Negative Electron Transfer Collision-Induced Dissociation of G-Quadruplexes: Uncovering the Guanine Radical Anion Loss Pathway.

G-quadruplex (G4) DNA can form highly stable secondary structures in the presence of metal cations, and research has shown its potential as a transcriptional regulator for oncogenes in the human genome. In order to explore the interactions of DNA with metal cations using mass spectrometry, employing complementary fragmentation methods can enhance structural information. This study explores the use of ion-ion reactions for sequential negative electron transfer collision-induced dissociation (nET-CID) as a complement to traditional ion-trap CID (IT-CID). The resulting nET-CID data for G4 anions with and without metal cations show an increase in fragment ion type diversity and yield of structurally informative ions relative to IT-CID. The nET-CID yields greater sequence coverage by virtue of fragmentation at the 3'-side of thymine residues, which is lacking with IT-CID. Potassium adductions to backbone fragments in IT-CID and nET-CID spectra were nearly identical. Of note is a prominent fragment resulting from a loss of a 149 Da anion seen in nET-CID of large, G-rich sequences, proposed to be radical anion guanine loss. Neutral loss of neutral guanine (151 Da) and deprotonated nucleobase loss (150 Da) have been previously reported, but this is the first report of radical anion guanine loss (149 Da). Confirmation of the identity of the 149 Da anion results from the examination of the homonucleobase sequence 5'-GGGGGGGG-3'. Loss of a charged adenine radical anion at much lower relative abundance was also noted for the sequence 5'-AAAAAAAA-3'. DFT modeling indicates that the loss of a nucleobase as a radical anion from odd-electron nucleic acid anions is a thermodynamically favorable fragmentation pathway for G.

The Use of an Antioxidant Enables Accurate Evaluation of the Interaction of Curcumin on Organic Anion-Transporting Polypeptides 4C1 by Preventing Auto-Oxidation.

Flavonoids have garnered attention because of their beneficial bioactivities. However, some flavonoids reportedly interact with drugs via transporters and may induce adverse drug reactions. This study investigated the effects of food ingredients on organic anion-transporting polypeptide (OATP) 4C1, which handles uremic toxins and some drugs, to understand the safety profile of food ingredients in renal drug excretion. Twenty-eight food ingredients, including flavonoids, were screened. We used ascorbic acid (AA) to prevent curcumin oxidative degradation in our method. Twelve compounds, including apigenin, daidzein, fisetin, genistein, isorhamnetin, kaempferol, luteolin, morin, quercetin, curcumin, resveratrol, and ellagic acid, altered OATP4C1-mediated transport. Kaempferol and curcumin strongly inhibited OATP4C1, and the Ki values of kaempferol (AA(-)), curcumin (AA(-)), and curcumin (AA(+)) were 25.1, 52.2, and 23.5 µM, respectively. The kinetic analysis revealed that these compounds affected OATP4C1 transport in a competitive manner. Antioxidant supplementation was determined to benefit transporter interaction studies investigating the effects of curcumin because the concentration-dependent curve evidently shifted in the presence of AA. In this study, we elucidated the food-drug interaction via OATP4C1 and indicated the utility of antioxidant usage. Our findings will provide essential information regarding food-drug interactions for both clinical practice and the commercial development of supplements.

Effects of negative dietary cation-anion difference and calcidiol supplementation in transition diets fed to sows on piglet survival, piglet weight, and sow metabolism.

