Excitonic splittings in molecular dimers: why static ab initio calculations cannot match them

After decades of research on molecular excitons, only few molecular dimers are available on which exciton and vibronic coupling theories can be rigorously tested. In centrosymmetric H-bonded dimers consisting of identical (hetero)aromatic chromophores, the monomer electronic transition dipole moment vectors subtract or add, yielding S0 → S1 and S0 → S2 transitions that are symmetry-forbidden or -allowed, respectively. Symmetry breaking by 12C/13C or H/D isotopic substitution renders the forbidden transition weakly allowed. The excitonic coupling (Davydov splitting) can then be measured between the S0 → S1 and S0 → S2 vibrationless bands. We discuss the mass-specific excitonic spectra of five H-bonded dimers that are supersonically cooled to a few K and investigated using two-color resonant two-photon ionization spectroscopy. The excitonic splittings Δcalc predicted by ab initio methods are 5–25 times larger than the experimental excitonic splittings Δexp. The purely electronic ab initio splittings need to be reduced (“quenched”), reflecting the coupling of the electronic transition to the optically active vibrations of the monomers. The so-called quenching factors Γ < 1 can be determined from experiment (Γexp) and/or calculation (Γcalc). The vibronically quenched splittings Γ·Δcalc are found to nicely reproduce the experimental exciton splittings.

The role of vulnerability factors in individuals with an at-risk mental state of psychosis

Background Several indicators of heightened vulnerability to psychosis and relevant stressors have been identified. However, it has rarely been studied prospectively to what extent these vulnerability factors are in fact more frequently present in individuals with an at-risk mental state for psychosis. Moreover, it remains unknown whether any of these contribute to the prediction of psychosis onset in at-risk mental state individuals. Methods There were 28 healthy controls, 86 first-episode psychosis patients and 127 at-risk mental state individuals recruited within the Basel “Früherkennung von Psychosen” project. Relative frequencies of selected vulnerability factors for psychosis were compared between healthy controls, psychosis patients, those at-risk mental state individuals with subsequent psychosis onset (n = 31) and those without subsequent psychosis onset (n = 55). Survival analyses were applied to determine associations between time to transition to psychosis and vulnerability factors in all 127 at-risk mental state individuals. Results The vulnerability factors/indicators such as “difficulties during school education or vocational training”, “difficulties during employment”, “being single”, “difficulties with intimate relationships” and “being burdened with specific stressful situations” were more commonly found in the at-risk mental state and first-episode psychosis group than in healthy controls. Conclusions At-risk mental state and first-episode psychosis individuals more frequently present with vulnerability factors. Individual vulnerability factors appear, however, not to be predictive for an onset of psychosis.

Matching Social and Ecological Systems in Complex Ocean Fisheries

This paper considers ocean fisheries as complex adaptive systems and addresses the question of how human institutions might be best matched to their structure and function. Ocean ecosystems operate at multiple scales, but the management of fisheries tends to be aimed at a single species considered at a single broad scale. The paper argues that this mismatch of ecological and management scale makes it difficult to address the fine-scale aspects of ocean ecosystems, and leads to fishing rights and strategies that tend to erode the underlying structure of populations and the system itself. A successful transition to ecosystem-based management will require institutions better able to economize on the acquisition of feedback about the impact of human activities. This is likely to be achieved by multiscale institutions whose organization mirrors the spatial organization of the ecosystem and whose communications occur through a polycentric network. Better feedback will allow the exploration of fine-scale science and the employment of fine-scale fishing restraints, better adapted to the behavior of fish and habitat. The scale and scope of individual fishing rights also needs to be congruent with the spatial structure of the ecosystem. Place-based rights can be expected to create a longer private planning horizon as well as stronger incentives for the private and public acquisition of system relevant knowledge.

The Nurturing of Seagliders By the National Oceanographic Partnership Program

The National Oceanographic Partnership Program provided critical support to the development of Seaglider long-range autonomous underwater vehicles. This support enabled: (1) development and integration of chemical and biological sensors, (2) transition to low-power, bi-directional satellite communication, and (3) software upgrades to enhance capability and reliability. Sponsored improvements led to setting the mission endurance and range records for autonomous underwater vehicles, wide use by the oceanographic community and licensing for commercialization.

