24,24-Difluoro-25-hydroxyvitamin D3-enhanced bone mineralization in rats. Comparison with 25-hydroxyvitamin3 and vitamin D3

The biological activity of 24,24-difluoro-25-hydroxyvitamin D₃ was assessed using elevation of serum phosphorus and healing of rickets of vitamin D-deficient rats. Various levels of 24,24-difluoro-25-hydroxyvitamin D₃ and 25-hydroxyvitamin D₃ were administered daily for 2 weeks in the dose range of 6.5 to 3250 pmol after feeding rats a low phosphorus, vitamin D-deficient diet for 3 weeks. Vitamin D₃ was concurrently tested at dose levels of 650 and 3250 pmol. 24,24-Difluoro-25-hydroxyvitamin D₃ is approximately equipotent with 25-hydroxyvitamin D₃ in stimulation of growth, mineralization of rachitic bone, and elevation of serum inorganic phosphorus. Radiological manifestations of rickets were also equally improved by 24,24-difluoro-25-hydroxyvitamin D₃ and 25-hydroxyvitamin D₃. Compared with vitamin D₃, these compounds were approximately 5 to 10 times more active in mineralization using rats on a low phosphorus, vitamin D-deficient diet. The functional role, if any, for 24-hydroxylated vitamin D compounds, such as 24,25-dihydroxyvitamin D₃, therefore remains obscure. It appears that vitamin D compounds that cannot be 24-hydroxylated evoke no disorder in bone mineralization.     

The agrochemical effectiveness of some phosphorus-nitrogen compounds with the direct P−N bond

Phosphorus-nitrogen compounds characterized by the direct P?N bond, represented by trimeric and tetrameric phosphorus nitridoamide—[PN(NH₂)₂]_3–4, phosphorus oxytriamide—PO(NH₂)₃ and ammonium diamidophosphate—NH₄PO₂(NH₂)₂, were applied as fertilizers in a vessel experiment with barley and their agrochemical effectiveness was compared with that of ammonium phosphate—(NH₄)₂HPO₄. The results obtained indicate that the above compounds are of nutritive value for plants.     

蔗叶堆肥中一株泡盛曲霉溶磷能力的鉴定及其对辣椒的促生效果

[目的]从甘蔗叶堆肥中分离筛选具有高效溶磷及促生功能的菌株,为微生物肥料制备提供一种可利用的菌种资源.[方法]以Ca3(PO4)2和Zn3(PO4)2为磷源,进行平板溶磷筛选实验;采用形态学特征和ITS rDNA序列分析法进行菌种鉴定;采用液体摇瓶培养测定菌株的溶磷能力;将溶磷菌接种至辣椒幼苗根部分析其促生效应.[结果...     

Solubility of phosphorus added to four Manitoba soils with different calcium and magnesium contents

Summary The solubility of phosphorus was found to approximate that of dicalcium phosphate dihydrate and/or dimagnesium phosphate trihydrate when KH₂-PO₄, H₃PO₄ and K₂HPO₄ were added to four Manitoba soils. Eighty to one hundred, seventy to ninety and sixty to eighty per cent of the phosphorus added remained in solution when H₃PO₄, KH₂PO₄ and K₂HPO₄ were added, respectively. The solubility of the added phosphorus was high in all samples and relatively soluble compounds, dicalcium phosphate dihydrate and dimagnesium phosphate trihydrate, were most likely formed in the samples indicating that phosphorus added to these soils would be readily available to plants. Associate Professor and Professor respectively.     

Reversible covalent modification of DNA

The reaction of bromomethylbenzoyl esters of choline and dimethylaminoethanol with DNA and model compounds led predominantly to phosphotriester formation. In model compounds the phosphotriester formation was verified by uv spectrometry. The bromomethylbenzoyl cationic esters reacted with DNA at room temperature at neutral pH values. The amount of the reagent chromophores was assessed semiquantitatively by spectrophotometry. The maximum binding appeared to be stoichiometric, i.e., one residue per phosphorus. The binding of one mole of reagent per phosphorus was confirmed by electron spectroscopic measurements of the phosphorus atom electron emission of maximally modified DNA. The modified DNA showed altered CD spectra indicating that the reagent chromophores are arranged in an orderly fashion affording a strong (Δ_? > 4), positive, apparently extrinsic CD band at ~240 nm; a double helical array is proposed. The introduced chromophores were readily removed by heat treatment or by treatment with nucleophiles at neutral pH values at moderate temperatures (<37 °C); no measurable fraction of the DNA became dialyzable. A decrease in viscosity accompanied the reversal, indicative of some chain breaking. The modified DNA's show higher T_m values than the native DNA and some display a higher and some a lower degree of cooperativity in their melting curves. No chemically detectable amounts of base alkylation, depurination, or depyrimidination were found when dialyzates of treated DNA and hydrolyzed samples of modified DNA were examined. However, presumptive evidence for some base alkylation by these novel alkylating agents was found utilizing Salmonella typhimurium tester strains sensitive to reversion by alkylation. No comparable binding of benzoylcholine, a nonalkylating analogue, by DNA was seen under conditions utilized here.     

