Phosphorus Groups Research Articles

Development of a Modified Process for the Kilogram-Scale Synthesis of c-Met/ALK Inhibitor HS-10168

A modified synthetic route to c-Met/ALK inhibitor HS-10168 has been developed on a kilogram scale. The key steps of the new process include a Suzuki coupling reaction of nitro-containing bromopyridine 6 and para-phenol boronate 9 to give intermediate 10, which was then converted to its triflate 11. The phosphorus group was introduced by coupling of 11 and dimethylphoshine oxide 8 to give compound 12, which was reduced to produce HS-10168.

Synthesis and properties of novel polyimide fibers containing phosphorus groups in the side chain (DATPPO)

A series of polyamic acid copolymers (co-PAAs) containing phosphorous groups in the side chains were synthesized from [2,5-bis(4-aminophenoxy) phenyl] diphenylphosphine oxide (DATPPO) and 4,4′-oxydianiline (ODA) with 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) through the polycondensation in N,N′-dimethyacetamide (DMAc). The co-PAA solutions were spun into fibers by a dry-jet wet spinning process followed by thermal imidization to obtain co-polyimide (co-PI) fibers. FTIR spectra and elemental analysis confirmed the chemical structure of PI fibers. SEM results indicated that the resulting PI fibers had a smooth and dense surface, a uniform and circle-shape diameter. The thermogravimetric measurements showed that with the increase of DATPPO content, the resulting PI fibers possessed high decomposition temperature and residual char yield, indicating that the PI fibers had good thermal stability. The corresponding limiting oxygen index (LOI) values from the experiment results showed that the co-PI fibers possessed good flame-retardant property. Furthermore, the mechanical properties of the co-PI fibers were investigated systematically. When the DATPPO content increased, the tensile strength and initial modulus of the co-PI fibers decreased. However, the mechanical properties were improved by increasing the draw ratio of the fibers. When the draw ratio was up to 2.5, the tensile strength and initial modulus of the co-PI fibers reached up to 0.64 and 10.02 GPa, respectively. The WAXD results showed that the order degree of amorphous matter increased with increased stretching. In addition, the SAXS results displayed that valuably drawing the fibers could eliminate the voids inside and lead to better mechanical property. WAXD revealed that the orientation of the amorphous polymer influenced the mechanical properties of the fibers.

Synthesis of phosphorus-containing polyurethanes and poly(urethane-acrylate)s

Solvent-based polyurethanes and poly(urethane-acrylate)s were synthesized using phosphorus-containing polyester polyols in order to compare the thermal properties of different polymer types. Since the location of the phosphorus group might have vital importance when comparing the thermal properties, phosphorus groups were kept on the pendant chains in poly(urethane-acrylate)s using phosphorus-containing urethane macromonomers while they were kept on the backbone in polyurethanes. The effect of molar mass of polyurethanes and pendant urethane chains of poly(urethane-acrylate)s on thermal properties was also investigated. Characterization of the synthesized polymers was carried out using FT-IR, GPC, NMR, and DSC followed by evaluation of the thermal properties.

Microhardness, Structure, and Morphology of Primary Enamel after Phosphoric Acid, Self-Etching Adhesive, and Er:YAG Laser Etching

Background. Phosphoric acid is the traditional etching agent; self-etching adhesives and Er:YAG laser are alternative methods. Knowledge of deciduous enamel etching is required.Aim. To evaluate primary enamel microhardness, structure, and morphology after phosphoric acid, self-etching, and Er:YAG laser etching.Design. Seventy primary incisors were assigned to five groups (n=14): I (control), II (35% phosphoric acid), III (self-etching adhesive), IV (Er:YAG laser at 15 J/cm2), and V (Er:YAG laser at 19.1 J/cm2). Microhardness was evaluated by Vickers indentation. Chemical composition was analyzed by energy dispersive X-ray spectroscopy and morphological changes by scanning electron microscopy. One-way ANOVA, Kruskal–Wallis, Mann–WhitneyU, and Pearson bivariate correlation were employed (α=0.05).Results. Vickers microhardness showed differences and no correlation with Ca/P ratio. Group II showed differences in carbon, oxygen, and phosphorus atomic percent and group V in Ca/P ratio. Morphological changes included exposed prisms, fractures, craters, and fusion.Conclusions. Enamel treated with phosphoric acid showed different chemical characterization among groups. Self-etching and Er:YAG laser irradiation at 19.1 J/cm2showed similar microhardness and chemical characterization. Er:YAG laser irradiation at 15 J/cm2maintained microhardness as untreated enamel. Er:YAG laser irradiation at 19.1 J/cm2enhanced mineral content. Morphological retentive changes were specific to each type of etching protocol.

