Dithiophosphoric Acids for Polymer Functionalization.

Dithiophosphoric acids (DTPAs) are an intriguing class of compounds that are sourced from elemental sulfur and white phosphorus and are prepared from the reaction of phosphorus pentasulfide with alcohols. The electrophilic addition of DTPAs to alkenes and unsaturated olefinic substrates is a known reaction, but has not been applied to polymer synthesis and polymer functionalization. We report on the synthesis and application of DTPAs for the functionalization of challenging poly-enes, namely polyisoprene (PI) and polynorbornene (pNB) prepared by ring-opening metathesis polymerization (ROMP). The high heteroatom content within DTPA moieties impart intriguing bulk properties to poly-ene materials after direct electrophilic addition reactions to the polymer backbone introducing DTPAs as side chain groups. The resulting materials possess both enhanced optical and flame retardant properties vs the poly-ene starting materials. Finally, we demonstrate the ability to prepare crosslinked polydiene films with di-functional DTPAs, where the crosslinking density and thermomechanical properties can be directly tuned by DTPA feed ratios.

Unraveling the rheology of inverse vulcanized polymers.

Multiple relaxation times are used to capture the numerous stress relaxation modes found in bulk polymer melts. Herein, inverse vulcanization is used to synthesize high sulfur content (≥50 wt%) polymers that only need a single relaxation time to describe their stress relaxation. The S-S bonds in these organopolysulfides undergo dissociative bond exchange when exposed to elevated temperatures, making the bond exchange dominate the stress relaxation. Through the introduction of a dimeric norbornadiene crosslinker that improves thermomechanical properties, we show that it is possible for the Maxwell model of viscoelasticity to describe both dissociative covalent adaptable networks and living polymers, which is one of the few experimental realizations of a Maxwellian material. Rheological master curves utilizing time-temperature superposition were constructed using relaxation times as nonarbitrary horizontal shift factors. Despite advances in inverse vulcanization, this is the first complete characterization of the rheological properties of this class of unique polymeric material.

Spatial organisation of the mesoscale connectome: A feature influencing synchrony and metastability of network dynamics.

Significant research has investigated synchronisation in brain networks, but the bulk of this work has explored the contribution of brain networks at the macroscale. Here we explore the effects of changing network topology on functional dynamics in spatially constrained random networks representing mesoscale neocortex. We use the Kuramoto model to simulate network dynamics and explore synchronisation and critical dynamics of the system as a function of topology in randomly generated networks with a distance-related wiring probability and no preferential attachment term. We show networks which predominantly make short-distance connections smooth out the critical coupling point and show much greater metastability, resulting in a wider range of coupling strengths demonstrating critical dynamics and metastability. We show the emergence of cluster synchronisation in these geometrically-constrained networks with functional organisation occurring along structural connections that minimise the participation coefficient of the cluster. We show that these cohorts of internally synchronised nodes also behave en masse as weakly coupled nodes and show intra-cluster desynchronisation and resynchronisation events related to inter-cluster interaction. While cluster synchronisation appears crucial to healthy brain function, it may also be pathological if it leads to unbreakable local synchronisation which may happen at extreme topologies, with implications for epilepsy research, wider brain function and other domains such as social networks.

Existential Issues in Psychotherapy.

Existential issues are common in patient experiences and can present as themes in any practice setting, but particularly in psychotherapy. Existential issues are any concerns that arise from distress or questions about difficult subjects, such as death, meaning, freedom, and isolation, and can be a source of psychiatric concerns or simply a modifying factor. Because of this, clinicians should be able to recognize and understand the basic tenets of addressing existential issues in psychotherapy. This article outlines the historical context and theoretical basis of existentialism. It also discusses existential issues in relation to psychotherapy and provides practical clinical tips for addressing these issues with patients, including helpful probing questions, tips for noticing existential themes, and ideas about how to address existential issues in session.

Vascular Thrombosis in Severe COVID-19 Requiring Extracorporeal Membrane Oxygenation: A Multicenter Study.