Direct proof of phosphorus oxytriamide in exudates of decapitatedPhaseolus vulgaris plants

Phosphorus oxytriamide PO(NH₂)₃ was proved chromatographically in the exudate of decapitatedPhaseolus vulgaris plants. This fact verified the presumption that covalent compounds of phosphorus and nitrogen enter roots without previous hydrolysis.     

Tertiary phosphines containing ortho-carborane as backbone. Some palladium(II) complexes

Coordination compounds of the type Pd(HPC)₂- X₂, Pd(DPC)X₂ and Pd(NPC)X₂, where X  Cl or Br and HPC = 1-diphenylphosphino-o-carborane; DPC = 1,2-bis(diphenylphoshino)-_o-carborane; and NPC= 1-bis(dimethylamminophosphino, 2-diphenylphosphino) -o-carborane, have been prepared and characterized by IR, Raman and electronic spectroscopy, magnetic and conductivity measurements, and elemental analyses. The compounds containing the monodentate HPC ligand possess a trans-planar structure, whereas for those containing the bidentate DPC and NPC ligands a cis-planar configuration was found. In all cases, the phosphorus atoms of the tertiary phosphine (HPC) and the ditertiary phosphines (DPC and NPC) are bonded to the palladium atom. The complex [Pd(HPC)Cl₂]₂ has also been prepared, and a halogen bridge dimeric structure is proposed on the basis of the IR and Raman spectra.     

UV-sensitive P compounds: release mechanism, seasonal fluctuation and inhibitory effects on alkaline phosphatase activity in a shallow Chinese freshwater lake (Donghu Lake)

Filtrable phosphorus compounds in a shallow Chinese freshwater lake (Donghu Lake) were fractionated by Sephadex G-25 gel-filtration chromatography. Some portions of those compounds released soluble reactive phosphorus upon irradiation with low dose ultraviolet light. Catalase and a hydroxyl radical scavenger (mannitol) markedly prevented photosensitive phosphorus release. The observed effects may be explained by the action of oxidizing reagents such as hydroxyl radicals, produced in photochemical reactions between UV irradiation and humic substances in the water. There was a strong seasonality in UV-sensitive P (UVSP) release. Michaels constants (K _m) of total alkaline phosphatase in the lake water showed a direct positive relation to UVSP Plot of K _m against the UVSP/phosphomonoester ratio reveals a strong relationship between the two variables. These results suggest that in some situations UVSP may be a competitive inhibitor of alkaline phosphatase activity in the lake. The competitive inhibition of fractionated UVSP on alkaline phosphatase reagent (Sigma) apparently supports this hypothesis.     

Stepwise selective oxidation of tris(2-(diphenylphosphino)ethyl)phosphine on thiolato palladium(II) complexes

One of the equatorially coordinated terminal phosphorus atoms of tris(2-(diphenylphosphino)ethyl)phosphine (pp₃) ligand on the five-coordinate trigonal-bipyramidal palladium(II) complex, [Pd(4-Cltp)(pp₃)](BF₄) (4-Cltp = 4-chlorothiophenolate), was selectively oxidized by photolysis to form the four-coordinate square-planar complex. Further selective oxidation of another coordinated terminal phosphorus atom proceeded quantitatively by the substitution reaction with 4-chlorothiophenolate. The solid state structures of these stepwise-oxidized square-planar complexes were determined by X-ray crystal structure analyses, and the structures of the starting trigonal-bipyramidal and the oxidized complexes in solution have been characterized by ³¹P NMR spectroscopy.     

施磷对川西北高寒草地土壤磷形态及有效性的影响

以川西北高寒草地为研究对象,采用随机区组设计,设置0、10、20、30、40、50、60 g/m²的过磷酸钙(P₂O₅,16%)施肥试验,分析土壤不同形态磷含量和有效磷(Olsen-P)含量变化特征,探究施磷对川西北高寒草地土壤磷形态及有效磷的影响。结果表明：(1)随施磷量增加,土壤总磷(TP)含量先增加后趋于平稳而Olsen-P含量减少。高水平(50、60 g/m²)施磷下氢氧化钠有机磷(NaOH-Po)及残留磷(Residual-P)是高寒草地主要的磷素累积形态,其含量显著高于不施磷处理;(2)树脂交换态磷(Resin-Pi)、碳酸氢钠无机磷(NaHCO₃-Pi)、碳酸氢钠有机磷(NaHCO₃-Po)和氢氧化钠无机磷(NaOH-Pi)含量随施磷量增加整体呈先增加后降低趋势,表层土壤30 g/m²磷肥用量下其值均为最高,分别为21.54、22.94、65.86、64.48 mg/kg。酸溶性无机磷(HCl-Pi)随施磷量增加整体呈下...     

