Conversion between Triplet Pair States Is Controlled by Molecular Coupling in Pentadithiophene Thin Films

In singlet fission (SF) the initially formed correlated triplet pair state, 1(TT), may evolve toward independent triplet excitons or higher spin states of the (TT) species. The latter result is often considered undesirable from a light harvesting perspective but may be attractive for quantum information sciences (QIS) applications, as the final exciton pair can be spin-entangled and magnetically active with relatively long room temperature decoherence times. In this study we use ultrafast transient absorption (TA) and time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy to monitor SF and triplet pair evolution in a series of alkyl silyl-functionalized pentadithiophene (PDT) thin films designed with systematically varying pairwise and long-range molecular interactions between PDT chromophores. The lifetime of the (TT) species varies from 40 ns to 1.5 μs, the latter of which is associated with extremely weak intermolecular coupling, sharp optical spectroscopic features, and complex TR-EPR spectra that are composed of a mixture of triplet and quintet-like features. On the other hand, more tightly coupled films produce broader transient optical spectra but simpler TR-EPR spectra consistent with significant population in 5(TT)0. These distinctions are rationalized through the role of exciton diffusion and predictions of TT state mixing with low exchange coupling J versus pure spin substate population with larger J. The connection between population evolution using electronic and spin spectroscopies enables assignments that provide a more detailed picture of triplet pair evolution than previously presented and provides critical guidance for designing molecular QIS systems based on light-induced spin coherence

Neocortical Connectivity during Episodic Memory Formation

During the formation of new episodic memories, a rich array of perceptual information is bound together for long-term storage. However, the brain mechanisms by which sensory representations (such as colors, objects, or individuals) are selected for episodic encoding are currently unknown. We describe a functional magnetic resonance imaging experiment in which participants encoded the association between two classes of visual stimuli that elicit selective responses in the extrastriate visual cortex (faces and houses). Using connectivity analyses, we show that correlation in the hemodynamic signal between face- and place-sensitive voxels and the left dorsolateral prefrontal cortex is a reliable predictor of successful face–house binding. These data support the view that during episodic encoding, “top-down” control signals originating in the prefrontal cortex help determine which perceptual information is fated to be bound into the new episodic memory trace

Task-Selective Memory Effects for Successfully Implemented Encoding Strategies

Previous behavioral evidence suggests that instructed strategy use benefits associative memory formation in paired associate tasks. Two such effective encoding strategies–visual imagery and sentence generation–facilitate memory through the production of different types of mediators (e.g., mental images and sentences). Neuroimaging evidence suggests that regions of the brain support memory reflecting the mental operations engaged at the time of study. That work, however, has not taken into account self-reported encoding task success (i.e., whether participants successfully generated a mediator). It is unknown, therefore, whether task-selective memory effects specific to each strategy might be found when encoding strategies are successfully implemented. In this experiment, participants studied pairs of abstract nouns under either visual imagery or sentence generation encoding instructions. At the time of study, participants reported their success at generating a mediator. Outside of the scanner, participants further reported the quality of the generated mediator (e.g., images, sentences) for each word pair. We observed task-selective memory effects for visual imagery in the left middle occipital gyrus, the left precuneus, and the lingual gyrus. No such task-selective effects were observed for sentence generation. Intriguingly, activity at the time of study in the left precuneus was modulated by the self-reported quality (vividness) of the generated mental images with greater activity for trials given higher ratings of quality. These data suggest that regions of the brain support memory in accord with the encoding operations engaged at the time of study

Known and unknown requirements in healthcare

We report experience in requirements elicitation of domain knowledge from experts in clinical and cognitive neurosciences. The elicitation target was a causal model for early signs of dementia indicated by changes in user behaviour and errors apparent in logs of computer activity. A Delphi-style process consisting of workshops with experts followed by a questionnaire was adopted. The paper describes how the elicitation process had to be adapted to deal with problems encountered in terminology and limited consensus among the experts. In spite of the difficulties encountered, a partial causal model of user behavioural pathologies and errors was elicited. This informed requirements for configuring data- and text-mining tools to search for the specific data patterns. Lessons learned for elicitation from experts are presented, and the implications for requirements are discussed as “unknown unknowns”, as well as configuration requirements for directing data-/text-mining tools towards refining awareness requirements in healthcare applications

Rock Climbing Emergencies in the Austrian Alps: Injury Patterns, Risk Analysis and Preventive Measures

To elucidate patterns of and risk factors for acute traumatic injuries in climbers in need of professional rescue, a retrospective evaluation was performed of the Austrian National Registry of Mountain Accidents regarding rock climbing incidents over a 13-year timeframe from 2005 to 2018. From 2992 recorded incidents, 1469 were uninjured but in need of recovery, mainly when alpine climbing. Acute traumatic injuries (n = 1217) were often classified as severe (UIAA ≥ 3; n = 709), and commonly involved fractures (n = 566). Main injury causes were falls (n = 894) frequently preceded by rockfall (n = 229), a stumble (n = 146), a grip or foothold break-out (n = 143), or a belaying error (n = 138). In fatal cases (n = 140), multiple trauma (n = 105) or head injuries (n = 56) were most common, whereas lower extremity injuries (n = 357) were most common in severely injured patients. The risk for severe or fatal injuries increased with age and fall height when ascending or bouldering, during the morning hours, and when climbing without a helmet or rope. The case fatality rate was 4.7%, and the estimated total mortality rate was 0.003–0.007 per 1000 h of rock climbing. Acute traumatic injuries requiring professional rescue when rock climbing are often severe or fatal. Consequent use of a helmet when sport climbing, consistent use of a rope (particularly when ascending), proper spotting when bouldering, and proper training, as well as high vigilance when belaying are likely to help prevent such injuries

