Minor Fraction Research Articles

Sparse and robust support vector machine with capped squared loss for large-scale pattern classification

Support vector machine (SVM), being considered one of the most efficient tools for classification, has received widespread attention in various fields. However, its performance is hindered when dealing with large-scale pattern classification tasks due to high memory requirements and running very slow. To address this challenge, we construct a novel sparse and robust SVM based on our newly proposed capped squared loss (named as Lcsl-SVM). To solve Lcsl-SVM, we first focus on establishing optimality theory of Lcsl-SVM via our defined proximal stationary point, which is convenient for us to efficiently characterize the Lcsl support vectors of Lcsl-SVM. We subsequently demonstrate that the Lcsl support vectors comprise merely a minor fraction of entire training data. This observation leads us to introduce the concept of the working set. Furthermore, we design a novel subspace fast algorithm with working set (named as Lcsl-ADMM) for solving Lcsl-SVM, which is proven that Lcsl-ADMM has both global convergence and relatively low computational complexity. Finally, numerical experiments show that Lcsl-ADMM has excellent performances in terms of getting the best classification accuracy, using the shortest time and presenting the smallest numbers of support vectors when solving large-scale pattern classification problems.

Flow cytometric analysis of immune cell populations in the bronchial and mesenteric lymph nodes of the dromedary camel.

Dromedary camel is an important livestock species with special economic value in arid and semi-arid regions of the world. Given the limited data on detailed immune cell composition and cell marker expression in the dromedary camel lymph node tissue, the present study was undertaken to investigate the immune cell composition of bronchial and mesenteric lymph nodes from healthy dromedary camels using flow cytometry. In this study, we applied flow cytometry and multicolor immuno-fluorescence to phenotype the main populations of immune cells in the bronchial and mesenteric camel lymph nodes and compared them with separated peripheral blood mononuclear cells and granulocytes. We used antibodies to detect several cell surface molecules associated with camel T cells (CD4, WC1), B cells (MHCII, BAQ44A), monocytes/macrophages (CD172a, CD14, CD163), in addition to the pan-leukocyte marker CD45 and the cell adhesion molecules CD44 and CD18. Compared to blood mononuclear cells, camel lymph node cells contained a higher percentage of lymphoid cells with only a minor fraction of myeloid cells. In addition, the lower expression of CD44 and CD18 on lymph node lymphocytes compared to lymphocytes from peripheral blood indicates higher frequency of naïve lymphocytes in the lymph nodes. The frequency of CD4+ T cells, B cells and γδ T cells within camel lymph node lymphocytes compared to blood indicates a similar tissue distribution pattern of lymphocyte subsets in camel and bovine and supports previous reports on the similarity between the camel immune system and the immune system of other ruminants. Lymph node neutrophils were identified as CD45++ CD172a++, CD14+, MHCIIlow, BAQ44A+, CD44++, CD18++ cells. In conclusion, the present study is describing the employment of flow cytometric single-cell analysis and immunostaining for the analysis of the immune cell composition in the camel lymph node.

Formation of non-evaporitic gypsum in gas hydrate-bearing sediments at Håkon Mosby mud volcano, SW Barents sea

Authigenic minerals such as carbonate and iron sulfide are known features at cold seeps worldwide and form as a result of the anaerobic oxidation of methane in the sulfate-methane transition zone (SMTZ). Recent findings of seep-related non-evaporitic gypsum raise questions regarding its distribution, formation mechanisms, and relationships with the other proxies for confident paleo-seep reconstructions. Here, we report new findings of gypsum in the seep-impacted sediments of the hydrate-bearing Håkon Mosby mud volcano, SW Barents Sea. We combined sediment core logging (XRF, X-Ray) with optical microscopy and scanning electron microscopy - electron dispersive energy to characterize the authigenic mineral fraction of the sediment. Three paleo-SMTZs marked by the co-occurrence of pyrite and gypsum accumulations were found at 7–10 cm, 13–18 cm and 19–21 cm, above the modern one (at ∼50 cm) and match with carbonate-poor and foraminifera-free sediment intervals. Our results indicate that gypsum formation required a descending SMTZ (decreasing methane flux), triggering the oxidation of previously-formed pyrite which supplied extra SO42− to the pore water. Acidic conditions caused by pyrite oxidation would have promoted the dissolution of carbonate particles, thus releasing Ca2+ that is available for gypsum formation. As seen in other studies, the presence of shallow gas hydrates seems to play an important role as a calcium source for gypsum precipitation, via ion exclusion during hydrate formation. HMMV represents an optimal natural laboratory to investigate the interplay between different processes in gypsum biogeochemistry and its potential use as a proxy for methane seeps in modern and ancient settings.

