Phosphoryl Research Articles

Magnetic bentonite with organic modification highly efficient for adsorption of Ce(III) and Y(III)

A simple organic magnetic adsorbent (PAA-MBent) was synthesized using 2-hydroxyphosphonylacetic acid and applied to the adsorption of Ce(III) and Y(III). It was confirmed that the phosphoryl groups could effectively regulate the homogeneous loading of magnetic particles on the bentonite during the synthesis process, and the hydroxyl and phosphoryl groups can be sufficiently used on the surface of bentonite to increase the abundance of adsorption sites, which have favorable coordination with Ce(III) and Y(III). The experimental results showed that the maximal adsorption capacity was increased to 99.11 mg/g and 65.65 mg/g for Ce(III) and Y(III), respectively, which was 2.52 and 2.91 times higher than magnetic bentonite. The adsorption behavior conformed to the Langmuir isothermal adsorption model and the pseudo-second-order kinetic model, and the adsorption of Ce(III) by PAA-MBent performed better than that of Y(III). The adsorption efficiency was affected by ionic strength and site inhibition of coexisting cations, and its adsorption selectivity was mainly disturbed by the competition of Al ions. The results after adsorption identified the key adsorption mechanisms as ion exchange, electrostatic attraction, functional group complexation, and hole filling. After five cycles, the adsorbent still exhibited good adsorption and magnetic recovery performance. These results reveal that PAA-MBent is promised to be a novel, inexpensive and effective adsorbent for the removal of Ce(III) and Y(III) from contaminated water.

Pomegranate-like cobalt Phosphides@P-Doped carbon Nanostructures with controlled phase as anode materials for Lithium-Ion batteries

Transition metal phosphides (TMPs) have recently emerged as prominent energy conversion and storage materials owing to their unique physicochemical property. Nevertheless, it’s still a difficult task to obtain phase-control of TMPs owing to multiple energetically favorable stoichiometries. Herein, a phase-controllable cobalt phosphide@C with the pomegranate core–shell structure are successfully realized by employing Co-glycerate as precursors and phytic acid (PA) as P sources, etching and coordination agents. With the presence of six phosphoryl groups and the strong coordination ability, PA allows the self-phosphating of Co atoms and the P-doped carbon shell, as well as the confinement of the obtained nanoparticles Additionally, as an organic acid, PA can etch the Co-glycerate precursors with the formation of hollow structures. With different etching time, metal-rich phosphides Co2P@C and monophosphides CoP@C are successfully achieved. When applied as anode materials, CoP@C demonstrates superior lithium storage performance by delivering a prominent reversible capacity up to 1187 mAh/g at 0.1 A/g and shows no capacity loss at 1 A/g after 500 cycles. This work presents a simple protocol to obtain TMPs with tunable metal/phosphorus ratios, phase selectivity and interface engineering, which could be applied in the field of energy storage and electrocatalysis.

Insight into the complexation of uranium with Bacillus sp. dwc-2 by multi-spectroscopic approaches: FT-IR, TRLF and XAFS spectroscopies

The micromechanisms of the interactions between uranium and microorganisms, especially chemical bonds and bonding numbers between uranium and microbe are not yet clear. In this work, uranium coordination with functional groups in/on Bacillus sp. dwc-2 has been rationally explored by X-ray absorption fine structure (XAFS), Fourier transform infrared (FT-IR), time-resolved laser-induced fluorescence (TRLF) spectroscopies. The results indicate that under acidic condition, 66.8 % of O atoms in coordination shell of U(VI) equatorial plane are provided by organic phosphoryl groups via monodentate coordination, 18.8 % and 15.5 % are provided by water molecules and carboxyl groups via monodentate and bidentate coordination, respectively. While under alkaline condition, these proportions change to 53.1 %, 34.4 % and 22.0 %, respectively. Under neutral condition, U(VI) is mainly deposited by complexing with inorganic phosphates released by microbial cells. Under anaerobic condition, partial U(VI) can be reduced to U(IV) which primarily complex with phosphorus containing groups via monodentate and bidentate coordination, existing as amorphous solids or coordination polymers. This is the first exploration of the binding mechanism between uranium and microorganisms at a semi-quantitative level under different conditions. Our studies will further enhance the contribute to the understanding of coordination mechanism of uranium with microorganism, and demonstrate the potential bioremediation value of this bacterium.

