We present a class of visible-light-driven molecular motors based on barbituric acid. Due to a serendipitous reactivity we observed during their synthesis, these motors possess a tertiary stereogenic centre on the upper half, characterised by a hydroxy group. Using a combination of femto- and nanosecond transient absorption spectroscopy, molecular dynamics simulations and low-temperature H NMR experiments we found that these motors operate similarly to push-pull second-generation overcrowded alkene-based molecular motors.
View Article and Find Full Text PDFCoupled motion is ubiquitous in Nature as it forms the base for the direction, amplification, propagation, and synchronization of movement. Herein, we present experimental proof for the coupling of the rocking motion of a dihydroanthracene stator moiety with the light-induced rotational movement of an overcrowded alkene-based molecular motor. The motor was desymmetrized, introducing two different alkyl substituents to the stator part of the molecular scaffold, resulting in the formation of two diastereomers with opposite axial chirality.
View Article and Find Full Text PDFSynthetic molecular machines hold tremendous potential to revolutionize chemical and materials sciences. Their autonomous motion controlled by external stimuli allows to develop smart materials whose properties can be adapted on command. For the realisation of more complex molecular machines, it is crucial to design building blocks whose properties can be controlled by multiple orthogonal stimuli.
View Article and Find Full Text PDFIntroduction: Enhanced prenatal/postnatal care home visiting programs for Medicaid-insured women have significant positive impacts on care and health outcomes. However, enhanced prenatal care participation rates are typically low, enrolling <30% of eligible women. This study investigates the impacts of a population-based systems approach on timely enhanced prenatal care participation and other healthcare utilization.
View Article and Find Full Text PDFPhotoacoustic (PA) imaging can be used to monitor flowing blood inside the microvascular and capillary bed. Ultrasound speckle decorrelation based velocimetry imaging was previously shown to accurately estimate blood flow velocity in mouse brain (micro-)vasculature. Translating this method to photoacoustic imaging will allow simultaneous imaging of flow velocity and extracting functional parameters like blood oxygenation.
View Article and Find Full Text PDFStud Health Technol Inform
September 2019
The steady increase in the number of patients equipped with mechanical heart support implants, such as left ventricular assist devices (LVAD), along with virtually ubiquitous 24/7 internet connectivity coverage is motive to investigate and develop remote patient monitoring. In this study we explore machine learning approaches to infection severity recognition on driveline exit site images. We apply a U-net convolutional neural network (CNN) for driveline tube segmentation, resulting in a Dice score coefficient of 0.
View Article and Find Full Text PDFBacteria regulate cell physiology in response to extra- and intracellular cues. Recent work showed that metabolic fluxes are reported by specific metabolites, whose concentrations correlate with flux through the respective metabolic pathway. An example of a flux-signaling metabolite is fructose-1,6-bisphosphate (FBP).
View Article and Find Full Text PDFMotivation: Polypeptide sequence length is the single dominant factor hampering the effectiveness of currently available software tools for de novo calculation of amino acid-specific protonation constants in disordered polypeptides.
Results: We have developed pepKalc, a robust simulation software for the comprehensive evaluation of protein electrostatics in unfolded states. Our software completely removes the limitations of the previously reported Monte-Carlo approaches in the computation of protein electrostatics by using a hybrid approach that effectively combines exact and mean-field calculations to rapidly obtain accurate results.
Three-dimensional ultrasound is a powerful imaging technique, but it requires thousands of sensors and complex hardware. Very recently, the discovery of compressive sensing has shown that the signal structure can be exploited to reduce the burden posed by traditional sensing requirements. In this spirit, we have designed a simple ultrasound imaging device that can perform three-dimensional imaging using just a single ultrasound sensor.
View Article and Find Full Text PDFPurpose While Healthy Start has emphasized the need for multi-sectorial community engagement and collaboration since its inception, in 2014 Healthy Start adopted Collective Impact (CI) as a framework for reducing infant mortality. This paper describes the development of a peer-focused capacity-building strategy that introduced key elements of CI and preliminary findings of Healthy Start grantees' progress with using CI as an approach to collaboration. Description The Collective Impact Peer Learning Networks (CI-PLNs) consisted of eight 90-min virtual monthly meetings and one face-to-face session that reviewed CI pre-conditions and conditions.
View Article and Find Full Text PDFSymmetric molecular motors based on two overcrowded alkenes with a notable absence of a stereogenic center show potential to function as novel mechanical systems in the development of more advanced nanomachines offering controlled motion over surfaces. Elucidation of the key parameters and limitations of these third-generation motors is essential for the design of optimized molecular machines based on light-driven rotary motion. Herein we demonstrate the thermal and photochemical rotational behavior of a series of third-generation light-driven molecular motors.
View Article and Find Full Text PDFObjective: The aim was to investigate the association between autoantibodies (autoAbs) and neuropsychiatric (NP) involvement in patients with SLE and to evaluate whether any autoAb or a combination of these autoAbs could indicate the underlying pathogenic process.
Methods: Using a multiplexed protein array for 94 antigens, we compared the serum autoAb profiles of 69 NPSLE patients, 203 SLE patients without NP involvement (non-NPSLE) and 51 healthy controls. Furthermore, we compared the profiles of NPSLE patients with clinical inflammatory (n = 38) and ischaemic (n = 31) NP involvement.