Anti-Cancer, Anti-Angiogenic, and Anti-Atherogenic Potential of Key Phenolic Compounds from Virgin Olive Oil.

The Mediterranean diet, renowned for its health benefits, especially in reducing cardiovascular risks and protecting against diseases like diabetes and cancer, emphasizes virgin olive oil as a key contributor to these advantages. Despite being a minor fraction, the phenolic compounds in olive oil significantly contribute to its bioactive effects. This review examines the bioactive properties of hydroxytyrosol and related molecules, including naturally occurring compounds (-)-oleocanthal and (-)-oleacein, as well as semisynthetic derivatives like hydroxytyrosyl esters and alkyl ethers. (-)-Oleocanthal and (-)-oleacein show promising anti-tumor and anti-inflammatory properties, which are particularly underexplored in the case of (-)-oleacein. Additionally, hydroxytyrosyl esters exhibit similar effectiveness to hydroxytyrosol, while certain alkyl ethers surpass their precursor's properties. Remarkably, the emerging research field of the effects of phenolic molecules related to virgin olive oil on cell autophagy presents significant opportunities for underscoring the anti-cancer and neuroprotective properties of these molecules. Furthermore, promising clinical data from studies on hydroxytyrosol, (-)-oleacein, and (-)-oleocanthal urge further investigation and support the initiation of clinical trials with semisynthetic hydroxytyrosol derivatives. This review provides valuable insights into the potential applications of olive oil-derived phenolics in preventing and managing diseases associated with cancer, angiogenesis, and atherosclerosis.

Magnetic properties and coupled spin‒phonon behavior of M‒type Sr1-xSmxFe12O19 (0 ≤ x ≤ 0.15) nanoparticles

We thoroughly investigated the effects of Sm³⁺ doping on the magnetic, structural, hyperfine, and vibrational properties of Sr1-xSmxFe12O19 (0 ≤ x ≤ 0.15) nanoparticles, which were synthesized using the proteic sol-gel process. The Rietveld refined XRD patterns confirmed the presence of M-type SrFe12O19, alongside a minor fraction of α-Fe2O3. As Sm³⁺ doping increased, the unit cell volume fluctuated, decreasing from 691.73 ų at x = 0 to 690.67 ų at x = 0.10 and slightly rising thereafter. The incorporation of Sm³⁺ induced a conversion of Fe3+ to Fe2+, affecting lattice parameters and crystallinity. At x = 0.10, maximum crystallite size (56.48 nm) and X-ray density (4.83 g/cm³) were attained, alongside decreased microstrain, indicating improved crystallinity and reduced defects. However, at x = 0.15, an increase in microstrain suggested lattice instability. FTIR confirmed that bands in the range 400–600 cm⁻1 might be due to the stretching vibration of oxygen and metal (Fe–O) ions, confirming the formation of hexaferrite. Temperature-dependent Raman spectroscopy studies confirmed the presence of spin-phonon coupling in all samples in the ferrimagnetic transition at ∼725-735 K. Mössbauer spectroscopy elucidated that the substitution of Sr2+ by Sm3+ induced the most pronounced effect on the 12k, 4f2, and 2a sites, corroborating the evolution of the lattice constants and the fact that these three sites have Sr sites in their close vicinity. The room-temperature hysteresis loops exhibited narrow features, indicative of soft magnetic behavior. Saturation magnetization (Ms), remanent magnetization (Mr), and coercivity (Hc) varied with Sm3+ doping content (x). Ms initially decreased from 62.62 emu/g and 22.03 emu/g at x = 0.00 to 54.96 emu/g and 19.63 emu/g at x = 0.10, respectively, and then increase to 59.77 emu/g and 21.86 emu/g at x = 0.15. Conversely, Mr and Hc showed a non-monotonic trend with x, suggesting complex interactions between dopant concentration and magnetic properties.