Selective nitrogen functionalization of phosphorus-containing activated carbons

Nitrogen-containing activated carbons are materials of great interest. However, their main preparation methods are not able to control the formation of specific nitrogen groups on the carbon surface. The method here proposed is the selective nitrogen functionalization of activated carbons, by different oxidation and reduction treatments. Results indicated that the presence of stable phosphorus groups in the carbon obtained by chemical activation with phosphoric acid (ACP), favored the incorporation of higher amounts of nitrogen heteroatoms, mainly in form of nitro groups, during the treatment with only nitric acid. Subsequently, the activated carbons were reduced by thermal or chemical treatments, this last one by only using NaBH4 as reducing reagent. Both methods were successfully used to reduce the nitro groups. Thermal reduction produced more condensed nitrogen (such as pyridinic and pyrrolic) structures in the activated carbons, containing (ACP) or not (AC) phosphorus groups on their surfaces. However, chemical reduction provided the selective formation of amine groups only with ACP carbons, suggesting the important role of phosphorus groups in the mechanism of amine formation. The presence of amine groups was confirmed by Ninhydrin test, for the first time, used in the detection of amino groups bonded to the carbon surface.

Phosphorus groups assisted growth of vertically oriented polyaniline nanothorns on N/P co-doped carbon nanofibers for high-performance supercapacitors

A series of highly homogeneous polyaniline@N/P co-doped carbon nanofibers (PANI@NPCNFs) composites have been prepared by in-situ polymerization of aniline on the surface of NPCNFs. Vertically oriented PANI nanothorns are achieved by introducing phosphorus groups on the surface of NPCNFs. The optimized PANI@NPCNFs composite demonstrates outstanding electrochemical performance with high specific capacitance (436Fg−1 at 0.5Ag−1), high rate capability (79% capacitance retention at 20Ag−1 relative to that at 0.5Ag−1), and good stability (96% capacitance retention after 1000 cycles at 10Ag−1). The excellent electrochemical performance can be attributed to the surface phosphorus-oxygen groups which bridge the gaps between PANI and NPCNFs, leading to highly enhanced charge transfer dynamics.

Effects of intermediate conductance calcium-activated potassium channel blocker TARAM-34 on β-glycerophosphate induced vascular smooth muscle cells calcification

