RESUMO
Chemical reactions without an obvious optical signal change, such as fluorescence or color, are difficult to monitor. Often, more advanced analytical techniques such as high-performance liquid chromatography and mass spectroscopy are needed. It would be useful to convert such reactions to those with changes in optical signals. In this work, we demonstrate that fluorescently labeled DNA oligonucleotides adsorbed on nanomaterials can probe such reactions, and oxidation of phosphorus-containing species was used as an example. Various metal oxides were tested, and CeO2 nanoparticles were found to be the most efficient for this purpose. Among phosphate, phosphite, and hypophosphite, only phosphate produced a large signal, indicating its strongest adsorption on CeO2 to displace the DNA. This was further used to screen oxidation agents to convert lower oxidation-state compounds to phosphate, and bleach was found to be able to oxidize phosphite. Canonical discriminant analysis was performed to discriminate various phosphorus species using a sensor array containing different metal oxides. On the basis of this, glyphosate was studied for its adsorption and oxidation. Although this method is not specific enough for selective biosensors, it is useful as a tool to produce sensitive optical signals to follow important chemical transformations.
Assuntos
Cério/química , Glicina/análogos & derivados , Nanopartículas/química , Oligodesoxirribonucleotídeos/química , Ácidos de Fósforo/química , Adsorção , Colorimetria/métodos , Fluorescência , Fluorometria/métodos , Glicina/química , Oxirredução , Ácidos Fosfínicos/química , Ácidos Fosfóricos/química , Ácidos Fosforosos/química , GlifosatoRESUMO
Two macrocyclic ligands based on cyclam with trans-disposed N-methyl and N-(4-aminobenzyl) substituents as well as two methylphosphinic (H2L1) or methylphosphonic (H4L2) acid pendant arms were synthesised and investigated in solution. The ligands form stable complexes with transition metal ions. Both ligands show high thermodynamic selectivity for divalent copper over nickel(II) and zinc(II)-K(CuL) is larger than K(Ni/ZnL) by about seven orders of magnitude. Complexation is significantly faster for the phosphonate ligand H4L2, probably due to the stronger coordination ability of the more basic phosphonate groups, which efficiently bind the metal ion in an "out-of-cage" complex and thus accelerate its "in-cage" binding. The rate of Cu(II) complexation by the phosphinate ligand H2L1 is comparable to that of cyclam itself and its derivatives with non-coordinating substituents. Acid-assisted decomplexation of the copper(II) complexes is relatively fast (τ1/2 = 44 and 42â s in 1 M aq. HClO4 at 25 °C for H2L1 and H4L2, respectively). This combination of properties is convenient for selective copper removal/purification. Thus, the title ligands were employed in the preparation of ion-selective resins for radiocopper(II) separation. Glycidyl methacrylate copolymer beads were modified with the ligands through a diazotisation reaction. The separation ability of the modified polymers was tested with cold copper(II) and non-carrier-added (64)Cu in the presence of a large excess of both nickel(II) and zinc(II). The experiments exhibited high overall separation efficiency leading to 60-70% recovery of radiocopper with high selectivity over the other metal ions, which were originally present in 900-fold molar excess. The results showed that chelating resins with properly tuned selectivity of their complexing moieties can be employed for radiocopper separation.
