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This study was commissioned to assess if there are regional differences in the acceptability of beef between consumers from Northern Ireland (NI), Republic of Ireland (ROI) and Great Britain (GB). Palatability traits were affected by socioeconomic and behavioural factors such as preferred cooking endpoint, animal welfare, value, health aspects of beef product, ease of preparation as well as consumption frequency for specific cuts. "Willingness to pay" (WTP) was influenced by income, preferred cooking endpoint, value of beef product, ease of preparation and consumption frequency for frying steak. Results showed that GB consumers scored higher for the same striploin steak compared to NI and ROI consumers. This may be due to differences in the motivation for beef choice and/or consumption habits. GB consumers were less concerned about the healthiness of beef product and beef origin. In addition, a higher consumption frequency for rump was reported in GB, which may explain the higher sensory scores observed among GB consumers for striploins.

The growing trend towards the utilisation of biomass to produce fuels and chemicals has the potential to produce large quantities of protein-rich wastes that may be unsuitable for use as a feed. This protein waste could instead serve as a sustainable feedstock for the production of useful nitrogen-containing bio-based chemicals. We report herein the production of γ-aminobutyric acid from glutamic acid via a microwave-assisted decarboxylation reaction using isophorone as an inducer reagent. High yields of 63% can be achieved with only short reaction times (7 min) required. The influences of inducer loading, reaction time and hydrochloric acid concentration used for hydrolysis step of the work up were investigated at different scales. As a proof of concept, glutamic acid was facilely isolated from waste gluten, via microwave assisted hydrolysis, and subsequently decarboxylated with success. To the best of our knowledge this is the first organocatalytic route to γ-aminobutyric acid using glutamic acid as a reagent, and represents an alternative cleaner route to a valuable precursor for bio-based solvents, polymers and pharmaceuticals.

The transitioning from synchronous machine generation to large-scale integration of inverter-based renewable generation introduces new challenges in power system frequency stability. This paper proposes a new approach for evaluating power system frequency stability based on network clusters. First, the most common metrics for power system frequency stability are presented, with their advantages and disadvantages. Then, we establish the link between frequency response and network topology. Based on the pros and cons of current frequency stability metrics and the influence of network topology, a proposal is made for a new approach to evaluate frequency stability using Spectral Graph Theory to partition a power system network into clusters for analysis. Consider the displacement of synchronous generator inertia, together with the spatial–temporal fluctuations/noise fed in from spatially distributed variable renewable energy sources. Then the proposed clustering approach has two main advantages over traditional methods for evaluating power system frequency robustness. The first is a spatial awareness of a power system network in terms of frequency-stable areas. The second advantage is the ease of interpretation of the metric result for robust network planning.

peer-reviewed Fatty acids (g/100 g total fatty acids) in M. longissimus thoracis et lumborum (LTL) and total branched chain fatty acids (μg/g fat) in subcutaneous adipose tissue (SAT) of rams and castrates from Scottish Blackface (SB) or Texel × Scottish Blackface (T × SB) lambs, slaughtered at mean ages of 196, 242, 293, 344 or 385 days were determined. Lambs were fed pasture prior to a 36-day finishing period on a barley/maize-based concentrate ration. The intramuscular fat content (IMF; %) was higher (P

Several recent reports suggest that HNO may be produced endogenously by reaction of H2S and S-nitrosoglutathione (GSNO). This hypothesis was tested using deoxymyoglobin (MbFeII) to trap the expected HNO released from the target reaction, which should generate the stable HNO adduct, HNO-Mb, under anaerobic conditions. Under numerous experimental conditions, the sole globin product was NO-Mb, as characterized by absorbance, EPR, and NMR spectroscopies. Analogous reactions of GSNO with other biological reductants such as ascorbic acid, dithiothreitol, glutathione, and dithionite also yielded NO-Mb as the sole globin product; however, whereas analogous reduction of GSNO using NaBH4 generates HNO-Mb in high yield. Quantitative GC/MS analyses of reactions of GS15NO with H2S showed that the main reaction product was 15NO, with 15N2 produced at a comparable level to 15N2O. Overall yield of N2O is unchanged by the presence of MbFeII, discounting the intermediacy of either NO or HNO in its formation. Taken together, these results argue against the generation of free HNO as a major pathway in the reactions of GSNO with H2S, and instead imply some as yet uncharacterized intermediates generate the nitrogenic gases.

Crystal structures of five first-row transition metal complexes of a recently-available bis-pyrazolylpyridine (bpp) ligand, 2,6-bis(3′,5′-diphenylpyrazolyl)pyridine (bdppp), prepared by reaction with transition metal chlorides, are reported. The ligand forms two types of structures, a 2:1 complex with Fe (II) chloride, and 1:1 complexes with Mn(II), Ni(II), Co(II), and Zn(II), chlorides, resulting in two different geometries. In all cases the ligand is tridentate, but in contrast to reported bpp structures, the plane of the pyridine ring coordinating with the metal is significantly distorted from the plane of the pyrazoles and metal.

This contribution deals with the investigation of greener conditions for the preparation of 2,5-diacetyl-isosorbide from the bio-based substances isosorbide and acetic acid. The influence of solvent, catalyst and reactant ratio on the course of the isosorbide conversion and selectivity to 2,5-diacetyl-isosorbide as well as to the intermediate 2-acetyl-isosorbide is examined. It was found that the conventionally used solvent toluene can be substituted by the greener solvent n-propyl acetate. Additionally, the homogeneous acid catalyst p-toluene sulfonic acid can be replaced by the heterogeneous catalyst Amberlyst-15, resulting in an easier isolation of the desired 2,5-diacetyl-isosorbide, this being an important precursor for the vasodilatory drug isosorbide-5-nitrate.