OBJECTIVES: Coronavirus disease 2019 has been reported to be a prothrombotic condition; however, multicenter data comparing this with other viral pneumonias in those requiring extracorporeal membrane oxygenation are lacking. We conducted a multicenter study using whole-body CT to examine the prevalence, severity, and nature of vascular complications in coronavirus disease 2019 in comparison with patients with other viral pneumonias. DESIGN: We analyzed whole-body CT scans for the presence of vascular thrombosis (defined as pulmonary artery thrombus, venous thrombus, systemic arterial thrombus, or end-organ infarct). The severity, distribution, and morphology of pulmonary artery thrombus were characterized. Competing risk cumulative incidence analysis was used to compare survival with discharge. SETTING: Three centers of the English national extracorporeal membrane oxygenation service. PATIENTS: Consecutive patients admitted with either coronavirus disease 2019 or noncoronavirus disease 2019 viral pneumonia admitted from January 2019. INTERVENTIONS: None. MEASUREMENTS AND MAIN RESULTS: One-hundred thirty-six patients (45.2 ± 10.6 yr old, 39/146 [27%] female) requiring extracorporeal membrane oxygenation support underwent whole-body CT scans at admission. Of these, 86 had coronavirus disease 2019 pneumonia, and 50 had noncoronavirus disease 2019 viral pneumonia. Vascular thrombosis was seen more often in patients with coronavirus disease 2019 (odds ratio, 12.9 [95% CI 4.5-36.8]). In those with coronavirus disease 2019, 57 (73%) demonstrated pulmonary artery thrombus or pulmonary perfusion defects. Eighty-two percent of thrombus exhibited emboli-like morphology. The location of pulmonary artery thrombus and parenchymal perfusion defects was only concordant in 30% of cases. The risk of mortality was higher in those with coronavirus disease 2019 compared with noncoronavirus disease 2019 pneumonia (χ2 = 3.94; p = 0.047). Mortality was no different in coronavirus disease 2019 patients with or without vascular thrombosis (χ2 = 0.44; p = 0.51). CONCLUSIONS: In patients who received extracorporeal membrane oxygenation, coronavirus disease 2019 is associated with a higher prevalence of vascular thrombosis compared with noncoronavirus disease viral pneumonias. The pattern of pulmonary vascular changes suggests concurrent embolic disease and small vessel disease. Despite this, vascular thrombosis was not linked to poorer short-term prognosis in those with coronavirus disease 2019.

Continuous hemadsorption with cytokine adsorber for severe COVID-19: A case series of 15 patients.

BACKGROUND: Hyperinflammation and cytokine release has been associated with severe Covid-19. Hemadsorption cartridges may have a potential role in treatment of cytokine storm associated with the development of severe Covid-19. METHODS: We retrospectively examined the case records of patients with severe Covid-19 receiving adjunctive hemadsorption (HA) in our ICU. We analyzed inflammatory biomarkers pre- and post- HA. RESULTS: Fifteen patients received HA during the study period. All were intubated, ventilated and required renal replacement therapy. 11/15 were supported on ECMO. Mean ferritin 2652 (±3286) ng/ml, mean CRP 154 (±92) mg/ml, median D-dimer 3071 (±2689) ng/ml, mean troponin 236 (±461) ng/L. We found significant difference in pre-and post- treatment ferritin 3622 ng/ml versus 1682 ng/ml (p = 0.022), CRP 222 mg/ml versus 103 mg/ml (p = 0.008, 95% CI 22.4-126.5), lactate 2 mmol/L versus 1.3 mmol/L (p = 0.017), and procalcitonin 15.3 ng/ml versus 4.2 ng/ml (p = 0.023). No significant difference in pre- and post- treatment IL-6 14 pg/ml versus 43 pg/ml (p = 0.32), IL-10 3.4 pg/ml versus 2.6 pg/ml (p = 0.31), IL1 ß 0.37 pg/ml versus 0.77 pg/ml (p = 0.75), TNF α 12.77 pg/ml versus 12.49 pg/ml (p = 0.75), VIS 10.04 versus 6.01 (p = 0.31, 95% CI 5.98-17.16) was seen. CONCLUSIONS: The use of HA as adjunctive treatment in a critically unwell group of COVID-19 patients lead to a reduction in ferritin, CRP, procalcitonin and lactate with no significant change in other parameters. The use of HA in the treatment of severe COVID-19 requires further larger randomized studies.

Impact of a Diabetes Toolkit on Weight Loss Among Veterans.

This quality improvement project aimed to answer the following clinical question: Among U.S. male veterans (N = 30) living with type 2 diabetes (T2D) receiving services from a Veterans Affairs (VA) endocrinology clinic, how does a diabetes toolkit influence knowledge and glycaemic control? All the study participants were male and from 31 to 91 years of age. A pre- and post-intervention diabetes knowledge test, body mass index (BMI), lipids, blood pressure, and lifestyle data were obtained as predictor variables. A1c levels were measured at baseline and fructosamine levels at 8-12 weeks post-intervention and converted to A1c levels. A diabetes toolkit was presented as an educational intervention to participating veterans. The pre- and post-intervention knowledge test measured an increase (p = 0.001) in diabetes knowledge. The pre- and post-intervention BMI, lipids, and blood pressure assessments measured changes in such variables associated with toolkit exposure. The regression model was marginally significant (p = 0.055) and the predictor variables explained 18.8% of variance in change of A1c. A multiple regression was conducted to determine the extent to which the following post-intervention outcome variables impacted glycemic control. Of four predictors, only one was significant: a patient's change in weight predicted (p = 0.016) a decrease in A1c.