Assuntos
Cobre/química , Compostos Heterocíclicos/química , Ácidos de Fósforo/química , Quelantes/química , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Radioisótopos de Cobre/química , Radioisótopos de Cobre/isolamento & purificação , Técnicas Eletroquímicas , Concentração de Íons de Hidrogênio , Cinética , Ligantes , Níquel/química , Ácidos Fosfínicos/síntese química , Ácidos Fosfínicos/química , Ácidos Fosforosos/síntese química , Ácidos Fosforosos/química , TermodinâmicaRESUMO
Diorganophosphane oxides were employed as preligands for the synthesis of catalytically active transition metal complexes of the phosphinous acids (CF3)2POH and (C2F5)2POH. Their reactions with solid PtCl2 and PdCl2 led to the formation of mononuclear phosphinous acid complexes [Cl2M{P(R(f))2OH}2] (M = Pd, Pt; R(f) = C2F5, CF3), which can be crystallized, for example, as its pyridinium salts, 2[HPy](+)[Cl2Pd{P(CF3)2O}2](2-). In vacuo HCl is liberated from the neutral palladium complexes affording mixtures of di- and polynuclear complexes. Moreover, (C2F5)2POH was reacted with several ß-diketonato complexes of palladium, platinum, and nickel yielding air- and moisture-stable complexes [(acac)M{[P(R(f))2O]2H}], featuring a quasichelating phosphinous acid phosphinito unit {P(R(f))2O···H···O(R(f))2P}(-). Treatment of [Ni(Cp)2] (Cp = cyclopentadienyl) and [(cod)RhCl]2 (cod = 1,5-cyclooctadiene) with (C2F5)2POH leads to the substitution of one Cp or chloro ligand by a quasichelating unit. The novel coordination compounds were characterized by NMR and IR spectroscopies, mass spectrometry, and X-ray diffraction analysis. The platinum complex [(acac)Pt{[P(C2F5)2O]2H}] (acac = acetylacetonato) was used for the construction of hetero-bimetallic complexes by the treatment with [(cod)RhCl]2 and [Ni(Cp)2]. The trinuclear bimetallic complex [{(acac)Pt[P(C2F5)2O]2}2Ni] is the first structurally characterized hetero-bimetallic species containing a bis(perfluoroalkyl)phosphinito bridge.
Assuntos
Quelantes/química , Compostos Organometálicos/química , Compostos Organometálicos/síntese química , Paládio/química , Ácidos de Fósforo/química , Platina/química , Técnicas de Química Sintética , Modelos Moleculares , Conformação MolecularRESUMO
This paper describes the synthesis of unsymmetrically substituted phosphinous acids and phosphane oxides featuring at least one electron-withdrawing pentafluoroethyl group. The presence of a diethylamino function as a protecting group allows a selective reaction of RClPNEt2 (R=CF3 , C6 F5 , C6 H5 ) with LiC2 F5 . On treatment with para-toluenesulfonic acid the isolated aminophosphanes R(C2 F5 )PNEt2 are readily converted into the corresponding phosphinous acids or phosphane oxides, respectively. Investigation of the tautomeric equilibrium between oxide and acid tautomer revealed (CF3 )(C2 F5 )POH as a stable phosphinous acid, whereas the pentafluorophenyl and phenyl derivatives constitute a solvent dependent equilibrium between the acid and the oxide tautomer.
Assuntos
Óxidos/síntese química , Fosfinas/síntese química , Ácidos de Fósforo/química , Catálise , Modelos Moleculares , Estrutura Molecular , Óxidos/química , Fosfinas/química , EstereoisomerismoRESUMO
Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture, water/propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl-aryls were satisfied. The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPd1 and POPd2, and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3. The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products. However in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.
Assuntos
Álcoois/química , Ácidos Borônicos/química , Paládio/química , Ácidos de Fósforo/química , Solventes/química , Água/química , CatáliseRESUMO
Secondary phosphane oxides, R(2)P(O)H, are commonly used as preligands for transition-metal complexes of phosphinous acids, R(2)P-OH (R=alkyl, aryl), which are relevant as efficient catalysts in cross-coupling processes. In contrast to previous work by other groups, we are interested in the ligating properties of an electron-deficient phosphinous acid, (R(f))(2)P-OH, bearing the strongly electron-withdrawing and sterically demanding 2,4-bis(trifluoromethyl)phenyl group towards catalysis-relevant metals, such as palladium and platinum. The preligand bis[2,4-bis(trifluoromethyl)phenyl]phosphane oxide, (R(f))(2)P(O)H, reacts smoothly with solid platinum(II) dichloride yielding the trans-configured phosphinous acid platinum complex trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)]. The deprotonation of one phosphinous acid ligand with an appropriate base leads to the cis-configured monoanion complex cis-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H](-), featuring the quasi-chelating phosphinous acid phosphinito unit, (R(f))(2)P-O-H···O=P(R(f))(2), which exhibits a strong hydrogen bridge substantiated by an O···O distance of 245.1(4) pm. The second deprotonation step is accompanied by a rearrangement to afford the trans-configured dianion trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)](2-). The reaction of (R(f))(2)P(O)H with solid palladium(II) dichloride initially yields a mononuclear palladium complex [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)], which condenses under liberation of HCl to the neutral dinuclear palladium complex [Pd(2)(µ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)]. The equilibrium between the mononuclear [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)] and dinuclear [Pd(2)(µ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)] palladium complexes is reversible and can be shifted in each direction by the addition of base or HCl, respectively. Treatment of palladium(II) hexafluoroacetylacetonate, [Pd(F(6)acac)(2)], with a slight excess of (R(f))(2)P(O)H yields the complex [Pd(F(6)acac)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H]. The quasi-chelating phosphinous acid phosphinito unit, which is formed by the liberation of HF(6)acac, is characterized by a O···O distance of 244.1(3) pm. These transition metal complexes are stable towards air and moisture and can be stored for months without any evidence of decomposition.