Surfactant use throughout mankind is extensive, from their initial applications as detergents extending to use in medicine, lubricant, cosmetics and even enhanced oil recovery. However, the image of surfactant use has in the past been tarnished by issues with low biodegradability and their synthesis from nonsustainable resources. Amino acid–based surfactants are a class of surfactants derived from a hydrophobe source coupled with simple amino acids, mixed amino acids from synthesis or from protein hydrolysates, and as such can be derived solely from renewable resources. There are several pathways for their synthesis and this allows for extensive structural diversity in this class of surfactants, resulting in widespread tuneable functionality in their physiochemical properties. This review includes the details of most of the available routes of synthesis for amino acid surfactants (AASs) and the impact of the diverse routes on their final physiochemical properties, including solubility, dispersability, toxicity and biodegradability. The diversity offered by the structural variation in AASs offers many exciting commercial opportunities for this ever-growing class of surfactants. It also includes a discussion on current and future potential uses of AASs.

Complexes of 2,6-bis-(3′,5′-diphenylpyrazolyl)pyridine (bdppp) with the chlorides of Ru(III), Pd(II), and Rh(III) have been synthesized. The X-ray structures of these complexes show that the ligand is tridentate and binds in a 1:1 ratio with the metal in all cases. The Ru and Rh complexes are octahedral, with one ligand and three chlorides around the metal, while the Pd complex is square planar, with one ligand and one chloride bound to the metal. The Pd complex features two Pd-bdppp complexes and a Pd2Cl62− counteranion. The electronic spectra of these complexes show strong UV absorbance bands from the phenyl rings present, with the Ru complex exhibiting several charge transfer bands and the Rh complex one charge transfer band. The 1H and 13C NMR spectra of the Rh and Pd complexes show slight differences from the free ligand, and the Ru complex is paramagnetic, featuring broad NMR peaks over a wide range. The Ru complex shows a quasi-reversible redox couple, while the Ru and Pd complexes show only irreversible reductions.

Supercritical carbon dioxide was utilized as a sustainable alternative to solvent extraction of waxes from the waste needles of two spruce species, namely Norwegian and Sitka spruce. These extracts were rich in nonacosan-10-ol, an organic compound with hydrophobic properties that lends its use in the preparation of superhydrophobic coatings. The highest crude yields were 1.7% w/w of needles obtained at 400 bar and 60 °C, while nonacosan-10-ol was selectively extracted at 200 bar and 60 °C (8070 ± 91.1 μg/g of needles). Purification of nonacosan-10-ol from the wax extracts was conducted using a simple rapid green recrystallization technique. This yielded a recovery of 44.6% ± 2% and 48.4% ± 2% of the total nonacosan-10-ol from the original crude Sitka (3600 μg/g of needles) and Norwegian wax (1920 μg/g of needles) respectively. Application of nonacosan-10-ol to a filter paper led to the formation of highly hydrophobic surfaces, with preliminary contact angles of up to 149°. This sustainable production method may develop opportunities to valorize forestry waste within a holistic biorefinery.

With the increase in variable inverter-based renewable energy sources, power systems become increasingly subjected to stochastic sources. Considering the decline in rotational inertia, the consequence of the continuous spatially distributed perturbations is stochastic frequency dynamics. In this paper, the stochastic dynamics of the power system dynamics, subjected to spatially distributed disturbances, are investigated using a stochastic differential equation and the Fokker-Planck equation. This research shows that the reactance distance between perturbation sources, like wind farms, and the location of system inertia (synchronous generators/condensers), reduces the variance of the system’s rate of change of frequency probability density function. Thus, for a power system under continuous and spatially distributed stochastic feed-in, greater reactance distances decrease the probability of significant frequency dynamics.

The ethical principles of self-determination and autonomy govern the practice of informed consent. A patient's right to shared decision-making and assent prior to invasive procedures, therapeutic interventions, and research projects is protected by law. Foundational nursing roles of communication, education, and patient advocacy compel advance practice nurses to formulate methods that safeguard patients' rights. Legal implications of informed consent may vary, leaving nurse practitioners juxtaposed between judicial and ethical responsibilities. The goal of this study is to examine legal and ethical components of informed consent and to assist nurse practitioners in developing proactive practice strategies related to informed consent.

The most important factors known to influence the eating quality of beef are well established and include both pre- and post-slaughter events with many of the determinants interacting with each other. A substantial programme of work has been conducted by the Agri-Food and Biosciences Institute in Northern Ireland aimed at quantifying those factors of most importance to the local beef industry. Post-slaughter effects such as carcase chilling and electrical stimulation, ageing, carcase hanging and cooking method have been shown to have a significant impact on eating quality when compared with pre-slaughter activities such as animal handling and lairage time in the Northern Ireland studies. However, the effect of animal breed, particularly the use of dairy breed animals, was shown to significantly improve eating quality. Many of these factors were found to interact with each other.

The development of suitable reaction conditions for the rapid “high” temperature lithiation-trapping of N-Boc pyrrolidine under batch and flow conditions is described. For optimisation of batch conditions, the lithiation-trapping was explored using s-BuLi at temperatures of −30 to 20 °C. Two new batch lithiation conditions were discovered using the biomass-derived, sustainable solvent, 2-MeTHF: diamine-free lithiation in 2-MeTHF gave α-substituted pyrrolidines in 50–69% yields at −20 °C or 0 °C. The requirement for very short lithiation times is explained by the chemical instability of the lithiated intermediate at high temperatures. A practical flow chemistry reaction manifold (s-BuLi, TMEDA, THF, 0 °C, 5 s) has been developed which delivered an α-substituted pyrrolidine in 59% yield. This flow process opens up new opportunities for scaling-up of lithiation-trapping reactions of N-Boc heterocycles.