100th Anniversary of Macromolecular Science Viewpoint: High Refractive Index Polymers from Elemental Sulfur for Infrared Thermal Imaging and Optics.

Optical technologies in the midwave and long wave infrared spectrum (MWIR, LWIR) are important systems for high resolution thermal imaging in near, or complete darkness. While IR thermal imaging has been extensively utilized in the defense sector, application of this technology is being driven toward emerging consumer markets and transportation. In this viewpoint, we review the field of IR thermal imaging and discuss the emerging use of synthetic organic and hybrid polymers as novel IR transmissive materials for this application. In particular, we review the critical role of elemental sulfur as a novel feedstock to prepare high refractive index polymers via inverse vulcanization and discuss the fundamental chemical insights required to impart improved IR transparency into these polymeric materials.

Taking Optogenetics into the Human Brain: Opportunities and Challenges in Clinical Trial Design.

Optogenetics, the use of light to control the activity of suitably sensitized cells, has led to major advances in the field of basic neuroscience since it first emerged in 2005. Already, the technique has entered clinical trials for conditions such as Retinitis Pigmentosa. A major focus of interest is the use of optogenetics within the brain, where the ability to precisely control the activity of specific subsets of neurons could lead to novel treatments for a wide range of disorders from epilepsy to schizophrenia. However, since any therapy would require both the use of gene therapy techniques to introduce non-human proteins, and implantable electronic devices to provide optical stimulation, applying this technique in the brain presents a unique set of obstacles and challenges. This review looks at the reasons why researchers are exploring the use of optogenetics within the brain. It then explores the challenges facing scientists, engineers and clinicians wanting to take this technology from the lab into the first human brain, discussing different possibilities for a first-in-human clinical trial from a sponsor, patient and regulatory perspective.

Infrared Fingerprint Engineering: A Molecular-Design Approach to Long-Wave Infrared Transparency with Polymeric Materials.

Optical technologies in the long-wave infrared (LWIR) spectrum (7-14 µm) offer important advantages for high-resolution thermal imaging in near or complete darkness. The use of polymeric transmissive materials for IR imaging offers numerous cost and processing advantages but suffers from inferior optical properties in the LWIR spectrum. A major challenge in the design of LWIR-transparent organic materials is that nearly all organic molecules absorb in this spectral window which lies within the so-called IR-fingerprint region. We report on a new molecular-design approach to prepare high refractive index polymers with enhanced LWIR transparency. Computational methods were used to accelerate the design of novel molecules and polymers. Using this approach, we have prepared chalcogenide hybrid inorganic/organic polymers (CHIPs) with enhanced LWIR transparency and thermomechanical properties via inverse vulcanization of elemental sulfur with new organic co-monomers.

A prospective feasibility trial of a novel intravascular catheter system with retractable coiled tip guidewire placed in difficult intravascular access (DIVA) patients in the Emergency Department.

The primary study objective was to evaluate insertion success rates. Secondary objectives included patient satisfaction, procedure time, complication rates, completion of therapy and dwell time of the novel AccuCath® 2.25″ Blood Control (BC) Catheter System (FDA approved) placed in difficult-access patients. This was a single-arm feasibility trial evaluating the AccuCath® 2.25″ BC Catheter System in a convenience sample of DIVA patients defined as at least two failed initial attempts or a history of difficult access plus the inability to directly visualize or palpate a target vein. All enrolled patients were 18 years of age or older. A total of 120 patients were enrolled. These patients had an average of 3.7 and median of 3 prior attempts at vascular access prior to AccuCath placement. Successful access was gained in 100% of the patients, 77% on the first attempt and all within three attempts; 88.5% of patients completed therapy, with the remaining 12.5% experiencing minor complications that required discontinuation of the catheter. The average patient satisfaction score on a 5-point Likert scale was highly positive at 4.6. Preliminary results show that the AccuCath® 2.25″ BC Catheter System has excellent success rates in gaining vascular access in an extremely difficult patient population. The device did not lead to any significant complications. Patients were also very satisfied with the procedure.