Assuntos
Quelantes/química , Compostos Organometálicos/química , Compostos Organoplatínicos/química , Paládio/química , Ácidos de Fósforo/química , Platina/química , Elementos de Transição/química , Ar , Catálise , Cristalografia por Raios X , Ligantes , Estrutura MolecularRESUMO
Reaction of the electrochemically inâ situ from elemental white phosphorus generated phosphine oxide H3 PO in a single electrochemical cell, supplied with lead cathode and aluminium anode, with cyclic ketones (cyclopentanone and cyclohexanone) results in formation of secondary phosphine oxides (bis(α-hydroxycyclopentyl)phosphine oxide 2 a, isolated yield 15 %, and bis(α-hydroxycyclohexyl)phosphine oxide 2 b, isolated yield 12 %) with two α-hydroxycycloalkyl substituents at the phosphorus atom. Bis(α-hydroxycyclopentyl)phosphine oxide reacts with [PdCl2 (COD)] (COD=1,5-cyclooctadiene) to give a new palladium complex trans-[PdCl2 {P(OH)(cyclo-C5 H8 -1-OH)2 }2 ] (3 a, isolated yield 11 %) bearing phosphinous acid as a ligand formed via tautomerization of the phosphine oxide. Finally, the cytotoxicity of the synthesized secondary phosphine oxides on tumor and healthy human cell lines was studied. It was found that at a concentration of 10-6 -10-4 â M, phosphine oxides 2 a,b exhibit similar IC50 values for the M-Hela cell line (ca. 50 mM), but are non-toxic for MCF-7 cells. For human alveolar adenocarcinoma cells (A-549), only 2 a is active (ca. 35â mM), while 2 b is not toxic.
Assuntos
Fosfinas/química , Fósforo/química , Complexos de Coordenação/química , Cristalografia por Raios X , Células HeLa , Humanos , Ligação de Hidrogênio , Ligantes , Conformação Molecular , Óxidos/química , Paládio/química , Fosfinas/síntese química , Ácidos de Fósforo/químicaRESUMO
The industrial product (C(2)F(5))(3)PF(2) is transformed into the phosphinic acid chloride (C(2)F(5))(2)P(O)Cl, which reacts with an excess of Bu(3)SnH in a clean, multistep reaction to give the stannyl derivative (C(2)F(5))(2)POSnBu(3). Subsequent treatment with gaseous HBr leads to the formation of (C(2)F(5))(2)POH, which is isolated in 70 % yield. Besides (CF(3))(2)POH, bis(pentafluoroethyl)phosphinous acid, (C(2)F(5))(2)POH, represents the second known example of a phosphinous acid that is predicted by using density functional theory calculations at the B3PW91/6-311G(3d,p) level to be more stable than the phosphane oxide tautomer, the energy difference being 11.7 kJ mol(-1). Only the phosphinous acid isomer is detectable in the gas phase and in solution. However, investigations of the neat liquid reveal a temperature-dependent tautomeric equilibrium with the phosphane oxide isomer (C(2)F(5))(2)P(O)H, which is characterized by vibrational and multinuclear NMR spectroscopic methods in combination with quantum-chemical calculations.
Assuntos
Ácidos de Fósforo/química , Espectroscopia de Ressonância Magnética , Ácidos de Fósforo/síntese química , Espectrofotometria Infravermelho , Estereoisomerismo , TermodinâmicaRESUMO
The thermodynamics and kinetics for base-pair opening of the P1 duplex of the Tetrahymena group I ribozyme were studied by NMR hydrogen exchange experiments. The apparent equilibrium constants for base pair opening were measured for most of the imino protons in the P1 duplex using the base catalysts NH3, HPO4(2-) or TRIS. These equilibrium constants were also measured for several modified P1 duplexes, and the C-2.G23 base pair was the most stable base pair in all the duplexes. The conserved U-1*G22 base pair is required for activity of the ribozyme and the data here show that this wobble base pair destabilizes neighboring base pairs on only one side of the wobble. A 2'-OMe modification on the U-3 residue stabilized its own base pair but had little effect on the neighboring base pairs. Three base pairs, U-1*G22, C-2*G23 and A2*U21 showed unusual equilibrium constants for opening and possible implications of the opening thermodynamics of these base pairs on the undocking rates of the P1 helix with catalytic core are discussed.
