Conformational Landscapes and Energetics of Carbon Nanohoops and their Ring-in-Ring Complexes.

Carbon nanohoops are promising precursors for the synthesis of nanotubes, whose structural dynamics are not well understood. Here, we investigate the conformational landscape and energetics of cycloparaphenylenes (CPPs), a methylene-bridged CPP and a carbon nanobelt. These nanohoops can form host-guest complexes with other rings, and understanding their structure is crucial for predicting their properties and identifying potential applications. We used a combination of ion mobility, tandem mass spectrometry, and density functional theory to characterize the nanohoops and their ring-in-ring complexes, following the energetics and conformations of their disassembly from intact complexes to fragment ions. Our results show structural integrity of the nanohoops and host-guest complexes. They also reveal interesting trends in size, packing density, stability, and structure between [6]CPP, the methylene-bridged CPP, and the carbon nanobelt as guests in ring-in-ring complexes. Taken together, our work illustrates how mass spectrometry data can help to unravel the rules that govern the formation of carbon nanohoop assemblies.

Experimental and Theoretical Structure Elucidation of the [2 : 1] Complex Ion of Carbo[n]helicene with n=6, 7 and 8 and Ag.

The front cover artwork illustrates the competition of [6]-, [7]- and [8]helicene for attaining a silver(I) cation. This struggle takes place in the electrospray process during solvent evaporation, leading to the well-known tweezer-like surrounding of Ag+ by the helicene in the [1:1] complex. In this competition, the larger helicenes outperform the smaller ones. The main topic of our investigation, however, is the resulting [2:1] complex in which a second helicene attaches via π-π stacking to the [1:1] tweezer complex. Read the full text of the Research Article at 10.1002/cphc.202300496.

New Insights into Ring-In-Ring Complexes of [n]Cycloparaphenylenes including the [12]Carbon Nanobelt.

The supramolecular chemistry of cycloparaphenylenes (CPPs) is characterized by the ability of the ring system to undergo both concave and convex π-π interactions. As a consequence, ring-in-ring complexes can be formed in which the CPP serves as the host as well as the guest molecule ([n + x]CPP⊃[n]CPP). In this work, host-guest ring-in-ring complexes of [n]CPPs (n = 5-12) are investigated by means of electrospray ionization-tandem mass spectrometry (ESI-MS2) and laser desorption ionization mass spectrometry (LDI-MS). Extending the experimentally known complexes with ring size differences of five and six phenyl units (x = 5 and 6), we observe complexes with ring size differences of three up to seven phenyl units (x = 3-7). Energy-resolved collision experiments reveal that the charge is mainly located at the inner ring and complexes with phenyl unit differences of five and six are the most stable. In complexes featuring the same size difference, the complex stabilities slightly increase with an increasing size of the involved [n]CPPs. Utilizing the π-extended [12]carbon nanobelt ([12]CNB) as the guest also revealed an increase in complex stability. This study paves the way for a deeper understanding of the host-guest chemistry of CPPs.

Experimental and Theoretical Structure Elucidation of the [2 : 1] Complex Ion of Carbo[n]helicene with n=6, 7 and 8 and Ag.

Gas-phase complexes of [n]helicenes with n=6, 7 and 8 and the silver(I) cation are generated utilizing electrospray ionization mass spectrometry (ESI-MS). Besides the well-established [1 : 1] helicene/Ag+ -complex in which the helicene provides a tweezer-like surrounding for the Ag+ , there is also a [2 : 1] complex formed. Density functional theory (DFT) calculations in conjunction with energy-resolved collision-induced dissociation (ER-CID) experiments reveal that the second helicene attaches via π-π stacking to the first helicene, which is part of the pre-formed [1 : 1] tweezer complex with Ag+ . For polycyclic aromatic hydrocarbons (PAHs) of planar structure, the [2 : 1] complex with silver(I) is typically structured as an Ag+ -bound dimer in which the Ag+ would bind to both PAHs as the central metal ion (PAH-Ag+ -PAH). For helicenes, the Ag+ -bound dimer is of similar thermochemical stability as the π-π stacked dimer, however, it is kinetically inaccessible. Coronene (Cor) is investigated in comparison to the helicenes as an essentially planar PAH. In analogy to the π-π stacked dimer of the helicenes, the Cor-Ag+ -Cor-Cor complex is also observed. Competition experiments using [n]helicene mixtures reveal that the tweezer complexes of Ag+ are preferably formed with the larger helicenes, with n=6 being entirely ignored as the host for Ag+ in the presence of n=7 or 8.