Diets that provide a negative dietary anion cation difference (DCAD) and supplement with a vitamin D metabolite 25-OH-D3 (calcidiol) may increase calcium availability at parturition, and enhance piglet survival and performance. This factorial study assessed the effects of DCAD, calcidiol (50 µg/kg), and parity (parity 1 or >1) and their interactions. Large White and Landrace sows (n = 328), parity 1 to 8 were randomly allocated in blocks to treatment diets from day 103 of gestation until day 3 postfarrow: 1) negative DCAD without calcidiol (negative DCAD + no CA), n = 84, 2) negative DCAD with calcidiol (negative DCAD + CA) n = 84, 3) positive DCAD without calcidiol (negative DCAD + no CA), n = 81, and 4) positive DCAD with calcidiol (positive DCAD + CA), n = 79. Negative DCAD diets were acidified with an anionic feed (2 kg/t) and magnesium sulfate (2 kg/t). All treatment diets contained cholecalciferol at 1,000 IU/kg. Dry sow diets contained 14.8% crude protein (CP), 5.4% crude fiber (CF), 0.8% Ca, and 83 mEq/kg DCAD. Treatment diets 1 and 2 contained 17.5% CP, 7.3% CF, 0.8% Ca, and -2 mEq/kg DCAD. Treatment diets 3 and 4 contained 17.4% CP, 7.4% CF, 0.8% Ca, and 68 mEq/kg DCAD. Before farrowing, all negative DCAD sows had lower urine pH than all sows fed a positive DCAD (5.66 ± 0.05 and 6.29 ± 0.05, respectively; P < 0.01); urinary pH was acidified for both DCAD treatments indicating metabolic acidification. The percentage of sows with stillborn piglets was not affected by DCAD, calcidiol, or parity alone but sows fed the negative DCAD + CA diet had a 28% reduction in odds of stillbirth compared to the negative DCAD + no CA diet and even lesser odds to the positive DCAD + CA diet. At day 1 after farrowing, blood gas, and mineral and metabolite concentrations were consistent with feeding a negative DCAD diet and that negative DCAD diets influence energy metabolism, as indicated by increased glucose, cholesterol, and osteocalcin concentrations and reduced nonesterified free fatty acids and 3-hydroxybutyrate concentrations. In the subsequent litter, total piglets born and born alive (14.7 ± 0.3 and 13.8 ± 0.3 piglets, respectively; P = 0.029) was greater for positive DCAD diets compared to negative DCAD diets; and there was an interaction between DCAD, calcidiol, and parity (P = 0.002). Feeding a negative DCAD diet influenced stillbirth, subsequent litter size, and metabolic responses at farrowing. More studies are needed to define optimal diets prefarrowing for sows.

The transition period between late gestation and lactation is critical to farrowing and successful lactation; sows with higher blood calcium have less risk of dystocia. We evaluated transition diets that provided a negative dietary cation­anion difference (DCAD) and supplemented with calcidiol (CA), both of which influence calcium metabolism. Purebred Landrace or Large White sows (n = 328) were enrolled in the experiment and selected sows that were either primiparous (n = 99) or multiparous (n = 229; average parity = 2.59 ± 1.51; parity range = 1 to 8) were fed a dry sow ration until day 103 of gestation and were then fed transition diets until day 3 postfarrowing in a factorial study. The diets were formulated to include 1) negative DCAD + no CA, 2) negative DCAD + CA, 3) positive DCAD + no CA, or 4) positive DCAD + CA. All diets induced a metabolic acidosis as indicated by urinary pH. Sows fed the negative DCAD with added calcidiol had a >28% reduction in odds of stillbirth over negative DCAD + no CA and positive DCAD + CA diets. Following weaning and re-mating, there were 0.9 more piglets born in the subsequent litter for both positive DCAD diets compared to negative DCAD diets. Blood gas, and mineral and metabolite concentrations provided evidence that negative DCAD diets positively influenced energy metabolism.

The interaction on HSA and the antibacterial activity from four polyoxometalate hybrids based on berberine.

Four organic-polyoxometalate hybrids BR4[SiW12O40] (BR-SiW), BR3[PMo12O40] (BR-PMo), BR4K[EuSiW11O40]·2H2O (BR-EuSiW) and BR6Na3[EuW10O36] (BR-EuW) were fabricated by the polyoxometalates (POMs) anions and berberine cations (BR) noted for the alkaloids in traditional Chinese herbal medicine. These hybrids have been characterized and confirmed. The interaction between hybrids and human serum albumin (HSA) was investigated in a buffer solution (pH 7.4) using ultraviolet-visible light absorption and fluorescence techniques. The classical Stern-Volmer equation was used to analyze the fluorescence quenching at three temperatures (296, 303 and 310 K), and the static quenching mechanism for interaction was proposed. The Thermodynamic parameters, enthalpy, entropy change, and Gibbs free energy of hybrids interacting on HSA were calculated by Scatchard equation. The results indicated that therewas one binding site on the protein and BR-POMs all showed stronger binding force than that of raw materials. Synchronous fluorescence results showed that the binding sites of BR-POMs and HSA were not effectively affected the surrounding microenvironment. The following antibacterial experiments implied that inhibitory effect of hybrids were synergistic effect from organic active ingredient and POMs but the simple combination. All these data were prepared for further research on biology.