Crystal Structures of the Acinetobacter baumannii Macrolide Phosphotransferase E.

Acinetobacter baumannii (A. baumannii) challenges clinical infection treatment due to its resistance to various antibiotics. Multiple resistance genes in the core genome or mobile elements contribute to multidrug resistance in A. baumannii. Macrolide phosphotransferase gene mphE has been identified in A. baumannii, which is particularly relevant to macrolide antibiotics. Here, we determined the structure of MphE protein in three states: the apo state, the complex state with erythromycin and guanosine triphosphate (GTP), and the complex state with azithromycin and guanosine. Interestingly, GTP and two magnesium ions were observed in the erythromycin-bound MphE complex. This structure captured the active state of MphE, in which the magnesium ions stabilized the active site and assisted the transfer of phosphoryl groups. Based on these structures, we verified that the conserved residues Asp29, Asp194, His199, and Asp213 play an important role in the catalytic phosphorylation of MphE leading to drug resistance. Our work helps to understand the molecular basis of drug resistance and provides reference targets for optimizing macrolide antibiotics.

1‐Alkynylphosphorus Compounds in Organic Synthesis，2010‐2024

Since the review of Yorimitsu and Oshima in 2010, the past 15 years have witnessed significant progresses in the application of 1‐alkynylphosphorus compounds in organic synthesis. Owing to the reactive carbon‐carbon triple bond in association with the electron‐withdrawing phosphoryl group, they easily undergo transition metal‐catalyzed nucleophilic addition reactions at the β‐position with carbon‐ and heteroatom‐based nucleophiles to afford structurally diverse 1‐alkenyl phosphorus compounds. Especially, when 1‐alkynylphosphonates or phosphinates are used, intramolecular substitution reactions on P‐atom might occur in some cases, which would result in the formation of P‐based heterocycles. In addition, the existing triple bond makes them prone to go through addition reaction initiated cyclization reactions and [2+2], [2+3], [2+4], [2+5] and [2+2+2] cycloaddition reactions with other unsaturated bonds, which provides an efficient access to various P‐based heterocycles and phosphorylated carbon‐ and heterocycles.

Promoting microalgal biofilm formation by crushed oyster shell-hydroxyapatite layer on micropatterned aluminum coating for heavy metal ions removal

Microalgal biomass has shown inspiring potential for the heavy metal removal from wastewater, and forming microalgal biofilm is one of the sustainable methods for the microalgal biomass production. Here we report the formation of microalgal biofilm by accelerated colonization of typical algae Chlorella on thermal sprayed aluminum (Al) coatings with biologically modified surfaces. Micro-patterning surface treatment of the Al coatings promotes the attachment of Chlorella from 6.31 % to 17.51 %. Further enhanced algae attachment is achieved through liquid flame spraying a bioactive crushed oyster shell-hydroxyapatite (CaCO3-HA) composite top layer on the micropatterned coating, reaching 46.03–49.62 % of Chlorella attachment ratio after soaking in Chlorella suspension for 5 days. The rapidly formed microalgal biofilm shows an adsorption ratio of 95.43 % and 85.23 % for low concentration Zn2+ and Cu2+ in artificial seawater respectively within 3 days. Quick interaction has been realized between heavy metal ions and the negatively-charged extracellular polymeric substances (EPS) matrix existing in the biofilm. Fourier transform infrared spectroscopy (FTIR) results indicate that both carboxyl and phosphoryl groups of biofilms are crucial in the adsorption of Cu2+ and the adsorption of Zn2+ is due to the hydroxyl and phosphate groups. Meanwhile, the biofilm could act as a barrier to protect Chlorella against the attack of the heavy metal ions with relatively low concentrations in aqueous solution. The route of quick cultivating microalgal biofilm on marine structures through constructing biological layer on their surfaces would give insight into developing new techniques for removing low concentration heavy metal ions from water for environmental bioremediation.

