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A family of ferrocenyl amino alcohols (14 examples) has been prepared from the corresponding planar chiral ketones and evaluated as a new class of chiral ligands for asymmetric ethyl‐ and phenylzinc additions to aldehydes. The highly enantioselective synthesis of these ligands is facile, scalable, robust and relies on the use of cheaply available starting materials. Asymmetric ethyl additions proceeded smoothly at ambient temperature, with reaction times as short as 1 hour furnishing the desired products in up to 90 % yield and 99 % ee. The corresponding phenyl additions afforded products in up to 81 % yield and 88 % ee. The observed stereochemical outcome for the addition of diethylzinc was rationalized and the key proposed transition state was supported by an analysis of the X‐ray structures of a series of amino alcohol ligands. [ABSTRACT FROM AUTHOR]

Diol scaffolds have been utilized as highly effective catalysts and ligands in a wide range of catalytic asymmetric transformations. For scaffolds to be successful as broadly used motifs, they should be prepared cheaply through facile routes and be easily handled. Herein, the synthesis of a family of planar chiral diols based on a modular and robust three‐step route is described, which yields catalytically active diols in >99 % de and >99 % ee, with up to seven different chiral elements. These diols have been characterized by X‐ray crystallographic analysis, which provides clear evidence for the likely transition state when applied in the asymmetric hetero‐Diels‐Alder reaction. Without altering the stereochemistry of the catalyst backbone, it is possible to access both enantiomers of the product by varying the substitution of the catalyst at the α‐position. [ABSTRACT FROM AUTHOR]

The enantioselective azo-based α-amination of an aldehyde followed by a Horner–Wadsworth–Emmons-based vinyl sulfone formation is reported. The thus obtained optically active N , N ′-diprotected trans -(phenylsulfonyl)vinyl hydrazine products were then converted into the corresponding N-functionalised trans -(phenylsulfonyl)vinyl amines. Specifically, reaction of 4-phenylbutanal with di- tert -butyl azodicarboxylate (DBAD) in the presence of l - or d -proline, followed by addition of diethyl [(phenylsulfonyl)methyl]phosphonate, gave either enantiomer of di- tert -butyl trans -1-[5-phenyl-1-(phenylsulfonyl)pent-1-en-3-yl]hydrazine-1,2-dicarboxylate. The enantiomeric excesses of the (+)- and (–)-enantiomers prepared in this manner were in the range 86–89%. The conversion of these γ-hydrazino vinyl sulfones into the corresponding γ-amino-substituted compounds was achieved following a Boc deprotection, Zn reduction, N-functionalisation sequence. This three-step sequence was reasonably efficient (approx. 50%) and no erosion of enantiopurity was found to have taken place. The compounds accessed via this process include both enantiomers of tert -butyl trans -[5-phenyl-1-(phenylsulfonyl)pent-1-en-3-yl]carbamate and epimeric dipeptide mimetics including 4-methyl- N -{(S)-1-oxo-3-phenyl-1-[((S , E)-5-phenyl-1-(phenylsulfonyl)pent-1-en-3-yl)amino]propan-2-yl}piperazine-1-carboxamide (also known as K777). [ABSTRACT FROM AUTHOR]

Sedimentary charcoal records are used for understanding fire as an earth system process; however, no standardized laboratory methodology exists. Varying sample volumes and chemical treatments (i.e., type of chemical for length of time) are used for the deflocculation and extraction of charcoal from sediment samples. Here, we present the first systematic assessment of the effect of commonly used chemicals on charcoal area and number of fragments. In modern charcoal the area of fragments was significantly different depending on the chemical treatment. We subsequently applied H2O2 (33%), NaClO (12.5%), and HNO3 (50%) to a late-glacial–early Holocene paleorecord and tested different sample volumes. The effects of the treatments were consistent between modern and fossil experiments, which demonstrates the validity of applying results from the modern experiment to the fossil records. Based on our experiments we suggest (1) H2O2 33%, especially for highly organic sediments; (2) avoidance of high concentrations of NaClO for prolonged periods of time, and of HNO3; and (3) samples of 1 cm3 provided typically consistent profiles. Our results indicate that charcoal properties can be influenced by treatment type and sample volume, thus emphasizing the need for a common protocol to enable reliable multi-study comparisons or composite fire histories. [ABSTRACT FROM AUTHOR]

