Green Enzymatic Synthesis of Geranyl Butyrate: Process Optimization and Mechanistic Insights.

Flavor esters are organic compounds widely used in the food industry to enhance the aroma and taste of products. However, most chemical processes for the production of these flavoring compounds use toxic organic solvents. Some organic solvents derived from petroleum can leave behind residual traces in food products, which may raise concerns about potential health risks and contamination. In this study, we employ Eversa Transform 2.0, a commercial lipase derived from the lipase from Thermomyces lanuginosus, to produce geranyl butyrate in aqueous media. The chemical process was optimized using the Taguchi method, and a conversion of 93% was obtained at the optimal reaction conditions of: 1:5 molar ratio (v/v), 15% biocatalyst load (w/w), at 50 °C, in 6 h. Classic (molecular dynamics) and quantum (density functional theory) simulations unveiled amino acid residues involved in the stabilization of the enzyme-substrate complex. Detailed QM/MM mechanistic studies identified the nucleophilic attack of the deacylation reaction as the rate-limiting step of the entire mechanism, which has a free energy barrier of 14.0 kcal/mol.

The complex circumstellar environment of supernova 2023ixf.

The early evolution of a supernova (SN) can reveal information about the environment and the progenitor star. When a star explodes in vacuum, the first photons to escape from its surface appear as a brief, hours-long shock-breakout flare1,2, followed by a cooling phase of emission. However, for stars exploding within a distribution of dense, optically thick circumstellar material (CSM), the first photons escape from the material beyond the stellar edge and the duration of the initial flare can extend to several days, during which the escaping emission indicates photospheric heating3. Early serendipitous observations2,4 that lacked ultraviolet (UV) data were unable to determine whether the early emission is heating or cooling and hence the nature of the early explosion event. Here we report UV spectra of the nearby SN 2023ixf in the galaxy Messier 101 (M101). Using the UV data as well as a comprehensive set of further multiwavelength observations, we temporally resolve the emergence of the explosion shock from a thick medium heated by the SN emission. We derive a reliable bolometric light curve that indicates that the shock breaks out from a dense layer with a radius substantially larger than typical supergiants.

A three-dimensional visualization of the full-field surgical region based on thin-slice MRI: A helpful approach for simultaneously guiding tumor resection and perforator flap elevation.

Background: The goal of the current study was to explore the application of preoperative three-dimensional reconstruction (3DR) based on thin-slice magnetic resonance imaging (MRI) in the simultaneous guidance of en bloc tumor resection and adjacent perforator flap elevation. Methods: The prospective cohort included 35 patients diagnosed with either soft tissue sarcoma or squamous cell skin cancer between 2019 and 2021. The preoperative 3DR based on thin-slice MRI illustrated the spatial anatomical relationship among the tumor, underlying muscle, adjacent perforator vessels, and bone around the surgical region. The accuracy of preoperative imaging data was verified by intraoperative vessel dissection and postoperative pathological measurements. Results: Tumor size from 3DR data showed relatively high concordance rates with pathological measurements within the 95% limits of agreement. An average of three perforators (range: 1-7) with a mean diameter of 0.32 cm (range: 0.18-0.74 cm) from the 3DR were present in our study. The average distance between tumor boundary and perforator piercing sites on the 3DR was 2.2 cm (range: 1.2-7.7 cm). The average length of artery perforator coursing along the subcutaneous tissue was 5.8 cm (range: 3.3-25.1 cm). The mean flap harvest time was 55 mins (range: 36-97 min). The average flap size was 92.2 cm2 (range: 32-126 cm2). One perforator flap occurred distal partial necrosis. Conclusion: A thorough understanding of anatomical structures in the surgical region according to full-field 3DR based on thin-slice MRI can improve the performance of radical resection of the tumor and adjacent perforator flap transfer, especially for junior surgeons with a poor experience.

Modified low-dose second window indocyanine green technique improves near-infrared fluorescence image-guided dermatofibrosarcoma protuberans resection: A randomized control trial.