Influence of prepartum dietary cation-anion difference and the magnitude of calcium decline at the onset of lactation on mineral metabolism and physiological responses.

The onset of lactation is characterized by substantially altered calcium (Ca) metabolism; recently, emphasis has been placed on understanding the dynamics of blood Ca in the peripartal cow in response to this change. Thus, the aim of our study was to delineate how prepartum dietary cation-anion difference (DCAD) diets and the magnitude of Ca decline at the onset of lactation altered blood Ca dynamics in the periparturient cow. Thirty-two multiparous Holstein cows were blocked by parity, previous 305-d milk yield and expected parturition date, and randomly allocated to either a positive (+120 mEq/kg) or negative (-120 mEq/kg) DCAD diet from 251 d of gestation until parturition (n = 16/diet). Immediately after parturition cows were continuously infused for 24 h with (1) an intravenous solution of 10% dextrose or (2) Ca gluconate (CaGlc) to maintain blood ionized (iCa) concentrations at ∼1.2 mM (normocalcemia) to form 4 treatment groups (n = 8/treatment). Blood was sampled every 6 h from 102 h before parturition until 96 h after parturition and every 30 min during 24 h continuous infusion. Cows fed a negative DCAD diet prepartum exhibited a less pronounced decline in blood iCa approaching parturition with lesser magnitude of decline relative to positive DCAD-fed cows. Cows fed a negative DCAD diet prepartum required lower rates of CaGlc infusion to maintain normocalcemia in the 24 h postpartum relative to positive DCAD-fed cows. Infusion of CaGlc disrupted blood Ca and P dynamics in the immediate 24 h after parturition and in the days following infusion. Collectively, these data demonstrate that prepartum negative DCAD diets facilitate a more transient hypocalcemia and improve blood Ca profiles at the onset of lactation whereas CaGlc infusion disrupts mineral metabolism.

Sugar Profile Method by High-Performance Anion-Exchange Chromatography with Pulsed Amperometric Detection in Food, Dietary Supplements, Pet Food, and Animal Feeds: Interlaboratory Validation Study, Final Action 2018.16.

BACKGROUND: A method for sugar profile analysis granted First Action 2018.16 was subjected to a multi-laboratory study. OBJECTIVE: Perform a multi-laboratory study with this method to determine the performance parameters of repeatability and reproducibility against the AOAC Standard Method Performance Requirements (AOAC SMPR 2018.001) for Final Action status. METHODS: Eleven laboratories from three different countries participated in the study. Each laboratory was provided practice materials for successful method setup. Each laboratory then proceeded with analysis of blind duplicates of 10 different products covering the scope of the method. Results were reported to the study directors with any modifications and assessed following the procedures of Appendix D of the AOAC Official Methods of AnalysisSM (guidelines for collaborative study procedures). RESULTS: The majority of results from the study met the SMPR requirements. The data is presented along with any outlying observations or modifications. The method was proven to be flexible across different instrumentation and laboratories, and the method was updated to provide further system suitability and guidelines to maintain the performance of the method across the large scope of matrixes. CONCLUSION: The results from the collaborative study supported the method for Final Action status. The Expert Review Panel reviewed and voted to move the method forward to Final Action and was followed by review from the Official Methods Board and granted approval. HIGHLIGHTS: The method was granted Final Action Official Methods status.

Huatanmaitong tablet alleviate cerebral ischemic reperfusion injury with hyperlipidaemia in rats by regulating OATPs/VEGF axis.