Phosphoryl group wires stabilize pathological tau fibrils as revealed by multiple quantum spin counting NMR.

Hyperphosphorylation of the protein tau is one of the biomarkers of neurodegenerative diseases in the category of tauopathies. However, the molecular level, mechanistic, role of this common post-translational modification (PTM) in enhancing or reducing the aggregation propensity of tau is unclear, especially considering that combinatorial phosphorylation of multiple sites can have complex, non-additive, effects on tau protein aggregation. Since tau proteins stack in register and parallel to elongate into pathological fibrils, phosphoryl groups from adjacent tau strands with 4.8 Å separation must find an energetically favorable spatial arrangement. At first glance, this appears to be an unfavorable configuration due to the proximity of negative charges between phosphate groups from adjacent neighboring tau fibrils. However, this study tests a counterhypothesis that phosphoryl groups within the fibril core-forming segments favorably assemble into highly ordered, hydrogen-bonded, one-dimensionally extended wires under biologically relevant conditions. We selected two phosphorylation sites associated with neurodegeneration, serine 305 (S305p) and tyrosine 310 (Y310p), on a model tau peptide jR2R3-P301L (tau295-313) spanning the R2/R3 splice junction of tau, that readily aggregate into a fibril with characteristics of a seed-competent mini prion. Using multiple quantum spin counting (MQ-SC) by 31P solid-state NMR of phosphorylated jR2R3-P301L tau peptide fibrils, enhanced by dynamic nuclear polarization, we find that at least six phosphorous spins must neatly arrange in 1D within fibrils or in 2D within a protofibril to yield the experimentally observed MQ-coherence orders of four. We found that S305p stabilizes the tau fibrils and leads to more seeding-competent fibrils compared to jR2R3 P301L or Y310p. This study introduces a new concept that phosphorylation of residues within a core forming tau segment can mechanically facilitate fibril registry and stability due a hitherto unrecognized role of phosphoryl groups to form highly ordered, extended, 1D wires that stabilize pathological tau fibrils.

Metal fluorides—multi-functional tools for the study of phosphoryl transfer enzymes, a practical guide

Enzymes facilitating the transfer of phosphate groups constitute the most extensive protein families across all kingdoms of life. They make up approximately 10% of the proteins found in the human genome. Understanding the mechanisms by which enzymes catalyze these reactions is essential in characterizing the processes they regulate. Metal fluorides can be used as multifunctional tools to study these enzymes. These ionic species bear the same charge as phosphate and the transferring phosphoryl group and, in addition, allow the enzyme to be trapped in catalytically important states with spectroscopically sensitive atoms interacting directly with active site residues. The ionic nature of these phosphate surrogates also allows their removal and replacement with other analogs. Here, we describe the best practices to obtain these complexes, their use in NMR, X-ray crystallography, cryo-EM, and SAXS and describe a new metal fluoride, scandium tetrafluoride, which has significant anomalous signal using soft X-rays.

6-Plex Tandem Phosphorus Tags (TPT) for Accurate Quantitative Proteomics.

Isobaric chemical labeling is a widely used strategy for high-throughput quantitative proteomics based on mass spectrometry. However, commercially available reagents have high costs in applications as well as the sensitivity limitations for detection of the trace protein samples. Previously, we developed a 2-plex isobaric labeling strategy based on phosphorus chemistry for ultrasensitive proteome quantification with high accuracy. In this work, 6-plex tandem phosphorus tags (TPT) were developed with 3-fold increase in the multiplexing quantitative capacity compared to the 2-plex isobaric phosphorus reagents introduced previously. High isotope enrichment of 18O labeling was incorporated into the phosphoryl group with three exchangeable oxygen atoms by using commercially available H218O. The combinational incorporations of 18O atom in reporter ions and balance group set up the low-cost foundation for development of multiplex TPT reagents. The novel 6-plex TPT reagents could produce phosphoramidate as unique reporter ions with approximately 1 Da mass difference and thus enable 6-plex quantitative analysis in high-resolution ESI-MS/MS analysis. Using HeLa cell tryptic peptides, we concluded that 6-plex TPT reagents could facilitate large-scale accurate quantitative proteomics with very high labeling efficiency.