Objective: Conventional second window indocyanine green (SWIG) technique has been widely attempted in near-infrared fluorescence (NIRF) imaging for intraoperative navigation of tumor radical resection. Nevertheless, the overuse of indocyanine green (ICG) led to an increased risk of drug lethal allergy and high medical cost. This prospective study was to explore clinical application of modified low-dose SWIG technique in guiding dermatofibrosarcoma protuberans (DFSPs) radical resection. Method: Patients with DFSPs were randomly assigned to control and experimental group. The ICG was injected intravenously 24 h before surgery, at a dose of 3.5 mg/kg in the control group and 25 mg/patient in the experiment group, respectively. Intraoperative NIRF imaging included serial views of gross tumor, tumor bed and cross-sectional specimen. Results: Although NIRF imaging of gross tumor and tumor bed in the experimental group demonstrated similar sensitivity and negative predictive value, the specificity and positive predictive value were obviously higher compared to control group. The tumor-to-background ratios of cross-sectional specimens in the experimental group was significantly higher than in the control group (P = 0.000). Data in both groups displayed that there was a positive correlation of tumor size in cross-sections between integrated histopathologic photomicrographs and NIRF imaging of specimen views (P = 0.000). NIRF imaging of cross-sectional specimens had a significant decrease in time cost, and an increase in the ability of examining more surgical margins (P = 0.000). Conclusion: This is the first study to demonstrate that a low-dose SWIG technique could improve the accuracy of near-infrared fluorescence image-guided dermatofibrosarcoma protuberans resection.Clinical Trial Registration: ChiCTR2100050174; date of registration: August 18, 2021 followed by "retrospectively registered".

College Campus Food Pantry Program Evaluation: What Barriers Do Students Face to Access On-Campus Food Pantries?

The purpose of this study was to explore barriers Texas Woman's University (TWU) students face in accessing on-campus food pantries. This cross-sectional, survey-based study was conducted in Fall 2021. Students' use of the food pantries and barriers to utilization, including qualitative questions, were evaluated using descriptive statistics and thematic analyses. Students (n = 529) completed the survey. Despite a high prevalence of food insecurity (49.2%), most students reported never using the pantries (89.8%). Almost half of the students were unaware that these pantries existed on campus (47.8%). More than one in four students believed there were barriers to accessing the pantries, with time tissues, lack of transportation, limited food pantry hours of operation, and social stigma most commonly cited as major barriers to access. Food insecurity remains an urgent problem at TWU since the prevalence has remained high since 2019 despite the institutions' efforts to reduce it. One of those resources has not been utilized as expected, which might impede improvements in food security among students. TWU on-campus food pantries can use these findings to address major barriers by offering after-hours access through the libraries or campus police, partnering with public transportation, and normalizing accessing food assistance.

A WC/WO star exploding within an expanding carbon-oxygen-neon nebula.

The final fate of massive stars, and the nature of the compact remnants they leave behind (black holes and neutron stars), are open questions in astrophysics. Many massive stars are stripped of their outer hydrogen envelopes as they evolve. Such Wolf-Rayet stars1 emit strong and rapidly expanding winds with speeds greater than 1,000 kilometres per second. A fraction of this population is also helium-depleted, with spectra dominated by highly ionized emission lines of carbon and oxygen (types WC/WO). Evidence indicates that the most commonly observed supernova explosions that lack hydrogen and helium (types Ib/Ic) cannot result from massive WC/WO stars2,3, leading some to suggest that most such stars collapse directly into black holes without a visible supernova explosion4. Here we report observations of SN 2019hgp, beginning about a day after the explosion. Its short rise time and rapid decline place it among an emerging population of rapidly evolving transients5-8. Spectroscopy reveals a rich set of emission lines indicating that the explosion occurred within a nebula composed of carbon, oxygen and neon. Narrow absorption features show that this material is expanding at high velocities (greater than 1,500 kilometres per second), requiring a compact progenitor. Our observations are consistent with an explosion of a massive WC/WO star, and suggest that massive Wolf-Rayet stars may be the progenitors of some rapidly evolving transients.

A transient radio source consistent with a merger-triggered core collapse supernova.

A core collapse supernova occurs when exothermic fusion ceases in the core of a massive star, which is typically caused by exhaustion of nuclear fuel. Theory predicts that fusion could be interrupted earlier by merging of the star with a compact binary companion. We report a luminous radio transient, VT J121001+495647, found in the Very Large Array Sky Survey. The radio emission is consistent with supernova ejecta colliding with a dense shell of material, potentially ejected by binary interaction in the centuries before explosion. We associate the supernova with an archival x-ray transient, which implies that a relativistic jet was launched during the explosion. The combination of an early relativistic jet and late-time dense interaction is consistent with expectations for a merger-driven explosion.