To observe the role of TRAM-34 (1-((2-chlorophenyl)diphenylmethyl)-1H-pyrazole), the blocker of intermediate conductance calcium-activated potassium channel (KCa3.1), on β-glycerophosphate induced vascular calcification in vitro. Vascular smooth muscle cells(VSMCs) were obtained from rat thoracic aorta, and VSMCs after the fourth passage and aortic rings were divided into control group (cultured in DMEM with 10% fetal bovine serum), high phosphorus group (cultured in DMEM with 10% fetal bovine serum and 10% β-glycerophosphate) and TRAM-34 group(20 nmol/L TRAM-34 was added into high phosphorus DMEM). Calcium deposition of VSMCs and aortic rings were measured by o-cresolphthalein complexone method.Calcium influx of VSMCs was measured by immunofluorescence probe Fluo-3 AM.The expression of runt-related transcription factor 2(Runx2)was detected by RT-PCR and Western blot for cells and immunohistochemistry for aortic rings.ALP activity was measured by alkaline phosphatase activity detection kit. (1) Compared with control group, calcification was significantly increased in high phosphorus group ((121.67±6.17) mg/g vs. (84.38±8.17) mg/g, P<0.05) and this effect could be attenuated by TRAM-34 ((93.31±11.36) mg/g, P<0.05 vs. high phosphorus group) after 12 days culture. Similar results were found in aortic rings cultured for 12 days-high phosphorus group: (7.17±0.57) mg/g vs. (1.18±0.13) mg/g (P<0.05) and TRAM-34: (4.71±0.42) mg/g, P<0.05 vs. high phosphorus group.(2) Compared with control group, the calcium influx was higher in high phosphorus group (349.22±40.47 vs. 151.67±16.94, P<0.05) and reduced in TRAM-34 group (194.67±22.21, P<0.05 vs. high phosphorus group) in VSMCs simulated for 4 days. (3) Both mRNA and protein expressions of Runx2 in high phosphorus groups were higher than in control group (0.630±0.033 vs.0.340±0.058 and 0.865±0.031 vs.0.414±0.011, both P<0.05) and lower in TRAM-34 group (0.399±0.023 and 0.575±0.014, both P<0.05 vs. high phosphorus group) in VSMCs simulated for 4 days.Besides, compared with high phosphorus group, the expression of Runx2 was decreased in control group(0.113±0.010 vs.0.067±0.008, P<0.05) and TRAM-34 group (0.069±0.006, P<0.05) after aortic rings were cultured for 4 days. (4) Compared with control group, the activity of ALP was significantly increased in high phosphorus group (96.56±9.84 vs.46.92±4.60, P<0.05) and decreased in TRAM-34 group(70.20±8.41, P<0.05 vs. high phosphorus group) in VSMCs simulated for 12 days. KCa3.1 blocker TRAM-34 can inhibit β-glycerophosphate induced VSMCs and aortic ring calcification through inhibiting calcium influx, downregulating Runx2 expression and attenuating osteogenic differentiation.

Impact of Perioperative Phosphorus and Glucose Levels on Liver Regeneration and Long-term Outcomes after Major Liver Resection

IntroductionThe impact of phosphorus as well as glycemic alterations on liver regeneration has not been directly examined. We sought to determine the impact of phosphorus and glucose on liver regeneration after major hepatectomy. MethodsEarly and late liver regeneration index was defined as the relative increase of liver volume (RLV) within 2[(RLV2m-RLVp)/RLVp] and 7 months[(RLV7m-RLVp)/RLVp] following surgery. The association of perioperative metabolic factors, liver regeneration, and outcomes was assessed. ResultsOn postoperative day 2, 50 (52.6 %) patients had a low phosphorus level (≤2.4 mg/dl), while 45 (47.4 %) had a normal/high phosphorus level (>2.4 mg/dl). Despite comparable clinicopathologic characteristics (all P > 0.05) and RLV/TLV at surgery (P = 0.84), regeneration index within 2 months was lower in the normal/high phosphorus group (P = 0.01) with these patients having increased risk for postoperative liver failure (P = 0.01). The inhibition of liver regeneration persisted at 7 months (P = 0.007) and was associated with a worse survival (P = 0.02). Preoperative hypoglycemia was associated only with a lower early regeneration index (P = 0.02). ConclusionsNormal/high phosphorus was associated with inhibition of early and late liver regeneration, as well as with an increased risk of liver failure and worse long-term outcomes. Immediate preoperative hypoglycemia was associated with a lower early volumetric gain. Metabolic factors may represent early indicators of liver failure that could identify patients at increased risk for worse outcomes.

Comparative study on characterization and adsorption properties of activated carbons by phosphoric acid activation from corncob and its acid and alkaline hydrolysis residues

Four activated carbons were prepared from corncob, acid hydrolysis residue, alkaline hydrolysis residue and China fir sawdust respectively with phosphoric acid activation under the same process condition. TG/DTG-DSC analysis revealed that the addition of phosphoric acid decreased the pyrolysis rate while increased the temperature and the yield. The findings showed that the acid and alkaline hydrolysis residue from corncob were both suitable to prepare high performance activated carbon. Moreover, different micropore volume, mesopore volume and mean pore width existed although activated carbons possessed the similar BET surface area and total pore volume. In addition, the liquid phase adsorption and pore properties of activated carbons were contrasted to show that the pore structure varied from one to another though with more or less the same iodine number, methylene blue adsorption and decolorization of caramel. Compared to China fir sawdust, activated carbons from corncob, acid hydrolysis residue and alkaline hydrolysis residue were easily made with a high decolorization of caramel. FTIR results suggested that four activated carbons were found with hydroxyl and phosphorus groups.