High schools try to help their students become college-career ready. Information literacy is part of that picture, although the role of teacher librarians is less clear. While the value of librarians within the education environment has been demonstrated, less research about the transferability between high school and higher education was evident. The research question emerged: what relationship exists between the presence of a high school teacher librarian and freshmen college students' academic success? To answer this question, this study examined five years of a large comprehensive university's freshmen data about their course load, the first semester GPA, and information about the high school from which they graduated: its Title I status and the presence of a high school librarian. The study found that the presence of a high school librarian employed at least half time is significantly correlated with college freshmen's grade point average, However, more explicit attention and support needs to be given to students in Title I schools.

Nurse practitioners (NPs) know the medical record is their essential source for clinical information and that a medical record accompanies every patient and each encounter is documented. As a primary legal document, the medical record is usually the best source of evidence. In addition, it communicates and stores data including protected health information. Legal implications innate in documentation relating to reimbursement, fraud and abuse, and data breach are key areas impacting NP practice. The aims of this article are to enhance NPs' understanding by exploring some essential functions of the medical record, thereby decreasing their risk of liability.

International audience; Delivering beef of consistent quality to the consumer is vital for consumer satisfaction and will help to ensure demand and therefore profitability within the beef industry. In Australia, this is being tackled with Meat Standards Australia (MSA), which uses carcass traits and processing factors to deliver an individual eating quality guarantee to the consumer for 135 different 'cut by cooking methods' from each carcass. The carcass traits used in the MSA model, such as ossification score, carcass weight and marbling explain the majority of the differences between breeds and sexes. Therefore, it was expected that the model would predict with eating quality of bulls and dairy breeds with good accuracy. In total, 8128 muscle samples from 482 carcasses from France, Poland, Ireland and Northern Ireland were MSA graded at slaughter then evaluated for tenderness, juiciness, flavour liking and overall liking by untrained consumers, according to MSA protocols. The scores were weighted (0.3, 0.1, 0.3, 0.3) and combined to form a global eating quality (meat quality (MQ4)) score. The carcasses were grouped into one of the three breed categories: beef breeds, dairy breeds and crosses. The difference between the actual and the MSA-predicted MQ4 scores were analysed using a linear mixed effects model including fixed effects for carcass hang method, cook type, muscle type, sex, country, breed category and postmortem ageing period, and random terms for animal identification, consumer country and kill group. Bulls had lower MQ4 scores than steers and females and were predicted less accurately by the MSA model. Beef breeds had lower eating quality scores than dairy breeds and crosses for five out of the 16 muscles tested. Beef breeds were also over predicted in comparison with the cross and dairy breeds for six out of the 16 muscles tested. Therefore, even after accounting for differences in carcass traits, bulls still differ in eating quality when compared with females and steers. Breed also influenced eating quality beyond differences in carcass traits. However, in this case, it was only for certain muscles. This should be taken into account when estimating the eating quality of meat. In addition, the coefficients used by the Australian MSA model for some muscles, marbling score and ultimate pH do not exactly reflect the influence of these factors on eating quality in this data set, and if this system was to be applied to Europe then the coefficients for these muscles and covariates would need further investigation.

The flavonol quercetin undergoes both enzymatic and non-enzymatic reactions with nitroxyl (HNO/NO − ), similar to analogous reactions with dioxygen, but in which N is regioselectively found in the ring-cleaved product. Here we report on kinetic and thermodynamic analysis of the non-enzymatic nitroxygenation reaction in water, which is orders of magnitude faster than the comparable dioxygenation. The second order rate constants were determined from variable temperature reactions, which allowed determination of the reaction activation enthalpy (Δ H ≠ = 9.4 kcal/mol), entropy (Δ S ≠ = −8.3 cal/mol K), and free energy (Δ G ≠ = 11.8 kcal/mol). The determined standard state energy (Δ G o ) and activation free energy, as well as the low entropic energy of reaction, are consistent with a proposed single electron transfer (SET) rate determining step.

This study evaluated the contributions of sensory traits to overall liking in Europe. Perceptions by untrained consumers of tenderness, juiciness, flavor liking and overall liking were determined using the Meat Standards Australia protocols. According to European consumer testing with European beef samples, flavor liking was the most important contributor (39%) to beef overall liking, followed by tenderness (31%) and juiciness (24%) (P0.94). The improvement in tenderness over the last decades may explain the highest contribution of flavor liking nowadays. Flavor liking is therefore the main driver of variability in overall liking. Juiciness is the least robust trait which could be influenced by other traits during consumer perception. For outstanding steaks, each sensory trait should have excellent scores and high contributions to overall liking. For medium cuts, one sensory trait with a low score has the potential to be compensated by other traits with higher scores and more emphasis will be placed on the trait with the lowest perception.

article i nfo Background: The net contribution of all muscles that act about a joint can be represented as an internal joint moment profile. This approach may be advantageous when studying footwear-induced perturbations during walking since the contribution of the smaller deeper muscles that cross the ankle joint cannot be evaluated with surface electromyography. Therefore, the present study aimed to advance the understanding of FitFlop™ footwear interaction by investigating lower extremity joint moment, and kinematic and centre of pressure profiles during gait. Methods: 28 healthy participants performed 5 walking trials in 3 conditions: a FitFlop™ sandal, a conventional sandal and an athletic trainer. Three-dimensional ankle joint, and sagittal plane knee and hip joint moments, as well as corresponding kinematics and centre of pressure trajectories were evaluated. Findings: FitFlop™ differed significantly to both the conventional sandal and athletic trainer in: average anterior position of centre of pressure trajectory (P b 0.0001) and peak hip extensor moment (P = 0.001) during early stance; average medial position of centre of pressure trajectory during late stance; peak ankle dorsiflexion and corresponding range of motion; peak plantarflexor moment and total negative work performed at the ankle (all P b 0.0001). Interpretation: The present findings demonstrate that FitFlop™ footwear significantly alters the gait pattern of wearers. An anterior displacement of the centre of pressure trajectory during early stance is the primary response to the destabilising effect of the mid-sole technology, and this leads to reductions in sagittal plane ankle joint range of motion and corresponding kinetics. Future investigations should consider the clinical implications of these findings.