Suppression of a BAHD acyltransferase decreases p-coumaroyl on arabinoxylan and improves biomass digestibility in the model grass Setaria viridis.

Grass cell walls have hydroxycinnamic acids attached to arabinosyl residues of arabinoxylan (AX), and certain BAHD acyltransferases are involved in their addition. In this study, we characterized one of these BAHD genes in the cell wall of the model grass Setaria viridis. RNAi silenced lines of S. viridis (SvBAHD05) presented a decrease of up to 42% of ester-linked p-coumarate (pCA) and 50% of pCA-arabinofuranosyl, across three generations. Biomass from SvBAHD05 silenced plants exhibited up to 32% increase in biomass saccharification after acid pre-treatment, with no change in total lignin. Molecular dynamics simulations suggested that SvBAHD05 is a p-coumaroyl coenzyme A transferase (PAT) mainly involved in the addition of pCA to the arabinofuranosyl residues of AX in Setaria. Thus, our results provide evidence of p-coumaroylation of AX promoted by SvBAHD05 acyltransferase in the cell wall of the model grass S. viridis. Furthermore, SvBAHD05 is a promising biotechnological target to engineer crops for improved biomass digestibility for biofuels, biorefineries and animal feeding.

A hot and fast ultra-stripped supernova that likely formed a compact neutron star binary.

Compact neutron star binary systems are produced from binary massive stars through stellar evolution involving up to two supernova explosions. The final stages in the formation of these systems have not been directly observed. We report the discovery of iPTF 14gqr (SN 2014ft), a type Ic supernova with a fast-evolving light curve indicating an extremely low ejecta mass (≈0.2 solar masses) and low kinetic energy (≈2 × 1050 ergs). Early photometry and spectroscopy reveal evidence of shock cooling of an extended helium-rich envelope, likely ejected in an intense pre-explosion mass-loss episode of the progenitor. Taken together, we interpret iPTF 14gqr as evidence for ultra-stripped supernovae that form neutron stars in compact binary systems.

Global rabies control: the role of international organisations and the Global Strategic Plan to eliminate dog-mediated human rabies.

International partners are united to reach the shared goal of zero dog-mediated human rabies deaths by 2030, worldwide. Under the Tripartite collaboration, the World Health Organization, the World Organisation for Animal Health and the Food and Agriculture Organization of the United Nations are prioritising rabies as a model for 'One Health' in action. In 2015, the Global Rabies Conference led to the development of the Global Framework for the Elimination of Dog-Mediated Human Rabies. This long-term strategy centres around five pillars of rabies elimination (STOP-R): i) Sociocultural; ii) Technical; iii) Organisational; iv) Political; and v) Resources. Together with their partners, the Tripartite are working to operationalise the Framework through: i) engaging communities to build rabies awareness; ii) strengthening human and animal health systems, surveillance, and providing proof of concept that rabies elimination is feasible; iii) promoting intersectoral and regional collaboration; iv) advocating for political engagement and support; and v) building the case for investment through public-private partnerships and a Global Strategic Plan to end human deaths from dog-mediated rabies. By creating an enabling environment for countries to prioritise rabies and implement existing tools, the Tripartite are committed to catalysing change, empowering nations and providing the necessary support to consign rabies to the history books.

