Water confinement in small polycyclic aromatic hydrocarbons.

The confinement of water molecules is vital in fields from biology to nanotechnology. The conditions allowing confinement in small finite polycyclic aromatic hydrocarbons (PAHs) are unclear, yet are crucial for understanding confinement in larger systems. Here, we report a computational study of water cluster confinement within PAHs dimers. Our results serve as a model for larger carbon allotropes and for understanding molecular interactions in confined systems. We identified size and structural motifs allowing confinement and demonstrated the motifs in various PAHs systems. We show that optimal OH⋯π interactions between water clusters and the PAH dimer permit optimal confinement to occur. However, the lack of such interactions leads to the formation of CH⋯O interactions, resulting in less ideal confinement. Confinement of layered clusters is also possible, provided that the optimal OH⋯π interactions are conserved.

Juggling between caregiving and self-actualization: Older parents' lifelong experience of caring for an adult child with developmental disabilities.

Recently, the number of adults with Developmental Disabilities (DD) who live with their parents has increased. This study aims to explore how parents report retrospectively and interpret their experience in the context of self-actualization in the long-term care of a child with a developmental disability. Four forms of parents' experiences emerged from the analysis: "This child is my whole world"-Total devotion; "I Can Do Both"-Actualizing personal and familial goals as well as caregiving issues; "It's a mission, it's a calling, it's a full-time job"-Self-actualization through caregiving; and "Disability will not stop me"-Emphasizing self-actualization. While prior studies have created a distinct separation between caregiving and self-actualization, the current study focuses on the complex dynamics of lifelong parental caregiving for a child with DD, illustrating the parents' ways of actualizing their life goals in the context of caregiving over the years.

"I Do Not Think She Will Understand, This is Not a Situation for a Girl Like Her:" Disenfranchised Grief Among Adults with Intellectual and Developmental Disabilities in the Ultra-orthodox Jewish Society.

This article examines the experience of aging ultra-Orthodox families alongside a person with intellectual and developmental disabilities (IDD) in relation to parents' illness and death, followed by grief. In-depth interviews were conducted with 14 family units. Each family unit included the person with IDD, a parent, and a sibling-a total of 43 participants. Three main themes emerged: A. The difficulty in confronting illness and dying of parents alongside a family member with IDD in an Ultra-Orthodox Context. B. Exclusion of the person with IDD from parents' memorial events. C. Religious ceremonies as a strategy for coping with mourning among persons with IDD. The discussion focuses on the concept of disenfranchised grief in a religious context and its impact on the family support system. Culturally sensitive therapeutic recommendations are made for professionals working with older ultra-Orthodox Jewish families alongside a person with IDD in the context of the subject.

Isomerization of hydrogen cyanide and hydrogen isocyanide in a cluster environment: quantum chemical study.

Hydrogen cyanide (HCN) and its isomer hydrogen isocyanide (HNC) are omnipresent in the interstellar medium (ISM). The ratio between the two isomers serves as an indicator of the physical conditions in different areas of the ISM. As such, the isomerization process between the two isomers has been extensively studied on the neutral potential energy surface. Moreover, HCN and HNC are thought to be precursors of important organic molecules, such as adenine. Here, we use quantum chemistry calculations and ab initio molecular dynamics simulations to focus on the chemistry that occurs upon ionization of pure HNC clusters. We demonstrate that upon ionization of HNC clusters, a distonic ion CN⋯HCNH+ is formed, and this formation is accompanied by HNC-to-HCN isomerization. Moreover, we show that the cluster environment and the network of hydrogen bonds are crucial for the isomerization process to occur and for the stabilization of the clusters. We demonstrate that, in contrast to HNC clusters, isomerization of ionized HCN clusters can occur only for the larger clusters. In addition, we discuss the formation of aminonitrile cation in the clusters and propose a barrierless route for diaminonitrile, a known precursor of amino acids and nucleobases, to form.

Molecular dynamics reveals formation path of benzonitrile and other molecules in conditions relevant to the interstellar medium.

Polycyclic aromatic hydrocarbons and polycyclic aromatic nitrogen heterocycles are believed to be widespread in different areas of the interstellar medium. However, the astronomical detection of specific aromatic molecules is extremely challenging. As a result, only a few aromatic molecules have been identified, and very little is known about how they are formed in different areas of the interstellar medium. Recently, McGuire et al. [Science 359, 202-205 (2018)] detected the simple aromatic molecule benzonitrile in Taurus Molecular Cloud-1. Although benzonitrile has been observed, the molecular mechanism for its formation is still unknown. In this study, we use quantum chemistry and ab initio molecular dynamics to model ionization processes of van der Waals clusters containing cyanoacetylene and acetylene molecules. We demonstrate computationally that the clusters' ionization leads to molecular formation. For pure cyanoacetylene clusters, we observe bond formation among two and three monomer units, whereas in mixed clusters, bond formation can also occur in up to four units. We show that the large amount of energy available to the system after ionization can lead to barrier crossing and the formation of complex molecules. Our study reveals the rich chemistry that is observed upon ionization of the clusters, with a wide variety of molecules being formed. Benzonitrile is among the observed molecules, and we study the potential energy path for its formation. These results also offer insights that can guide astronomers in their search for aromatic molecules in the interstellar medium.