Proximate data, consumer palatability scores and volatile compounds were investigated for four beef muscles (Longissimus lumborum, Psoas major, Semimembranosus and Gluteus medius) and five USDA quality grades(Prime, Upper 2/3 Choice, Low Choice, Select, and Standard). Quality grade did not directly affect consumer scores or volatiles but interactions (P < 0.05) between muscle and grade were determined. Consumer scores and volatiles differed (P < 0.05) between muscles. Consumers scored Psoas major highest for tenderness, juiciness, flavor liking and overall liking, followed by Longissimus lumborum, Gluteus medius, and Semimembranosus (P < 0.05). Principal component analysis revealed clustering of compound classes, formed by related mechanisms. Volatile n-aldehydes were inversely related to percent fat. Increases in lipid oxidation compounds were associated with Gluteus medius and Semimembranosus, while greater quantities of sulfur-containing compounds were associated with Psoas major. Relationships between palatability scores and volatile compound classes suggest that differences in the pattern of volatile compounds may play a valuable role in explaining consumer liking.

In this study, important eating quality attributes that influence consumer liking for grilled lamb loin have been identified using preference mapping techniques. The eating quality attributes identified as driving the consumer liking of lamb loin steaks were “tenderness”, “sweet flavour”, “meaty aftertaste”, “roast lamb flavour” and “roast lamb aftertaste”. In contrast, the texture attribute “rubbery” and the flavour attributes “bitter flavour” and “bitter aftertaste” had a negative influence on consumer perceptions. Associations were observed between eating quality and a number of instrumental and chemical measurements. Warner Bratzler Shear Force showed an association with “rubbery” texture and a negative association with “tenderness” and consumer liking scores. The compounds, glucose, glucose-6-phosphate, inosine, inosine monophosphate and adenosine monophosphate were associated with the attributes, “sweet flavour”, “meaty aftertaste”, “roast lamb flavour”, “roast lamb aftertaste” and with consumer scores for liking of lamb which is probably caused by the role some of these compounds play as precursors of flavour and as taste compounds.

Through a series of case studies it is demonstrated that microwave dielectric heating can be a powerfultool to recover and synthesize valuable molecules from a wide range of biomass types. In addition, undermicrowave irradiation the production of chemicals from biomass proceeds at markedly lower temper-atures (up to 150?C) compared to conventional heating. This has a secondary benefit in that moleculeswith a high degree of functionality are produced while conventional heating tends to produce a greatproportion of lower value gases. Furthermore, the technical set-up of a microwave reactor can easilyaccommodate for an in-situ separation of acids and valuable products therewith improving the shelf lifeof the latter. The benefits of combining hydrothermal conditions with microwave irradiation are alsoillustrated. In addition, a specialized case of selective heating in a biphasic reaction system is discussed,allowing for improved yields and selectivity.

Photographs have been used to enhance consumer reporting of preference of meat doneness, however, the use of photographs has not been validated for this purpose. This study used standard cooking methods to produce steaks of five different degrees of doneness (rare medium, medium well, well done and very well done) to study the consumer's perception of doneness, from both the external and internal surface of the cooked steak and also from corresponding photographs of each sample. Consumers evaluated each surface of the cooked steaks in relation to doneness for acceptability, 'just about right' and perception of doneness. Data were analysed using a split plot ANOVA and least significant test. Perception scores (for both external and internal surfaces) between different presentation methods (steak samples and corresponding photos), were not significantly different (p>0.05). The result indicates that photographs can be used as a valid approach for assessing preference for meat doneness.

The reactions of several horse heart myoglobin species with nitrosyl hydride, HNO, derived from Angeli's salt (AS) and Piloty's acid (PA) have been followed by UV-visible, (1)H NMR and EPR spectroscopies. Spectral analysis of myoglobin-derived speciation during the reactions was obtained by using singular value decomposition methods combined with a global analysis to obtain the rate constants of complex sequential reactions. The analysis also provided spectra for the derived absorbers, which allowed self-consistent calibration to the spectra of known myoglobin species. Using this method, the determined rate for trapping of HNO by metmyoglobin, which produces NO-myoglobin, is found to be 2.7 × 10(5)M(-1)s(-1) at pH7.0 and 1.1 × 10(5)M(-1)s(-1) at pH9.4. The reaction of deoxymyoglobin with HNO generates the adduct HNO-myoglobin directly, but is followed by a secondary reaction of that product with HNO yielding NO-myoglobin; the determined bimolecular rate constants for these reactions are 3.7 × 10(5)M(-1)s(-1) and 1.67 × 10(4)M(-1)s(-1) respectively, and are independent of pH. The derived spectrum for HNO-myoglobin is characterized by a Soret absorbance maximum at 423 nm with an extinction coefficient of 1.66 × 10(5)M(-1)cm(-1). The rate constant for unimolecular loss of HNO from HNO-myoglobin was determined by competitive trapping with CO at 8.9 × 10(-5)s(-1), which gives the thermodynamic binding affinity of HNO to deoxymyoglobin as 4.2 × 10(9)M(-1). These results suggest that the formation of HNO-ferrous heme protein adducts represents an important consideration in the biological action of HNO-releasing drugs.