The article reports that the Laura Cunningham grew up in Kensington, California, where she became interested in observing nature at the local parks, such as Tilden-Wildcat Canyon Regional Park. It mentions that she hiked about and was never without binoculars and a notepad to observe and sketch lizards, snakes, salamanders, treefrogs, birds, mammal tracks, and plants.

The non-destructive testing of austenitic welds using ultrasound plays an important role in the assessment of the structural integrity of safety critical structures. The internal microstructure of these welds is highly scattering and can lead to the obscuration of defects when investigated by traditional imaging algorithms. This paper proposes an alternative objective method for the detection of flaws embedded in austenitic welds based on the singular value decomposition of the time-frequency domain response matrices. The distribution of the singular values is examined in the cases where a flaw exists and where there is no flaw present. A lower threshold on the singular values, specific to austenitic welds, is derived which, when exceeded, indicates the presence of a flaw. The detection criterion is successfully implemented on both synthetic and experimental data. The datasets arising from welds containing a flaw are further interrogated using the decomposition of the timereversal operator (DORT) method and the total focusing method (TFM), and it is shown that images constructed via the DORT algorithm typically exhibit a higher signal-to-noise ratio than those constructed by the TFM algorithm. [ABSTRACT FROM AUTHOR]

This article describes a graduate-level service learning usability project and illustrates the practical tensions generated by increasing complexity in technology design. Although a foundational body of usability research prescribes standards for high-quality test design, such guidelines may not be applicable or practical in a particular context. Usability students and professionals benefit from allowing themselves the space for adaptation in order to conduct rigorous testing and meet client needs. An agile attitude-theory based but not theory bound-emphasizes user-centeredness, functionality, customer collaboration, and flexibility. Such an attitude emerges from basic principles of rhetorical theory, such as timing (kairos), user-centeredness (audience), genre, and rhetorical context. Bridging industry and academia, service-learning projects provide a compelling opportunity to experience the tensions and decision making required at the nexus of theory and practice. [ABSTRACT FROM AUTHOR]

Counselors work in diverse locations. Yet, very little is known about each setting's optimal person-environment match, which contributes to burnout and turnover in the field settings (Knudsen, Ducharme, Roman, 2006; Lawson, 2007; Maslach, Jackson, & Leiter, 1986; Rupert & Morgan, 2005; Watkins, 1983; Witmer & Young, 1996). One hundred and thirty-five counselors comprised the sample in a descriptive correlational study from a large city in the Southeastern region of the United States. Instrumentation included: the Schwartz Value Survey, the abridged Job Descriptive Index and Job In General Scale, and the Counselor History Questionnaire. Two one-way MANOVA's and four standard multiple regressions were performed for the analyses. Significant results (F [2,133] = 9.88, p = .000]) supported practitioners rated a higher level of job satisfaction than their counterparts in agency settings, with 12.9% of the variance being accounted for by the variable of work location. The non-significant results of value priorities included that counselors possess similar value priorities. Implications for counselors and counselor educators are presented, along with areas of future research. [ABSTRACT FROM AUTHOR]