The International Financial Reporting Standards and Their Implementation into the US Accounting System

This paper examines the differences between the International Financial Reporting Standards (IFRS) and Generally Accepted Accounting Principles (GAAP). The areas closely examined are the differences inrevenue recognition and reporting of intangibles. By investigating the differences in the two sets of standards I put into context the changes that would be necessary for domestic companies adopting the IFRS. The differences between these two standards are important because the implementation of IFRS into the U.S. is a current issue for domestic companies. It is important to note how the new standards will affect different companies in different ways. Depending on the size and industry, some companies will have a harder time transitioning to the new standards. However, once these companies make the transition to IFRS they will have better recognition and reporting of revenues and intangibles.

Labeling in the Classroom: Teacher Expectations and their Effects on Students' Academic Potential

The transition to high school can be challenging for some adolescents, resulting in drops of academic functioning (Barber & Olsen, 2004; Smith, 2006). While changes in academic demands and the disparity between adolescent needs and the environmental characteristics of high school have both been cited as possible contributors to this decrease in academic and personal functioning (Barber & Olsen, 2004), it is possible that teachers may play an even larger role in undermining these students’ functioning, specifically through labeling. Although labeling, and how it can lead to self-fulfilling prophesies, is a concept that has been thoroughly researched and applied to the field of criminology and deviant behavior, it is the goal of this current study to investigate if labeling also occurs in the classroom setting and how such labels ultimately effect the academic potential of high school students.

Improving the health and well-being of women at risk for neural tube defect recurrence

There is growing interest in providing women with internatal care, a package of healthcare and ancillary services that can improve their health during the period after the termination of one pregnancy but before the conception of the next pregnancy. Women who have had a pregnancy affected by a neural tube defect can especially benefit from internatal care because they are at increased risk for recurrence and improvements to their health during the inter-pregnancy period can prevent future negative birth outcomes. The dissertation provides three papers that inform the content of internatal care for women at risk for recurrence by examining descriptive epidemiology to develop an accurate risk profile of the population, assessing whether women at risk for recurrence would benefit from a psychosocial intervention, and determining how to improve health promotion efforts targeting folic acid use.^ Paper one identifies information relevant for developing risk profiles and conducting risk assessments. A number of investigations have found that the risk for neural tube defects differs between non-Hispanic Whites and Hispanics. To understand the risk difference, the descriptive epidemiology of spina bifida and anencephaly was examined for Hispanics and non-Hispanic Whites based on data from the Texas Birth Defects Registry for the years 1999 through 2004. Crude and adjusted birth prevalence ratios and corresponding 95% confidence intervals were calculated between descriptive epidemiologic characteristics and anencephaly and spina bifida for non-Hispanic Whites and for Hispanics. In both race/ethnic groups, anencephaly expressed an inverse relationship with maternal age and a positive linear relationship with parity. Both relationships were stronger in non-Hispanic Whites. Female infants had a higher risk for anencephaly in non-Hispanic Whites. Lower maternal education was associated with increased risk for spina bifida in Hispanics.^ Paper two assesses the need for a psychosocial intervention. For mothers who have children with spina bifida, the transition to motherhood can be stressful. This qualitative study explored the process of becoming a mother to a child with spina bifida focusing particularly on stress and coping in the immediate postnatal environment. Semi-structured interviews were conducted with six mothers who have children with spina bifida. Mothers were asked about their initial emotional and problem-based coping efforts, the quality and kind of support provided by health providers, and the characteristics of their meaning-based coping efforts; questions matched Transactional Model of Stress and Coping (TMSC) constructs. Analysis of the responses revealed a number of modifiable stress and coping transactions, the most salient being: health providers are in a position to address beliefs about self-causality and prevent mothers from experiencing the repercussions that stem from maintaining these beliefs. ^ Paper three identifies considerations when creating health promotion materials targeting folic acid use. A brochure was designed using concepts from the Precaution Adoption Process Model (PAPM). Three focus groups comprising 26 mothers of children with spina bifida evaluated the brochure. One focus group was conducted in Spanish-only, the other two focus groups were conducted in English and Spanish combined. Qualitative analysis of coded transcripts revealed that a brochure is a helpful adjunct. Questions about folic acid support the inclusion of an insert with basic information. There may be a need to develop different educational material for Hispanics so the importance of folic acid is provided in a situational context. Some participants blamed themselves for their pregnancy outcome which may affect their receptivity to messages in the brochure. The women's desire for photographs that affect their perception of threat and their identification with the second role model indicate they belong to PAPM Stage 2 and 3. Participants preferred colorful envelopes, high quality paper, intimidating photographs, simple words, conversational style sentences, and positive messages.^ These papers develop the content of risk assessment, psychosocial intervention, and health promotion components of internatal care as they apply to women at risk for recurrence. The findings provided evidence for considering parity and maternal age when assessing nutritional risk. The two dissimilarities between the two race/ethnic groups, infant sex and maternal education lent support to creating separate risk profiles. Interviews with mothers of children with spina bifida revealed the existence of unmet needs-suggesting that a psychosocial intervention provided as part of internatal care can strengthen and support women's well-being. Segmenting the audience according to race/ethnicity and PAPM stage can improve the relevance of print materials promoting folic acid use.^