Structural and functional insights underlying recognition of histidine phosphotransfer protein in fungal phosphorelay systems

In human pathogenic fungi, receiver domains from hybrid histidine kinases (hHK) have to recognize one HPt. To understand the recognition mechanism, we have assessed phosphorelay from receiver domains of five hHKs of group III, IV, V, VI, and XI to HPt from Chaetomium thermophilum and obtained the structures of Ct_HPt alone and in complex with the receiver domain of hHK group VI. Our data indicate that receiver domains phosphotransfer to Ct_HPt, show a low affinity for complex formation, and prevent a Leu-Thr switch to stabilize phosphoryl groups, also derived from the structures of the receiver domains of hHK group III and Candida albicans Sln1. Moreover, we have elucidated the envelope structure of C. albicans Ypd1 using small-angle X-ray scattering which reveals an extended flexible conformation of the long loop αD–αE which is not involved in phosphotransfer. Finally, we have analyzed the role of salt bridges in the structure of Ct_HPt alone.

The effects of plastisphere on the physicochemical properties of microplastics.

The plastisphere is the microbial communities that grow on the surface of plastic debris, often used interchangeably with plastic biofilm or biofouled plastics. It can affect the properties of the plastic debris in multiple ways. This review aims to present the effects of the plastisphere on the physicochemical properties of microplastics systematically. It highlights that the plastisphere modifies the buoyancy and movement of microplastics by increasing their density, causing them to sink and settle out. Smaller and film microplastics are likely to settle sooner because of larger surface areas and higher rates of biofouling. Biofouled microplastics may show an oscillating movement in waterbodies when settling due to diurnal and seasonal changes in the growth of the plastisphere until they come close to the bottom of the waterbodies and are entrapped by sediments. The plastisphere enhances the adsorption of microplastics for metals and organic pollutants and shifts the adsorption mechanism from intraparticle diffusion to film diffusion. The plastisphere also increases surface roughness, reduces the pore size, and alters the overall charge of microplastics. Charge alteration is primarily attributed to changes in the functional groups on microplastic surfaces. The plastisphere introduces carbonyl, amine, amide, hydroxyl, and phosphoryl groups to microplastics, causing an increase in their surface hydrophilicity, which could alter their adsorption behaviors for heavy metals. The plastisphere may act as a reactive barrier that enhances the leaching of polar additives. It may anchor bacteria that can break down plastic additives, resulting in decreased crystallinity of microplastics. This review contributes to a better understanding of how the plastisphere alters the fate, transport, and environmental impacts of microplastics. It points to the possibility of engineering the plastisphere to improve microplastic biodegradation.

CKB Promotes Mitochondrial ATP Production by Suppressing Permeability Transition Pore.

Creatine kinases are essential for maintaining cellular energy balance by facilitating the reversible transfer of a phosphoryl group from ATP to creatine, however, their role in mitochondrial ATP production remains unknown. This study shows creatine kinases, including CKMT1A, CKMT1B, and CKB, are highly expressed in cells relying on the mitochondrial F1F0 ATP synthase for survival. Interestingly, silencing CKB, but not CKMT1A or CKMT1B, leads to a loss of sensitivity to the inhibition of F1F0 ATP synthase in these cells. Mechanistically, CKB promotes mitochondrial ATP but reduces glycolytic ATP production by suppressing mitochondrial calcium (mCa2+) levels, thereby preventing the activation of mitochondrial permeability transition pore (mPTP) and ensuring efficient mitochondrial ATP generation. Further, CKB achieves this regulation by suppressing mCa2+ levels through the inhibition of AKT activity. Notably, the CKB-AKT signaling axis boosts mitochondrial ATP production in cancer cells growing in a mouse tumor model. Moreover, this study also uncovers a decline in CKB expression in peripheral blood mononuclear cells with aging, accompanied by an increase in AKT signaling in these cells. These findings thus shed light on a novel signaling pathway involving CKB that directly regulates mitochondrial ATP production, potentially playing a role in both pathological and physiological conditions.