Abstract: The Last Interglacial Period (LIP) is often regarded as a good analogue for potential climatic conditions under predicted global warming scenarios. Despite this, there is still debate over the nature, duration and frequency of climatic changes during this period. One particularly contentious issue has been the apparent evidence of climatic instability identified in many marine cores but seemingly lacking from many terrestrial archives, especially within the Arctic, a key region for global climate change research. In this paper, geochemical records from Lake El'gygytgyn, north-eastern Russia, are used to infer past climatic changes during the LIP from within the high Arctic. With a sampling resolution of ~20–~90years, these records offer the potential for detailed, high-resolution palaeoclimate reconstruction. This study shows that the LIP commenced in central Chukotka ~129thousand years ago (ka), with the warmest climatic conditions occurring between ~128 and 127ka before being interrupted by a short-lived cold reversal. Mild climatic conditions then persisted until ~122ka when a marked reduction in the sedimentation rate suggests a decrease in precipitation. A further climatic deterioration at ~118ka marks the return to glacial conditions. This study highlights the value of incorporating several geochemical proxies when inferring past climatic conditions, thus providing the potential to identify signals related to environmental change within the catchment. We also demonstrate the importance of considering how changes in sedimentation rate influence proxy records, in order to develop robust palaeoenvironmental reconstructions. [Copyright &y& Elsevier]

We undertake the first comprehensive effort to integrate North Atlantic marine climate records for the last millennium, highlighting some key components common within this system at a range of temporal and spatial scales. In such an approach, careful consideration needs to be given to the complexities inherent to the marine system. Composites therefore need to be hydrographically constrained and sensitive to both surface water mass variability and three-dimensional ocean dynamics. This study focuses on the northeast (NE) North Atlantic Ocean, particularly sites influenced by the North Atlantic Current. A composite plus regression approach is used to create an inter-regional NE North Atlantic reconstruction of sea surface temperature (SST) for the last 1000 years. We highlight the loss of spatial information associated with large-scale composite reconstructions of the marine environment. Regional reconstructions of SSTs off the Norwegian and Icelandic margins are presented, along with a larger-scale reconstruction spanning the NE North Atlantic. The latter indicates that the ‘Medieval Climate Anomaly’ warming was most pronounced before ad 1200, with a long-term cooling trend apparent after ad 1250. This trend persisted until the early 20th century, while in recent decades temperatures have been similar to those inferred for the ‘Medieval Climate Anomaly’. The reconstructions are consistent with other independent records of sea-surface and surface air temperatures from the region, indicating that they are adequately capturing the climate dynamics of the last millennium. Consequently, this method could potentially be used to develop large-scale reconstructions of SSTs for other hydrographically constrained regions. [ABSTRACT FROM AUTHOR]

The prevalence of Parkinson's disease (PD) is increasing due to an ageing population. It is an unpredictable disease which requires regular assessment and monitoring. Current techniques used to assess PD are subjective. Clinicians observe movements made by a patient and subsequently rate the level of severity of, for example tremor or slowness of movement. Within this work, we have developed and evaluated a prototype computer-based assessment tool capable of collecting information on the movement difficulties present in PD. Twenty participants took part in an assessment of the tool, 10 of whom were diagnosed with PD and 10 were without the disease. Following the usage of the tool, it was found that there was a significant difference (p = 0.038) in the speed of movement between the two groups. We envisage that this tool could have the potential to enable more objective clinical conclusions to be made. [ABSTRACT FROM AUTHOR]