Deep-rooted winter wheat cover crop promotes subsoil organic carbon storage through improved microbial functional traits

Emerging microbial trait-based approaches for soil organic carbon (SOC) storage advocate enhancing specific soil microbial functional traits, such as increased carbon use efficiency (CUE) and enzymatic efficiency (EE) and decreased metabolic quotient (qCO2). These traits facilitate the efficient conversion of crop residues into microbial biomass C (MBC), that is subsequently stabilized as SOC in the soil mineral fraction. However, our current understanding of SOC dynamics in croplands is mainly confined to topsoil or tillage zone, and the field-based evidence for subsoil microbial functional trait dynamics is sparse. To address this knowledge gap, we studied the effect of contrasting long-term agricultural management practices on microbial functional traits favoring SOC accumulation in topsoil and subsoil by conducting a laboratory experiment using 13C labeled glucose addition. Our results show a 19 % increase in Cgrowth (C allocated for microbial biomass growth), 11 % increase in CUE and 14 % increase in EE under no-till (NT) compared to conventional till (CT) in topsoil (0–10 cm) and no difference in these microbial parameters in subsoil (30–40 cm) between NT and CT. Growing a deep-rooted winter wheat (WW) cover crop increased CUE by 28 % in the topsoil and 11 % in the subsoil compared to no-cover treatment. We found separate drivers controlling SOC accumulation in topsoil and subsoil. These drivers are increased particulate organic matter C (POM–C) and Cgrowth, under NT in topsoil and increased Cgrowth over respiration and mineral associated organic matter C (MAOM–C), under WW in subsoil. Overall, our results provide experimental evidence that different microbial functional traits, molded by different long-term conservation practices, dictate SOC storage in agricultural topsoil and subsoil.

Enhancing the Tensile Properties and Ductile-Brittle Transition Behavior of the EN S355 Grade Rolled Steel via Cost-Saving Processing Routes.

Structural rolled steels are the primary products of modern ferrous metallurgy. Consequently, enhancing the mechanical properties of rolled steel using energy-saving processing routes without furnace heating for additional heat treatment is advisable. This study compared the effect on the mechanical properties of structural steel for different processing routes, like conventional hot rolling, normalizing rolling, thermo-mechanically controlled processing (TMCP), and TMCP with accelerating cooling (AC) to 550 °C or 460 °C. The material studied was a 20 mm-thick sheet of S355N grade (EN 10025) made of low-carbon (V+Nb+Al)-micro-alloyed steel. The research methodology included standard mechanical testing and microstructure characterization using optical microscopy, scanning and transmission electronic microscopies, energy dispersive X-ray spectrometry, and X-ray diffraction. It was found that using different processing routes could increase the mechanical properties of the steel sheets from S355N to S550QL1 grade without additional heat treatment costs. TMCP followed by AC to 550 °C ensured the best combination of strength and cold-temperature resistance due to formation of a quasi-polygonal/acicular ferrite structure with minor fractions of dispersed pearlite and martensite/austenite islands. The contribution of different structural factors to the yield tensile strength and ductile-brittle transition temperature of steel was analyzed using theoretical calculations. The calculated results complied well with the experimental data. The effectiveness of the cost-saving processing routes which may bring definite economic benefits is concluded.