Acquisition of a Digital Intraoral Scanning Device: An Examination of Practice Volume Changes and the Economic Impact via an Interrupted Time Series Analysis.

OBJECTIVES: To evaluate the impact of digital scanning in general dental practices and orthodontic practices to determine the percentage of lift, i.e., the percent increase in gross receipts, of Invisalign® treatment starts following the introduction of an iTero® intraoral scanner. METHODS: An interrupted time series analysis was conducted on 48 months (24 pre- and 24 post-scanner introduction) of Invisalign receipt data from 1,871 general practitioner (GP) and orthodontic practices located worldwide. Analyses also explored the presence of a longer shift in the trend of monthly Invisalign receipts after scanner introduction (i.e., pre-post slope change), and projected the impact of the introduction of the scanner within a specific subset of practices (n = 319) that represented North American GPs with low initial practice volumes (i.e., 5 or fewer receipts in the 12 months prior to acquiring the scanner). RESULTS: For the entire sample, introduction of the iTero intraoral scanner at month 25 showed a significant and abrupt increase in receipts for Invisalign therapy (b = 0.49; p < 0.001). When compared to the counterfactual regression line prediction without the scanner, in month 25 Invisalign practice receipts increased from the predicted value of 2.38 to 2.88, an increase of 20.71%. When the analysis was conducted using only low-volume GP practices in North America, the introduction of the scanner at month 25 also led to a significant and abrupt increase in practice receipts (b = 0.28; p < 0.001), and this increase was still evident 24 months after scanner introduction. CONCLUSIONS: The results show that acquiring an iTero intraoral scanner as a precursor to Invisalign therapy is associated with a significant increase in Invisalign practice receipts. When projected across the first 12 months, this increase amounts to an additional 5.92 receipts for the entire sample (i.e., 1,871 GP and orthodontic practices worldwide) and an additional 3.41 receipts for the subset of 319 low-volume, North American GPs.

Seizure self-prediction: Myth or missed opportunity?

PURPOSE: Many patients report being able to predict their own seizures, and yet most seizures appear to strike out of the blue. This inherent contradiction makes the topic of seizure self-prediction controversial as well as difficult to study. Here we review the evidence for whether this ability exists, how many patients are capable of self-prediction and the nature of this capability, and whether this could provide a target for intervention. METHODS: Systematic searches of bibliographic databases including MEDLINE, EMBASE and PsycINFO through OVID were performed to identify relevant papers which were then screened by the study authors for inclusion in the study. 18 papers were selected for inclusion as the focus of this review. RESULTS: On the basis of two studies, between 17% and 41% of patients demonstrate a significantly greater than chance ability to predict an upcoming seizure in the following 12-h time window. This risk is correlated with self-reported anxiety, stress, sleep deprivation, mood and certain prodromal symptoms. However, there is no evidence for any subjective experience which directly heralds an imminent seizure. Thus, while patients may be aware of seizure risk, and have some ability to predict seizure occurrence over a wide time window, they are unable to subjectively recognise seizure onset in advance. CONCLUSION: Utilising subjectively acquired knowledge of seizure risk may provide a widely implementable tool for targeted intervention. The risk fluctuates over a time course appropriate for pharmacotherapy which may improve seizure control and the side-effect profile of anti-epileptic medication.

Chalcogenide Hybrid Inorganic/Organic Polymers: Ultrahigh Refractive Index Polymers for Infrared Imaging.

We report on the preparation of ultrahigh refractive index polymers via the inverse vulcanization of elemental sulfur, selenium, and 1,3-diisopropenylbenzene for use as novel transmissive materials for mid-infrared (IR) imaging applications. Poly(sulfur-random-selenium-random-(1,3-diisopropenylbenzene)) (poly(S-r-Se-r-DIB) terpolymer materials from this process exhibit the highest refractive index of any synthetic polymer (n > 2.0) and excellent IR transparency, which can be directly tuned by terpolymer composition. Sulfur or selenium containing (co)polymers prepared via inverse vulcanization can be described as Chalcogenide Hybrid Inorganic/Organic Polymers (CHIPs) and are polymeric analogues to wholly inorganic Chalcogenide Glasses (ChGs), which are commonly used as transmissive materials in mid-IR imaging. Finally, we demonstrate that CHIPs composed of (poly(S-r-Se-r-DIB) can be melt processed into windows that enabled high quality mid-IR thermal imaging of human subjects and highly resolved imaging of human vasculature.

The link between employee attitudes and employee effectiveness: Data matrix of meta-analytic estimates based on 1161 unique correlations.