The effects of metals and petroleum hydrocarbons on benthic marine diatom communities were assessed using a manipulative field experiment at Casey Station, Antarctica. Uncontaminated, metal contaminated, and petroleum hydrocarbon contaminated sediments were deployed for 11 weeks during the 1999 austral summer. The treatments were deployed at three different locations: Brown Bay, which has elevated levels of anthropogenic contaminants, and two uncontaminated reference locations, O'Brien Bay and Sparkes Bay, the latter of which has naturally occurring high concentrations of some heavy metals. At each location, significant differences between the composition of diatom communities recruiting to control and petroleum hydrocarbon contaminated treatments were observed. Navicula directa (Smith) Ralfs occurred at lower abundances in the petroleum hydrocarbon contaminated treatments than in the control treatments. In contrast, Navicula cancellata Donkin occurred at higher relative abundances in both contaminated treatments relative to the control treatment. Interactions between treatment and location were also observed for several species, including Navicula glaciei Van Heurck. Significant differences in the overall community composition of diatom communities between control and metal contaminated treatments and metal contaminated and petroleum hydrocarbon contaminated treatments were only observed within Brown Bay. The location of deployment also had a significant influence on the composition of diatom communities. Brown Bay had higher abundances of Achnanthes brevipes Agardh but lower abundances of Navicula aff. cincta (Ehrenberg) Van Heurck than either reference locations. This experiment demonstrated that benthic diatom communities are sensitive to sediment contamination and would be suitable for future monitoring work within this and other areas of Antarctica. [ABSTRACT FROM AUTHOR]

Describes a `reserved bandwidth' service as a quality of service enhancement in the vBNS, a high-speed image processing (IP)- -over-asynchronous transfer mode (ATM) backbone network for research and education. vBNS service and architecture; Description of the implementation; Class of service; Conclusion.

The effects of climatic variables on lake-water total organic carbon (TOC) concentrations and benthic and pelagic primary producers during the past 45 yr were assessed using the sediment records of two subarctic lakes, one with mires and one without mires connected to the lake. The lake with a mire showed large and synchronous changes in the planktonic to benthic (P : B) ratio of diatoms and concentrations of TOC inferred from nearinfrared spectroscopy. During periods of warm temperatures, high precipitation, and long ice-free conditions, we inferred high TOC in the lake, and the diatom community was dominated by planktonic species. The stable carbon isotopic (δ13C) values of sediment organic matter were negatively correlated with inferred TOC concentration and P :B ratio. We suggest that the changes in TOC and P : B ratio were a result of changing climate, permafrost degradation, and related changes in the catchment. Terrestrial organic matter, by its strong effect on the penetration of light through the lake water, possibly affected the habitats available for benthic photosynthesis and thus the d13C of the sediment organic matter. The large changes in recent times may also be because of unusually long ice-free periods, warmer temperatures, and other associated limnological changes. The lake with no mire next to the lake showed only minor changes in lake-water TOC during the same period and P :B ratio remained almost constant until the past 5 yr, when the P :B ratio increased rapidly. The observed changes in P :B ratio within this lake may be because of complex interactions of several climate-related variables. [ABSTRACT FROM AUTHOR]

Fourier transform infrared spectroscopy (FTIRS) can provide detailed information on organic and minerogenic constituents of sediment records. Based on a large number of sediment samples of varying age (0-340 000 yrs) and from very diverse lake settings in Antarctica, Argentina, Canada, Macedonia/Albania, Siberia, and Sweden, we have developed universally applicable calibration models for the quantitative determination of biogenic silica (BSi; n = 816), total inorganic carbon (TIC; n = 879), and total organic carbon (TOC; n = 3164) using FTIRS. These models are based on the differential absorbance of infrared radiation at specific wavelengths with varying concentrations of individual parameters, due to molecular vibrations associated with each parameter. The calibration models have low prediction errors and the predicted values are highly correlated with conventionally measured values (R = 0.94-0.99). Robustness tests indicate the accuracy of the newly developed FTIRS calibration models is similar to that of conventional geochemical analyses. Consequently FTIRS offers a useful and rapid alternative to conventional analyses for the quantitative determination of BSi, TIC, and TOC. The rapidity, cost-effectiveness, and small sample size required enables FTIRS determination of geochemical properties to be undertaken at higher resolutions than would otherwise be possible with the same resource allocation, thus providing crucial sedimentological information for climatic and environmental reconstructions. [ABSTRACT FROM AUTHOR]

Meditation has been studied as a way of reducing stress in counseling clients since the 1960s. Alcoholics Anonymous, Narcotics Anonymous, and new wave behavior therapies incorporate meditation techniques in their programs. This article identifies meditation's curative factors and limitations when using medita- tion in addiction settings. [ABSTRACT FROM AUTHOR]