Economic heavy minerals in the stream sediments of wadi Shaàb, southern coast of the Red Sea, Egypt; characterization and upgrading for investigation of their potential recovery

The southern coast of the Red Sea is one of the most promising areas for the occurrence of economic minerals. Therefore, studying the characterization and evaluation of these minerals in the Wadi Shaàb Quaternary sediments and investigating their ability to concentrate and physically separate using economical and ecofriendly techniques is the main goal of this work. The results showed that the representative sample contains an average of 0.06% ilmenite, 0.08% zircon, 0.07% rutile, 0.07% leucoxene, 0.008% cassiterite, 0.004% xenotime, 0.0004% monazite, 0.022% almandine garnet, and 0.46% magnetite. The recovery of economic heavy minerals was applied using a combination of wet-gravity technique via shaking table and magnetic separation using high intensity magnetic separator. The results demonstrated the success of gravity separation in raising the grade from 7.63% to 45.03% in a yield of 13.74% out of the original sample, and also valuable metallurgical recoveries that greater than 89% for tabling multi-stages (rougher and scavenging) was obtained. Concentrated mineral fractions of magnetite, ilmenite, almandine, heavy silicates, and the non-magnetic fraction bearing zircon and rutile were obtained using a high intensity magnetic separator at different ampere range

Quantifying the cooperative evolution of microphase segregation and nanostructural order in annealed polyurethanes of MDI‐BDO‐PTHF

AbstractHere, we quantify the relationship between microphase segregation and local structure development in thermoplastic polyurethanes. Samples were prepared with varying ratios of 4,4′‐methylene diphenyl diisocyanate (MDI) and 1,4‐butanediol (BDO) to polytetrahydrofuran (PTHF) and annealed at temperatures between RT–140 °C for 20 h each. Distinct populations of smaller and larger ordered domains are distinguished by pair distribution function analysis. The intermediate‐range order of nanoscale hard domains in the paracrystalline state (form I) is directly extracted and characterized. The results suggest that form I of the MDI‐BDO:PTHF system presents a conformational and packing order similar to the form III structure, typically obtained from stretching/annealing, but with limited spatial coherence of 3–7 nm. Heating above of the hard segments is necessary to achieve a substantial structural response from the annealing treatment. Increasing promotes purification of the soft phase via microphase segregation, coalescence of the hard blocks, and growth of paracrystalline phase, while a minority fraction of longer‐range ordered domains left over from production remains relatively constant. We observe a composition‐dependent decrease in the average nearest‐neighbor distance that can be correlated with the greater number of CC, CN, and CO bonds with increased hard segment content. A non‐linear deviation in the trend is observed to correlate with sample densification. The mechanical and thermal behavior of the samples is intimately tied to the segregation state.

Geochemical Evidence of Plume Sources for High-MgO Lavas in the Western Kunlun Orogenic Belt

Abstract Plume-derived high-MgO lavas provide important information on the lithological, thermal and chemical variations of Earth’s deep mantle. Here we present results from detailed field, mineralogical and geochemical studies of Late Permian–Late Triassic high-MgO lavas near the Chalukou area in the Western Kunlun (WK) orogenic belt, NW China. The major element compositions of the lavas show extremely high MgO contents (26.6–33.8 wt %) in accordance with olivine accumulation. The parental magma is inferred to be picritic in composition with MgO of 17.2 ± 0.9 wt %. Olivine Zn/Fe and Mn/Zn ratios suggest a peridotite-dominated source with a minor fraction of pyroxenite. The temperature and oxygen fugacity estimates based on multi-methods including olivine-melt Mg–Fe equilibria, Al-in-olivine and olivine–spinel thermometry and oxybarometer yield a mantle potential temperature of 1522–1556 °C and high oxygen fugacity of FMQ (fayalite-magnetite-quartz) + 0.93. The H2O contents in the picrite flows are estimated as 3.67 ± 1.0 wt %, indicating the volatile-rich nature of parental magma and its mantle source. The immobile trace element features show that the WK picrites are OIB (oceanic island basalt)-like, with the enrichment in light rare earth elements and positive Nb, Ta, Zr and Hf anomalies. Furthermore, the Nd–O–Os isotopes display typical mantle values without involvement of recycled materials. Our results suggest the high-MgO volcanism in the WK orogenic belt originated from a volatile-rich plume source.

