2-versus CH3-SO2- bond, which was confirmed for both the bare and coordinating sulfinate anions by energies computed using a relativistic multireference perturbative approach (XMS-CASPT2 with spin-orbit coupling). The results demonstrate shutting off a ligand fragmentation channel by increasing the strength of a particular bond, here a sulfinate C-S bond. The [(AnVO2)(CH3SO2)(SO2)]- complexes produced by CID spontaneously react with O2 to eliminate SO2, yielding [(AnO2)(CH3SO2)(O2)]-, a process previously reported for An = U and found here for An = Np and Pu. Computations confirm that the O2/SO2 displacement reactions should be exothermic or thermoneutral for all three An, as was experimentally established. The computations furthermore reveal that the products are superoxides [(AnVO2)(CH3SO2)(O2)]- for An = Np and Pu, but peroxide [(UVIO2)(CH3SO2)(O2)]-. Distinctive reduction of O2- to O22- concomitant with oxidation of U(v) to U(vi) reflects the relatively higher stability of hexavalent uranium versus neptunium and plutonium

Facing the challenge of predicting the standard formation enthalpies of n-butyl-phosphate species with ab initio methods

Tributyl-phosphate (TBP), a ligand used in the PUREX liquid-liquid separation process of spent nuclear fuel, can form explosive mixture in contact with nitric acid, that might lead to violent explosive thermal runaway. In the context of safety of a nuclear reprocessing plant facility, it is crucial to predict the stability of TBP at elevated temperatures. So far, only the enthalpies of formation of TBP is available in the literature with a rather large uncertainties, while those of its degradation products, di-(HDBP) and mono-(H$_2$MBP}) are unknown. In this goal, we have used state-of-the art quantum chemical methods to compute the formation enthalpies and entropies of TBP and its degradation products di-(HDBP), mono-(H$_2$MBP) in gas and liquid phases. Comparisons of levels of quantum chemical theory revealed that there are significant effects of correlation on their electronic structures, pushing for the need of not only high level of electronic correlation treatment, namely local coupled cluster with single and double excitation operators and perturbative treatment of triple excitations [LCCSD(T)], but also extrapolations to the complete basis to produce reliable and accurate thermodynamics data. Solvation enthalpies were computed with the conductor like screening model for real solvents [COSMO-RS], for which we observe errors not exceeding 22 kJ mol$^{-1}$. We thus propose with final uncertainty of about 20 kJ mol$^{-1}$ standard enthalpies of formation of TBP, HDBP, and H$_2$MBP which amounts to -1281.7$\pm$24.4, -1229.4$\pm$19.6 and -1176.7$\pm$14.8 kJ mol$^{-1}$, respectively, in the gas phase. In the liquid phase, the predicted values are -1367.3$\pm$24.4, -1348.7$\pm$19.6 and -1323.8$\pm$14.8 kJ mol$^{-1}$, to which we may add about -22 kJ mol$^{-1}$ error from the COSMO-RS solvent model. From these data, we predict the complete hydrolysis of TBP to be nearly thermoneutral

Anti- Forensics: The Tampering of Media

In the context of forensic investigations, the traditional understanding of evidence is changing where nowadays most prosecutors, lawyers and judges heavily rely on multimedia signs. This modern shift has allowed the law enforcement to better reconstruct the crime scenes or reveal the truth of any critical event.In this paper we shed the light on the role of video, audio and photos as forensic evidences presenting the possibility of their tampering by various easy-to-use, available anti-forensics softwares. We proved that along with the forensic analysis, digital processing, enhancement and authentication via forgery detection algorithms to testify the integrity of the content and the respective source of each, differentiating between an original and altered evidence is now feasible. These operations assist the court to attain higher degree of intelligibility of the multimedia data handled and assert the information retrieved from each that support the success of the investigation process

Enhancing men's awareness of testicular disorders using a virtual reality intervention: the E-MAT study

Introduction: Testicular cancer is the most common solid tumour among men aged less than 50 years. The incidence of this malignancy is on the rise globally. Benign testicular disorders such as testicular torsion and epididymitis can be life-threatening if left untreated. Men’s awareness of testicular disorders is lacking and their help-seeking intentions for testicular symptoms are low. Aim: To design and pilot-test an intervention (E-MAT) aimed at enhancing men’s testicular awareness and promoting early help-seeking for testicular symptoms. Methods: The Medical Research Council framework helped develop and pilot-test the E-MAT intervention. The evidence-base was identified by conducting one integrative and two systematic reviews of the literature on men’s awareness of testicular disorders. A qualitative study was conducted to explore men’s (n=29) awareness of testicular disorders; help-seeking intentions for testicular symptoms; and preferred strategies for learning about testicular disorders. The theoretical literature was reviewed and the Pre-Conscious Awareness to Action framework was developed to underpin E-MAT. The feasibility and usability of the intervention were tested with 15 men and its effectiveness was pilot-tested with 49 men. Results: Men lacked awareness of testicular disorders and intended to delay help-seeking for testicular symptoms. Participants recommended novel, humorous, and interactive strategies to raise testicular awareness. E-MAT was developed as a virtual reality experience with three levels aimed at familiarising men with the normal testes and testicular symptoms and diseases and was underpinned by the Pre-Conscious Awareness to Action framework. The E-MAT intervention was found to be feasible, user-friendly, and effective in enhancing men’s knowledge, testicular awareness, help-seeking intentions, and intentions and behaviours pertaining to feeling their testes. Conclusion: Full-scale testing of E-MAT is recommended by conducting a randomised controlled trial. E-MAT can be made publicly available using various platforms and virtual reality can be used to promote men’s awareness of different health topics