Stroke is the top priority pathogenesis of disability and death globally, affecting people worldwide. The presence of high levels of lipids in the blood has been confirmed as a vital factor of ischemic stroke. We aim to examine the effectiveness of Huatanmaitong tablet in hyperlipidemia rats that have experienced an ischemic stroke. We created a rat model of middle cerebral artery occlusion (MCAO) with hyperlipidemia as a basis. Following 8 weeks of high-fat diet, the model rats underwent MCAO surgery. Subsequently, the rats were administered huatanmaitong tablets and lipitor tablets as treatments. Therefore there are five groups, CONTROL, MCAO, hyperlipidemia (HLP), Huatanmaitong tablet (HTMTT) and Lipitor (LIPITOR) groups respective ly. To assess the efficacy of the medication, the serum lipid levels of rats were measured both prior to and following administration. Hematoxylin eosin staining was used to observe the alterations in the brain and liver structures within each group. VEGF and OATPs related factors were detected in brain, liver by using immunohistochemistry, Western blotting, and Quantitative PCR. After the model was established successfully, the infarct volume and behavioral scores of the model group, hyperlipidemia group, Huatan Maitong tablet group and Lipitor group had statistical differences (P<0.05). Blood lipid levels of rats were measured before and after treatment, and it was found that Huatanmaitong tablets effectively reduced these levels. Hematoxylin and eosin staining of the brain and liver showed that huatanmaitong tablets maintained the microstructure stability. Western blotting and real-time PCR revealed that Huatanmaitong tablets improved the expression level of organic anion transport (OATP1B1, OATP2B1) in rat tissues with ischemic stroke, enhancing the transmembrane transport of exogenous substances and maintaining homeostatic balance. Additionally, it down-regulated the expression of VEGF in various organs such as the brain, and liver, demonstrating the ability of Huatanmaitong tablets to remove phlegm, blood stasis, and promote circulation by regulating serum lipid levels, organic anion transport peptide, and VEGF in rats. The behavioral score of ischemic stroke rats can be improved and the neurological impairment symptoms of rats can be alleviated by Huatanmaitong tablet through the regulation of OATPS/VEGF axis.

Sorption of ionic liquids in soil enriched with polystyrene microplastic reveals independent behavior of cations and anions.

Recently, much attention has been focused on the application of the Ionic Liquids (ILs) with herbicidal activity in agriculture. It has been suggested that through the appropriate selection of cations and anions, one can adjust the properties of ILs, particularly the hydrophobicity, solubility, bioavailability, toxicity. In practical agricultural conditions, it will be beneficial to reduce the mobility of herbicidal anions, such as the commonly applied 2,4-dichlorophenoxyacetic acid [2,4-D] in the soil. Furthermore, microplastics are becoming increasingly prevalent in the soil, potentially stimulating herbicidal sorption. Therefore, we investigated whether cations in ILs influence the mobility of anions in OECD soil supplemented with polystyrene microplastic (PS). For this purpose, we used the 2,4-D based ILs consisting of: a hydrophilic choline cation [Chol][2,4-D] and a hydrophobic choline cation with a C12chain [C12Chol][2,4-D]. Characterization of selected micropolystyrene was carried out using the BET sorption-desorption isotherm, particle size distribution and changes in soil sorption parameters such as soil sorption capacity and cation exchange capacity. Based on the batch sorption experiment, the effect of microplastic on the sorption of individual cations and anions in soil contaminated with micropolystyrene was evaluated. The results obtained indicate that the introduction of a 1-10% (w/w) PS resulted in an 18-23% increase of the soil sorption capacity. However, the sorption of both ILs' cations increased only by 3-5%. No sorption of the [2,4-D] anion was noted. This suggests that cations and anions forming ILs, behave independently of each other in the environment. The results indicate the fact that ILs upon introduction into the environment are not a new type of emerging contaminant, but rather a typical mixture of ions. It is worth noting that when analyzing the behavior of ILs in the environment, it is necessary to follow the fate of both cations and anions.

Molecular basis for selective uptake and elimination of organic anions in the kidney by OAT1.

In mammals, the kidney plays an essential role in maintaining blood homeostasis through the selective uptake, retention or elimination of toxins, drugs and metabolites. Organic anion transporters (OATs) are responsible for the recognition of metabolites and toxins in the nephron and their eventual urinary excretion. Inhibition of OATs is used therapeutically to improve drug efficacy and reduce nephrotoxicity. The founding member of the renal organic anion transporter family, OAT1 (also known as SLC22A6), uses the export of α-ketoglutarate (α-KG), a key intermediate in the Krebs cycle, to drive selective transport and is allosterically regulated by intracellular chloride. However, the mechanisms linking metabolite cycling, drug transport and intracellular chloride remain obscure. Here, we present cryogenic-electron microscopy structures of OAT1 bound to α-KG, the antiviral tenofovir and clinical inhibitor probenecid, used in the treatment of Gout. Complementary in vivo cellular assays explain the molecular basis for α-KG driven drug elimination and the allosteric regulation of organic anion transport in the kidney by chloride.

Effects on rumen pH and feed intake of a dietary concentrate challenge in cows fed rations containing pH modulators with different neutralizing capacity.