Legionella effector LnaB is a phosphoryl-AMPylase that impairs phosphosignalling

AMPylation is a post-translational modification in which AMP is added to the amino acid side chains of proteins1,2. Here we show that, with ATP as the ligand and actin as the host activator, the effector protein LnaB of Legionella pneumophila exhibits AMPylase activity towards the phosphoryl group of phosphoribose on PRR42-Ub that is generated by the SidE family of effectors, and deubiquitinases DupA and DupB in an E1- and E2-independent ubiquitination process3-7. The product of LnaB is further hydrolysed by an ADP-ribosylhydrolase, MavL, to Ub, thereby preventing the accumulation of PRR42-Ub and ADPRR42-Ub and protecting canonical ubiquitination in host cells. LnaB represents a large family of AMPylases that adopt a common structural fold, distinct from those of the previously known AMPylases, and LnaB homologues are found in more than 20 species of bacterial pathogens. Moreover, LnaB also exhibits robust phosphoryl AMPylase activity towards phosphorylated residues and produces unique ADPylation modifications in proteins. During infection, LnaB AMPylates the conserved phosphorylated tyrosine residues in the activation loop of the Src family of kinases8,9, which dampens downstream phosphorylation signalling in the host. Structural studies reveal the actin-dependent activation and catalytic mechanisms of the LnaB family of AMPylases. This study identifies, to our knowledge, an unprecedented molecular regulation mechanism in bacterial pathogenesis and protein phosphorylation.

Use of di-(2-ethylhexyl)-orthophosphoric acid for the extraction of lanthanum, neodymium, samarium and yttrium from nitric acid solutions

The process of separating rare-earth elements into individual components is considered the most important problem in rare-earth technology because of the similarity in their physical and chemical properties. Currently in the world dialkyl phosphate compounds are widely used as effective extractors for rare earths. However, most extraction processes have been studied from hydrochloric acid or perchlorate solutions. In Russia, tributyl phosphate has long been used to extract rare earths from nitric acid solutions, but the distribution coefficients of the elements are not high, and the process must be repeated multiple times. In this study di-(2-ethylhexyl)-orthophosphoric acid was used for the extraction of lanthanum, neodymium, samarium, and yttrium from nitric acid solutions. When the concentration of nitric acid increased, distribution coefficient of elements gradually decreased to minimum (in the range of 1 to 5M) then increased backward. However, when the concentration was too high (C > 5M), nitric acid was extracted to the organic phase due to the properties of the phosphoryl group. Moreover, the study of dependence of solvation number of neodymium on the concentrations of nitric acid shows that rare earths in the organic phase can be extracted as Re(HA2)3 (C < 1M) or Re(NO3)3«3HA (C > 5M).

Tailoring supramolecular solvents with phosphoryl groups for highly efficient extraction of chlorophenols in natural waters