Two Rings Around One Ball: Stability and Charge Localization of [1 : 1] and [2 : 1] Complex Ions of [10]CPP and C60/70 [ *].

We investigate the gas-phase chemistry of noncovalent complexes of [10]cycloparaphenylene ([10]CPP) with C60 and C70 by means of atmospheric pressure photoionization and electrospray ionization mass spectrometry. The literature-known [1 : 1] complexes, namely [10]CPP⊃C60 and [10]CPP⊃C70 , are observed as radical cations and anions. Their stability and charge distribution are studied using energy-resolved collision-induced dissociation (ER-CID). These measurements reveal that complexes with a C70 core exhibit a greater stability and, on the other hand, that the radical cations are more stable than the respective radical anions. Regarding the charge distribution, in anionic complexes charges are exclusively located on C60 or C70 , while the charges reside on [10]CPP in the case of cationic complexes. [2 : 1] complexes of the ([10]CPP2 ⊃C60/70 )+ ⋅/- ⋅ type are observed for the first time as isolated solitary gas-phase species. Here, C60 -based [2 : 1] complexes are less stable than the respective C70 analogues. By virtue of the high stability of cationic [1 : 1] complexes, [2 : 1] complexes show a strongly reduced stability of the radical cations. DFT analyses of the minimum geometries as well as molecular dynamics calculations support the experimental data. Furthermore, our novel gas-phase [2 : 1] complexes are also found in 1,2-dichlorobenzene. Insights into the thermodynamic parameters of the binding process as well as the species distribution are derived from isothermal titration calorimetry (ITC) measurements.

Adjusting the energy of interfacial states in organic photovoltaics for maximum efficiency.

A critical bottleneck for improving the performance of organic solar cells (OSC) is minimising non-radiative losses in the interfacial charge-transfer (CT) state via the formation of hybrid energetic states. This requires small energetic offsets often detrimental for high external quantum efficiency (EQE). Here, we obtain OSC with both non-radiative voltage losses (0.24 V) and photocurrent losses (EQE > 80%) simultaneously minimised. The interfacial CT states separate into free carriers with ≈40-ps time constant. We combine device and spectroscopic data to model the thermodynamics of charge separation and extraction, revealing that the relatively high performance of the devices arises from an optimal adjustment of the CT state energy, which determines how the available overall driving force is efficiently used to maximize both exciton splitting and charge separation. The model proposed is universal for donor:acceptor (D:A) with low driving forces and predicts which D:A will benefit from a morphology optimization for highly efficient OSC.

Investigation of Cycloparaphenylenes (CPPs) and their Noncovalent Ring-in-Ring and Fullerene-in-Ring Complexes by (Matrix-Assisted) Laser Desorption/Ionization and Density Functional Theory.

[n]Cycloparaphenylenes ([n]CPPs) with n=5, 8, 10 and 12 and their noncovalent ring-in-ring and [m]fullerene-in-ring complexes with m=60, 70 and 84 have been studied by direct and matrix-assisted laser desorption ionization ((MA)LDI) and density-functional theory (DFT). LDI is introduced as a straightforward approach for the sensitive analysis of CPPs, free from unwanted decomposition and without the need of a matrix. The ring-in-ring system of [[10]CPP⊃[5]CPP]+. was studied in positive-ion MALDI. Fragmentation and DFT indicate that the positive charge is exclusively located on the inner ring, while in [[10]CPP⊃C60 ]+. it is located solely on the outer nanohoop. Positive-ion MALDI is introduced as a new sensitive method for analysis of CPP⊃fullerene complexes, enabling the detection of novel complexes [[12]CPP⊃C60, 70 and 84 ]+. and [[10]CPP⊃C84 ]+. . Selective binding can be observed when mixing one fullerene with two CPPs or vice versa, reflecting ideal size requirements for efficient complex formation. Geometries, binding and fragmentation energies of CPP⊃fullerene complexes from DFT calculations explain the observed fragmentation behavior.

[Raising awareness about depression together with service users and relatives - results of workshops for police officers in Lower Austria]. / "Ein ordentlicher Polizist erschießt sich, bevor er sich aufhängt!" (Oberst Peter M., Bezirkspolizeikommandant in Y.): Ergebnisse von Schulungsveranstaltungen für Polizeibeamte in Niederösterreich.