Forty-five Holstein lactating cows (41 ± 8.8 kg/d of milk yield, 96 ± 35.6 days in milk, and 607 ± 80.4 kg of body weight) were enrolled in this study to assess the effects of diets supplemented with sodium bicarbonate or a magnesium-based product and their corresponding differences in dietary cation-anion difference (DCAD) on rumen pH, rumen microbial population, and milk performance of dairy cattle exposed to an induced decrease in rumen pH through a dietary challenge. Cows were randomly allocated to 3 total mixed rations (TMR) differing in the type of supplement to modulate rumen pH: (1) control, no supplementation; (2) SB, supplemented with 0.82% of sodium bicarbonate with a neutralizing capacity (NC) of 12 mEq/g; and (3) MG, supplemented with 0.25% of magnesium oxide (pHix-Up, Timab Magnesium) with a NC of 39 mEq/g. Thus, SB and MG rations had, in theory, the same NC. The 3 TMR differed for control, SB, and MG in their DCAD-S (calculated considering Na, K, Cl, and S), which was on average 13.2, 21.2, and 13.7 mEq/100 g, respectively, or DCAD-Mg (calculated accounting for Mg, Ca, and P), which was 31.4, 41.2, and 35.2 mEq/100 g, respectively. The study lasted 63 d, with the first 7 d serving as a baseline, followed by a fortnightly progressive decrease of dietary forage-to-concentrate ratio (FCR) starting at 48:52, then 44:56, then 40:60, and finishing at 36:64. Individual dry matter intake (DMI) was recorded daily. Seven cows per treatment were equipped with electronic rumen boluses to monitor rumen pH. Control and SB cows consumed less dry matter (DM; 23.5 ± 0.31 kg/d) than MG cows (25.1 ± 0.31 kg/d) when fed dietary FCR of 44:56 and 40:60. Energy-corrected milk decreased from 40.8 ± 1.21 to 39.5 ± 1.21 kg/d as dietary FCR decreased, independently of dietary treatments. Rumen pH decreased and the proportion of the day with rumen pH <5.8 increased as dietary FCR decreased, and at low dietary FCR (i.e., 36:64) rumen pH was greater in MG cows than in control and SB cows. Reducing the DCAD-S from 28 to 18 mEq/100 g or the DCAD-Mg from 45 to 39 mEq/kg had no effects on DMI or milk yield. Cows supplemented with ∼62 g/d of magnesium oxide (pHix-Up) maintained a greater rumen pH and consumed more DM than cows supplemented with ∼200 g/d of sodium bicarbonate when fed a diet with low FCR.

Novel Y2O3 based calcium-alginate beads for highly selective adsorption of phosphate from aqueous solution.

Recently, selective phosphorus removal from aqueous solution has been a highly desirable strategy to combat eutrophication due to the increasingly stringent phosphorous emission standards. However, conventional adsorbents pose the limitations in phosphate removal suffering from lack of selectivity and stability under complicated condition and poor separation. In this study, novel Y2O3 based calcium-alginate (Y2O3/SA) beads of feasible stability and highly selectivity towards phosphate by encapsulating Y2O3 nanoparticles inside calcium-alginate beads via Ca2+ controlled gelation process was synthesized and characterized. The phosphate adsorption performance and mechanism were investigated. In general, a high selectivity among co-existing anions was found with co-existing anion concentration up to 62.5 times of the phosphate concentration. Additionally, phosphate adsorption by Y2O3/SA beads exhibited stable performance over a wide pH range between 2 and 10, while reaching the maximum adsorption capacity at pH 3 (48.54 mg-P/g). The value of point of zero charge (pHpzc) of Y2O3/SA beads was approximately 3.45. Pseudo-second-order and Freundlich isotherm models can well accord with kinetics and isotherms data. The FTIR and XPS characterizations analyzed that inner-sphere complexes were proposed to be the major contributor of Y2O3/SA beads for phosphate removal. In conclusion, Y2O3/SA beads as the mesoporous material exhibited excellent stability and selectivity towards phosphate removal.

Possible implementation of salicylate anions in lead detoxification.