Beef longissimus dorsi muscle samples matured over a 21 day period were analysed using three different analytical techniques; (1)H NMR, GC-MS and HPLC. The data from the three experimental techniques were correlated with each other to determine if the results were statistically similar to each other. From our analysis we determined that the metabolites measured using (1)H NMR were statistically similar to the compounds quantified using the chromatography techniques (p

Mg/Ca ratio measurements have been produced from IMAGES piston core MD99-2251 using two species of planktonic foraminifera: the surface dwelling Globigerina bulloides and the thermocline dwelling Globorotalia inflata. Holocene Mg/Ca values for G. bulloides are higher and more variable (1.8–3.0 mmol/mol), with lower Mg/Ca ratios of 1.1–1.9 mmol/mol recorded for G. inflata. At no time do the thermocline Mg/Ca ratios exceed those of the surface. Comparison of the Mg/Ca records reveals a complex evolution of the upper water mass characteristics through the Holocene. The early Holocene exhibits far less distinction between surface and thermocline ratios and the Mg/Ca calibration derived temperatures in the upper water column, with the 0.4 mmol/mol offset equivalent to a temperature difference of 1–2 °C. Mg/Ca ratios diverge from early to mid Holocene and despite the increase in G. inflata ratios from ~ 6.5 ka onwards, the much more marked increase in G. bulloides after ~ 4 ka results in a clear separation of the surface and thermocline records for the remainder of the Holocene. Despite the long term increase in thermal contrast between surface and subsurface waters, there is a clear correlation between short-lived events evident in both of the Mg/Ca records, reflecting multi-decadal to centennial scale temperature fluctuations. Coolings at ~ 9 and 8.2 ka are well represented in both records, as too are further warm–cold fluctuations at ~ 5.5, 1.5 and 0.8 ka. This indicates that these rapid climate events had a common forcing that was recorded throughout the upper water column. Comparisons with the GISP2 glacio-chemical indicators of atmospheric circulation suggest that the enhanced intensity of the atmospheric circulation during the early Holocene (11–10 ka) probably explain the reduced surface thermal stratification indicated by the Mg/Ca data.

Background/Aims Recent work both from our laboratory and in marsupial models of testicular descent suggests a strong connection between the mammary line and gubernacular migration. This study investigated the relationship between the mammary fat pad (MFP) that underlies the mammary line and the developing gubernaculum by fluorescent immunohistochemistry. Methods Rats at E17 and E19 were fixed and processed for immunohistochemistry. Sagittal sections of male fetuses were stained with antibodies against androgen receptor (AR), prolyl-4 hydroxylase β , Desmin, activated Notch-1, Jagged-1, and Ki-67. These were analyzed by fluorescent confocal microscopy. Results At E17 and E19, the MFP anlage forms a continuous distribution of fibroblasts passing immediately adjacent the gubernaculum to the future scrotum. Within this exists a distinct subpopulation of fibroblasts expressing AR distributed over the path of inguinoscrotal descent of the gubernaculum. Proliferation and Notch-1 signaling were similar throughout the MFP with differential Notch-1 signaling in the E19 gubernaculum. Conclusion This investigation has identified the presence of a distinct AR-expressing subpopulation of MFP fibroblasts over the path of inguinoscrotal descent during the key androgenic programming window of this phase. This unique developmental pattern is consistent with a prime role for the MFP in testicular descent.

In situ DRIFT spectroscopy is used in the current study to follow sorption/desorption of water vapor on several clay minerals that vary in surface charge and morphological character. Spectra of the dried sorbents indicate the significant effect of those factors on both liquid and vapor phase water remaining within the particles. Changes in the IR bands recorded during exposure to water vapor at 50% RH confirm the assignment of those bands to water. They also indicate that the dynamics of liquid phase sorption/desorption for all the sorbents investigated is consistent with the concept of capillary condensation within nanometer scale pores that was advanced in previous studies conducted with 1,2-dihaloethanes. The intraparticle accumulation of the vapor phase water, however, was found to be profoundly affected by both surface charge and particle morphology. These differences are attributed to the high polarity and hydration capabilities of water molecules. Band area changes documented during a second sorption/desorption cycle are nearly identical to those occurring during the first with regard to both timing and extent. They also confirm that some liquid phase water is retained by the sorbents even after five days of desorption and amounts of sorbed vapor phase water increase over the course of the experiments.

An efficient method for mass spectral data analyses and visualization of sulfur speciation in the reaction between S- nitroso glutathione (GSNO) and hydrogen sulfide (H2S) based on Kendrick mass defect (KMD) methodology is described. KMD is defined as the difference in exact mass and Kendrick mass of any species detected by the mass spectrometry study. GSNO + H2S → GSSxG + GSSx H + GSNSxH2 + GSSxOH + GSSxO3H + HSxOyH The mass spectral data of modified terminal thiol in glutathione, containing persulfane and polysulfides and as well small oxoacids of sulfur products, generated in the reaction between GSNO and H2S recorded using Orbitrap high resolution liquid chromatography (LC/MS) were used to perform the KMD analysis. The traditional KMD method utilizing the mass scale of the methylene unit (CH2) set to 14.000 u for rapid graphical identification of members of a homologous series for species like GSSxG, GSSH, GSNSxH, GSSxOH and GSSxO3H produced a cumbersome plot for visual recognition. We present here an effective methodology for mass spectral data visualization by simply substituting the mass scale of methylene unit to sulfur (32 u) in Kendrick mass significantly enhancing the graphical representation of the S- modified glutathione and SOS species. The broad applicability of this new method is demonstrated by a range electrophilic and nucleophilic trapping reagent like dimedone, 1-trimethylsiloxycyclohexene, monobromobimane, phenyl acetylene, t-butyl styrene, benzyl bromide, iodoacetamide, N-ethylmaleimide, 4-Chloro-7-nitrobenzofurazan, and 3-Bromo-1,1,1-trifluoroacetone in the trapping of reactive species generated in the reaction between GSNO and H2S. We also show that the inclusion of mass spectral intensity in the KMD analysis allows to quantify and differentiate concentration of species generated within and across various other homologous series.