Les partenaires internationaux agissent de concert afin d'atteindre l'objectif de réduire à zéro le nombre de décès dus à la rage humaine transmise par les chiens dans le monde d'ici 2030. Dans le cadre de leur collaboration tripartite, l'Organisation mondiale de la santé, l'Organisation mondiale de la santé animale et l'Organisation des Nations Unies pour l'alimentation et l'agriculture ont fait de la rage la maladie phare de leur action gouvernée par le principe « Une seule santé ¼. En 2015, la Conférence mondiale sur la rage a abouti à la création du Cadre stratégique mondial d'élimination de la rage humaine transmise par les chiens. Cette stratégie à long terme repose sur cinq piliers visant l'élimination de la rage (STOP-R) : i) aspects socioculturels ; ii) aspects techniques ; iii) aspects organisationnels ; iv) aspects politiques ; v) ressources. Avec ses partenaires, la Tripartite met tout en oeuvre pour rendre ce cadre opérationnel, notamment à travers i) la participation des communautés à des activités de sensibilisation sur la rage ; ii) le renforcement des systèmes de santé humaine et animale, l'application de la surveillance et la démonstration de la faisabilité de l'élimination de la rage ; iii) la promotion de la collaboration intersectorielle et régionale ; iv) l'appel actif en faveur d'un engagement et d'un soutien politiques ; v) la justification de la rentabilité des investissements à travers des partenariats public-privé et un plan d'activités pour l'élimination mondiale de la rage. En créant un environnement propice permettant aux pays de prioriser la rage et de mettre en application les instruments existants, la Tripartite s'est engagée à dynamiser le changement, à donner aux pays les capacités d'agir et à fournir le soutien nécessaire pour que le rage soit un jour reléguée dans les livres d'histoire.

Una serie de asociados internacionales trabajan codo a codo para alcanzar el objetivo común de que para 2030 no haya en el mundo ninguna persona que muera de rabia transmitida por perros. Como parte de una alianza tripartita, la Organización Mundial de la Salud (OMS), la Organización Mundial de Sanidad Animal (OIE) y la Organización de las Naciones Unidas para la Alimentación y la Agricultura (FAO) están otorgando prioridad a la lucha antirrábica como modelo para poner en práctica los postulados de «Una sola salud¼. En 2015, la conferencia mundial dedicada a la lucha contra la rabia culminó con la elaboración de un marco estratégico mundial para eliminar la rabia humana transmitida por perros. Se trata de una estrategia a largo plazo (STOP-R) edificada en torno a cinco grandes pilares: i) aspectos socioculturales; ii) aspectos técnicos; iii) aspectos organizativos; iv) políticas; y v) recursos. Junto con sus colaboradores, la alianza tripartita trabaja para llevar ese marco a la práctica: i) haciendo participar a las comunidades en la sensibilización respecto de la rabia; ii) fortaleciendo los sistemas sanitarios y zoosanitarios, efectuando labores de vigilancia y demostrando empíricamente que la eliminación de la rabia es un objetivo factible; iii) promoviendo la colaboración intersectorial y regional; iv) presionando para lograr el compromiso y apoyo políticos; y v) aportando argumentos en defensa de la inversión por la vía de alianzas publicoprivadas y elaborando un plan de trabajo para la eliminación de la rabia a escala mundial. La alianza tripartita, al crear condiciones propicias para que los países otorguen prioridad a la rabia y apliquen las herramientas existentes, está impulsando el cambio, dotando a las naciones de capacidad de acción y prestando el apoyo necesario para conseguir que un día la rabia quede relegada a los libros de historia.

A mildly relativistic wide-angle outflow in the neutron-star merger event GW170817.

GW170817 was the first gravitational-wave detection of a binary neutron-star merger. It was accompanied by radiation across the electromagnetic spectrum and localized to the galaxy NGC 4993 at a distance of 40 megaparsecs. It has been proposed that the observed γ-ray, X-ray and radio emission is due to an ultra-relativistic jet being launched during the merger (and successfully breaking out of the surrounding material), directed away from our line of sight (off-axis). The presence of such a jet is predicted from models that posit neutron-star mergers as the drivers of short hard-γ-ray bursts. Here we report that the radio light curve of GW170817 has no direct signature of the afterglow of an off-axis jet. Although we cannot completely rule out the existence of a jet directed away from the line of sight, the observed γ-ray emission could not have originated from such a jet. Instead, the radio data require the existence of a mildly relativistic wide-angle outflow moving towards us. This outflow could be the high-velocity tail of the neutron-rich material that was ejected dynamically during the merger, or a cocoon of material that breaks out when a jet launched during the merger transfers its energy to the dynamical ejecta. Because the cocoon model explains the radio light curve of GW170817, as well as the γ-ray and X-ray emission (and possibly also the ultraviolet and optical emission), it is the model that is most consistent with the observational data. Cocoons may be a ubiquitous phenomenon produced in neutron-star mergers, giving rise to a hitherto unidentified population of radio, ultraviolet, X-ray and γ-ray transients in the local Universe.