The water-soluble coordination polymer of formula {[Pb(Sal)2(H2O)]n} (SaLead), was obtained from the reaction between Pb(NO3)2 and the potassium salt of salicylic acid (SalH), an anti-inflammatory drug, which is also use as food preservation, in cosmetics etc. The compound was characterized by melting point, Attenuated Total Reflectance-Fourier Transform Infra-Red (ATR-FTIR) spectroscopy and X-ray diffraction crystallography (XRD) in solid state and in solution by Ultra Violet (UV) and 1H NMR spectroscopies. The binding affinity of SalK to Pb(II) ions towards SaLead was determined in order to examine its possible implementation in lead detoxification. The in vitro non-toxic behaviour of SalK and its complex SaLead was evaluated against normal human fetal lung fibroblast cells (MRC-5). The corresponding IC50 values are 260 ± 13 and > 1600 µM respectively. The non-genotoxic in vitro activity of SaLead was confirmed with the micronucleus (MN) assay, while its in vivo non-toxicity behaviour was evaluated with Allium cepa and Artemia salina assays.

Sodium removal from bauxite desilication product (sodalite) aided by chelating effects of inorganic and organic acids.

Dealkalization is a prerequisite to converting bauxite residue into non-hazardous materials that can be used for various upcycling applications. Structural alkali (Na+) lodged inside the densely packed aluminosilicate-cages of sodalite, the dominant desilication product from refining alumina, is a common culprit in the persistence of strong alkalinity of bauxite residue. The present study unravelled chemical and mineralogical processes involved in sodalite dealkalization, driven by organic and inorganic acids. These acids have different H+ dissociation coefficients and their anions have different chelation abilities with surface metal atoms of aluminosilicate minerals. The efficacy of sodium removal by exposure to the acids was found not only dependent on the acid strength (pKa), but also on the chelating property of dissociated conjugate anions. Following an initial H+-Na+ exchange, Na+ removal from sodalite was correlated with partial hydrolysis of aluminosilicate network and resultant chelating reactions with acid anions. The selection of organic and inorganic acids whose conjugate bases possess good chelating capability in the pH buffer zone 7-9 (e.g., oxalate or phosphate), would provide significant aid to the dealkalization process. The findings in this study are crucial in understanding the conversion of bauxite residue into a soil-like growth media (technosol) for sustainable mined land rehabilitation.

Negative dietary cation-anion difference in prepartum dairy cow diets: a pragmatic study in two commercial dairy farms.

Pragmatic studies, evaluating the effectiveness of an intervention under its usual conditions, are less commonly reported than the explanatory trials. For instance, the effectiveness of prepartum negative dietary cation-anion difference (DCAD) diets on inducing a compensated metabolic acidosis that promotes a higher blood Ca concentration at calving has not been frequently described under commercial farm management conditions without researchers' interference. Thus, the objectives were to study cows under commercial farm management conditions to (1) describe the daily close-up dairy cows' urine pH and fed DCAD, and (2) evaluate the association between urine pH and fed DCAD, and preceding urine pH and blood Ca at calving. A total of 129 close-up Jersey cows about to commence their ≥2nd lactation were enrolled in the study after 7 days of exposure to DCAD diets in two commercial dairy herds. Urine pH was determined daily from mid-stream urine samples from enrollment to calving. Fed DCAD was determined from feed bunk samples obtained during 29 (Herd 1) and 23 (Herd 2) consecutive days. Plasma Ca concentration was determined within 12 h after calving. Descriptive statistics were generated at the herd- and cow-level. Multiple linear regression was used to evaluate the associations between urine pH and fed DCAD for each herd, and preceding urine pH and plasma Ca concentration at calving for both herds. At herd-level, the average urine pH and CV during the study period were 6.1 and 12.0% (Herd 1) and 5.9 and 10.9% (Herd 2), respectively. At the cow-level, the average urine pH and CV during the study period were 6.1 and 10.3% (Herd 1) and 6.1 and 12.3% (Herd 2), respectively. During the study period, fed DCAD averages were -121.3 and -165.7 mEq/kg of DM and CV 22.8 and 60.6% for Herd 1 and Herd 2, respectively. No evidence of association between cows' urine pH and fed DCAD was observed in Herd 1, whereas a quadratic association was observed in Herd 2. When both herds were combined, a quadratic association was observed between the urine pH intercept (at calving) and plasma Ca concentration. Although average urine pH and fed DCAD were within recommended ranges, the high variability observed indicates that acidification and fed DCAD are not constant, and often outside the recommended ranges in commercial settings. Monitoring of DCAD programs is warranted to ensure their effectiveness under commercial settings.