Stereoselective Diels-Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers.

Although gem-diborylalkenes are known to be among the most valuable reagents in modern organic synthesis, providing a rapid access to a wide array of transformations, including the construction of C-C and C-heteroatom bonds, their use as dienophile-reactive groups has been rare. Herein we report the Diels-Alder (DA) reaction of (unsymmetrical) gem-diborylalkenes. These reactions provide a general and efficient method for the stereoselective conversion of gem-diborylalkenes to rapidly access 1,1-bisborylcyclohexenes. Using the same DA reaction manifold with borylated-dienes and gem-diborylalkenes, we also developed a concise, highly regioselective synthesis of 1,1,2-tris- and 1,1,3,4-tetrakis(boronates)cyclohexenes, a family of compounds that currently lack efficient synthetic access. Furthermore, DFT calculations provided insight into the underlying factors that control the chemo-, regio-, and stereoselectivity of these DA reactions. This method also provides stereodivergent syntheses of gem-diborylnorbornenes. The utility of the gem-diborylnorbornene building blocks was demonstrated by ring-opening metathesis polymerization (ROMP), providing a highly modular approach to the first synthesis of the gem-diboron-based polymers. Additionally, these polymers have been successfully submitted to postpolymerization modification reactions. Given its simplicity and versatility, we believe that this novel DA and ROMP approach holds great promise for organoboron synthesis as well as organoboron-based polymers and that it will result in more novel transformations in both academic and industrial research.

Factors affecting the will to live among elderly jews living in israel.

Objectives: The aim of this qualitative study was to explore factors that influence older persons' will to live (WTL).Methods: Twenty-five Israeli elders were interviewed about what weakens and/or strengthens their WTL. Elements of the grounded theory method guided the data collection and analysis.Results: Our analysis revealed that the elements that pertain to WTL could potentially both increase and decrease the WTL in elders. These factors included social networks, financial security, religious faith, working and volunteering, and honor versus ageism.Conclusions: Five factors represent different aspects of older persons' lives that influence the WTL. The first four themes including Social Networks, Religious Faith, Honor versus Ageism, and Working and Volunteering are consistent with the findings of the study of Blue Zones. Blue Zones are areas characterized by high life expectancy. Israel shares cultural characteristics with the Blue Zones, being a society with traditional collective characteristics stemming from the Jewish tradition. The last theme of financial security is related to the characteristics of Israel as a society in which the social gaps are large and many elderly are pushed to the social margins, and lack financial security. This study points to the unique cultural characteristics of Israel that affect the WTL among elderly Jews and proposes a hypothesis linking Israeli culture to the high life expectancy in Israel.

Influences of Nationalism and Historical Traumatic Events on the Will-to-Live of Elderly Israelis.

PURPOSE OF THE STUDY: Existing research suggests that will-to-live (WTL) is an indicator of subjective well-being (SWB), and that similar personal variables including physical and mental health, quality-of-life, and sociodemographic characteristics influence elderly people's WTL. The purpose of this qualitative study was to explore additional factors which influence older persons' WTL. DESIGN AND METHODS: Twenty-five elderly Israelis across the country were interviewed about what weakens and strengthens their WTL. The grounded theory method guided the data collection and analysis. RESULTS: In addition to the previously reported aspects influencing WTL, analysis resulted in two new categories: nationalism and historical traumatic events. Negative influences of nationalism-related emotions on participants' WTL included themes of disappointment with the state, with children leaving the state, and with existential insecurity. Among the positive influences on WTL, participants mentioned pride in the state and in its development, personal security, and hope for a peaceful future. Under the category of historical traumatic events, participants reported posttraumatic stress and war anxieties, as well as satisfaction and revenge in continued existence, and appreciation for life in Israel compared with life before immigrating to Israel. IMPLICATIONS: Our findings indicate that nationalism and feelings of personal involvement in national developments play an important role in the lives of elderly Israelis to the degree that they contribute to their SWB and motivation to continue living. Practitioners and family members can intentionally arouse and strengthen positive nationalistic feelings in the elderly as a way to maintain and promote SWB and WTL.