Background: Hospital-based studies have reported variable associations between outcome after spontaneous intracerebral hemorrhage and peri-hematomal edema volume. Aims: In a community-based study, we aimed to investigate the existence, strength, direction, and independence of associations between intracerebral hemorrhage and peri-hematomal edema volumes on diagnostic brain CT and one-year functional outcome and long-term survival. Methods: We identified all adults, resident in Lothian, diagnosed with first-ever, symptomatic spontaneous intracerebral hemorrhage between June 2010 and May 2013 in a community-based, prospective inception cohort study. We defined regions of interest manually and used a semi-automated approach to measure intracerebral hemorrhage volume, peri-hematomal edema volume, and the sum of these measurements (total lesion volume) on first diagnostic brain CT performed at ≤3 days after symptom onset. The primary outcome was death or dependence (scores 3–6 on the modified Rankin Scale) at one-year after intracerebral hemorrhage. Results: Two hundred ninety-two (85%) of 342 patients (median age 77.5 y, IQR 68–83, 186 (54%) female, median time from onset to CT 6.5 h (IQR 2.9–21.7)) were dead or dependent one year after intracerebral hemorrhage. Peri-hematomal edema and intracerebral hemorrhage volumes were colinear (R 2 = 0.77). In models using both intracerebral hemorrhage and peri-hematomal edema, 10 mL increments in intracerebral hemorrhage (adjusted odds ratio (aOR) 1.72 (95% CI 1.08–2.87); p = 0.029) but not peri-hematomal edema volume (aOR 0.92 (0.63–1.45); p = 0.69) were independently associated with one-year death or dependence. 10 mL increments in total lesion volume were independently associated with one-year death or dependence (aOR 1.24 (1.11–1.42); p = 0.0004). Conclusion: Total volume of intracerebral hemorrhage and peri-hematomal edema, and intracerebral hemorrhage volume alone on diagnostic brain CT, undertaken at three days or sooner, are independently associated with death or dependence one-year after intracerebral hemorrhage, but peri-hematomal edema volume is not. Data access statement: Anonymized summary data may be requested from the corresponding author. [ABSTRACT FROM AUTHOR]

While the number of violent crimes in the United States is decreasing, financial crimes against the elderly are increasing due to the aging of the overall population and greater concentration of wealth among older people. The United States, along with the rest of the world, is experiencing dramatic growth of its senior populace; and financial abuse of the elderly is also dramatically rising. Santa Clara County, California's response to this problem via their model program emphasizing a multi-disciplinary approach to combating financial abuse will be discussed. [ABSTRACT FROM AUTHOR]

Objectives: Launched in 1989, the Scottish Motor Neuron Disease Register (SMNDR) has provided a resource for prospective clinical data collection. However, in 2015 we aimed to evolve a system to allow: i) A patient-centered approach to care based on recognized standards, ii) Harmonized data sharing between Scottish health professionals in "real-time", iii) Regular audit of care to facilitate timely improvements in service delivery, and iv) Patient participation in a diverse range of observational and interventional research studies including clinical trials. Methods: We developed a standardized national electronic data platform—Clinical Audit Research and Evaluation of MND (CARE-MND) which integrates clinical audit and research data fields. Data completion pre- and post-CARE-MND were compared, guided by recently published National Institute for Clinical Excellence (NICE) recommendations. Statistical difference in data capture between time periods was assessed using Z-test of proportions. Results: Data field completion for the historical 2011–2014 period ranged from 4 to 95%; median 50%. CARE-MND capture ranged from 32 to 98%; median 87%. 15/17 fields were significantly more complete post-CARE-MND (p < 0.001). All MND nurse/allied health specialists in Scotland use the CARE-MND platform. Management of MND in Scotland is now coordinated through a standardized template. Conclusions: Through CARE-MND, national audits of MND care and interventions have been possible, leading to protocols for harmonized service provision. Stratification of the MND population is facilitating participation in observational and interventional studies. CARE-MND can act as a template for other neurological disorders. [ABSTRACT FROM AUTHOR]