Decoloration and alkaloid enrichment of Dactylicapnos scandens extracts based on the use of strong anion-exchange resins in tandem with strong cation-exchange silica-based materials.

Alkaloids are natural bioactive ingredients but are usually present in low amounts in plant extracts. In addition, the dark color of plant extracts increases the difficulty in separation and identification of alkaloids. Therefore, effective decoloration and alkaloid enrichment methods are necessary for purification and further pharmacological studies of alkaloids. In this study, a simple and efficient strategy is developed for the decoloration and alkaloid enrichment of Dactylicapnos scandens (D. scandens) extracts. In feasibility experiments, we evaluated two anion-exchange resins and two cation-exchange silica-based materials with different functional groups using a standard mixture composed of alkaloids and nonalkaloids. By virtue of its high adsorbability of nonalkaloids, the strong anion-exchange resin PA408 is considered a better choice for the removal of nonalkaloids, and the strong cation-exchange silica-based material HSCX was selected for its great adsorption capacity for alkaloids. Furthermore, the optimized elution system was applied for the decoloration and alkaloid enrichment of D. scandens extracts. Nonalkaloid impurities in the extracts were removed by the use of PA408 in tandem with HSCX treatment, and the total alkaloid recovery, decoloration and impurity removal ratios are determined to be 98.74%, 81.45% and 87.33%, respectively. This strategy can contribute to further alkaloid purification and pharmacological profiling of D. scandens extracts, as well as other plants with medicinal value.

Application of imidazolium based ionic liquids grafted on microcrystalline cellulose as demulsifiers for water in crude oil (W/O) emulsions.

Separation of water and oil from water-in-oil (W/O) emulsion before transportation and refining is very important and critical. Ionic liquids (ILs) and their derivatives have recently attracted much attention as efficient chemical agents for breaking emulsions. So, here, a series of microcrystalline cellulose (MCC) grafted with imidazolium-based ionic liquids (IM-ILs) were synthesized, named as MCC@IM-ILs, and evaluated as eco-friendly surface-active agents for the separation of water from the crude oil. Structure of the synthesized compounds was confirmed by different characterization techniques. Dehydration efficiency percent (DE%) of the synthesized demulsifiers was measured and compared with each other. Synthesized MCC@IM-ILs showed an acceptable DE% to demulsify three kinds of W/O emulsions with different water content after 5 min. Concentration, alkyl chain length, and counter-anion of the synthesized MCC@IM-ILs play a key role in separating water from crude oil. Demulsifier with C10 alkyl chain length showed better DE% than the corresponding demulsifier with C6 alkyl chain length in the W/O (30:70 v/v) emulsion. Also, demulsifier with Br counter anion showed lower DE% than the corresponding BF4 ion-exchanged compound with higher hydrophilicity. Synthesized demulsifiers immobilized on ILs have significant advantages compared to unsupported ILs due to the use of green and economical cellulosic substrate.

Comparison of Usefulness of Four Chelating Agents (EDTA, NTA, ODA and IDA) for the Chromatographic Separation of Micro and Macro Amounts of Rare Earth Elements.

Literature on the use of four chelating agents namely: ethylenediaminetetraacetic acid, nitrilotriacetic acid, diglycolic acid and iminodiacetic acid for the chromatographic separation of micro and macro amounts of rare earth elements was critically reviewed and supplemented with some new unpublished data from our Laboratory. Advantages and disadvantages of ion exchange chromatography both in cation and anion mode as well as ion interaction chromatography techniques, which were used for rare earth elements separation, are discussed. The usefulness of some of the chromatographic systems for micro-macro separations was discussed and demonstrated. The importance of resilience of the separation method to column overloading in some analytical and larger scale separations was emphasized. The methods described in this article might suit well for recovering of individual lanthanides and yttrium from e-waste and other industrial wastes which were fast accumulating in recent years.

Sustainable carbon nano-onions as an adsorbent for the efficient removal of oxo-anions.