BackgroundChlorophenols are routinely determined in aquatic systems to check compliance with the restrictive international legislations set for protection of human and aquatic life. Their control requires affordable analytical methods, particularly in labs at low- and medium-income countries. Liquid chromatography-UV detection is a convenient technique for this purpose, but the availability of suitable sample processing remains pending. Organic solvents are inefficient for extracting the whole range of chlorophenols whereas solid-phase extractions are expensive and labour-intensive. So, an efficient, fast and cheap extraction of chlorophenols, amenable to any lab, would help to cope with their worldwide analytical control in natural waters. ResultsA supramolecular solvent (SUPRAS) was tailored for providing mixed interaction mechanisms aimed at the efficient extraction of chlorophenols prior to LC-UV. The SUPRAS was synthesized from the self-assembly of hexylphosphonic acid under acidic conditions and consisted of sponge-like nanostructures made up of amphiphile and water. The phosphoryl (PO) group was selected as the major driver of the extraction because of its ability to act as halogen and hydrogen bond acceptor for chlorophenols. Additional interactions were hydrogen bonds from O–H amphiphilic groups and the surrounding water, and dispersion and CH-π interactions in the hydrocarbon chains. The number of binding sites in the SUPRAS could be modulated by addition of salt. The SUPRAS formed in situ in the sample, the extraction took 5 min, the concentration factor was around 220, quantification limits (0.1–0.3 μg L−1) were below the EU standards, and the method worked for natural waters. SignificanceA fast, low-cost, and organic solvent-free sample processing only requiring conventional lab equipment (stirrers and centrifuges) provided SUPRAS extracts that could be directly analyzed by LC-UV. SUPRAS synthesis occurred spontaneously in the water sample under addition of hexylphosphonic acid and the whole process required low skills. The method meets the analytical and operational performances for the analytical control of chlorophenols in natural waters and it is within the reach of any lab.

Facile InCl3-catalyzed room temperature synthesis and electrochemical behavior of ferrocene appended (R, S)-α-aminophosphonates

α-Aminophosphonates represent a significant category of the phosphorus family. Due to the additional ‘N’ atom(s), these compounds exhibit interesting electronic, coordination, and electrochemical properties. In this regard, the present work is focused on the In(III)-catalyzed synthesis of new ferrocene-appended α-aminophosphonates using the well-known Kabachnik−Fields reaction. Notably, all the reactions proceed to complete at room temperature in ethanol to provide the products with excellent yields in the range of 87–95%. The reaction proceeded smoothly with a broader substrate scope containing -Cl, Br, F, NO2, t‑butyl, and 3,5-dimethyl substituents at various positions. The purity of the products was assessed by analytical and spectroscopic techniques including 1H, 13C and 31P NMR along with HR-MS spectroscopic analysis. Among 18 compounds, 17 derivatives were crystallized in triclinic and monoclinic systems with P-1, P21/n, or P21/c space groups. From the results, the length of P = O bonds exhibits a range spanning from 1.447(2) Å (4c) to 1.469(2) Å (4l). Additionally, the electrochemical studies of all the synthesized compounds showed an effective redox response. The presence of the phosphoryl group and the substituents have a distinct influence on the electrochemical behavior of the synthesized molecules.

Arginine Kinase Activates Arginine for Phosphorylation by Pyramidalization and Polarization.

Arginine phosphorylation plays numerous roles throughout biology. Arginine kinase (AK) catalyzes the delivery of an anionic phosphoryl group (PO3-) from ATP to a planar, trigonal nitrogen in a guanidinium cation. Density functional theory (DFT) calculations have yielded a model of the transition state (TS) for the AK-catalyzed reaction. They reveal a network of over 50 hydrogen bonds that delivers unprecedented pyramidalization and out-of-plane polarization of the arginine guanidinium nitrogen (Nη2) and aligns the electron density on Nη2 with the scissile P-O bond, leading to in-line phosphoryl transfer via an associative mechanism. In the reverse reaction, the hydrogen-bonding network enforces the conformational distortion of a bound phosphoarginine substrate to increase the basicity of Nη2. This enables Nη2 protonation, which triggers PO3- migration to generate ATP. This polarization-pyramidalization of nitrogen in the arginine side chain is likely a general phenomenon that is exploited by many classes of enzymes mediating the post-translational modification of arginine.

