Evidence of environmental strains on charge injection in silole based organic light emitting diodes

Using d. functional theory (DFT) computations, the authors demonstrated a substantial skeletal relaxation when the structure of 2,5-bis-[4-anthracene-9-yl-phenyl]-1,1-dimethyl-3,4-diphenyl-silole (BAS) is optimized in the gas-phase comparing with the mol. structure detd. from monocrystal x-ray diffraction. The origin of such a relaxation is explained by a strong environmental strains induced by the presence of anthracene entities. Also, the estn. of the frontier orbital levels showed that this structural relaxation affects mainly the LUMO that is lowered of 190 meV in the gas phase. To check if these theor. findings would be confirmed for thin films of BAS, the authors turned to UV photoemission spectroscopy and/or inverse photoemission spectroscopy and electrooptical measurements. The study of the c.d. or voltage and luminance or voltage characteristics of an ITO/PEDOT/BAS/Au device clearly demonstrated a very unusual temp.-dependent behavior. Using a thermally assisted tunnel transfer model, this behavior likely originated from the variation of the electronic affinity of the silole deriv. with the temp. The thermal agitation relaxes the mol. strains in thin films as it is shown when passing from the cryst. to the gas phase. The relaxation of the intramol. thus induces an increase of the electronic affinity and, as a consequence, the more efficient electron injection in org. light-emitting diodes

Enantioselective Synthesis of the Lomaiviticin Aglycon Full Carbon Skeleton Reveals Remarkable Remote Substituent Effects During the Dimerization Event

Chemistry and Chemical Biolog

Progress Toward the Total Synthesis of the Lomaiviticins and a Biomimetic Unified Strategy for the Synthesis of 7-Membered Ring-Containing Lycopodium Alkaloids

Lomaiviticin A (1) and B (2) are natural products with remarkably complex C2-symmetric structures and potent antiproliferative properties. Achieving total syntheses of 1 and 2 has been a long-standing project in the Shair group and part one of this thesis describes our first successful synthesis of the C4-epi-lomaiviticin A and B core structures. A key stereoselective oxidative enolate dimerization of an oxanorbornanone system was employed to establish the highly hindered C2-C2' bond. Crucial to our completion of the lomaiviticin core structures was the discovery of subtle yet far-reaching stereoelectronic effects imparted by the C4/C4'-stereocenters. The Lycopodium alkaloids are a family of complex polycyclic alkaloid natural products that have long served as popular targets for developing synthetic chemistry. More recently, select members have been reported to exhibit neurological effects. Part two of this thesis presents the development of a biomimetic, unified strategy for the synthesis of 7-membered ring-containing Lycopodium alkaloids and its successful application toward the first total syntheses of the proposed structure of (-)-himeradine A (38), (-)-lycopecurine (39), and (-)-dehydrolycopecurine (199), and the syntheses of (+)-lyconadin A (31) and (-)-lyconadin B (32). A biosynthetically inspired one-pot cascade reaction sequence was developed to construct the strained polycyclic core structure shared amongst these alkaloids. Additionally, the syntheses of 38, 39, and 199 featured a biomimetic intramolecular Mannich reaction to furnish the tetracyclic ring system. The successful application of our unifying strategy toward the synthesis of a diverse set of alkaloids lends support to our biosynthetic hypothesis that 7-membered ring-containing Lycopodium alkaloids arise from a common precursor. Our synthetic approach can potentially provide access to all such natural products.Chemistry and Chemical Biolog