The role of workplace absence as an organizational mechanism in predicting employee alcohol and drug disorders

Background. EAP programs for airline pilots in companies with a well developed recovery management program are known to reduce pilot absenteeism following treatment. Given the costs and safety consequences to society, it is important to identify pilots who may be experiencing an AOD disorder to get them into treatment. ^ Hypotheses. This study investigated the predictive power of workplace absenteeism in identifying alcohol or drug disorders (AOD). The first hypothesis was that higher absenteeism in a 12-month period is associated with higher risk that an employee is experiencing AOD. The second hypothesis was that AOD treatment would reduce subsequent absence rates and the costs of replacing pilots on missed flights. ^ Methods. A case control design using eight years (time period) of monthly archival absence data (53,000 pay records) was conducted with a sample of (N = 76) employees having an AOD diagnosis (cases) matched 1:4 with (N = 304) non-diagnosed employees (controls) of the same profession and company (male commercial airline pilots). Cases and controls were matched on the variables age, rank and date of hire. Absence rate was defined as sick time hours used over the sum of the minimum guarantee pay hours annualized using the months the pilot worked for the year. Conditional logistic regression was used to determine if absence predicts employees experiencing an AOD disorder, starting 3 years prior to the cases receiving the AOD diagnosis. A repeated measures ANOVA, t tests and rate ratios (with 95% confidence intervals) were conducted to determine differences between cases and controls in absence usage for 3 years pre and 5 years post treatment. Mean replacement costs were calculated for sick leave usage 3 years pre and 5 years post treatment to estimate the cost of sick leave from the perspective of the company. ^ Results. Sick leave, as measured by absence rate, predicted the risk of being diagnosed with an AOD disorder (OR 1.10, 95% CI = 1.06, 1.15) during the 12 months prior to receiving the diagnosis. Mean absence rates for diagnosed employees increased over the three years before treatment, particularly in the year before treatment, whereas the controls’ did not (three years, x = 6.80 vs. 5.52; two years, x = 7.81 vs. 6.30, and one year, x = 11.00cases vs. 5.51controls. In the first year post treatment compared to the year prior to treatment, rate ratios indicated a significant (60%) post treatment reduction in absence rates (OR = 0.40, CI = 0.28, 0.57). Absence rates for cases remained lower than controls for the first three years after completion of treatment. Upon discharge from the FAA and company’s three year AOD monitoring program, case’s absence rates increased slightly during the fourth year (controls, x = 0.09, SD = 0.14, cases, x = 0.12, SD = 0.21). However, the following year, their mean absence rates were again below those of the controls (controls, x = 0.08, SD = 0.12, cases, x¯ = 0.06, SD = 0.07). Significant reductions in costs associated with replacing pilots calling in sick, were found to be 60% less, between the year of diagnosis for the cases and the first year after returning to work. A reduction in replacement costs continued over the next two years for the treated employees. ^ Conclusions. This research demonstrates the potential for workplace absences as an active organizational surveillance mechanism to assist managers and supervisors in identifying employees who may be experiencing or at risk of experiencing an alcohol/drug disorder. Currently, many workplaces use only performance problems and ignore the employee’s absence record. A referral to an EAP or alcohol/drug evaluation based on the employee’s absence/sick leave record as incorporated into company policy can provide another useful indicator that may also carry less stigma, thus reducing barriers to seeking help. This research also confirms two conclusions heretofore based only on cross-sectional studies: (1) higher absence rates are associated with employees experiencing an AOD disorder; (2) treatment is associated with lower costs for replacing absent pilots. Due to the uniqueness of the employee population studied (commercial airline pilots) and the organizational documentation of absence, the generalizability of this study to other professions and occupations should be considered limited. ^ Transition to Practice. The odds ratios for the relationship between absence rates and an AOD diagnosis are precise; the OR for year of diagnosis indicates the likelihood of being diagnosed increases 10% for every hour change in sick leave taken. In practice, however, a pilot uses approximately 20 hours of sick leave for one trip, because the replacement will have to be paid the guaranteed minimum of 20 hour. Thus, the rate based on hourly changes is precise but not practical. ^ To provide the organization with practical recommendations the yearly mean absence rates were used. A pilot flies on average, 90 hours a month, 1080 annually. Cases used almost twice the mean rate of sick time the year prior to diagnosis (T-1) compared to controls (cases, x = .11, controls, x = .06). Cases are expected to use on average 119 hours annually (total annual hours*mean annual absence rate), while controls will use 60 hours. The cases’ 60 hours could translate to 3 trips of 20 hours each. Management could use a standard of 80 hours or more of sick time claimed in a year as the threshold for unacceptable absence, a 25% increase over the controls (a cost to the company of approximately of $4000). At the 80-hour mark, the Chief Pilot would be able to call the pilot in for a routine check as to the nature of the pilot’s excessive absence. This management action would be based on a company standard, rather than a behavioral or performance issue. Using absence data in this fashion would make it an active surveillance mechanism. ^