Abstract: Here we present δ18Odiatom data from two high-latitude lakes; one has short residence time and a water isotopic composition (δ18Olake) that fluctuate due to seasonal variations in precipitation and temperature, and the other has δ18Olake that is influenced by longer lake water residence times and evaporation. The δ18Odiatom records reveal common responses to precipitation forcing over the past millennium. Relatively wet summers are inferred from δ18Odiatom between 1000 and 1080 AD, 1300 and 1440 AD, and during the early 19th century, coincided with periods of high cloud cover inferred from tree-ring carbon isotopes, and other data for high Arctic Oscillation index. While relatively dry summers with increasing influence of winter snow are indicated between 1600 and 1750 AD. The co-response between carbon isotopes in trees and oxygen isotopes in diatoms strengthens the relationship between cloud cover and precipitation and the hypothesis that these changes were the result of significant regional shifts in atmospheric circulation. [Copyright &y& Elsevier]

We present a millennial long dendroclimatic reconstruction of spring/summer precipitation for southern-central England. Previous research identified a significant moisture stress signal in ring-width data measured from oak trees growing in southern England. In this study, we build upon this earlier work, specifically targeting south-central England, to derive a well replicated oak ring-width composite chronology using both living and historical material. The data-set includes 352 living trees (AD 1629-2009) and 1540 individual historical series (AD 663-1925). The period expressed by at least 50 trees in any year is AD 980-2009. Calibration experiments identify the optimal seasonal predictand target as March-July precipitation (1901-2007: r = 0.33). However, comparison with the long Kew Gardens precipitation record indicates a weakening in tree-growth/climate response from ~1800 to 1920 which we speculate may be related to smoke and sulphur dioxide (SO) emissions at that time which may have also contributed to a decrease in tree productivity. The time-series derived using the regional curve standardisation method to capture lower frequency information shows a mediaeval period with alternating multi-decade-long dry and wet periods, with AD 1153-1172 being the wettest reconstructed 20-year period in the whole record. Drier conditions are prevalent from ~1300 to the early sixteenth century followed by a period of increasing precipitation levels. The most recent four centuries of the record appear similar to the mediaeval period with multiple decade-long dry and wet periods. The late twentieth century is the second reconstructed wettest period. These centennial hydroclimatic trends are in broad agreement with independent regional scale hydroclimatic reconstructions from tree-ring (East Anglia), historical, speleothem and peat water level proxy archives in the United Kingdom and appear coupled with reconstructed sea surface temperature changes in the North Atlantic which in turn influence the Atlantic meridional overturning circulation and westerly airflow across the UK. [ABSTRACT FROM AUTHOR]

Tree rings dominate millennium-long temperature reconstructions and many records originate from Scandinavia, an area for which the relative roles of external forcing and internal variation on climatic changes are, however, not yet fully understood. Here we compile 1,179 series of maximum latewood density measurements from 25 conifer sites in northern Scandinavia, establish a suite of 36 subset chronologies, and analyse their climate signal. A new reconstruction for the 1483-2006 period correlates at 0.80 with June-August temperatures back to 1860. Summer cooling during the early 17th century and peak warming in the 1930s translate into a decadal amplitude of 2.9°C, which agrees with existing Scandinavian tree-ring proxies. Climate model simulations reveal similar amounts of mid to low frequency variability, suggesting that internal oceanatmosphere feedbacks likely influenced Scandinavian temperatures more than external forcing. Projected 21st century warming under the SRES A2 scenario would, however, exceed the reconstructed temperature envelope of the past 1,500 years. [ABSTRACT FROM AUTHOR]