Synthesis and properties of novel polyimide fibers containing phosphorus groups in the main chain

Different diamines ratios synthesized co-polyimide (co-PI) fibers and these fibers had good thermal properties and mechanical performances with increased DAMPO contents.

Effect of phosphorus supplementation on weight gain and waist circumference of overweight/obese adults: a randomized clinical trial.

Background:Phosphorus status is inversely correlated with body weight; however, the effect of phosphorus supplementation on body weight in a controlled design has not been studied.Methods:This is a double-blind, randomized, placebo-controlled trial of 63 adults aged 18–45 years with a body mass index (BMI) of ⩾25 kg m−2 and normal kidney function at the American University of Beirut. Participants were randomly assigned to the placebo or phosphorus group where daily placebo or phosphorus supplements were ingested with three main meals (breakfast, lunch and dinner) for a period of 12 weeks. Primary outcomes were changes in anthropometric measures, blood metabolites (including lipid profile, glucose and insulin) and subjective appetite scores. The trial is registered with Clinical Trial.gov, NCT02329990.Results:Body weight was significantly lower in the phosphorus group when compared with the placebo group (−0.65 kg (95% confidence interval (CI) −1.69 to 0.40) vs 1.13 kg (95% CI 0.19 to 2.06), P=0.01). Similarly, BMI and waist circumference were significantly lower in the phosphorus group when compared with the placebo group (−0.24 kg m−2 (95% CI −0.59 to 0.12) vs 0.42 kg m−2 (95% CI 0.05 to 0.78), P=0.01; −3.62 cm (95% CI−4.90 to −2.33) vs 0.38 cm ( 95% CI−0.44 to 1.20), P<0.001; respectively). Several parameters of subjective appetite scores were decreased in the phosphorus-supplemented group.Conclusions:Phosphorus supplementation for 12 weeks significantly decreases body weight, BMI, waist circumference and subjective appetite scores. These findings support a promising role of the mineral phosphorus in the prevention and management of obesity, especially abdominal adiposity. The exact mechanisms of action and longer-term effects still need to be elucidated.

ChemInform Abstract: Transition Metal‐Catalyzed Ketone‐Directed or Mediated C—H Functionalization

AbstractReview: [111 refs.

Advanced Sodium Ion Battery Anode Constructed via Chemical Bonding between Phosphorus, Carbon Nanotube, and Cross-Linked Polymer Binder.

Maintaining structural stability is a great challenge for high-capacity conversion electrodes with large volume change but is necessary for the development of high-energy-density, long-cycling batteries. Here, we report a stable phosphorus anode for sodium ion batteries by the synergistic use of chemically bonded phosphorus-carbon nanotube (P-CNT) hybrid and cross-linked polymer binder. The P-CNT hybrid was synthesized through ball-milling of red phosphorus and carboxylic group functionalized carbon nanotubes. The P-O-C bonds formed in this process help maintain contact between phosphorus and CNTs, leading to a durable hybrid. In addition, cross-linked carboxymethyl cellulose-citric acid binder was used to form a robust electrode. As a result, this anode delivers a stable cycling capacity of 1586.2 mAh/g after 100 cycles, along with high initial Coulombic efficiency of 84.7% and subsequent cycling efficiency of ∼99%. The unique electrode framework through chemical bonding strategy reported here is potentially inspirable for other electrode materials with large volume change in use.

