Understanding the Carbyne Formation from CH Complexes.

Nature chooses a high-valent tungsten center at the active site of the enzyme acetylene hydratase to facilitate acetylene hydration to acetaldehyde. However, the reactions of tungsten-coordinated acetylene are still not well understood, which prevents the development of sustainable bioinspired alkyne hydration catalysts. Here we report the reactivity of two bioinspired tungsten complexes with the acetylene ligand acting as a four-: [W(CO)(CH)(PymS)] () and a two-electron donor: [WO(CH)(PymS)] (), with PMe as a nucleophile to simulate the enzyme's reactivity (PymS = 4-(trifluoromethyl)-6-methylpyrimidine-2-thiolate).

Closed-loop recyclability of a biomass-derived epoxy-amine thermoset by methanolysis.

Epoxy resin thermosets (ERTs) are an important class of polymeric materials. However, owing to their highly cross-linked nature, they suffer from poor recyclability, which contributes to an unacceptable level of environmental pollution. There is a clear need for the design of inherently recyclable ERTs that are based on renewable resources.

Development of Visceral and Subcutaneous-Abdominal Adipose Tissue in Breastfed Infants during First Year of Lactation.

This study aimed to investigate relationships between infant abdominal visceral and subcutaneous adiposity and human milk (HM) components and maternal body composition (BC) during first year of lactation. Subcutaneous-abdominal depth (SAD), subcutaneous-abdominal fat area (SFA), visceral depth (VD) and preperitoneal fat area of 20 breastfed infants were assessed at 2, 5, 9 and 12 months using ultrasound. Maternal BC was determined with bioimpedance spectroscopy.

25 Years of Research in Human Lactation: From Discovery to Translation.

Researchers have recently called for human lactation research to be conceptualized as a biological framework where maternal and infant factors impacting human milk, in terms of composition, volume and energy content are studied along with relationships to infant growth, development and health. This approach allows for the development of evidence-based interventions that are more likely to support breastfeeding and lactation in pursuit of global breastfeeding goals. Here we summarize the seminal findings of our research programme using a biological systems approach traversing breast anatomy, milk secretion, physiology of milk removal with respect to breastfeeding and expression, milk composition and infant intake, and infant gastric emptying, culminating in the exploration of relationships with infant growth, development of body composition, and health.

Asymmetric Allylation Catalyzed by Chiral Phosphoric Acids: Stereoselective Synthesis of Tertiary Alcohols and a Reagent-Based Switch in Stereopreference.

The substrate scope of the asymmetric allylation with zinc organyls catalyzed by 3,3-bis(2,4,6-triisopropylphenyl)-1,1-binaphthyl-2,2-diyl hydrogenphosphate (TRIP) has been extended to non-cyclic ester organozinc reagents and ketones. Tertiary chiral alcohols are obtained with ee's up to 94% and two stereogenic centers can be created. Compared to the previous lactone reagent the stereopreference switches almost completely, proving the fact that the nature of the organometallic compound is of immense importance for the asymmetry of the product.

Anomalous behavior of plasma response functions at strong coupling.

Using data from equilibrium molecular dynamics computer simulations we have built up a catalog of response functions for the Coulomb one-component plasma over a wide range of Γ coupling values, including the strongly coupled Γ>1 liquid regime. We focus on the domain of negative compressibility (Γ>3), where the proper response displays an acausal behavior, implying a modification of the relation between its real and imaginary parts in the Kramers-Kronig relations. We give a description of the details of this acausal feature, in both the frequency and time domains.

Integrating approaches for quality guideline development in LactaMap, an online lactation care support system.

Background: Health professionals caring for women and infants experiencing difficulty with breastfeeding have reported deficiencies in evidence-based lactation knowledge. LactaMap is an online lactation care support system with more than 100 clinical practice guidelines to support breastfeeding care. Clinical practice guidelines support medical decision-making by summarising scientific evidence into systematically developed statements for specific clinical circumstances.

Acoustically Induced Vocal Training for Individuals With Impaired Hearing.

Objectives/hypothesis: Articulation, phonation, and resonance disorders in the speech of hearing-impaired-speakers reduces intelligibility. The study focusses on (1) whether nonacoustic feedback may facilitate the adjustment of the vocal tract, leading to increased vocal tract resonance, and (2) whether training with the feedback would be helpful for the subsequent formation of vowels.