The interplay between NO and H2S signaling has attracted much interest in redox proteomics of nitrosative and oxidative stress. Both small molecules appear to target similar pathways in organisms, by reacting with protein free thiols or metalloenzymes to alter or enhance function. We have previously investigated the N-based product speciation in the reaction of GSNO with H2S, specifically noting that the N-based gas product distributions are analogous to those of reactions of GSNO with reductants (e.g. ascorbic acid). We have also identified a plethora of unique glutathione-based products by LC-HRMS analysis. Single Ion Chromatograms (SICs) confirm that these species are present in the reaction mixture and are separated on the LC column prior to ionization. A number of small reactive thiols can be trapped with iodoacetamide (IA), including polysulfides (SnH2), glutathione polysulfides (GSSnH) and trithionitrates, GSN(SnH)2. Unusual trithionitrates are also observed as acetamide adducts, GSN(SnA)2, but only at low ratios of H2S to GSNO. Competition experiments suggest one initial product, the sulfenic acid GSOH, acts as precursor to persulfide and oxidized glutathione-based products. Addition of a non-electrophilic radical trap, vinyl cyclopropane, has little effect on the product distributions, suggesting radical intermediates are short-lived. Other unique dimedone adducts were observed that are attributable to the sulfinyl (GS(O)H) tautomer. We also observe small S-oxoacids, HSOH and S(OH)2, as the derivatized ISnD and DSnD adducts. As with GSOH, unique thioacetals are observed which derive from the sulfenyl tautomers of both HS(O)H and GS(O)H. These unique mixed-valence sulfides have little precedent in the literature but remain observable in reaction mixtures after many hours on the bench.

Background/Purpose: Inguinoscrotal testicular descent is controlled by androgens and the genitofemoral nerve, but the trigger for what makes the gubernaculum become a migratory organ like a limb bud remains unknown. Recent observations in the flutamide-treated rat suggested a link with the mammary line. We aimed, therefore, to reassess histologic anatomy in 2 different rodent models of androgen blockade, the testicular feminisation mouse (TFM) and the flutamide-treated rat. Methods: Neonatal TFM mice and fetal and neonatal rats after pretreatment of dams with an antiandrogen, flutamide (75 mg/kg; sunflower oil; days 16-19), were prepared for histologic analysis of the inguinal region and compared with fetal and neonatal controls. Results: Fetal control rats (E15.5 days) showed a mammary bud just outside the future inguinal canal adjacent to the gubernaculum. Neonatal TFM mice showed persistence of the inguinal breast bud supplied by the genitofemoral nerve. Flutamide-treated rats (D2) showed the gubernaculum surrounded by a persisting breast bud. Conclusions: The inguinal mammary line is adjacent to the gubernaculum in fetal rodents, and after androgen blockade, the gubernaculum becomes connected to the breast. The male mammary line, which is hidden in plain sight outside the inguinal canal, is made visible by androgen blockade. It may be the missing link in testicular descent, regulating gubernacular migration.

Aim Inadequate androgen activity is a likely cause of cryptorchidism in humans, affecting inguinoscrotal testicular descent. Flutamide, a nonsteroidal antiandrogen, produces cryptorchidism in rats. We aimed to determine the anatomical and histologic effects of flutamide. Methods Time-mated Sprague-Dawley female rats were injected subcutaneously with flutamide (75 mg/kg in sunflower oil) on days 16 to 19 of pregnancy. Embryonic (E) and postnatal (P) male offspring were collected (E16, E19, P0, P2, P4, P8) in control and flutamide-treated groups (n = 5-10). Samples were fixed in 4% paraformaldehyde. Five-micrometer-thick sections were prepared for hematoxylin and eosin, trichrome and immunohistochemical stains (Desmin, TuJ1, Ki67). This identified muscle and neural cells and areas of cell proliferation. Results Postnatally, the gubernaculum in flutamide-treated rats had more mesenchyme and muscle than controls. Gubernacular eversion failed, and mammary tissue persisted around the gubernaculum in flutamide-treated rats. Flutamide had no effect on embryonic gubernacular anatomy and histology. Conclusions Prenatal androgens altered postnatal gubernacular anatomy and histology in the postnatal period. Our findings indicate that the failure of gubernacular differentiation and migration may be because of the ongoing presence of mammary tissue in the region of the external inguinal ring.

Ferredoxin (Fd) is the major iron-containing protein in photosynthetic organisms and is central to reductive metabolism in the chloroplast. The Chlamydomonas reinhardtii genome encodes six plant type [Fe2S2] ferredoxins, products of PETF, FDX2-FDX6. We performed the functional analysis of these ferredoxins by localizing Fd, Fdx2, Fdx3, and Fdx6 to the chloroplast by using isoform-specific antibodies and monitoring the pattern of gene expression by iron and copper nutrition, nitrogen source, and hydrogen peroxide stress. In addition, we also measured the midpoint redox potentials of Fd and Fdx2 and determined the kinetic parameters of their reactions with several ferredoxin-interacting proteins, namely nitrite reductase, Fd:NADP+ oxidoreductase, and Fd:thioredoxin reductase. We found that each of the FDX genes is differently regulated in response to changes in nutrient supply. Moreover, we show that Fdx2 (Em = -321 mV), whose expression is regulated by nitrate, is a more efficient electron donor to nitrite reductase relative to Fd. Overall, the results suggest that each ferredoxin isoform has substrate specificity and that the presence of multiple ferredoxin isoforms allows for the allocation of reducing power to specific metabolic pathways in the chloroplast under various growth conditions.