A radio counterpart to a neutron star merger.

Gravitational waves have been detected from a binary neutron star merger event, GW170817. The detection of electromagnetic radiation from the same source has shown that the merger occurred in the outskirts of the galaxy NGC 4993, at a distance of 40 megaparsecs from Earth. We report the detection of a counterpart radio source that appears 16 days after the event, allowing us to diagnose the energetics and environment of the merger. The observed radio emission can be explained by either a collimated ultrarelativistic jet, viewed off-axis, or a cocoon of mildly relativistic ejecta. Within 100 days of the merger, the radio light curves will enable observers to distinguish between these models, and the angular velocity and geometry of the debris will be directly measurable by very long baseline interferometry.

Illuminating gravitational waves: A concordant picture of photons from a neutron star merger.

Merging neutron stars offer an excellent laboratory for simultaneously studying strong-field gravity and matter in extreme environments. We establish the physical association of an electromagnetic counterpart (EM170817) with gravitational waves (GW170817) detected from merging neutron stars. By synthesizing a panchromatic data set, we demonstrate that merging neutron stars are a long-sought production site forging heavy elements by r-process nucleosynthesis. The weak gamma rays seen in EM170817 are dissimilar to classical short gamma-ray bursts with ultrarelativistic jets. Instead, we suggest that breakout of a wide-angle, mildly relativistic cocoon engulfing the jet explains the low-luminosity gamma rays, the high-luminosity ultraviolet-optical-infrared, and the delayed radio and x-ray emission. We posit that all neutron star mergers may lead to a wide-angle cocoon breakout, sometimes accompanied by a successful jet and sometimes by a choked jet.

General route to synthesize of metal (Ni, Co, Mn, Fe) oxide nanostructure and their optical and magnetic behaviour.

Here we report a generalised way to prepare transitional metal (Ni, Co, Mn, Fe) oxide nanostructures via solvothermal route followed by controlled heat treatment. The method has been successfully involved to produce structurally uniform and well crystalline phase of the different metal (Ni, Co, Mn) oxide faceted nanoparticles and porous nanorods (Fe2O3) with highly anisotropic surfaces. The product materials were characterized by the X-ray powder diffraction and electron microscope (SEM, TEM) to investigate the structural and morphological details. Optical absorption study was carried out by UV-VIS spectrophotometer and the results are analysed on the basis of their electronic transitions of 3d shell and band energies. The details magnetic investigation was carried out by the measurement of magnetization with varying magnetic field and temperature. The observed magnetic behaviour is explained on the basis of uncompensated spins lying on the surface which is extremely anisotropic in the present systems of the synthesized materials.

Effect of supplementation of vitamin E, copper and zinc on the in vitro phagocytic activity and lymphocyte proliferation index of peripartum Sahiwal (Bos indicus) cows.

To study the effect of vitamin E (VE), copper (Cu) and zinc (Zn) supplementation on the in vitro phagocytic activity (PA) and lymphocyte proliferation response (LPR) of blood neutrophils and lymphocytes, thirty Sahiwal pregnant cows (six in each group) in their late gestation at 30 days before the expected date of calving were selected from the NDRI experimental herd and supplemented with various micronutrients from 30 days before calving to 45 days after calving. Cows were supplemented individually with VE (1000 IU/cow/day), Cu (20 ppm/cow/day) and Zn (80 ppm/cow/day) and also with a combination of VE, Cu and Zn to study cumulative effect of all micronutrients. One group without any supplementation acted as a control. Blood neutrophils and lymphocytes were isolated and studied for their PA and LPR. Supplementation of micronutrients like VE, Cu, Zn and a combination of all these nutrients significantly (p < 0.01) increased the PA of experimental cows as compared to control (unsupplemented) cows during the pre-partum period. During post-partum, all the micronutrients (VE, Cu, Zn and their combination) showed a significant (p < 0.01) increase in the PA of experimental cows as compared to control cows. Of all the groups, significant (p < 0.01) and maximum PA was observed in the combination group followed by Zn-supplemented group during both the pre- and post-partum period. A significant (p < 0.01) increase in LPR of B lymphocytes was observed in combination-supplemented group during the pre-partum period and during both the pre- and post-partum period in the Cu-supplemented group.