Exploring awareness and help-seeking intentions for testicular symptoms among heterosexual, gay, and bisexual men in Ireland: a qualitative descriptive study

Background: The incidence of malignant and benign testicular disorders among young men is on the rise. Evidence from three reviews suggest that men's knowledge of these disorders is lacking and their help seeking intention for testicular symptoms is suboptimal. Qualitative studies have addressed men's awareness of testicular cancer, with none exploring their awareness of non-malignant diseases such as epididymitis, testicular torsion, and varicocele and none including sexual minorities. Objective: To explore, in-depth, heterosexual, gay, and bisexual men's awareness of testicular disorders and their help-seeking intentions for testicular symptoms in the Irish context. Design: This study used a qualitative descriptive approach. Data were collected via face-to-face individual interviews and focus groups. Settings: Participation was sought from a number of community and youth organisations and one university in Southern Ireland. Participants: Maximum variation and snowball sampling were used to recruit a heterogeneous sample. A total of 29 men partook in this study. Participants were men, aged between 18 and 50 years, and residents of the Republic of Ireland. Methods: All interviews were audio-recorded and transcribed verbatim. Reflective field notes were taken following each interview. A summary of the interview was shared with selected participants for member check. Data were analysed and validated by three researchers. Inductive qualitative analysis of manifest content was used. Latent content was captured in the field notes. Data analysis yielded two key themes. Results: The themes that emerged from the interviews were: Awareness of testicular disorders and their screening, and help-seeking intentions for testicular symptoms. Although most participants heard of testicular cancer, most did not know the different aspects of this malignancy including its risk factors, symptoms, treatments, and screening. Several men had a number of misconceptions around testicular disorders which negatively impacted their intentions to seek prompt help. Intentions to delay help seeking for testicular symptoms were often linked to a number of emotional factors including fear and embarrassment, and social normative factors such as machoism and stoicism. In this study, culture was perceived by some participants as a barrier to awareness and help-seeking. In contrast, many believed that young men, especially those who self-identify as gay, are becoming increasingly interested in their own health. Conclusion: Findings suggest the need to educate young men about testicular disorders and symptoms. This could be achieved through conducting health promotion campaigns that appeal to younger men, drafting national men's health policies, and normalising open discussions about testicular health at a young age

The Preconscious Awareness to Action Framework: an application to promote testicular awareness

Objectives: The purpose of the study is to present a theory-focused analysis of the preconscious awareness to action framework (PAAF), developed to enhance testicular awareness and help-seeking intentions and behaviors among men. Methods: The following approach was used to develop the PAAF: The empirical literature on men’s awareness of testicular disorders was reviewed. A qualitative study was conducted to explore men’s awareness of testicular disorders, help-seeking intentions for testicular symptoms, and preferred learning strategies in relation to testicular disorders and symptoms. An iterative narrative review process of the theoretical literature on health promotion and symptom appraisal was undertaken. Results: The PAAF comprises seven steps: preconscious awareness, unconscious awareness, conscious awareness, unconscious appraisal, conscious appraisal, intention, and behavior. The concept of testicular awareness was developed to familiarize men with their own testes and promote timely help-seeking. Discussion: Researchers are encouraged to use the PAAF to design health-promoting interventions aimed at enhancing testicular awareness, symptom appraisal, and help-seeking

Promoting testicular cancer awareness and screening: a systematic review of interventions

Background: Testicular cancer (TC) is a relatively curable malignancy that predominantly affects young males. Key decision makers discourage TC screening because of lack of evidence about the benefits of this practice, whereas others argue that men must be aware of normal versus abnormal testicular findings. Despite the debate on TC surveillance, a number of research efforts are still being made to increase men’s awareness of TC and its screening. Objective: The aim of this study was to systematically review studies that were conducted to enhance men’s knowledge and awareness regarding TC and its screening and increase their TC screening intentions and practices. Methods: Studies published in English between 2004 and 2014 were reviewed using 3 e-databases, and interventions that were in line with the review aims were selected. Results: A total of 3076 records were screened for eligibility, and 11 studies met the inclusion criteria. The majority of the reviewed interventions successfully enhanced men’s awareness of TC and its screening and increased their intentions to perform testicular self-examination. Examples include videos about TC, shower gel sachets, stickers, and posters, a television show, a university campaign, and high self-efficacy messages about TC screening. Men at risk of health disparities were underrepresented in the reviewed literature. Conclusions: A number of interesting channels through which men can learn about TC were identified. Examples include social media and mass media. Implications for Practice: Given the controversy that surrounds TC screening, nurses can play a key role in increasing men’s awareness of TC rather than advising periodical TC self-examination