It has been previously proposed that nitric oxide (NO) is the only biologically relevant nitrogen oxide capable of activating the enzyme soluble guanylate cyclase (sGC). However, recent reports implicate HNO as another possible activator of sGC. Herein, we examine the affect of HNO donors on the activity of purified bovine lung sGC and find that, indeed, HNO is capable of activating this enzyme. Like NO, HNO activation appears to occur via interaction with the regulatory ferrous heme on sGC. Somewhat unexpectedly, HNO does not activate the ferric form of the enzyme. Finally, HNO-mediated cysteine thiol modification appears to also affect enzyme activity leading to inhibition. Thus, sGC activity can be regulated by HNO via interactions at both the regulatory heme and cysteine thiols.

Previous work has shown that mono-oxygenation of Ru(bpy)2(N,N′-dimethyldithiocarbamate)+, 1, yields two different linkage isomers: S,S-bound 2a and O,S-bound 2b, as well as a stable dioxygenate, Ru(bpy)2(N,N-dimethylthiocarbamate-sulfinate-S,S)+, 3. In this report, the interconversion of the two peroxydithiocarbamate isomers was investigated using photolysis and thermal activations. The O,S-bound 2b undergoes phototriggered linkage isomerization to form the less stable S,S-bound 2a at low temperatures in non-coordinating solvents. The more reactive S,S-bound 2a then converts to O,S-bound 2b by a thermal isomerization at moderate temperatures in polar solvents. The different solvent and temperature dependences suggest distinct pathways for the two isomerizations.

Testicular descent is proposed to occur in 2 stages. During the second stage, calcitonin gene-related peptide (CGRP) released from the genitofemoral nerve (GFN) causes maximal mitosis in the gubernacular bulb. As normal development requires a balance between cell proliferation and apoptosis, this study explored the effect of CGRP on apoptosis in the rat gubernacular bulb.Gubernacula were collected from male Sprague-Dawley rats at birth (D0) or 2 days post birth (D2), and placed in organ culture for 24 hours with or without CGRP (0.001 mol/L). The D2 rats were pretreated with capsaicin (sensory nerve toxin) or flutamide (antiandrogen) or untreated. D0 rats were untreated (n = 64). Sections of the bulb were stained using the TUNEL method to identify apoptotic cells. Apoptosis was calculated as the percentage of positive cells per hundred cells.Normal Sprague-Dawley rat gubernacula showed reduced apoptosis when cultured with CGRP, in D0 (7.0% vs 4.8%, P.05) and D2 (4.9% vs 2.3%, P.001). Greater apoptosis occurred at D0 compared to D2, without CGRP added (7.0% vs 4.9%, P.05) and with CGRP (4.8% vs 2.3%, P.001). For D2 gubernacula, capsaicin treatment increased apoptosis compared to controls, without CGRP added (4.9% vs 7.3%, P.05) and with CGRP (2.3% vs 6.7%, P.001). There was no difference in apoptosis when cultured with or without CGRP (7.3% vs 6.7%, nonsignificant) after capsaicin treatment. Flutamide treatment increased apoptosis compared to controls, but only with CGRP (2.3% vs 7.3%, P.001). There was no difference in apoptosis when cultured with or without CGRP (7.1% vs 7.3%, nonsignificant) after flutamide.Calcitonin gene-related peptide (CGRP) acts as a survival factor in the rat gubernaculum, possibly to steer cells away from a defined apoptotic pathway. Greater apoptosis occurs earlier in development. However, in vivo CGRP released from the genitofemoral nerve may be required to prevent apoptosis, as shown by pretreatment with the sensory nerve toxin capsaicin. Androgen is also involved in the pathway controlling apoptosis, as androgen blockade with flutamide inhibited the action of CGRP.

The detection of outgassing water vapor from Enceladus is one of the great breakthroughs of the Cassini mission. The fate of this water once ionized has been widely studied; here we investigate the effects of purely neutral-neutral interactions within the Enceladus torus. We find that, thanks in part to the polar nature of the water molecule, a cold (~180 K) neutral torus would undergo rapid viscous heating and spread to the extent of the observed hydroxyl cloud, before plasma effects become important. We investigate the physics behind the spreading of the torus, paying particular attention to the competition between heating and rotational line cooling. A steady-state torus model is constructed, and it is demonstrated that the torus will be observable in the millimeter band with the upcoming Herschel satellite. The relative strength of rotational lines could be used to distinguish between physical models for the neutral cloud., Comment: submitted to Icarus updated: references fixed

Recent studies suggest that testicular descent is accomplished by outgrowth of the gubernaculum from the abdominal wall. The tip of the gubernaculum has been proposed as the primary site of growth, similar to an embryonic limb bud. We aimed to determine the maximum site of growth in organ culture.Gubernacula from 1-day-old Sprague-Dawley rats (n = 40) were collected and divided into 4 groups as follows: whole gubernaculum (control), truncated gubernaculum (tip excised), gubernacular tip alone, and grafted gubernaculum with an extra tip on its side. Tissues were cultured with or without calcitonin gene-related peptide (CGRP) (714nmol/L) in medium for 24 hours. The area of each gubernaculum was determined by "Image J" analysis of digital photos collected via a Leica Wild M28 microscope (Leica Microsystems, Wetzler GmbH Germany) taken before and after culture.In organ culture, the neonatal rat gubernaculum normally shrank 10% to 15%, but this was prevented by the presence of exogenous CGRP (0.8% vs 11.8%; P.003). By contrast, gubernacula with their tips excised were not affected by CGRP (3.4% vs 4.7%; not significant). Gubernacular tips alone did respond to CGRP (2.7% vs 13.5%; P.03). Transplantation of the tip to another gubernaculum caused it to develop 2 tips.These results suggest that the rat gubernaculum contains a growth centre in its distal tip that can respond to CGRP. This is consistent with a limb bud model of gubernacular growth during the inguinoscrotal descent of the testis.