Expression of p53, {\it * ras\/} and PCNA in human colonic neoplasms: Possible biomarkers of malignant potential

Colorectal cancer is a leading cause of cancer mortality and early detection can significantly improve the clinical outcome. Most colorectal cancers arise from benign neoplastic lesions recognized as adenomas. Only a small percentage of all adenomas will become malignant. Thus, there is a need to identify specific markers of malignant potential. Studies at the molecular level have demonstrated an accumulation of genetic alterations, some hereditary but for the most occurring in somatic cells. The most common are the activation of ras, an oncogene involved in signal transduction, and the inactivation of p53, a tumor suppressor gene implicated in cell cycle regulation. In this study, 38 carcinomas, 95 adenomas and 20 benign polyps were analyzed by immunohistochemistry for the abnormal expression of p53 and ras proteins. An index of cellular proliferation was also measured by labeling with PCNA. A general overexpression of p53 was immunodetected in 66% of the carcinomas, while 26% of adenomas displayed scattered individual positive cells or a focal high concentration of positive cells. This later was more associated with severe dysplasia. Ras protein was detected in 37% of carcinomas and 32% of adenomas mostly throughout the tissue. p53 immunodetection was more frequent in adenomas originating in colons with synchronous carcinomas, particularly in patients with familial adenomatous polyposis and it may be a useful marker in these cases. Difference in the frequency of p53 and ras alterationbs was related to the location of the neoplasm. Immunodetection of p53 protein was correlated to the presence of a mutation in p53 gene at exon 7 and 5 in 4/6 carcinomas studied and 2 villous adenomas. Thus, we characterized in adenomas the abnormal expression of two proteins encoded by the most commonly altered genes in colorectal cancer. p53 alteration appears to be more specifically associated with transition to malignancy than ras. By using immunohistochemistry, a technique that keeps the architecture of the tissue intact, it was possible to correlate these alterations to histopathological characteristics that were associated with higher risks for transformation: villous content, dysplasia and size of adenoma. ^