Study Design: Prospective.

Strongly coupled Yukawa trilayer liquid: Structure and dynamics.

The equilibrium structure and the dispersion relations of collective excitations in trilayer Yukawa systems in the strongly coupled liquid regime are examined. The equilibrium correlations reveal a variety of structures in the liquid phase, reminiscent of the corresponding structures in the solid phase. At small layer separation substitutional disorder becomes the governing feature.

High-dynamic-range areal profilometry using an imaging, dispersion-encoded low-coherence interferometer.

This work presents the design and characterization of an approach for areal surface profilometry with sub-nm axial resolution. The developed approach is based on a low-coherence interferometer enhanced by an dispersive element to control the axial resolution and measurement range. Optical path differences are detected by an imaging spectrometer where equalization wavelengths are determined as a basis for fitting spectra.

Mechanistic Studies of the TRIP-Catalyzed Allylation with Organozinc Reagents.

3,3-Bis(2,4,6-triisopropylphenyl)-1,1-binaphthyl-2,2-diyl hydrogenphosphate (TRIP) catalyzes the asymmetric allylation of aldehydes with organozinc compounds, leading to highly valuable structural motifs, like precursors to lignan natural products. Our previously reported mechanistic proposal relies on two reaction intermediates and requires further investigation to really understand the mode of action and the origins of stereoselectivity. Detailed ab initio calculations, supported by experimental data, render a substantially different mode of action to the allyl boronate congener.

Human milk immunomodulatory proteins are related to development of infant body composition during the first year of lactation.

Background: To investigate relationships between infant body composition (BC) and human milk (HM) immunomodulatory proteins (IMPs) during the first 12 months of lactation.

Methods: BC of breastfeeding dyads (n = 20) was measured with ultrasound skinfolds (infants) and bioimpedance spectroscopy (infants/mothers) at 2, 5, 9, and/or 12 months post partum. Breastfeeding frequency, 24-h milk intake, and IMP concentrations (lactoferrin, lysozyme, secretory immunoglobulin A (sIgA)) were measured, and calculated daily intakes (CDIs) were determined.

Development of LactaPedia: A lactation glossary for science and medicine.

During the last decade, there have been several publications highlighting the need for consistent terminology in breastfeeding research. Standard terms and definitions are essential for the comparison and interpretation of scientific studies that, in turn, support evidence-based education, consistency of health care, and breastfeeding policy. Inconsistent advice is commonly reported by mothers to contribute to early weaning.

Sound speed in Yukawa one-component plasmas across coupling regimes.

A many-body system of charged particles interacting via a pairwise Yukawa potential, the so-called Yukawa one-component plasma (YOCP), is a good approximation for a variety of physical systems. Such systems are completely characterized by two parameters: the screening parameter, κ, and the nominal coupling strength, Γ. It is well known that the collective spectrum of the YOCP is governed by a longitudinal acoustic mode, both in the weakly and strongly coupled regimes.

Short-term rate of milk synthesis and expression interval of preterm mothers.

Aim: To determine the impact of the pumping regimes of women with preterm infants on the daily milk production, and on the short-term rate of milk synthesis during early lactation to support evidence-based recommendations for optimising milk production.

Methods: Mothers of preterm infants (n=25) recorded start time, finish time and expression volumes from every breast expression on days 10, 15-20 postpartum.

Results: Expressing more often than five times per day did not result in a significant increase in daily milk production.

Carbohydrates in Human Milk and Body Composition of Term Infants during the First 12 Months of Lactation.

Human milk (HM) carbohydrates may affect infant appetite regulation, breastfeeding patterns, and body composition (BC). We investigated relationships between concentrations/calculated daily intakes (CDI) of HM carbohydrates in first year postpartum and maternal/term infant BC, as well as breastfeeding parameters. BC of dyads ( = 20) was determined at 2, 5, 9, and/or 12 months postpartum using ultrasound skinfolds (infants) and bioelectrical impedance spectroscopy (infants/mothers).

The Potential of Liming to Improve Drought Tolerance of Norway Spruce [ (L.) Karst.].