OBJECTIVE: Within the European Alliance Against Depression (EAAD), community mental health services inform in their service region in Lower Austria (pop. 1.600.000) about symptoms of depression, about treatment options and service characteristics. Social distance can be overcome preferably by public mental health projects involving users and relatives. Therefore, community mental health services in Lower Austria routinely inform the public about depression, treatment options and services together with service users and relatives. This paper presents an evaluation of workshops for police officers. METHODS: During the year 2010, 38 workshops for the police were conducted. All officers were asked to fill in the Gotland Scale of Male Depression, and to rate social distance and stereotypes regarding a case vignette of a fictitious depressive person. One week after the workshop, social distance and stereotypes were again rated. RESULTS: 852 police officers took part in the workshops, 703 were screened by the Gotland Scale of Male Depression. 9 % showed depressive symptoms. The officers were content with the workshops, they felt better informed afterwards and thought they could better help affected persons. The interpretation of the case vignette was more often "mentally ill" or "insane". CONCLUSIONS: Personal experience with depression was more strongly related to present depressive symptoms than age or years on duty. Personal contact with a person that had been affected by depression before, and the slogan "depression can affect anybody" may have increased feelings of anxiety in officers that had taken part in the workshops.

[Psychiatry@home--establishing contact to a community mental health service via www]. / "Verlorene Seele an Psychiatrie"--Fallbeispiel einer Online-Behandlungsvorbereitung.

BACKGROUND: Psychiatric services increasingly use internet technologies to enhance and support usual therapies, which are based on direct personal contact. METHODS: An anonymous e-mail-request of a young girl obviously requiring psychiatric support and treatment is illustrated, characterized by the intention of the service to establish personal contact. CONCLUSIONS: Chances and limitations of psychiatric interventions using the internet are discussed.

[Quality assurance of take-over from in-patient to out-patient care: experiences in Lower Austria]. / Zum Schnittstellenmanagement zwischen einem psychiatrischen Krankenhaus und einem gemeindepsychiatrischem Dienst.

OBJECTIVE: Community mental health teams (CMHT) provide support for severely disabled, chronic mentally ill patients. In this study, referrals to CMHT by a psychiatric hospital in Lower Austria were analysed, as were the first few weeks of care for referred patients. METHODS: Referrals to CMHT of a catchment area (pop 250.000) were analysed for 2002- 2006. RESULTS: In the first 6 months of each year, 124 to 189 patients were referred to CMHT. Between 2002 and 2006, the percentage of affective disorders (ICD-10: F3: 40.0 %), and substance use disorders (F1: 38.9 %) within the referrals diminished, as compared to patients suffering from schizophrenia (F2 initially 25.4 % of referrals vs. 49.7 %) and personality disorders (F6 initially 6.4 % of referrals vs. 22.4 %). In 30.7 % vs. 56.6 % of patients, CMHT workers managed to establish contact to patients after discharge from hospital. They actively sought contact with 39.9 to 74.6 % of referred patients (by means of telephone calls, letters, home visits, etc.). In 26.5 to 46.9 % of the referrals, continuous care was planned. CONCLUSIONS: This study emphasizes the advantage of specific referrals to CMHT, if care for severely disabled individuals is needed and should be provided. Furthermore, a description of outreach activities, which are intended to maintain contact with patients characterized by poor compliance, is presented. These activities are not yet part of routine care in German speaking countries.

[At home in a home? Did de-hospitalisation mean de-institutionalisation?]. / Da-Heim im Heim!? Bedeutete Ent-Hospitalisierung auch Ent-Institutionalisierung?

OBJECTIVES: In the last decades, long-time patients were systematically discharged from psychiatric hospitals in order to integrate this disadvantaged population into the community. This procedures where adequately evaluated and are regarded to be completed in the western world today. However, few evidence has been presented regarding the further course of integration following discharge from mental hospitals: was integration into community really successful or were patients permanently placed in sheltered housing staffed 24 hours 7 days a week. This review focuses on the question whether papers describing large de-institutionalisation projects mention the level of institutional support in the years following discharge from hospital. Furthermore we tried to find out which parameters are dealt with when describing successful community integration. METHODS: "Pubmed" was searched for studies on de-institutionalisation projects published between 1997 and 2007. RESULTS: The discharge from the mental hospital wards was in all studies described as successful, positive effects like an increased quality of life were found. However, studies describing the years following discharge mentioned that patients continuously stayed in sheltered housing with care offered 24 hours a day. CONCLUSION: Reviewing the available data about the level of support regarding accommodation of former long time patients, the danger of "trans-institutionalisation" has to be pointed out. Evidence is lacking concerning support models tailored to the individual needs of the patients. Similarly, possible side effects of long-term stays in sheltered housing staffed 24 hours a day have not yet been established. Therefore, we see a need for further evaluation of different models of supported housing for former long-term hospitalised patients, as well as for new chronic mentally ill patients.