Geochemistry of Cenozoic sediments from the central Artic Ocean

Integrated Ocean Drilling Program (IODP) Expedition 302 (Arctic Coring Expedition, ACEX) recovered a unique sediment record from the central Arctic Ocean, revealing that this region underwent major environmental fluctuations since the Late Cretaceous. Major and trace element composition of 1,300 samples were determined using X-ray fluorescence (XRF). The results show significant compositional variability of the sediments with depth that can be attributed to changes in (a) provenance and pathways of detrital material, (b) paleoenvironmental conditions and depositional processes, and (c) diagenetic overprint of the primary record. In addition to existing lithological units, we introduce new geochemical units for a more process-related approach interpreting the ACEX record. In detail, via the geochemical signature of Siberian flood basalts we are able to reconstruct the discontinuous rifting and deepening of the central Lomonosov Ridge during the Paleogene, accompanied by changing current regimes and the onset of sea ice. Eocene biosiliceous sedimentation took place in a relatively shallow setting under predominantly anoxic bottom water conditions, causing a positive anoxia-productivity feedback, although water column stratification was repeatedly interrupted by ventilation events. Anoxic to sulfidic conditions were even more extreme after biosilica production ceased, and significant amounts of pyrite were deposited on the Lomonosov Ridge. Especially in organic matter-rich Paleogene deposits, diagenetic processes obscured the paleoenvironmental signals. Fundamental environmental changes occurred in the Middle Eocene, but geochemical and micropaleontological proxies point not to the identical sediment depth. After approximately 26 Ma of non-deposition or erosion, the Middle Miocene record shows the transition to dominantly oxic bottom water conditions, although suboxic diagenesis seemingly affected these deposits.

Mineralogy of sediments from the Exmouth Plateau and Argo Basin

Correlation of mineral associations from sediment recovered on the northwestern Australian continental margin document the juvenile-to-mature evolution of a segment of the Indian Ocean. Lower Cretaceous sediments contain sandy-to-silty radiolarian claystone that consists of highly smectitic mixed-layered illite/smectite (I/S) in addition to minor amounts of diagenetic pyrite, barite, and rhodochrosite. These immature, poorly sorted sediments were derived from nearby continental margin sources. Discrete bentonite layers and abundant smectite are the alteration products of volcanic material deposited during early basin formation. Abundant quartz-replaced radiolarian tests suggest high surface-water productivity, and calcareous fossils indicate water depths were above the calcite compensation depth (CCD) in the juvenile Indian Ocean. The increase in pelagic carbonate from the mid- to Late Cretaceous signals the transition to mature, open-ocean conditions. Similar to other slowly deposited contemporaneous deep-sea sediments, mid- to Upper Cretaceous sediments of the northwestern margin of Australia contain palygorskite. This palygorskite is associated with calcareous sediment across the ooze-to-chalk transition, detrital mixed-layered I/S, and zeolite minerals in places. This palygorskite occurs above the transformation from opal-A to opal-CT. The underlying opal-CT sediment contains abundant smectite and zeolite minerals. Calcareous sediment dominates the Cenozoic, except at abyssal sites that were not inundated by calcareous turbidites. Paleocene and Eocene sediments contain abundant smectite and zeolite minerals derived from the alteration of volcanic material. Palygorskite was found to be associated with sepiolite and dolomite in Miocene sediments from Site 765 in the Argo Basin. Pliocene and Quaternary sediments contain detrital kaolinite and mixed-layered I/S, abundant opal-A radiolarian tests, and minor amounts of pyrite

Geochemistry at DSDP Legs 36 and 71 Holes

For Middle Jurassic to Pleistocene times, clay mineralogical and geochemical data provide information on the evolution of continental and marine paleoenvironments. They are a source of information on marginal instability, on the continental and shallow marine environments related to the development of the Southern Ocean during the Middle and Late Jurassic, and on tectonic relaxation of the continental margins at the end of the Late Jurassic. They also provide evidence for the influences of the South Atlantic opening and the movement of the Falkland Plateau in a reduced marine environment until Aptian-Albian times, and the transition to an open marine environment during Albian time; the influences of the Albian-Turonian and Coniacian-Santonian Andean deformations in an open marine environment; the limited tectonic effects and strong influence of marine currents at the Cretaceous/Tertiary boundary; the influences of the global climatic cooling and inferred bottom water circulation during the late Eocene and Oligocene; the widening of the South Atlantic Ocean during Oligocene time, which was accompanied by an increased influence of the biogenic components on sedimentation; increased carbonate dissolution from late Oligocene to early Miocene, related to the deepening of the ocean; limited mineralogical and important geochemical modifications when the Drake Passage opened in the early Miocene; the influence of the late Miocene development of the Antarctic ice-sheet; the major Antarctic cooling and Patagonian glaciation during Pliocene time; and the change in the Antarctic Bottom Water circulation at the Pliocene/Pleistocene boundary.