Analgesia in pediatric trauma patients in physician-staffed Austrian helicopter rescue: a 12-year registry analysis

Background As pediatric patients are typically rare among helicopter emergency medical systems (HEMS), children might be at risk for oligo-analgesia due to the rescuer’s lack of experience and the fear of side effects. Methods In this retrospective analysis, data was obtained from the ÖAMTC HEMS digital database including 14 physician staffed helicopter bases in Austria over a 12-year timeframe. Primary missions involving pediatric trauma patients (< 15 years) not mechanically ventilated on-site were included. Analgesia was assessed and compared between the age groups 0–5, 6–10 and 11–14 years. Results Of all flight missions, 8.2% were dedicated to children  75%) suffered moderate to severe pain, justifying immediate analgesia. HEMS physicians typically chose a monotherapy with an opioid (n = 1277; 44.3%) or Esketamine (n = 1187; 41.1%) followed by the combination of both (n = 324; 11.2%). Opioid use increased (37.2% to 63.4%) and Esketamine use decreased (66.1% to 48.3%) in children  10 years. Esketamine was more often administered in extremity (57.3%) than in head (41.5%) or spine injuries (32.3%). An intravenous access was less often established in children < 6 years (74.3% vs. 90.8%; p < 0.001). Despite the use of potent analgesics, 396 missions (13.7%) were performed without technical monitoring. Particularly regarding patient data at handover in hospital, merely < 10% of all missions featured complete documentation. Therefore, sufficient evaluation of the efficacy of pain relief was not possible. Yet, by means of respiratory measures required during transport, severe side effects such as respiratory insufficiency, were barely noted. Conclusions In the physician-staffed HEMS setting, pediatric trauma patients liberally receive opioids and Esketamine for analgesia. With regard to severe respiratory insufficiency during transport, the application of these potent analgesics seems safe.publishedVersio

The Link between Hypermetabolism and Hypernatremia in Severely Burned Patients

Hypernatremia is common in critical care, especially in severely burned patients. Its occurrence has been linked to increased mortality. Causes of hypernatremia involve a net gain of sodium or a loss of free water. Renal loss of electrolyte-free water due to urea-induced osmotic diuresis has been described as causative in up to 10% of hypernatremic critical ill patients. In this context, excessive urea production due to protein catabolism acts as major contributor. In severe burn injury, muscle wasting occurs as result of hypermetabolism triggered by ongoing systemic inflammation. In this retrospective study, severely burned patients were analysed for the occurrence of hypernatremia and subsequent signs of hypermetabolism. The urea: creatinine ratio&mdash;as a surrogate for hypermetabolism&mdash;sufficiently discriminated between two groups. Four of nine hypernatremic burn patients (44%) had a highly elevated urea: creatinine ratio, which was clearly associated with an increased urea production and catabolic index. This hypermetabolism was linked to hypernatremia via an elevated urea- and reduced electrolyte-fraction in renal osmole excretion, which resulted in an increased renal loss of electrolyte-free water. In hypermetabolic severely burned patients, the electrolyte-free water clearance is a major contributor to hypernatremia. A positive correlation to serum sodium concentration was shown

ICU-Acquired Hypernatremia Is Associated with Persistent Inflammation, Immunosuppression and Catabolism Syndrome

Developing hypernatremia while on intensive care unit (ICU) is a common problem with various undesirable effects. A link to persistent inflammation, immunosuppression and catabolism syndrome (PICS) can be established in two ways. On the one hand, hypernatremia can lead to inflammation and catabolism via hyperosmolar cell stress, and on the other, profound catabolism can lead to hypernatremia via urea-induced osmotic diuresis. In this retrospective single-center study, we examined 115 patients with prolonged ICU stays (&ge;14 days) and sufficient renal function. Depending on their serum sodium concentrations between ICU day 7 and 21, allocation to a hypernatremic (high) and a nonhypernatremic group (low) took place. Distinct signs of PICS were detectable within the complete cohort. Thirty-three of them (28.7%) suffered from ICU-acquired hypernatremia, which was associated with explicitly higher signs of inflammation and ongoing catabolism as well as a prolonged ICU length of stay. Catabolism was discriminated better by the urea generation rate and the urea-to-creatinine ratio than by serum albumin concentration. An assignable cause for hypernatremia was the urea-induced osmotic diuresis. When dealing with ICU patients requiring prolonged treatment, hypernatremia should at least trigger thoughts on PICS as a contributing factor. In this regard, the urea-to-creatinine ratio is an easily accessible biomarker for catabolism