Adsorption of Ciprofloxacin on Clay Minerals in Argentinian Santa Rosa-Corrientes Soils.

The presence of antibiotics in soils is increasing drastically in last decades due to the intensive farming industry and excessive human consumption. Clay minerals are one of the soil components with great adsorption capacity for organic pollutants. The study of interactions between antibiotics and mineral surfaces will give us scientific knowledge of these pollutants through soils. In this work, we study the adsorption of the antibiotic ciprofloxacin in the clay mineral fraction of soils from the Argentinian zone of Santa Rosa (Corrientes), in a collaborative research of experiments and atomistic modelling calculations of the intercalation of ciprofloxacin in the interlayer space of montmorillonite. Adsorption and desorption isotherms were performed and compared with different isotherm models. Additionally, enthalpy, entropy, and free energy were determined from equilibrium constants at a function of temperature. All these experiments and calculations lead to the conclusions that two adsorption types of ciprofloxacin are found on clay minerals: one weakly sorbed that is released during the desorption experiments, and other one strongly joined that remains in the soil.

Mitochondrial Fraction of Circulating Cell-Free DNA as an Indicator of Human Pathology.

Circulating cell-free DNA (ccfDNA) of mitochondrial origin (ccf-mtDNA) consists of a minor fraction of total ccfDNA in blood or in other biological fluids. Aberrant levels of ccf-mtDNA have been observed in many pathologies. Here, we introduce a simple and effective standardized Taqman probe-based dual-qPCR assay for the simultaneous detection and relative quantification of nuclear and mitochondrial fragments of ccfDNA. Three pathologies of major burden, one malignancy (Breast Cancer, BrCa), one inflammatory (Osteoarthritis, OA) and one metabolic (Type 2 Diabetes, T2D), were studied. Higher levels of ccf-mtDNA were detected both in BrCa and T2D in relation to health, but not in OA. In BrCa, hormonal receptor status was associated with ccf-mtDNA levels. Machine learning analysis of ccf-mtDNA datasets was used to build biosignatures of clinical relevance. (A) a three-feature biosignature discriminating between health and BrCa (AUC: 0.887) and a five-feature biosignature for predicting the overall survival of BrCa patients (Concordance Index: 0.756). (B) a five-feature biosignature stratifying among T2D, prediabetes and health (AUC: 0.772); a five-feature biosignature discriminating between T2D and health (AUC: 0.797); and a four-feature biosignature identifying prediabetes from health (AUC: 0.795). (C) a biosignature including total plasma ccfDNA with very high performance in discriminating OA from health (AUC: 0.934). Aberrant ccf-mtDNA levels could have diagnostic/prognostic potential in BrCa and Diabetes, while the developed multiparameter biosignatures can add value to their clinical management.

Correlation between induced polarization and sulfide content of rock samples obtained from seafloor hydrothermal mounds in the Okinawa Trough, Japan