(Table 1) Presence of sublittoral macroalgae in the investigated profiles in Potter Cove, King George Island, Antarctica

The vegetation of a small fjord and its adjacent open shore was documented by subaquatic video. The distribution of individual species of macroalgae and the composition of assemblages were compared with gradients of light availability, hydrography, slope inclination, substratum, and exposition to turbulence and ice. The sublittoral fringe is usually abraded by winterly ice floes and devoid of large, perennial algae. Below this zone, the upper sublittoral is dominated by Desmarestia menziesii on steep rock faces, where water movements become irregular, or by Ascoseira mirabilis and Palmaria decipiens on weakly inclined slopes with steady rolling water movements. In the central sublittoral above 15 m, where turbulence is still active, Desmarestia anceps is outcompeting all other species on solid substratum, However, the species is not able to persist on loose material under these conditions. Instead, Himantothallus grandifolius may occur. Deeper, where turbulence usually is negligible, Desmarestia anceps also covers loose material. The change of dominance to Himantothallus grandifolius in the deep sublittoral cannot completely be explained at present. Himantothallus grandifolius also prevails in a mixed assemblage under the influence of grounding icebergs. Most of the smaller algae are opportunists with different degrees of tolerance for turbulence, but some apparently need more stable microhabitats and thus are dependent from continuing suppression of competitive large phaeophytes.

Accumulation rates for western Dronning Maud Land from firn cores and snow pits

As a result of intensive field activities carried out by several nations over the past 15 years, a set of accumulation measurements for western Dronning Maud Land, Antarctica, was collected, based on firn-core drilling and snow-pit sampling. This new information was supplemented by earlier data taken from the literature, resulting in 111 accumulation values. Using Geographical Information Systems software, a first region-wide mean annual snow-accumulation field was derived. In order to define suitable interpolation criteria, the accumulation records were analyzed with respect to their spatial autocorrelation and statistical properties. The resulting accumulation pattern resembles well known characteristics such as a relatively wet coastal area with a sharp transition to the dry interior, but also reveals complex topographic effects. Furthermore, this work identifies new high-return shallow drilling sites by uncovering areas of insufficient sampling density.

Pigments at time series station DYNAPROC

Phytoplankton taxonomic pigments and primary production were measured at the JGOFS-France time-series station DYFAMED in the northwestern Mediterranean Sea during May 1995 to investigate changes in phytoplankton composition and the biogeochemical implications (DYNAPROC experiment). The study period covered the transitional situation from late spring bloom to pre-oligotrophic. The late spring bloom situation, occurring at the beginning of the study, revealed high chlorophyll a concentrations (maximum 3 mg/m**3 at 30 m) and high primary production (maximum 497 mg C/m**2/ 14 h). At the end of the experiment, the trophic regime shifted towards pre-oligotrophic and was characterized by lower chlorophyll a concentrations (<1 mg/m**3), although primary production still remained high (659 mg C/m**2/ 14 h). At termination of the spring bloom, the phytoplankton community was composed of chromophyte nanoflagellates (38±4%), diatoms (29±2%), cryptophytes (12±1%) and cyanobacteria (8±1%). During the transition to the pre-oligotrophic period, the contribution of small cells increased (e.g. cyanobacteria 18±2%, green flagellates 5±1%). Vertical profiles of pigments revealed a partition of the phytoplankton groups: cyanobacteria were most abundant in the surface layer, nanoflagellates containing 19'-HF+19'BF at the depth of chlorophyll maximum, whereas diatoms were located below the chlorophyll maximum. At termination of the spring bloom, a wind event induced vertical transport of nutrients into the euphotic layer. Phytoplankton groups responded differently to the event: initially, diatom concentrations increased (for 24 h) then rapidly decreased. In contrast, all others groups decreased just after the event. The long-term effect was a decrease of biomass of dominant groups (diatoms and chromophyte nanoflagellates), which accelerated the community succession and hence contributed to the oligotrophic transition.