间伐和凋落物处理对华北落叶松人工林土壤磷形态的影响

土壤磷在维持生态系统功能稳定性中发挥重要作用,研究间伐和凋落物处理下的土壤磷组分特征及转化机理,对森林生态系统磷素管理和可持续发展具有重要意义。采用Tiessen改良的Hedley分级方法,探究了不同间伐强度(未间伐、轻度间伐、中度间伐、重度间伐)和凋落物处理(对照、加倍、去凋、切根去凋)下土壤磷形态的变化特征及其驱动因子。结果显示:随着间伐强度的增大,土壤活性磷(Resin-Pi、NaHCO_3-Pi和NaHCO_3-Po)、土壤微生物量磷和酸性磷酸酶活性呈先增加后降低的趋势,且在中度间伐最高。凋落物加倍(DL)显著增加了土壤活性磷(Resin-Pi、NaHCO_3-Pi和NaHCO_3-Po)、土壤微生物量磷和酸性磷酸酶活性。稳定态磷(HCl-Pi、浓HCl-Pi和浓HCl-Po)、残留态磷(Residual-P)不受间伐和凋落物处理的影响。冗余分析(RDA)显示,土壤微生物量磷、酸性磷酸酶活性和土壤有机碳是引起华北落叶松人工林表层土壤磷组分变化的重要因子。研究表明,适度的间伐和增加凋落物能够显著提高华北落叶松人工林表层土壤磷素的活化能力。本研究为华北落叶松人工林的可持续经营提供依据。     

Evaluation of enantioselectivity in lipase-catalyzed acylation of hydroxyalkylphosphine oxides

The lipase-catalyzed optical resolution of 2-, 3-, and 5-hydroxyalkyl phosphorus compounds 1 provided the corresponding optically pure diastereomers in good yields. (S_P, R)- and (R_P, S)-1 were acylated faster than (S_P, S)- and (R_P, R)-1. The stereoselectivity at the phosphorus atom changed with the flexibility of the active sites in the lipases. The stereoselectivity at the phosphorus atom was higher in the reaction of 1a than in the reaction of 1b,c. The reaction rate of ɛ-hydroxyalkylphosphine oxide 1c was faster than that of 1a, although less enantioselectivity was observed at the phosphorus atom.     

Highly selective screening of the bioactive compounds in Huoxue capsule using immobilized β2-adrenoceptor affinity chromatography

A highly selective assay was developed for screening compounds that bind to the porcine recombinant β₂-adrenoceptor (β₂-AR) with affinity chromatography coupled to quadrupole time-of-flight mass spectrometry (Q-TOF–MS). The methodology involved selective screening with immobilized β₂-AR, a highly accurate identification via Q-TOF–MS, and a functional evaluation of the screened compounds with a sensitive myograph system. Ferulic acid, hydroxysafflor yellow A (HSYA), and naringin were confirmed to be the bioactive compounds in Huoxue capsule that specifically bound to the β₂-AR. These compounds produced a concentration-dependent relaxation of arteries that were contracted by treatment with phenylephrine, and the relaxation caused by these compounds was attenuated in the presence of ICI 118551, a type of β₂-AR antagonist. Our data indicate that the use of an immobilized receptor is potentially an alternative method for the rapid screening of bioactive compounds in a complex matrix because of its high specificity. β₂-AR affinity chromatography was valuable in focusing attention on the further investigation of ferulic acid, HSYA, and naringin as β₂-AR agonists.     

A proposal for a convenient notation for P-chiral nucleotide analogues. Part 3. Compounds with one nucleoside residue and nonnucleosidic derivatives

Recently, we have proposed a new D_P/L_P stereochemical notation for P-chiral dinucleoside monophosphate analogues that permits simple correlation between spatial arrangement of the substituents and the configuration at the phosphorus center. As an extension of this work, we present here applications of the D_P/L_P notation to derivatives containing only one nucleoside unit (e.g., alkyl nucleoside phosphodiesters, nucleoside phosphomonoesters, cyclic phosphate derivatives, nucleoside di-, and triphosphates) and to nonnucleosidic phosphorus compounds.     