Thermodynamics of interactions and structural peculiarities of interpenetrating polymer networks based on polyurethane and copolymer of 2-hydroxyethyl methacrylate with methacryloyloxyethylphosphorylcholine

Interpenetrating polymer networks based on biocompatible components – polyurethane and copolymer of 2-hydroxyethyl methacrylate with methacryloyloxyethylyphosphorylcholine (HEMA-MPC) were synthesized and thermodynamic parameters of interactions in the system and morphology were investigated. The thermodynamic parameters of interactions between polymer components of the IPNs were calculated based on sorption isotherms of methylene chloride vapors by samples of the created polymer systems. It is shown that MPC plays the role of a compatibilizer in the system, increasing the thermodynamic compatibility between polyurethane and the HEMA-MPC copolymer at small amounts of the copolymer in the IPNs. As the amount of copolymer HEMA-MPC in the IPNs increases, the value of the free energy of the polyurethane and copolymer mixing shifts to the positive value, which is associated with the formation of ionic clusters of MPC. This may mean that with an increasing amount of the MPC in the system, interactions between the negatively charged phosphoryl groups and the positively charged nitrogen atom of various MPC polymer chains occur, i.e., the part of intermolecular interactions (polyurethane and copolymer) decreases, while the part of intramolecular interactions (between different groups of MPC) increases. The results of the morphology investigations of the IPN samples are consistent with the data of the thermodynamic compatibility study of polymers during the formation of the IPNs. With a significant increase in the positive values of the free energy of the polyurethane and copolymer mixing in the IPNs with 41 % and 51 % of the copolymer content, a significant phase separation is observed in the IPNs, with phase inclusions ranging from 1 to 5 mm.

Silica extracts from fly ash modified via sol-gel methods and functionalized with CMPO for potential scavenging of rare earth elements La³⁺ and Ce³⁺

A mesoporous material was synthesized using silica extracts from fly ash and its properties were studied. Subsequently, it was functionalized with carbamoylmethylphosphine oxide (CMPO) to capture La3+ and Ce3+. The developed mesoporous material was obtained by the sol-gel method and was called Si-MMS (siliceous mesoporous materials), subsequently functionalized with APTMS (1-(2-aminoethyl)-3-aminopropyl trimethoxysilane) in a reflux system, which led to the synthesis of Si-MMS-APTMS. This derivative was modified with carbonyldiimidazole (CDI) and diethylphosphonoacetic acid, which finally resulted in the synthesis of Si-MMS-CMPO as the final product. The materials were characterized by DRIFT, XRD, SEM-EDS, TEM, XPS, elemental analysis and nitrogen isotherms at −196 °C, confirming that the synthesis and subsequent modification of the mesoporous structure was successful. Adsorption studies in batch systems indicated that the optimal pH for La3+ was 6, the Langmuir isotherm model and the non-linear Sips models were perfectly fitted and the best fitting kinetics is the Elovich model. For Ce3+ the optimal pH was 7.5, the non-linear Sips isotherm fit the best and the non-linear Pseudo-second order kinetics was the mechanism that best represents the adsorption. The maximum experimental adsorption capacity qe of La3+ was 17.00 mg g−1 and for Ce3+ was 30.09 mg g−1. In both cases, the rapid adsorption suggests an open porous matrix that facilitates the formation of chelates between the adsorbates and the phosphoryl group -PO32-.

Phosphonium-Catalyzed Monoreduction of Bisphosphine Dioxides: Origin of Selectivity and Synthetic Applications.

Controlling product selectivity in successive reactions of the same type is challenging owing to the comparable thermodynamic and kinetic properties of the reactions involved. Here, the synergistic interaction of the two phosphoryl groups in bisphosphine dioxides (BPDOs) with a bromo-phosphonium cation was studied experimentally to provide a practical tool for substrate-catalyst recognition. As the eventual result, we have developed a phosphonium-catalyzed monoreduction of chiral BPDOs to access an array of synthetically useful bisphosphine monoxides (BPMOs) with axial, spiro, and planar chirality, which are otherwise challenging to synthesize before. The reaction features excellent selectivity and impressive reactivity. It proceeds under mild conditions, avoiding the use of superstoichiometric amounts of additives and metal catalysts to simplify the synthetic procedure. The accessibility and scalability of the reaction allowed for the rapid construction of a ligand library for optimization of asymmetric Heck-type cyclization, laying the foundation for a broad range of applications of chiral BPMOs in catalysis.