[Health habits of patients with schizophrenia: a general pattern?]. / Das Gesundheitsverhalten schizophrener erkrankter Patienten: ein typisches Verhaltensmuster?

OBJECTIVE: Schizophrenia patients have in many aspects an unhealthier lifestyle than the general population. The aim of this study is to determine if disadvantageous health habits of schizophrenia patients present a general pattern that repeats itself in other regions and if psychosocial consequences of schizophrenia (singleness, unemployment) influence patients' health habits. METHODS: 95 schizophrenia outpatients from Germany and 97 from Austria were examined regarding eating-, drinking-, smoking- and physical-activity habits. Differences in health habits and the influence of psychosocial parameters were examined with regression analyses. RESULTS: Health habits of schizophrenia patients in Germany and Austria were very similar. Subjects from Austria lived unhealthier only regarding cigarette consumption and grocery choices, while they had a healthier lifestyle regarding physical activity on the weekend. Singleness had no influence on health habits, unemployment was connected with less physical activity on workdays. CONCLUSIONS: Health habits of schizophrenia patients seem to have a general pattern, but psychosocial consequences of schizophrenia explain little about the patients' health habits.

Gender aspects of parents' needs of schizophrenia patients.

BACKGROUND: Most studies about the problems and needs of schizophrenia carers included only one care-giving relative, usually the patients' mothers. METHODS: 101 mothers and fathers of the same patients suffering from schizophrenia were included into this study. Their needs were assessed by means of the "Carers' Needs Assessment for Schizophrenia". RESULTS: Mothers reported significantly more often problems than fathers concerning stress due to earlier life events and burn-out. Mothers needed interventions such as individual psychoeducation or family counselling more than twice as often as fathers. Overall, mothers reported higher numbers of problems and needs for intervention than fathers. The number of mothers' problems was predicted by not living with a partner and by a shorter duration of the patients' illness. The number of mothers' needs was predicted by more psychiatric symptoms, not living with a partner and a shorter duration of the patients' illness. Among fathers we could not identify any predictors, neither for the number of problems nor for the number of needs. CONCLUSIONS: Fathers and mothers often report problems and frequently need professional support. Overall, mothers exhibited more problems and needs for interventions than fathers. The differences between mothers and fathers indicate the importance of considering the carer's gender in clinical work.

[Vocational rehabilitation for mentally ill persons--an overview of predictors for successful integration]. / Arbeitsrehabilitation psychisch kranker Menschen--ein Uberblick über Erfolgsprädiktoren.

OBJECTIVES: Unemployment has a strong negative impact on quality of life and on the further course of the disease of mentally disordered individuals. Therefore, vocational rehabilitation programmes are necessary to help people with mental disorders to obtain work. There is increasing scientific evidence concerning positive predictors for vocational integration. This paper intends to give an overview about established predictors for successful integration. METHODS: "Pubmed" was searched for studies on psychiatric vocational rehabilitation programmes published between 1997 and 2007, which had the focus on predictors of successful outcome. RESULTS: Some of the most important predictors are a better history of work integration and better work performance measured during psychiatric vocational rehabilitation. Successful vocational integration is harder if negative symptoms or cognitive deficits are present. The impact of sociodemographic factors, diagnosis, motivation to work and social skills is discussed controversially. CONCLUSION: Future research should be directed to design vocational rehabilitation programmes, which address the specific needs of psychiatric patients.

[VISCI--Viennese Instrument for Suicidality in Correctional Institutions]. / Das Wiener Instrument für Suizidgefahr in Haft.

OBJECTIVE: The assessment and estimation of suicidal risk constitutes a serious and difficult task for any mental health professional. If we add to this the challenges that may be presented by a specific population at higher risk with little possibilities for thorough psychiatric evaluation, the task appears even more complicated. METHOD: The "Viennese Instrument for Suicidality in Correctional Institutions" ("VISCI") presented here is based on the results of a case control study including all suicides in all Austrian jails and prisons between 1975 and 1999 and on research on literature examining suicide prevention in general and prison population in particular. RESULTS: Sensitivity and specificity of VISCI are presented. CONCLUSIONS: As suicide rates in custody are higher than in the general population, and these rates have been increasing within the last 20 years, the screening of offenders newly admitted to prison for their propensity to suicide is necessary to give a better estimation of the suicide risk and hopefully to stop further increase of suicide rates in jails and prisons.

[The "Gretchen question" for psychiatry--the importance of religion and spirituality in psychiatric treatment]. / Die "Gretchenfrage" für die Psychiatrie. Der Stellenwert von Religion und Spiritualität in der Behandlung psychisch Kranker.