AbstractThe physical properties of seafloor massive sulfides are crucial for interpreting sub-seafloor images from geophysical surveys, shedding light on the evolution of seafloor mineral deposits. While some studies have explored the relationship between electrical properties and the volume of conductive minerals in rocks from seafloor massive sulfide deposits, they primarily focused on artificial samples, leaving the characteristics of natural samples less understood. Moreover, there has been no comprehensive study detailing the general characteristics of electrical properties, particularly chargeability and relaxation time, in relation to the volumetric fraction of sulfides in rocks from massive sulfide mounds in typical hydrothermal areas. In this study, we employed complex conductivity measurements, elemental concentration analysis, and mineral content identification on to rock samples from the active hydrothermal zones of the Okinawa Trough in Japan. The complex conductivity observed was remarkably high, with a pronounced imaginary component and a broad frequency range. This is attributed to induced polarization extending beyond our measurement range. The rock samples were rich in conductive sulfide minerals such as pyrite, chalcopyrite, and galena. Using the Cole–Cole rock physics model, we established a correlation between rock chargeability and relaxation time coefficient with the volume fraction of conductive sulfide minerals, which deviated from previous findings. The intensity of induced polarization was notably higher than anticipated in earlier studies using artificial samples. Furthermore, we observed a distinct positive correlation between the coefficient of relaxation time and the increase in sulfide volume, likely due to the geometric characteristics of the sulfide minerals. Our findings suggest that rocks in massive sulfide mounds may generally construct sulfide clusters that lengthen the conductive path of the electrical carrier. Graphical Abstract

Magnesium isotope behavior during titanomagnetite fractionation in basaltic lavas

Knowledge of the behavior of magnesium (Mg) isotopes during magmatic differentiation is a prerequisite for applying Mg isotopes as a tracer of crustal recycling and mantle heterogeneity. Crystal fractionation of mafic silicate minerals leads to limited Mg isotope fractionation; hence, Mg isotopic variations in basalts largely result from contributions of subducted crustal materials into their mantle sources. However, recent studies have revealed that the segregation of iron oxides, such as chromite during early-stage basaltic differentiation and titanomagnetite and ilmenite during late-stage differentiation, can potentially modify Mg isotopic compositions of mantle-derived lavas. Titanomagnetite is much more commonly observed in terrestrial basaltic lavas than chromite and ilmenite, and can also form during early-stage basaltic differentiation. To constrain the effects of titanomagnetite crystallization on Mg isotopic systematics of basaltic magma, we report Mg isotopic data for a suite of well-characterized alkaline basaltic lavas (MgO wt% = 4.99 to 6.52) from Gerba Guracha, western Ethiopian Plateau, which have undergone extensive titanomagnetite fractionation. Their δ26Mg values range from −0.29‰ to −0.17‰ and do not correlate with indicators of titanomagnetite fractionation such as TiO2 and V. These observations suggest that the segregation of titanomagnetite produced limited Mg isotope fractionation, possibly because of its composition-dependent, highly variable Δ26MgTi-Mgt−melt (Δ26MgTi-Mgt−melt = δ26MgTi-Mgt − δ26Mgmelt) values. Considering that most iron oxides occur as complex solid solutions that are controlled by the oxygen fugacity of magmas, the effects of oxide segregation on Mg isotopic systematics of basalts require further evaluation.

Stock of Carbon and Soil Organic Fractions in No-Tillage and Crop–Livestock Integration Systems

Soil use and management practices influence the quantity and quality of soil organic matter (SOM). From this perspective, the objective of this work was to evaluate the carbon stock and SOM fractions in a no-tillage (NT) and crop–livestock integration (CL) system in the Cerrado biome. The treatments were divided into four areas, subdivided into an area under NT with 11 years of cultivation, two areas under CL with 5 or 10 years of cultivation, and an area of native vegetation (NV). Undisturbed and disturbed soil (Ferralsols) samples were collected in layers 0.0–0.1, 0.1–0.2, 0.2–0.4, and 0.4–0.6 m for the evaluations of soil properties, including bulk density, weighted mean diameter, clay content, carbon stock, carbon stock of light and mineral fractions, humification rate, and carbon management index. The results obtained suggest that the environments with the highest conservation of the physical properties of the soil are those that contain the highest levels of stable C. The main mechanism for C protection in the systems evaluated was mainly associated with physical protection, promoted by soil aggregates, capable of keeping C protected, and mitigation of C into the atmosphere. The values of the carbon management index in the agriculture areas were >100, indicating that these production systems could approach the soil quality of the native vegetation reference system.