Distribution of phosphorus and hydroxypropyl groups within granules of modified sweet potato starches as determined after chemical peeling

The distributions of phosphorus and hydroxypropyl groups within granules of cross-linked and hydroxypropylated sweet potato starches were investigated. Chemical surface peeling of starch granules was performed after sieving of native and modified starches into large-size (diameter≥20μm) and small-size (diameter<20μm) fractions. Starch granules were surface gelatinized in a 4M calcium chloride solution at different levels. After the peeling step, the remaining starch granules were analysed for the content of phosphorus and hydroxypropyl groups. The phosphorus level of the parental starch gradually decreased from periphery to core of the granules. The increase in phosphorus content after cross-linking in periphery was higher than that in core. The subsequent hydroxypropylation reaction resulted in lower phosphate levels. Hydroxypropylation resulted in a gradient of hydroxypropyl group concentration from periphery to core. Cross-linking prior to the hydroxypropylation resulted in lower levels of hydroxypropyl groups and less pronounced differences between periphery and core.

Level and position of substituents in cross-linked and hydroxypropylated sweet potato starches using nuclear magnetic resonance spectroscopy

Sweet potato starch was cross-linked using sodium trimetaphosphate and hydroxypropylated using propylene oxide. The level and position of phosphorus and hydroxypropyl groups within cross-linked and hydroxypropylated sweet potato starch was investigated by phosphorus and proton nuclear magnetic resonance spectroscopy (31P, 1H NMR). The cross-linking reaction produced monostarch monophosphate and distarch monophosphate in a molar ratio of 1:1.03, indicating that only half of the introduced phosphorus resulted in a possible cross-link. One cross-link per approximately 2900 glucose residues was found. Phosphorylation leading to monostarch monophosphate mainly occurred at O-3 and O-6 (ratio 1:1). It was inferred that the majority of the cross-links formed in distarch monophosphate were between two glucose residues positioned in different starch chains, while a minor part of the cross-links may be formed between two glucose residues within the same starch chain. Hydroxypropylation under alkaline conditions resulted in the formation of intra-molecular phosphorus cross-links, subsequent hydroxypropylation following cross-linking lowered both the level of intra- and inter-molecular cross-linking.Using 1H NMR the molar substitution of hydroxypropylation was determined to be 0.155–0.165. The hydroxypropylation predominantly occurred at O-2 (61%), and the level of substitution at O-6 (21%) was slightly higher than that at O-3 (17%). In dual modified starch, the preceding cross-linking procedure resulted in a slightly lower level of hydroxypropylation, where the substitution at O-6 decreased more compared to the substitution at O-2 and O-3.

Effect of super dosing of phytase on growth performance, ileal digestibility and bone characteristics in broilers fed corn-soya-based diets.

A feeding trial was designed to assess the effect of super dosing of phytase in corn-soya-based diets of broiler chicken. One hundred and sixty-eight day-old broilers were selected and randomly allocated to four dietary treatment groups, with 6 replicates having 7 chicks per treatment group. Two-phased diets were used. The starter and finisher diet was fed from 0 to 3 weeks and 4 to 5 weeks of age respectively. The dietary treatments were consisted of normal phosphorus (NP) group without any phytase enzyme (4.5 g/kg available/non-phytin phosphorus (P) during starter and 4.0 g/kg during finisher phase), three low-phosphorus (LP) groups (3.2 g/kg available/non-phytin P during starter and 2.8 g/kg during finisher phase) supplemented with phytase at 500, 2500, 5000 FTU/kg diet, respectively, to full fill their phosphorus requirements. The results showed that super doses of phytase (at 2500 FTU and 5000 FTU/kg) on low-phosphorus diet improved feed intake, body weight gain, ileal digestibility (serine, aspartic acid, calcium, phosphorus), blood P levels and bone minerals such as calcium (Ca), P, magnesium (Mg) and zinc (Zn) content. It could be concluded that super doses of phytase in low-phosphorus diet were beneficial than the normal standard dose (at 500 FTU/kg) of phytase in diet of broiler chicken.