Assuntos
RNA Catalítico/química , Tetrahymena/enzimologia , Termodinâmica , Amônia/química , Animais , Pareamento de Bases , Hidrogênio/química , Íntrons , Cinética , Ressonância Magnética Nuclear Biomolecular , Ácidos de Fósforo/química , Prótons , Tetrahymena/genética , Trometamina/químicaRESUMO
Palladium-catalyzed cross-coupling reactions utilizing aryl halides have become a widely used strategy for the formation of new carbon-carbon bonds and in particular for the synthesis of biaryls. The replacement of expensive, toxic, and flammable organic solvents by water is highly desirable for reducing costs and for developing environmentally benign synthetic reactions that facilitate catalyst recycling. Herein, we report an efficient Suzuki-Miyaura cross-coupling reaction using a variety of heterocyclic halides in neat water. Employing air- and moisture-stable palladium-phosphinous acid catalyst [(t-Bu)2P(OH)]2PdCl2(POPd) allows formation of substituted aryl heterocyclics in moderate to high yields. The organic cosolvents are not required. The feasibility of catalyst recycling has also been demonstrated.
Assuntos
Química Orgânica/métodos , Compostos Heterocíclicos/química , Água/química , Ácidos Borônicos/química , Catálise , Halogênios/química , Paládio/química , Ácidos de Fósforo/química , ReciclagemRESUMO
An air-stable catalyst system Ir-(P-Phos) catalyst was found to be highly effective in the asymmetric hydrogenation of quinoline derivatives. The catalyst immobilized in DMPEG was efficiently recovered and reused eight times, retaining reactivity and enantioselectivity.
Assuntos
Irídio/química , Fosfinas/química , Ácidos de Fósforo/química , Polietilenoglicóis/química , Ácido Pirrolidonocarboxílico/análogos & derivados , Quinolinas/química , Ar , Catálise , Hidrogenação , Estrutura Molecular , Ácido Pirrolidonocarboxílico/química , EstereoisomerismoRESUMO
Several economical methods for geometry optimisation, applicable to larger molecules, have been evaluated for phosphorus acid derivatives. MP2/cc-pVDZ and B3LYP/6-31+G(d) geometry optimizations are used as reference points, results from geometry optimizations for other methods and their subsequent single point energy calculations are compared to these references. The geometries from HF/MIDI! optimizations were close to those of the references and subsequent single point energies with B3LYP/6-31+G(d,p) or EDF1/6-31+G(d) gave a mean average deviation (MAD) of less than 0.5 kcal mol-1 from those obtained with the reference geometries.
Assuntos
Ácidos de Fósforo/química , Teoria Quântica , Conformação Molecular , TermodinâmicaRESUMO
Chiral phosphonium salts induce the kinetic resolution of racemic α-substituted unsaturated carboxylic acids through asymmetric protolactonization. Both the lactones and the recovered carboxylic acids are obtained with high enantioselectivities and high S (= kfast/kslow) values. Asymmetric protolactonization also leads to the desymmetrization of achiral carboxylic acids. Notably, chiral phosphonous acid diester not only induced the enantioselectivity but also promoted protolactonization.