Near-Infrared II Photobiomodulation Preconditioning Ameliorates Stroke Injury via Phosphorylation of eNOS.

The current management of patients with stroke with intravenous thrombolysis and endovascular thrombectomy is effective only when it is timely performed on an appropriately selected but minor fraction of patients. The development of novel adjunctive therapy is highly desired to reduce morbidity and mortality with stroke. Since endothelial dysfunction is implicated in the pathogenesis of stroke and is featured with suppressed endothelial nitric oxide synthase (eNOS) with concomitant nitric oxide deficiency, restoring endothelial nitric oxide represents a promising approach to treating stroke injury. This is a preclinical proof-of-concept study to determine the therapeutic effect of transcranial treatment with a low-power near-infrared laser in a mouse model of ischemic stroke. The laser treatment was performed before the middle cerebral artery occlusion with a filament. To determine the involvement of eNOS phosphorylation, unphosphorylatable eNOS S1176A knock-in mice were used. Each measurement was analyzed by a 2-way ANOVA to assess the effect of the treatment on cerebral blood flow with laser Doppler flowmetry, eNOS phosphorylation by immunoblot analysis, and stroke outcomes by infarct volumes and neurological deficits. Pretreatment with a 1064-nm laser at an irradiance of 50 mW/cm2 improved cerebral blood flow, eNOS phosphorylation, and stroke outcomes. Near-infrared II photobiomodulation could offer a noninvasive and low-risk adjunctive therapy for stroke injury. This new modality using a physical parameter merits further consideration to develop innovative therapies to prevent and treat a wide array of cardiovascular diseases.

Structural characterization of fatty acid anions via gas-phase charge inversion using Mg(tri-butyl-terpyridine)2 2+ reagent ions.

Free fatty acids and lipid classes containing fatty acid esters are major components of lipidome. In the absence of a chemical derivatization step, FA anions do not yield all of the structural information that may be of interest under commonly used collision-induced dissociation (CID) conditions. A line of work that avoids condensed-phase derivatization takes advantage of gas-phase ion/ion chemistry to charge invert FA anions to an ion type that provides the structural information of interest using conventional CID. This work was motivated by the potential for significant improvement in overall efficiency for obtaining FA chain structural information. A hybrid triple quadrupole/linear ion-trap tandem mass spectrometer that has been modified to enable the execution of ion/ion reaction experiments was used to evaluate the use of 4,4',4″-tri-tert-butyl-2,2':6',2″-terpyridine (ttb-Terpy) as the ligand in divalent magnesium complexes for charge inversion of FA anions. Mg(ttb-Terpy)2 2+ complexes provide significantly improved efficiency in producing structurally informative products from FA ions relative to Mg(Terpy)2 2+ complexes, as demonstrated for straight-chain FAs, branched-chain FAs, unsaturated FAs, and cyclopropane-containing FAs. It was discovered that most of the structurally informative fragmentation from [FA-H + Mg(ttb-Terpy)]+ results from the loss of a methyl radical from the ligand followed by radical-directed dissociation (RDD), which stands in contrast to the charge-remote fragmentation (CRF) believed to be operative with the [FA-H + Mg(Terpy)]+ ions. This work demonstrates that a large fraction of product ions from the CID of ions of the form [FA-H + Mg(ttb-Terpy)]+ are derived from RDD of the FA backbone, with a very minor fraction arising from structurally uninformative dissociation channels. This ligand provides an alternative to previously used ligands for the structural characterization of FAs via CRF.