Midwest Evaluation of the Adult Functioning of Former Foster Youth

The Midwest Evaluation of the Adult Functioning of Former Foster Youth (Midwest Study) is a prospective study that has been following a sample of young people from Iowa, Wisconsin, and Illinois as they transition out of foster care into adulthood. It is a collaborative effort involving Chapin Hall at the University of Chicago; Partners for Our Children at the University of Washington, Seattle; the University of Wisconsin Survey Center; and the public child welfare agencies in Illinois, Iowa, and Wisconsin.The Midwest Study provides a comprehensive picture of how foster youth are faring during this transition since the Foster Care Independence Act of 1999 became law. Foster youth in Iowa, Wisconsin, and Illinois were eligible to participate in the study if they had entered care before their 16th birthday, were still in care at age 17, and had been removed from home for reasons other than delinquency. Baseline survey data were collected from 732 study participants when they were 17 or 18 years old. Study participants were re-interviewed at ages 19 (n = 603), 21 (n = 591), and 23 or 24 (n = 602). A fifth wave of survey data will be collected when study participants are 25 or 26 years old.Because many of the questions Midwest Study participants were also asked as part of the National Longitudinal Study of Adolescent Health, it is possible to make comparisons between this sample of former foster youth and a nationally representative sample of young people in the general population. These comparisons indicate that young people who have aged out of foster care are faring poorly as a group relative to their peers across a variety of domains.The Midwest Study also presents a unique opportunity to compare the outcomes of young people from one state (i.e., Illinois) that allows foster youth to remain in care until their 21st birthday to the outcomes of young people from two other states (i.e., Iowa and Wisconsin) in which foster youth generally age out when they are 18 years old. The data suggest that extending foster care until age 21 may be associated with better outcomes, at least in some domains

Crisaborole Ointment Improves Quality of Life of Patients with Mild to Moderate Atopic Dermatitis and Their Families.

IntroductionThe impact of crisaborole ointment, a nonsteroidal phosphodiesterase 4 inhibitor for the treatment of mild to moderate atopic dermatitis (AD), on quality of life (QoL) was assessed in two identically designed phase 3 studies (AD-301: NCT02118766; AD-302: NCT02118792, both at http://www.clinicaltrials.gov ).MethodsIn both studies, patients aged ≥ 2 years with mild to moderate AD per the Investigator's Static Global Assessment were randomly assigned 2:1 to receive crisaborole or vehicle twice daily for 28 days. QoL was assessed using the Children's Dermatology Life Quality Index (CDLQI) (2-15 years), the Dermatology Life Quality Index (DLQI) (≥ 16 years), and the Dermatitis Family Impact Questionnaire (DFI) (parents/caregivers/family of patients aged 2-17 years). Established QoL score severity bands provided clinical context.ResultsGreater mean improvement in QoL was observed in crisaborole-treated patients than in vehicle-treated patients at day 29 [mean change from baseline (∆BL), CDLQI: - 4.6 vs. - 3.0; P < 0.001; DLQI: - 5.2 vs. - 3.5; P = 0.015]. At baseline, more than half the patients had a "moderate effect" or higher of AD on QoL. At day 29, there was a trend toward more crisaborole- than vehicle-treated patients having "small effect" to "no effect", The QoL of parents/caregivers/family improved more for crisaborole-treated than for vehicle-treated patients (∆BL, DFI: - 3.7 vs. - 2.7; P = 0.003).ConclusionCrisaborole treatment results in clinically meaningful improvement in QoL for patients and their parents/caregivers/families.Trial registrationAD-301: http://www.clinicaltrials.gov , NCT02118766; AD-302: http://www.clinicaltrials.gov , NCT02118792.FundingAnacor Pharmaceuticals, Inc., a wholly owned subsidiary of Pfizer Inc., New York, NY

Mass production of volume phase holographic gratings for the VIRUS spectrograph array

The Visible Integral-field Replicable Unit Spectrograph (VIRUS) is a baseline array of 150 copies of a simple, fiber-fed integral field spectrograph that will be deployed on the Hobby-Eberly Telescope (HET). VIRUS is the first optical astronomical instrument to be replicated on an industrial scale, and represents a relatively inexpensive solution for carrying out large-area spectroscopic surveys, such as the HET Dark Energy Experiment (HETDEX). Each spectrograph contains a volume phase holographic (VPH) grating with a 138 mm diameter clear aperture as its dispersing element. The instrument utilizes the grating in first-order for 350-550 nm. Including witness samples, a suite of 170 VPH gratings has been mass produced for VIRUS. Here, we present the design of the VIRUS VPH gratings and a discussion of their mass production. We additionally present the design and functionality of a custom apparatus that has been used to rapidly test the first-order diffraction efficiency of the gratings for various discrete wavelengths within the VIRUS spectral range. This device has been used to perform both in-situ tests to monitor the effects of adjustments to the production prescription as well as to carry out the final acceptance tests of the gratings' diffraction efficiency. Finally, we present the as-built performance results for the entire suite of VPH gratings.Comment: 16 pages, 11 figures, 2 tables. To be published in Proc. SPIE, 2014, "Advances in Optical and Mechanical Technologies for Telescopes and Instrumentation", 9151-53. The work presented in this article follows from arXiv:1207:448