Assuntos
Ácidos Carboxílicos/química , Lactonas/química , Ácidos de Fósforo/química , Estrutura Molecular , EstereoisomerismoRESUMO
The preparation of activated carbons (AC-H(x)P(y)O(z)) by four kinds of oxyacids of phosphorus (H(3)PO(4), H(4)P(2)O(7), HPO(3) and H(3)PO(3)) activation of lotus stalk (LS) was studied, with a particular focus on the effect of these H(x)P(y)O(z) on both surface chemistry and porous texture. The XRD analysis of the samples after H(x)P(y)O(z) impregnation showed H(4)P(2)O(7) had the strongest influence on the crystallinity of LS. Thermo gravimetric studies of the pyrolysis of LS-H(x)P(y)O(z) indicated that these H(x)P(y)O(z) had a very different influence on the thermal degradation of LS. The prepared activated carbons were characterized by SEM, N(2) sorption/desorption isotherms, XRD, FTIR and Boehm's titration. Batched sorption studies were performed to compare adsorptive properties of the carbons toward trimethoprim (TMP). The surface area and pore volume of AC-H(3)PO(4) and AC-H(4)P(2)O(7) were much higher than AC-HPO(3) and AC-H(3)PO(3). Boehm's titration results indicated that AC-H(4)P(2)O(7) and AC-H(3)PO(3) possessed more acidic oxygen functionalities than AC-H(3)PO(4) and AC-HPO(3). The structure of the AC-HPO(3) was kept as its starting material after activation. Activation with H(3)PO(3) would result in the aromatization of the carbon. The sorption affinities of TMP follows an order of AC-H(4)P(2)O(7)>AC-H(3)PO(4)>AC-H(3)PO(3)>AC-HPO(3).
Assuntos
Carbono/química , Poluentes Ambientais/química , Lotus , Ácidos de Fósforo/química , Trimetoprima/química , Adsorção , Caules de Planta/química , Porosidade , Propriedades de SuperfícieRESUMO
Novel chiral N-phosphinamide and N-phosphinyl imines have been designed, synthesized and applied to asymmetric aza-Henry reaction to give excellent chemical yields (92%- quant.) and diastereoselectivity (91% to >99%de). The reaction showed a great substrate scope in which aromatic/aliphatic aldehyde- and ketone-derived N-phosphinyl imines can be employed as electrophiles. The chiral N-phosphinamide can be stored at room temperature for more than 2 months without inert gas protection, and chiral N-phosphinyl imines were also proven to be highly stable at room temperature for a long period under inert gas protection. The N-phosphinyl group enabled the product purification to be performed simply by washing crude product with EtOAc and hexane. This reaction joined other eight GAP (Group-Assistant-Purification) chemistry processes that were developed in our laboratories. The absolute configuration has been unambiguously determined by converting a ß-nitroamine product into a known N-Boc sample.
Assuntos
Aldeídos/química , Aminas/química , Iminas , Cetonas/química , Ácidos de Fósforo , Iminas/química , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Ácidos de Fósforo/química , EstereoisomerismoRESUMO
Kinetic and DFT studies have been carried out on the reaction of the [Mo(3)M'S(4)(H(2)O)(10)](4+) clusters (M' = Pd, Ni) with H(3)PO(2) to form the [Mo(3)M'(pyr-H(3)PO(2))S(4)(H(2)O)(9)](4+) complexes, in which the rare pyramidal form of H(3)PO(2) is stabilized by coordination to the M' site of the clusters. The reaction proceeds with biphasic kinetics, both steps showing a first order dependence with respect to H(3)PO(2). These results are interpreted in terms of a mechanism that involves an initial substitution step in which one tetrahedral H(3)PO(2) molecule coordinates to M' through the oxygen atom of the P=O bond, followed by a second step that consists in tautomerization of coordinated H(3)PO(2) assisted by a second H(3)PO(2) molecule. DFT studies have been carried out to obtain information on the details of both kinetic steps, the major finding being that the role of the additional H(3)PO(2) molecule in the second step consists in catalysing a hydrogen shift from phosphorus to oxygen in O-coordinated H(3)PO(2), which is made possible by its capability of accepting a proton from P-H to form H(4)PO(2)(+) and then transfer it to the oxygen. DFT studies have been also carried out on the reaction at the Mo centres to understand the reasons that make these metal centres ineffective for promoting tautomerization.
Assuntos
Níquel/química , Paládio/química , Ácidos de Fósforo/química , Teoria Quântica , Enxofre/química , Cinética , Espectroscopia de Ressonância Magnética , Modelos MolecularesRESUMO
A series of sterically hindered biaryls have been obtained by palladium- and nickel-phosphinous acid-catalyzed Kumada-Corriu cross-coupling of ortho-substituted aryl halides and Grignard reagents. This method allows formation of di- and tri-ortho-substituted biaryls in 87-98% yield under mild reaction conditions even when electron-rich aryl chlorides are used. The reaction also proceeds with aryl iodides at -20 degrees C, and under these conditions, functional groups that are generally not compatible with Grignard reagents are tolerated.