The GRAVITY young stellar object survey

Context. The region of protoplanetary disks closest to a star (within 1–2 au) is shaped by a number of different processes, from accretion of the disk material onto the central star to ejection in the form of winds and jets. Optical and near-IR emission lines are potentially good tracers of inner disk processes if very high spatial and/or spectral resolution are achieved. Aims. In this paper, we exploit the capabilities of the VLTI-GRAVITY near-IR interferometer to determine the location and kinematics of the hydrogen emission line Brγ. Methods. We present VLTI-GRAVITY observations of the Brγ line for a sample of 26 stars of intermediate mass (HAEBE), the largest sample so far analysed with near-IR interferometry. Results. The Brγ line was detected in 17 objects. The emission is very compact (in most cases only marginally resolved), with a size of 10–30 R*(1–5 mas). About half of the total flux comes from even smaller regions, which are unresolved in our data. For eight objects, it was possible to determine the position angle (PA) of the line-emitting region, which is generally in agreement with that of the inner-dusty disk emitting the K-band continuum. The position-velocity pattern of the Brγ line-emitting region of the sampled objects is roughly consistent with Keplerian rotation. The exception is HD 45677, which shows more extended emission and more complex kinematics. The most likely scenario for the Brγ origin is that the emission comes from an MHD wind launched very close to the central star, in a region well within the dust sublimation radius. An origin in the bound gas layer at the disk surface cannot be ruled out, while accreting matter provides only a minor fraction of the total flux. Conclusions. These results show the potential of near-IR spectro-interferometry to study line emission in young stellar objects.

In Vitro bioaccessibility evaluation of minerals in Camu-Camu and Spirulina dietary supplements

This study aimed to determine the total concentration of minerals (Mg, Ca, Zn, Fe, Mn, and Cu) in Spirulina and camu-camu dietary supplements, to evaluate the bioaccessibility of minerals using in vitro digestion method, and to assess the correlation with protein, ash, lipids, dietary fibers and with the bioaccessible fraction (BF) of minerals. The vitamin C content of camu-camu was also determined, and its correlation with the mineral bioaccessible fraction was evaluated. Spirulina presented higher bioaccessible fractions in the gastrointestinal phase (%) for Mg (82−91), Zn (82−90), and Mn (64−81), followed by Cu (59−100), Ca (50−76), and Fe (37−45). Camu-camu supplements presented higher bioaccessible fractions (%) for Cu (100), Fe (32−104) and Ca (64−89), followed by Mn (7−93), Mg (4−99) and Zn (31−51), in the gastrointestinal phase. Mineral bioaccessibility showed negative correlations with the matrix, mainly with dietary fiber. It was evident that vitamin C was found to have favored the bioaccessibility of Fe and Ca in camu-camu. For 1 g intake of Spirulina, BF Fe contributes 6.6% of the Recommended Dietary Intake (RDI) of Fe and 3.6% of the RDI of Mg for camu-camu. Based on this study, an insight into the nutritional value of Spirulina and camu-camu in terms of minerals and the correlation with proximate composition was demonstrated.

Contrasting packing modes for tubular assemblies in chlorosomes

The largest light-harvesting antenna in nature, the chlorosome, is a heterogeneous helical BChl self-assembly that has evolved in green bacteria to harvest light for performing photosynthesis in low-light environments. Guided by NMR chemical shifts and distance constraints for Chlorobaculum tepidum wild-type chlorosomes, the two contrasting packing modes for syn-anti parallel stacks of BChl c to form polar 2D arrays, with dipole moments adding up, are explored. Layered assemblies were optimized using local orbital density functional and plane wave pseudopotential methods. The packing mode with the lowest energy contains syn-anti and anti-syn H-bonding between stacks. It can accommodate R and S epimers, and side chain variability. For this packing, a match with the available EM data on the subunit axial repeat and optical data is obtained with multiple concentric cylinders for a rolling vector with the stacks running at an angle of 21° to the cylinder axis and with the BChl dipole moments running at an angle ß ∼ 55° to the tube axis, in accordance with optical data. A packing mode involving alternating syn and anti parallel stacks that is at variance with EM appears higher in energy. A weak cross-peak at -6 ppm in the MAS NMR with 50 kHz spinning, assigned to C-181, matches the shift of antiparallel dimers, which possibly reflects a minor impurity-type fraction in the self-assembled BChl c.