In response to a wide-spread decline in forest vitality associated with acid rain in the 1980s, liming of soils has been implemented in many federal states in Germany to buffer further acid deposition and improve availability of nutrients such as calcium and magnesium. As a consequence, it may also increase vitality and depth of fine-root systems and hence improve the drought tolerance of species such as Norway spruce [ (L.) Karst.

TRIP-Catalyzed Asymmetric Synthesis of (+)-Yatein, (-)-α-Conidendrin, (+)-Isostegane, and (+)-Neoisostegane.

The asymmetric allylation under the assistance of catalytic amounts of 3,3'-bis(2,4,6-triisopropylphenyl)-1,1'-binaphthyl-2,2'-diyl hydrogen phosphate (TRIP) allows the concise construction of the lignan scaffold from simple aldehydes and allylic bromides with full control of the two formed stereocenters. This young methodology has been employed to synthesize four naturally and pharmaceutically active lignans. Members of the dibenzylbutyrolactone, the tetraline, and the dibenzocyclooctadiene classes have been synthesized in 40-47% overall yield along four-step synthetic routes.

Chemoenzymatic Total Synthesis of Deoxy-, epi-, and Podophyllotoxin and a Biocatalytic Kinetic Resolution of Dibenzylbutyrolactones.

Podophyllotoxin is probably the most prominent representative of lignan natural products. Deoxy-, epi-, and podophyllotoxin, which are all precursors to frequently used chemotherapeutic agents, were prepared by a stereodivergent biotransformation and a biocatalytic kinetic resolution of the corresponding dibenzylbutyrolactones with the same 2-oxoglutarate-dependent dioxygenase. The reaction can be conducted on 2 g scale, and the enzyme allows tailoring of the initial, "natural" structure and thus transforms various non-natural derivatives.

Spatially Resolved Cross-Linking Characterization by Imaging Low-Coherence Interferometry.

A method to characterize cross-linking differences in polymers such as waveguide polymers has been developed. The method is based on the scan-free information acquisition utilizing a low-coherence interferometer in conjunction with an imaging spectrometer. By the introduction of a novel analyzing algorithm, the recorded spectral-phase data was interpreted as wavelength-dependent optical thickness which is matchable with the refractive index and therefore with the degree of cross-linking.

Disrupting the spatio-temporal symmetry of the electron dynamics in atmospheric pressure plasmas by voltage waveform tailoring.

Single frequency, geometrically symmetric Radio-Frequency (rf) driven atmospheric pressure plasmas exhibit temporally and spatially symmetric patterns of electron heating, and consequently, charged particle densities and fluxes. Using a combination of phase-resolved optical emission spectroscopy and kinetic plasma simulations, we demonstrate that tailored voltage waveforms consisting of multiple rf harmonics induce targeted disruption of these symmetries. This confines the electron heating to small regions of time and space and enables the electron energy distribution function to be tailored.

Supercontinuum-based nondisruptive scattering analyses of mouse fibroblast L929 cells before and after necrosis.

The scattering properties of biological tissue are highly dependent on the structure size, refractive index, and wavelength of the incident light. Furthermore, these scattering characteristics are strongly influenced by movements of the scattering objects. A method is developed to determine the angular- and spectral-resolved scattering properties that enabled the characterization of biological nano- and microscaled cell structures.

Human Milk Casein and Whey Protein and Infant Body Composition over the First 12 Months of Lactation.

Human milk (HM) influences infant feeding patterns and body composition (BC). This small proof-of concept longitudinal study investigated relationships between infant/maternal BC and HM casein, whey and total protein during the first 12 months of lactation. BC of breastfeeding dyads ( = 20) was measured at 2 ( = 15), 5 ( = 20), 9 ( = 19), and/or 12 ( = 18) months postpartum with ultrasound skinfolds (infants) and bioimpedance spectroscopy (infants/mothers).

Hourly Breast Expression to Estimate the Rate of Synthesis of Milk and Fat.

Objective measurement of the rate of synthesis of breast milk and fat in breastfeeding mothers requires test-weighing of each breastfeed and the measurement of each expression from each breast over 24 h, with the collection of milk samples before and after each breastfeed and expression. We sought an abbreviated technique for measuring these rates of synthesis. Participants completed a 24-h breastfeeding milk profile, and expressed their breasts on arrival at the research room and each hour thereafter for 3 h (4 expressions).