A series of SYK inhibitors based on the phenylamino pyrimidine thiazole lead 4 were prepared and evaluated for biological activity. Lead optimization provided compounds with nanomolar Ki’s against SYK and potent inhibition in mast cell degranulation assays.

From the X-ray crystal structures of linezolid and the non-selective antibiotic sparsomycin, we have derived a new family of hybrid oxazolidinones. From this initial compound set we have developed a new biaryloxazolidinone scaffold that shows both potent antimicrobial activity as well as selective inhibition of ribosomal translation. The synthesis of these compounds is outlined.

Background Extrapolation of rat testicular descent studies to humans has been criticized because of anatomical differences of the cremaster muscle. Human cremaster is described as a thin strip rather than a large, complete sac as in rats, which is proposed to be more important in propelling the testis during descent. This study investigated cremaster muscle anatomy and ontogeny in both normal and cryptorchid rat models. Methods Gubernacula from 4 groups of neonatal rats were sectioned longitudinally and transversely: normal Sprague-Dawley, capsaicin pretreated, flutamide pretreated, and congenital cryptorchid rats. Gubernacula were stained with hematoxylin-eosin, Masson trichrome, and desmin immunohistochemistry to study muscle development. Results Myoblasts are more numerous at the gubernacular tip, whereas the most differentiated muscle is proximal. Rat cremaster develops as an elongated strip rather than a complete sac derived from abdominal wall muscles. Flutamide and capsaicin pretreatment disrupts development. Conclusion Rat cremaster muscle develops as a strip, bearing close resemblance to human cremaster muscle, permitting extrapolation of cremaster function to human testicular descent. The cremaster muscle appears to differentiate from the gubernacular tip during elongation to the scrotum, and requires intact sensory innervation and androgen.

How the gubernaculum guides the testis into the scrotum remains controversial, with various proposals from passive inversion to active growth. We aimed to determine if the gubernaculum contains an area of active proliferation, such as a "progress zone" in a growing embryonic limb bud, using a fluorescent cell membrane marker, 1,1'-didodecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate [DiIC12(3)], to trace cell migration, and 5-bromodeoxyuridine (BUDR) (a thymidine analogue) as a mitotic marker.Gubernacula were collected from neonatal male rats (n = 42, day 1-2, Sprague-Dawley) and cultured with calcitonin gene-related peptide (CGRP; 714 nmol/L). 1,1'-didodecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate-coated glass beads (diameter, 150-212 microm) were placed next to the bulb for the first 3 hours. Gubernacula were cultured for 3, 18, and 24 hours, then frozen sections cut and examined by confocal microscopy (wavelength, 549 nm). In a second experiment, pups not exposed to exogenous CGRP (n = 53, day 0, Sprague-Dawley) were injected intraperitoneally with BUDR (50 mg/kg of body weight); gubernacula were collected at 2, 48, 72, and 96 hours postinjection (PI), sectioned, and stained using immunohistochemistry to count the number of BUDR-positive cells per 100 cells (labeling index) in the bulb, cremaster, cord, and epididymis.After 24 hours' culture with CGRP, the bulb showed an oval region (diameter, 300 microm) of high fluorescence, and the cremaster region showed elongated cells migrating out of the bulb. When cultured without CGRP, the same oval region contained no fluorescence. In vivo BUDR labeling index increased in all areas until 48 hours postinjection and then decreased most rapidly in the bulb (P.05), in the presence of endogenous CGRP from the genitofemoral nerve.The rat gubernaculum contains a putative progress zone, such as in a growing limb bud, in the presence of CGRP. Cells migrate out of this zone to form cremaster muscle. We hypothesize that proliferation in the bulb elongates the gubernaculum, whereas proliferation of cremaster cells would increase gubernacular diameter. This brings to "life" the gubernaculum as an actively growing organ in contrast to the inert ligament connecting the testis to the scrotum portrayed in most anatomy textbooks.

The discovery of a molecular oxygen atmosphere around Saturn's rings has important implications for the electrodynamics of the ring system. Its existence was inferred from the Cassini in situ detection of molecular oxygen ions above the rings during Saturn Orbit Insertion in 2004. Molecular oxygen is difficult to observe remotely, and theoretical estimates have yielded only a lower limit ( N n ≳ 10 13 cm −2 ) to the O2 column density. Comparison with observations has previously concerned matching ion densities at spacecraft altitudes far larger than the scale height of the neutral atmosphere. This is further complicated by charged particle propagation effects in Saturn's offset magnetic field. In this study we adopt a complementary approach, by focusing on bulk atmospheric properties and using additional aspects of the Cassini observations to place an upper limit on the column density. We develop a simple analytic model of the molecular atmosphere and its photo-ionization and dissociation products, with N n a free parameter. Heating of the neutrals by viscous stirring, cooling by collisions with the rings, and torquing by collisions with pickup ions are all included in the model. We limit the neutral scale height to h ≲ 3000 km using the INMS neutral density nondetection over the A ring. A first upper limit to the neutral column is derived by using our model to reassess O2 production and loss rates. Two further limits are then obtained from Cassini observations: corotation of the observed ions with the planet implies that the height-integrated conductivity of the ring atmosphere is less than that of Saturn's ionosphere; and the nondetection of fluorescent atomic oxygen over the rings constrains the molecular column from which it is produced via photo-dissociation. These latter limits are independent of production and loss rates and are only weakly dependent on temperature. From the three independent methods described, we obtain similar limits: N n ≲ 2 × 10 15 cm −2 . The mean free path for collisions between neutrals thus cannot be very much smaller than the scale height.