Motivational Interviewing to Improve Self-Care for Patients with Chronic Heart Failure: MITI-HF Randomized Controlled Trial

OBJECTIVE: The purpose of this study was to test the efficacy of a tailored motivational interviewing (MI) intervention versus usual care for improving HF self-care behaviors, physical HF symptoms and quality of life. METHODS: This is a single-center, randomized controlled trial. Participants were enrolled in the hospital. Immediately after discharge, those in the intervention group received a single home visit and 3-4 follow-up phone calls by a nurse over 90 days. RESULTS: A total of 67 participants completed the study (mean age 62±12.8 years), of which 54% were African American, 30% were female, 84% had class III/IV symptoms, and 63% were educated at a high school level or less. There were no differences between the groups in self-care maintenance, self-care confidence, physical HF symptoms, or quality of life at 90 days. CONCLUSION: Patients who received the MI intervention had significant and clinically meaningful improvements in HF self-care maintenance over 90 days that exceeded that of usual care. PRACTICE IMPLICATIONS: These data support the use of a nurse-led MI intervention for improving HF self-care. Identifying methods to improve HF self-care may lead to improved clinical outcomes

The influence of end of day silicone hydrogel daily disposable contact lens fit on ocular comfort, physiology and lens wettability

Purpose: To quantify the end-of-day silicone-hydrogel daily disposable contact lens fit and its influence of on ocular comfort, physiology and lens wettability. Methods: Thirty-nine subjects (22.1. ±. 3.5 years) were randomised to wear each of 3 silicone-hydrogel daily-disposable contact lenses (narafilcon A, delefilcon A and filcon II 3), bilaterally, for one week. Lens fit was assessed objectively using a digital video slit-lamp at 8, 12 and 16. h after lens insertion. Hyperaemia, non-invasive tear break-up time, tear meniscus height and comfort were also evaluated at these timepoints, while corneal and conjunctival staining were assessed on lens removal. Results: Lens fit assessments were not different between brands (P > 0.05), with the exception of the movement at blink where narafilcon A was more mobile. Overall, lag reduced but push-up speed increased from 8 to 12. h (P 0.05). Movement-on-blink was unaffected by wear-time (F = 0.403, P = 0.670). A more mobile lens fit with one brand did not indicate that person would have a more mobile fit with another brand (r = -0.06 to 0.63). Lens fit was not correlated with comfort, ocular physiology or lens wettability (P > 0.01). Conclusions: Among the lenses tested, objective lens fit changed between 8. h and 12. h of lens wear. The weak correlation in individual lens fit between brands indicates that fit is dependent on more than ocular shape. Consequently, substitution of a different lens brand with similar parameters will not necessarily provide comparable lens fit

Robotic-Assisted Laparoscopic Gynecologic Procedures in a Fellowship Training Program

An early evaluation of the feasibility of training fellows in robotic surgery suggests that it is feasible to incorporate a systematic approach to robotic-assisted laparoscopic training at the onset of incorporating this technology into current practice

Cerebral Small Vessel Disease: Cognition, Mood, Daily Functioning, and Imaging Findings from a Small Pilot Sample

Cerebral small vessel disease, a leading cause of cognitive decline, is considered a relatively homogeneous disease process, and it can co-occur with Alzheimer's disease. Clinical reports of magnetic resonance imaging (MRI)/computed tomography and single photon emission computed tomography (SPECT) imaging and neuropsychology testing for a small pilot sample of 14 patients are presented to illustrate disease characteristics through findings from structural and functional imaging and cognitive assessment. Participants showed some decreases in executive functioning, attention, processing speed, and memory retrieval, consistent with previous literature. An older subgroup showed lower age-corrected scores at a single time point compared to younger participants. Performance on a computer-administered cognitive measure showed a slight overall decline over a period of 8–28 months. For a case study with mild neuropsychology findings, the MRI report was normal while the SPECT report identified perfusion abnormalities. Future research can test whether advances in imaging analysis allow for identification of cerebral small vessel disease before changes are detected in cognition