This article offers a correlation matrix of meta-analytic estimates between various employee job attitudes (i.e., Employee engagement, job satisfaction, job involvement, and organizational commitment) and indicators of employee effectiveness (i.e., Focal performance, contextual performance, turnover intention, and absenteeism). The meta-analytic correlations in the matrix are based on over 1100 individual studies representing over 340,000 employees. Data was collected worldwide via employee self-report surveys. Structural path analyses based on the matrix, and the interpretation of the data, can be found in "Investigating the incremental validity of employee engagement in the prediction of employee effectiveness: a meta-analytic path analysis" (Mackay et al., 2016) [1].

Information and Communication Technology, Well-Being, and Ethnicity.

The relationship between use of information and communication technologies (ICTs) and well-being is an increasingly debated public health issue. Currently, there is limited understanding of how the ethnic digital divide influences this association. Thus, this study assessed how ethnicity has historically moderated relations between ICT (mobile phone, computer, and TV) uptake, and several well-being indicators: (a) long-term health (chronic illness), (b) cigarette smoking, and (c) self-perceptions of personal health. Archived data from a U.K. Office for National Statistics household survey 2007-2011 (97,697 participant records) were analyzed, controlling for multiple sociodemographic confounders. Mobile phone dependence was associated with poorer health perceptions in Caucasian women, but more favorable appraisals in ethnic minority females (OR = 0.51). Furthermore, mobile phone uptake was more strongly related to increased behavioral risk (cigarette smoking) in Caucasian men compared with ethnic minority males (OR = 1.68). Ethnicity did not influence relations between ICT uptake and long-term health. Overall, ethnicity was implicated in relations between mobile phone use and well-being indicators: unfavorable associations occurred primarily in Caucasians.

High Refractive Index Copolymers with Improved Thermomechanical Properties via the Inverse Vulcanization of Sulfur and 1,3,5-Triisopropenylbenzene.

The synthesis of a novel high sulfur content material possessing improved thermomechanical properties is reported via the inverse vulcanization of elemental sulfur (S8) and 1,3,5-triisopropenylbenzene (TIB). A key feature of this system was the ability to afford highly cross-linked, thermosetting materials, where the use of TIB as a comonomer enabled facile control of the network structure and dramatically improved the glass transition temperature (relative to our earlier sulfur copolymers) of poly(sulfur-random-(1,3,5-triisopropenylbenzene)) (poly(S-r-TIB)) materials over a range from T = 68 to 130 °C. This approach allowed for the incorporation of a high content of sulfur-sulfur (S-S) units in the copolymer that enabled thermomechanical scission of these dynamic covalent bonds and thermal reprocessing of the material, which we confirmed via dynamic rheological characterization. Furthermore, the high sulfur content also imparted high refractive index (n > 1.75) and IR transparency to poly(S-r-TIB) copolymers, which offered a route to enhanced optical transmitting materials for IR thermal imaging applications with improved thermomechanical properties.

Ethnic differences in diabetes prevalence and ICT use.

BACKGROUND: Uptake of information and communication technology (ICT) by individuals with diabetes can assist nursing care delivery, and improve patient outcomes. However, it is unclear how such uptake relates to ethnic differences in diabetes risk. AIM: To assess the moderating effects of ICT uptake on South Asian excess diabetes prevalence over a specific elapsed timeframe, accounting for selected environmental, socio-economic, and behavioural risk factors. METHOD: Archived data from a UK Office for National Statistics household survey 2006-2011 (120 621 partly non-orthogonal participant records) were analysed using hierarchical binary logistic regression analyses. RESULTS: ICT uptake qualified ethnic differences in diabetes prevalence. Non-smoking diabetes cases living in terraced housing with a home computer were more likely to be South Asian than Caucasian. By contrast, such cases were more likely to be Caucasian if a computer was unavailable (OR: 0.61; CI: 0.43-0.86; P=0.005). Furthermore, diabetes cases from low-income, mobile-dependent homes were probably South Asian (OR: 0.05; CI: 0.00-0.50; P=0.012). CONCLUSIONS: Home computing was linked to better tobacco control among South Asians with diabetes living in terraced properties. Mobile phone dependence was pronounced in those that received income support. Implications for nursing care are considered.

Meter-long multiblock copolymer microfibers via interfacial bioorthogonal polymerization.

High-molecular-weight multiblock copolymers are synthesized as robust polymer fibers via interfacial bioorthogonal polymerization employing the rapid cycloaddition of s-tetrazines with strained trans-cyclooctenes. When cell-adhesive peptide is incorporated in the tetrazine monomer, the resulting protein-mimetic polymer fibers provide guidance cues for cell attachment and elongation.