Exploring men's preferred strategies for learning about testicular disorders inclusive of testicular cancer: a qualitative descriptive study

Purpose: Men's awareness of testicular disorders is lacking and their intention to seek help for testicular symptoms is sub-optimal. Studies conducted to explore and raise men's awareness of testicular disorders did not address their preferred learning strategies and failed to include men who are at risk for health inequities. The aim of this study was to explore, in-depth, the preferred strategies for learning about testicular disorders inclusive of testicular cancer among men who self-identify as heterosexual, gay, or bisexual. Methods: Maximum variation and snowball sampling were used to recruit 29 men aged 18-47 years. Participation was sought from community and youth organizations and a university in the Republic of Ireland. Semi-structured individual interviews and focus groups were conducted. Interviews were audio recorded and transcribed verbatim. Inductive analysis of manifest content was used. Results: Seventeen informants self-identified as heterosexual, 11 as gay, and one as bisexual. Four main categories emerged, namely: strategies to enhance awareness (television, internet, campaigns, print media), educational dos and don'ts (tailoring effective messages, drawbacks of national initiatives, ineffective learning strategies), implications of raising awareness (risks and benefits of increasing awareness), and learning among gay and bisexual men (learning needs and strategies). Conclusion: Future studies promoting awareness of testicular disorders should take into account men's preferred learning strategies. National campaigns should be delivered frequently and altered occasionally in order to achieve a top-up effect. Clinicians are encouraged to educate young men about the seriousness of testicular symptoms and the importance of seeking timely medical attention for any abnormalities

Testicular awareness: The what, the why, and the how

Health outcomes among men are poorer than women and little efforts have been made by health organizations to promote men’s health. Testicular disorders can have a negative effect on men’s health and are rarely addressed in pre-existing men’s health policies. Findings from the empirical literature on men’s awareness of testicular disorders suggest that men’s knowledge of testicular disorders is lacking and their intentions to seek timely medical attention for testicular symptoms are low. This paper aims to introduce the concept of ‘testicular awareness’ and explore its implications for health research, practice, and education. The key attributes of ‘testicular awareness’ include: (i) familiarity with own testes; (ii) knowing what is normal versus abnormal; (iii) ability to detect an abnormality; and (iv) knowing own risk factors. Testicular awareness is an all-encompassing concept since it helps men become familiar with a body part that is seldom discussed and enables them to detect testicular abnormalities and to seek timely medical attentions for testicular symptoms, regardless of the ultimate diagnosis. Testicular awareness can be promoted using a number of strategies; these include but are not limited to: (i) involving men in drafting men’s health policies that address testicular awareness; (ii) partnering with men to develop and test interventions promoting testicular awareness; (iii) being cognizant of the learning needs of men who are at risk of health disparities including those with low literacy and health literacy; (iv) promoting testicular awareness in clinical practice and health education; and (v) using men’s daily spheres of information (e.g. workplaces, universities, gyms, and community organizations) to promote testicular awareness

Males' awareness of benign testicular disorders: an integrative review

Disorders that affect the testes can range from painless and benign to debilitating and life threatening. Despite the availability of literature on the etiology, diagnosis, and treatment of benign testicular disorders (BTD), very little is known about men’s awareness of these conditions. The aim of this review was to extract and analyze evidence from studies that explored males’ awareness of BTD. Four e-databases (CINAHL, MEDLINE, PsychINFO, and PubMed) were thoroughly searched and four articles met the review inclusion criteria. The quality of the included studies was appraised and data were extracted and cross-checked using a standardized data extraction table. It was determined that participants lacked education about testicular self-examination and scrotal signs and symptoms which contributed to their lack of awareness of BTD. Help seeking in the event of scrotal abnormalities was suboptimal which is alarming given the acuteness of some BTD such as testicular torsion. Individuals who are at risk for health disparities were underrepresented in the reviewed literature. Findings from this review highlight the need to address barriers to BTD knowledge and help seeking. This could be achieved through making use of past interventions that succeeded in increasing men’s awareness of testicular cancer such as university campaigns and mass media. From a practical standpoint, clinicians must be encouraged to educate young men about BTD. This could be attained through tailoring creative educational interventions that are sensitive to the needs of individuals who are at risk for health disparities