Synthesis and flammability testing of epoxy functionalized phosphorous‐based flame retardants

ABSTRACTSeveral potential new phosphorus‐containing flame retardant molecules were evaluated for heat release reduction potential by incorporation of the molecules into a polyurethane, generated from methylene diphenyl diisocyanate and 1,3‐propane diol. The heat release reduction potential of these substances was evaluated using the pyrolysis combustion flow calorimeter (PCFC). The polyurethanes were prepared in the presence of the potential flame retardants via solvent mixing and copolymerization methods to qualitatively evaluate their potential reactivity into the polyurethane prior to heat release testing. The functionality of the flame retardants was epoxide based that would potentially react with the diol during polyurethane synthesis. Flammability testing via PCFC showed that the heat release reduction potential of each of the flame retardants was structure dependent, with phosphates tending to show more effectiveness than phosphonates in this study, and alkyl functionalized phosphorus groups (phosphate or phosphonate) being more effective at heat release reduction than cyclic functionalized groups. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42296.

Effect of fluorine and nitrogen on the chemical durability of lithium phosphate glasses

The dissolution of glasses belonging to the systems of composition xLi2O·(100−x)P2O5 (x=38–55mol%) and (55−x/2)Li2O·xLiF·(45−x/2)P2O5 (x=10–30mol%), with and without nitrogen, has been studied through immersion of the samples in water at 95°C using a Soxhlet extractor. In this work, a wide range of compositions prepared by melting has allowed a detailed study of the effect of nitrogen and fluorine in the chemical properties of glasses with variable lithium contents. In lithium phosphorus oxynitride glasses, it was demonstrated that low lithium and high nitrogen contents improve the chemical durability. However, there is a maximum of nitrogen percentage from which the durability is not further improved. In lithium phosphorus fluoro-oxynitride glasses, fluorine introduction leads to a deterioration of the phosphate glasses; however, the introduction of nitrogen in these glasses increases significantly the chemical durability. The structural changes obtained by NMR and XPS are used to explain the effect of lithium, fluorine and nitrogen on the chemical properties. In general, the decrease of non-bridging oxygens and the increase percentage of phosphorus groups with nitrogen increase the chemical resistance.

Functionalization of carbon nanotubes using aminobenzene acids and electrochemical methods. Electroactivity for the oxygen reduction reaction

Functionalized carbon nanotubes (CNTs) using three aminobenzene acids with different functional groups (carboxylic, sulphonic, phosphonic) in para position have been synthesized through potentiodynamic treatment in acid media under oxidative conditions. A noticeable increase in the capacitance for the functionalized carbon nanotubes mainly due to redox processes points out the formation of an electroactive polymer thin film on the CNTs surface along with covalently bonded functionalities. The CNTs functionalized using aminobenzoic acid rendered the highest capacitance values and surface nitrogen content, while the presence of sulfur and/or phosphorus groups in the aminobenzene structure yielded a lower functionalization degree. The oxygen reduction reaction (ORR) activity of the functionalized samples was similar to that of the parent CNTs, independently of the functional group present in the aminobenzene acid. Interestingly, a heat treatment in N2 atmosphere with a very low O2 concentration (3125 ppm) at 800 °C of the CNTs functionalized with aminobenzoic acid produced a material with high amounts of surface oxygen and nitrogen groups (12 and 4% at., respectively), that seem to modulate the electron-donor properties of the resulting material. The onset potential and limiting current for ORR was enhanced for this material. These are promising results that validates the use of electrochemistry for the synthesis of novel N-doped electrocatalysts for ORR in combination with adequate heat treatments.

Sulfur-containing DalPhos ligand variants: synthesis and application in Buchwald−Hartwig amination

We report herein on our synthetic, structural, and catalytic investigations of new P,S-DalPhos ligands featuring pairings of phosphorus and sulfur donor groups as well as new sulfur-containing analogues of the previously reported P,N-ligands Me-DalPhos and Mor-DalPhos, featuring a 2,3-disubstituted thiophenyl backbone. In examining the catalytic performance of these new sulfur-containing ligands in the Buchwald–Hartwig amination of octylamine, aniline, or ammonia with 4-chlorotoluene, noteworthy differences in reactivity behavior relative to Me-DalPhos and Mor-DalPhos were observed.