Primary sclerosing cholangitis, Crohn's disease and HLA-B27 in black South African women.

Crohn's disease is rare in South African black people and primary sclerosing cholangitis (PSC) is also rare in black patients with IBD, from South Africa. The presence of HLA-B27 is generally associated with seronegative spondylo-arthropathies and correlates with the occurrence of ankylosing spondylitis, recurrent mouth ulcers and uveitis, in patients with IBD. We describe two women with the combination of Crohn's disease, PSC and HLA-B27 from our cohort of the last 5 years of three black patients with Crohn's disease. Crohn's disease, PSC and HLA-B27 respectively, occur rarely in black South Africans and their concurrent presence in two black women suggests a pathogenetic link of HLA-B27 between Crohn's disease and PSC in this population. Female gender might be an additional determinant in this setting.

A survey of the prevalence of blowfly strike and the control measures used in the Rûens area of the Western Cape Province of South Africa.

Blowfly strike and the methods used to combat blowfly strike were recorded on 33 properties in the Rûens area of South Africa during 2003/2004. Data were recorded on Merino and Dohne Merino hoggets (n = 4951) with at least 3 months' wool growth. The following data were captured: presence or absence of strike, site of the strike (body or breech), presence or absence of dermatophilosis as well as subjective scores for wool quality and wool colour. Control measures recorded include: chemical treatment (preventative and spot treatment), crutching, mulesing and the use of the Lucitrap system. Blowfly strike was not significantly influenced by gender or breed. Hoggets suffering from dermatophilosis were more likely to be struck, compared with contemporaries not suffering from the skin disorder (0.057 vs 0.027; P < 0.05). Merino hoggets generally had higher scores than their Dohne Merino contemporaries for wool quality (32.6 vs 27.4; P < 0.05) and wool colour (29.0 vs 27.2; P < 0.05). There was an indication that the Lucitrap system may have reduced flystrike, but the effect was not statistically significant (P = 0.19 for overall strikes and P = 0.12 for body strike). The Mules operation benefited overall flystrike (0.013 vs 0.110; P < 0.05); mainly through an effect on breech strike (0.010 vs 0.109; P < 0.05). The proportion of fly strikes increased with wool length, and declined with an increase in farm size in wool colour score. None of the ethically acceptable control measures assessed could substantially reduce blowfly strike on their own, and an integrated pest management programme was proposed.

Reply to comment on 'Particle size dependent exchange bias and cluster-glass states in LaMn(0.7)Fe(0.3)O(3) '.

In reply to the comment by Geshev we emphasize that loop shift in the compounds is not a simplified phenomenon of minor loop effect of a ferromagnet rather, it is a genuine signature of exchange bias effect. The estimate of anisotropy field and the plot of exchange bias field at 5 K with the maximum field used for the measurement of hysteresis loop, in addition to the previously reported results such as temperature dependence of exchange bias field, training effect, etc, confirm the exchange bias effect.

Synthetic and structural studies on amine coordination to Pd-N-heterocyclic carbene complexes.

The reaction between 2-chlorobenzylamine or 2-chlorobenzylalcohol and Pd(I(t)Bu)(2) (I(t)Bu = 1,3-di-tert-butylimidazol-2-ylidene) in benzene affords the dimeric complexes [Pd(I(t)Bu)(mu-NH{2-CH(2)C(6)H(4)})](2) and [Pd(I(t)Bu)(mu-O{2-CH(2)C(6)H(4)})](2); the latter has been structurally characterised. The syntheses, structural characterisation and reactivity of the Pd-NHC amine complexes [(I(t)Bu)Pd(R-4-C(6)H(4))(morpholine)Cl] (R = Me, OMe, CO(2)Me), intermediates in the Buchwald-Hartwig aryl amination reaction, are also reported.

Synthesis and reactivity of alkyl-palladium N-heterocyclic carbene complexes.

The transamination of alkyl-palladium halide N-heterocyclic carbene complexes has enabled the isolation of products that reveal interesting insights into the factors which might be barriers to the development of a palladium-catalysed alkyl-amination reaction.