Background: As a result of effective combination antiretroviral therapy (cART) and advanced supportive healthcare, a growing number of human immunodeficiency virus (HIV)-infected children survive into adulthood. The period of transition to adult care is often associated with impaired adherence to treatment and discontinuity of care. We aimed to evaluate virological and social outcomes of HIV-infected adolescents and young adults (AYAs) before and after transition, and explore which factors are associated with virological failure.
View Article and Find Full Text PDFPurpose: Complete interferon-γ receptor 1 (IFN-γR1) deficiency is a primary immunodeficiency causing predisposition to severe infection due to intracellular pathogens. Only 36 cases have been reported worldwide. The purpose of this article is to describe a large novel deletion found in 3 related cases, which resulted in the complete removal of the IFNGR1 gene.
View Article and Find Full Text PDFThe external photocontrol over peptide folding, by the incorporation of molecular photoswitches into their structure, provides a powerful tool to study biological processes. However, it is limited so far to switches that exhibit only a rather limited geometrical change upon photoisomerization and that show thermal instability of the photoisomer. Here we describe the use of an overcrowded alkene photoswitch to control a model β-hairpin peptide.
View Article and Find Full Text PDFThe fragmentation pattern of the peptide model system, N-methylacetamide, is investigated using ion time-of-flight (TOF) spectroscopy after resonant K-shell excitation. Corresponding near-edge X-ray absorption fine structure (NEXAFS) spectra recorded at high resolution at the C1s, N1s and O1s edges are presented. Analysis of the ion TOF data reveals a multitude of fragmentation channels and dissociation pathways.
View Article and Find Full Text PDFWhen exposed to ultraintense x-radiation sources such as free electron lasers (FELs) the innermost electronic shell can efficiently be emptied, creating a transient hollow atom or molecule. Understanding the femtosecond dynamics of such systems is fundamental to achieving atomic resolution in flash diffraction imaging of noncrystallized complex biological samples. We demonstrate the capacity of a correlation method called "partial covariance mapping" to probe the electron dynamics of neon atoms exposed to intense 8 fs pulses of 1062 eV photons.
View Article and Find Full Text PDFWe have performed x-ray two-photon photoelectron spectroscopy using the Linac Coherent Light Source x-ray free-electron laser in order to study double core-hole (DCH) states of CO2, N2O, and N2. The experiment verifies the theory behind the chemical sensitivity of two-site DCH states by comparing a set of small molecules with respect to the energy shift of the two-site DCH state and by extracting the relevant parameters from this shift.
View Article and Find Full Text PDFFor more than 25 years, computer-aided design and computer-aided manufacturing (CAD/CAM) technology has been used in implant restorative dentistry. Today this technology offers a means of milling titanium frameworks that fit dental implants accurately. This report presents a restoratively driven protocol employing advanced implant restorative and surgical techniques.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
October 2011
Theory predicts that double-core-hole (DCH) spectroscopy can provide a new powerful means of differentiating between similar chemical systems with a sensitivity not hitherto possible. Although DCH ionization on a single site in molecules was recently measured with double- and single-photon absorption, double-core holes with single vacancies on two different sites, allowing unambiguous chemical analysis, have remained elusive. Here we report that direct observation of double-core holes with single vacancies on two different sites produced via sequential two-photon absorption, using short, intense X-ray pulses from the Linac Coherent Light Source free-electron laser and compare it with theoretical modeling.
View Article and Find Full Text PDFInt Urogynecol J Pelvic Floor Dysfunct
February 2009
A study was carried out to evaluate efficacy of Macroplastique(R) (MPQ) Implantation System (MIS) in women with urodynamic stress urinary incontinence (SUI) and urethral hypermobility after an unsuccessful conservative treatment. This is a prospective randomized controlled trial in women without previous incontinence surgery. Twenty-four women received MPQ.
View Article and Find Full Text PDFBackground: HIV-infected patients are at increased risk of venous and arterial thrombosis. We hypothesized that acquired thrombophilic abnormalities that could predispose to thrombosis are most pronounced in patients in advanced stages of HIV infection.
Methods: We included 109 consecutive HIV-infected patients in the study and tested them twice for currently known thrombophilic abnormalities at an interval of at least 3 months (median, 3 months; range, 3-12 months).
Femtosecond transient absorption pump-probe spectroscopy has been used to study the third- and fifth-order nonlinear susceptibility of UV-grade fused silica. Theoretical simulations support the experimental evidence of interference between the third- and fifth-order contributions to the signal. Approximate values of the second-order nonlinear refractive index n(4) and of the three-photon absorption coefficient gamma are obtained.
View Article and Find Full Text PDFObjective: To assess the efficacy of silicone microimplants (Macroplastique; polydimethylsiloxane) therapy for stress urinary incontinence in adult women, using a systematic review of identified studies.
Materials And Methods: A computer-aided and manual search for published studies investigating silicone microimplants therapy for stress urinary incontinence in adult women. The methodological quality of the included studies was assessed using criteria based on generally accepted principles of interventional research.