OBJECTIVE: The subject of religion and spirituality has attracted little attention in psychiatric research so far. The aim of the study was to give an overview of the attitudes of patients as well as psychiatrists towards regarding the importance of religion and spirituality in the treatment of mental illness. Furthermore we tried to give a description of established ideas involving both dimensions into the treatment of psychiatric patients. METHODS: We performed a search for relevant literature using the electronic databases Medline, PubMed, Psyndex and Embase. In addition we used the internet search engines Scopus and Google Scholar. RESULTS: Patients mention religion twice as often as an important factor in their lives as compared to psychiatrists. Consecutively, particular emphasis should be paid to the integration of both dimensions into clinical treatment. Additionally, the education of mental health professionals, consultation and the enrollment of religious or spiritual needs of patients when taking their medical history are essential factors. Religious coping and positive and negative components in matters of mental health are highlighted. CONCLUSIONS: More attention should be paid to the "religiosity gap" between patients and their psychiatrists. The entirety of a human being includes a physical, emotional, social as well as a spiritual dimension. Mental health professionals ignoring one of these aspects may delay recovery.

[How do community-based mental health staff in Austria perceive their job? -- a qualitative study]. / Wie erleben Professionelle der gemeindepsychiatrischen Versorgung in Osterreich ihre Tätigkeit? -- Eine inhaltsanalytische Studie.

OBJECTIVE: The aim of this study was to explore, using a simple qualitative design, how community mental health staff in Austria perceive their job. METHOD: 195 community-based mental health professionals answered seven open questions on how they perceive their job. The main areas covered were the most important tasks of the job, skills necessary to perform these tasks, as well as positive and negative aspects of the job. Answers were subjected to thematic content analysis. RESULTS: For most professionals, contact with clients and team colleagues were the major rewards of the job. Aspects experienced as stressful were the clients' illness, role ambiguity, team conflicts and lack of time. Necessary skills many respondents did not feel competent in were specialised knowledge and psychosocial skills. CONCLUSIONS: It might be useful to revise existing forms of collaboration within multiprofessional teams. The responsibility for difficult patients may be shared by several members of the team, who should contribute their specific knowledge. Training should be tailored towards the needs of the different professional groups and focus on those skills that are required in community mental health care.

[Suicide behind bars -- an international review]. / Suizide hinter Gittern im internationalen Vergleich.

OBJECTIVE: International surveys found an increase of mentally disordered individuals in correctional institutions. As a consequence, suicides and suicide rates in jails and prisons are increasing. Mental health services and criminal justice authorities have identified this problem, but there is a lack of knowledge concerning risk factors for inmate suicides and practicable prevention. METHOD: A literature research was conducted through "medline" searching for studies addressing the problem of jail and/or prison suicide. Subsequently, results of relevant surveys were compared and depicted in several tables. RESULTS: Suicide rates in correctional facilities significantly exceed those in the general male population. Suicide rates in custody have been increasing within the last decades. Pre-trial prisoners have the highest suicide risk within the total prison population. Long-term sentences, single-cell use, mental illness, substance abuse and a history of suicidality are associated with an increased suicide risk. DISCUSSION: The impact of suicide prevention strategies and future directions of research in this high-risk setting are highlighted.

[Job satisfaction and burnout in professionals in austrian mental health services]. / Jobzufriedenheit und Burn-out bei Professionellen der gemeindepsychiatrischen Versorgung in Osterreich.

OBJECTIVE: The aim of this study was to explore job satisfaction, professional role and burnout among community mental health staff in Austria. METHODS: The Minnesota Job Satisfaction Questionnaire, the GHQ-12, the Maslach Burnout Inventory and a questionnaire exploring staff's professional role and team identity were administered to 195 community-based mental health professionals in two Austrian regions. Staff's job perception was assessed in open questions. Predictors of burnout scores were identified in multivariate analyses. RESULTS: While the mental health professionals had elevated scores on the GHQ-12, their levels on the three burnout subscales were low. Social workers and psychologists showed the lowest job satisfaction, social workers also had low role identity scores. Being in the current job for a short time and disposing of psychosocial skills were predictors of high job satisfaction. High burnout scores were predicted by the lack of basic psychosocial competence and a lack of general knowledge in mental health care. The effect of caseload on psychological well-being was positive as well as negative. CONCLUSIONS: Even if the mental health professionals in our study show high levels of general stress, they seem to have less emotional problems resulting from extensively dealing with troubled individuals. Improving basic psychosocial competence and general expertise in mental health care might have a protective effect against developing a burnout syndrome.