The increasing threats of oxo-anions in drinking water have posed a serious threat to human health, aquatic environment, ecology, and sustainability. Accordingly, developments of cost-effective and sustainable nanomaterials for water remediation are on top priority and highly sought in global research community. Carbon nano-onions (CNOs) are one of the emerging nanomaterials for water purification because of its unique morphology, surface reactivity, high density of surface-active sites, and microporous structure. Herein, flaxseed oil-derived CNOs are utilized as efficient adsorbent for the removal of toxic oxo-anions. Aside from the green and economic nature, CNOs provide high adsorption efficiency ~ 806.45 mg g-1 for the removal of [Formula: see text] (99.9%) from aqueous system at ambient temperature, neutral pH in 70 min. The adsorption of [Formula: see text] onto CNOs was well fitted in pseudo-second order kinetics and followed the Langmuir adsorption isotherm model. The adsorption process was determined to be exothermic and spontaneous from the resulting thermodynamic characteristics. Furthermore, the high hydrophobic nature of CNOs make it recycling simpler. The real-life applicability of CNOs towards [Formula: see text] removal was tested in tap water, river water, and dam water. With all these observed results, CNOs show promise for practical water remediation applications.

Click Chemistry of Selenium Dihalides: Novel Bicyclic Organoselenium Compounds Based on Selenenylation/Bis-Functionalization Reactions and Evaluation of Glutathione Peroxidase-like Activity.

A number of highly efficient methods for the preparation of novel derivatives of 9-selenabicyclo[3.3.1]nonane in high yields based on selenium dibromide and cis,cis-1,5-cyclooctadiene are reported. The one-pot syntheses of 2,6-diorganyloxy-9-selenabicyclo[3.3.1]nonanes using various O-nucleophiles including alkanols, phenols, benzyl, allyl, and propargyl alcohols were developed. New 2,6-bis(1,2,3-triazol-1-yl)-9-selenabicyclo[3.3.1]nonanes were obtained by the copper-catalyzed 1,3-dipolar cycloaddition of 2,6-diazido-9-selenabicyclo[3.3.1]nonane with unsubstituted gaseous acetylene and propargyl alcohol. The synthesis of 2,6-bis(vinylsulfanyl)-9-selenabicyclo[3.3.1]nonane, based on the generation of corresponding dithiolate anion from bis[amino(iminio)methylsulfanyl]-9-selenabicyclo[3.3.1]nonane dibromide, followed by the nucleophilic addition of the dithiolate anion to unsubstituted acetylene, was developed. The glutathione peroxidase-like activity of the obtained water-soluble products was estimated and compounds with high activity were found. Overall, 2,6-Diazido-9-selenabicyclo[3.3.1]nonane exhibits the highest activity among the obtained compounds.

Nitrate and Nitrite Reductions at Copper(II) Sites: Role of Noncovalent Interactions from Second-Coordination-Sphere.

Reductions of nitrate and nitrite (NOx-) are of prime importance in combatting water pollution arising from the excessive use of N-rich fertilizers. While examples of NOx- reductions are known, this report illustrates hydrazine (N2H4)-mediated transformations of NOx- to nitric oxide (NO)/nitrous oxide (N2O). For nitrate reduction to NO, initial coordination of the weakly coordinating NO3- anion at [(mC)CuII]2+ cryptate has been demonstrated to play a crucial role. A set of complementary analyses (X-ray diffraction and Fourier-transform infrared spectroscopy (FTIR), UV-vis, and NMR spectroscopies) on NO3--bound metal-cryptates [(mC)MII(NO3)](ClO4) (1-M, M = Cu/Zn) demonstrates the binding of NO3- through noncovalent (NH···O, CH···O, and anion···π) and metal-ligand coordinate interactions. Subsequently, reactions of [(mC)CuII(14/15NO3)](ClO4) (1-Cu or 1-Cu/15N) with N2H4·H2O have been illustrated to reduce 14/15NO3- to 14/15NO. Intriguingly, in the absence of the second-coordination-sphere interactions, a closely related coordination motif [(Bz3Tren)CuII]2+ (in 3-Cu) does not bind NO3- and is unable to assist in N2H4·H2O-mediated NO3- reduction. In contrast, nitrite coordinates at the tripodal CuII sites in both [(mC)CuII]2+ and [(Bz3Tren)CuII]2+ irrespective of the additional noncovalent interactions, and hence, the N2H4 reactions of the copper(II)-nitrite complexes [(mC)CuII(O14/15NO)]+ and [(Bz3Tren)CuII(O14/15NO)]+ (in 2-Cu/4-Cu) result in a mixture of 14/15NO and N14/15NO.