31P NMR Studies of the Binding of the Oligonucleotide (Ap)3A to an Oligodeoxythymidylate Covalently Linked to an Acridine Derivative

Abstract

³¹P NMR was used to study the specific interaction of an oligodeoxynucleotide containing four thymines and covalently attached to an acridine derivative through its 3-phosphate [(Tp)₄(CH₂)₅Acr] with a complementary oligoribonucleotide (Ap)₃A.³¹P-¹H and ¹H-¹H chemical shift correlation spectroscopies were jointly used to provide the assignment of the phosphorus resonances. A downfield shift of two phosphorus resonances of (Tp)₄(CH₂)₅Acr and of two phosphorus resonances of (Ap)₄A was observed upon complex formation. The assignment of the phosphorus resonances which are downfield shifted allowed us to propose a model involving an equilibrium between several 1:1 complexes where the acridine ring is intercalated between different A.T base pairs.     

亚热带米槠天然林凋落物和根系输入变化对土壤磷组分的影响

植物残体添加和去除试验(The Detritus Input and Removal Treatments, DIRT)是研究地上凋落物以及植物根系对土壤营养物质循环过程及机制探究的一种试验设计。于2012年6月选择福建省三明森林生态系统与全球变化研究站的米槠常绿阔叶天然林,设置5种处理:对照(CT)、去除凋落物(NL)、去除根系(NR)、去除凋落物与根系(NI)、添加双倍凋落物(DL),在2018年12月对各处理不同土层(0—10cm、10—20cm)土壤磷组分及其影响因子进行研究,结果表明:(1)在0—10cm土层中DL处理总磷含量显著大于NL处理,NI处理无机磷含量最低,在10—20cm中DL处理有机磷含量显著大于其他处理;(2)DL处理活性磷(Resin-P、NaHCO₃-Pi、NaHCO₃-Po)含量在0—10cm土层中显著大于其他处理。在10—20cm土层中NR处理活性磷以及中等活性磷显著大于NL处理。残留态磷(Residual-P)含量最高,但在各处理与土层之间并没有明显差异;(3)酸性磷酸酶在0—10 cm土层不同处理间的变化...     

High-resolution preparative gel electrophoresis: separation and recovery of functional messenger RNA species

Certain open-chain polyols were shown to interfere with the determination of phosphorus of the Lowry-Lopez method by forming a complex with Mo₇O₂₄^6?. The ability to interfere with the assay increased with increasing chain length of the polyols: Ethylene glycol and glycerol did not react at all; i-erythritol reacted to a small extent, but hexitols and perseitol formed stronger complexes. Depending on the polyol, interference occurred even at 0.2 mm (hexitols) or 2 mm (xylitol) concentrations. At these concentrations the polyols interfered only to a small extent with the phosphorus assays based on the use of Triton X-100 and molybdate. The complex formation was exploited in the development of a colorimetric polyol assay.     

Evaluation of enantioselectivity in lipase-catalyzed acylation of hydroxyalkylphosphine oxides

The lipase-catalyzed optical resolution of 2-, 3-, and 5-hydroxyalkyl phosphorus compounds 1 provided the corresponding optically pure diastereomers in good yields. (S_P, R)- and (R_P, S)-1 were acylated faster than (S_P, S)- and (R_P, R)-1. The stereoselectivity at the phosphorus atom changed with the flexibility of the active sites in the lipases. The stereoselectivity at the phosphorus atom was higher in the reaction of 1a than in the reaction of 1b,c. The reaction rate of -hydroxyalkylphosphine oxide 1c was faster than that of 1a, although less enantioselectivity was observed at the phosphorus atom.     

Synthesis under solvent free conditions and photoluminescence study of ionic intermediate sitting-atop complexes of meso-tetraarylporphyrins and phosphorus oxychloride

The reaction of meso-tetraarylporphyrins with phosphorus oxychloride was studied. The reaction product is the so-called intermediate sitting-atop (i-SAT) complex where two pyrrolic nitrogen atoms of the porphyrin core coordinate to the phosphorus atom and two protons on the pyrrolic nitrogen atoms remain. Selection of solvent free conditions is caused that the reaction does not progress until deprotonation step of porphyrin and stopped in the intermediate step for formation of the sitting-atop complex, [POCl₂(H₂t(X)pp)]Cl. The sitting-atop complexes were characterized by (¹H, ³¹P, ¹³C) NMR, FT-IR, UV-vis and photoluminescence spectroscopy (PL), elemental analysis and electrical conductometry. Photoluminescence study of the complexes indicates that their emission spectra are different from those of free base porphyrins.