Phosphorus Chemistry Research Articles

Modeling Synthetic Spectra for Transiting Extrasolar Giant Planets: Detectability of H2S and PH3 with the James Webb Space Telescope

Abstract The James Webb Space Telescope (JWST)’s large aperture and wide wavelength coverage will enable it to collect the highest-quality transit spectra observed so far. For exoplanetary atmospheres we expect to retrieve the abundance of the most abundant molecules, such as H2O, CO, and CH4. Other molecules, such as H2S and PH3, have been observed in Jupiter and Saturn but their chemistry and detectability in strongly irradiated planets are largely unknown. In this paper, we make the first effort to study their spectral features in solar composition atmospheres, and evaluate their detectability with the JWST. We model the chemistry of phosphorus and sulfur in solar composition atmospheres. Our model includes the effect of vertical transport. Photochemistry effects are not included in our calculations. Using the abundance profiles, we model the JWST transmission and emission spectra for a K = 6.8 G-type star and for planets with cloud-free solar composition atmospheres. We find PH3 is detectable at 3σ from transmission spectra of the simulated atmosphere with K using the NIRCam LW grism F444W mode with a total observing time of 28.8 hr. H2S is detectable at 3σ in the transmission and emission spectra for the simulated planet with K using the NIRCam LW grism F322W2 mode with a total observing time of 24.0 hr. Our results specifically highlight the importance of including H2S for future abundance retrieval with the JWST. The presence of clouds and hazes challenges the detections of PH3 and H2S, but H2S features are still expected to be present in the emission spectra.

Exotic Physics and Chemistry of Two-Dimensional Phosphorus: Phosphorene.

Phosphorene, the monolayer form of black phosphorus, is the most recent addition to graphene-like van der Waals two-dimensional (2D) systems. Due to its several interesting properties, namely its tunable direct band gap, high carrier mobility, and unique in-plane anisotropy, it has emerged as a promising candidate for electronic and optoelectronic devices. Phosphorene (Pn) reveals a much richer phase diagram than graphene, and it comprises the two forms namely the stapler-clip like (black Pn, α form) and chairlike (blue Pn, β form) structures. Regardless of its favorable properties, black Pn suffers from instability in oxygen and water, which limits its successful applications in electronic devices. In this Perspective, the cause of structural diversity of Pn, which leads to different properties of both black and blue Pn, is discussed. We provide possible solutions for protecting phosphorene from chemical degradation and its applications in the field of energy storage namely for Li and Na ion batteries.

Stable isotope N-phosphoryl amino acids labeling for quantitative profiling of amine-containing metabolites using liquid chromatography mass spectrometry

Stable isotope chemical labeling liquid chromatography-mass spectrometry (LC-MS) is a powerful strategy for comprehensive metabolomics profiling, which can improve metabolites coverage and quantitative information for exploration of metabolic regulation in complex biological systems. In the current work, a novel stable isotope N-phosphoryl amino acids labeling strategy (SIPAL) has been successful developed for quantitative profiling of amine-containing metabolites in urine based on organic phosphorus chemistry. Two isotopic reagents, 16O2- and 18O2-N-diisopropyl phosphoryl l-alanine N-hydroxysuccinimide esters (16O/18O-DIPP-L-Ala-NHS), were firstly synthesized in high yields for labeling the amine-containing metabolites. The performance of SIPAL strategy was tested by analyzing standard samples including 20 l-amino acids, 10 d-amino acids and small peptides by using LC-MS. We observed highly efficient and selective labeling for SIPAL strategy within 15 min in a one-pot derivatization reaction under aqueous reaction conditions. The introduction of a neutral phosphate group at N-terminus can increase the proton affinity and overall hydrophobicity of targeted metabolites, leading to the better ionization efficiency in electrospray ionization processes and chromatographic separations of hydrophilic metabolites on reversed-phase column. Furthermore, the chiral metabolites, such as d-amino acids, could be converted to diastereomers after SIPAL and successfully separated on regular reversed-phase column. The chirality of labeled enantiomers can be determined by using different detection methods such as 31P NMR, UV, and MS, demonstrating the potential application of SIPAL strategy. In addition, absolute quantification of chiral metabolites in biological samples can be easily achieved by using SIPAL strategy. For this purpose, urine samples collected from a healthy volunteer were analyzed by using LC-ESI-Orbitrap MS. Over 300 pairs of different amine-containing metabolites have been manually identified with high relative abundance (signal-to-noise ratios greater than 10). Finally, a standard peptide could be relatively quantified by using SIPAL strategy in combination with MALDI-TOF MS, suggesting the potential application of this strategy for quantitative proteomics.

Research Papers from the 21st International Conference on Phosphorus Chemistry (ICPC-21)

Research Papers from the 21^st International Conference on Phosphorus Chemistry (ICPC-21)

Spatial and historical distribution of organic phosphorus driven by environment conditions in lake sediments

The chemistry of sedimentary organic phosphorus (OP) and its fraction distribution in sediments are greatly influenced by environmental conditions such as terrestrial inputs and runoffs. The linkage of OP with environmental conditions was analyzed on the basis of OP spatial and historical distributions in lake sediments. The redundancy analysis and OP spatial distribution results suggested that both NaOH-OP (OP extracted by NaOH) and Re-OP (residual OP) in surface sediments from the selected 13 lakes reflected the gradient effects of environmental conditions and the autochthonous and/or allochthonous inputs driven by latitude zonality in China. The lake level and salinity of Lake Hulun and the runoff and precipitation of its drainage basin were reconstructed on the basis of the geochemistry index. This work showed that a gradient in weather conditions presented by the latitude zonality in China impacts the OP accumulation through multiple drivers and in many ways. The drivers are mainly precipitation and temperature, governing organic matter (OM) production, degradation rate and transportation in the watershed. Over a long temporal dimension (4000years), the vertical distributions of Re-OP and NaOH-OP based on a dated sediment profile from HLH were largely regulated by the autochthonous and/or allochthonous inputs, which depended on the environmental and climate conditions and anthropogenic activities in the drainage basin. This work provides useful environmental geochemistry information to understand the inherent linkage of OP fractionation with environmental conditions and lake evolution.

Ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions - a novel dichotomy in phosphorus chemistry.

A novel ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions is described. The outcome of the reaction with hexafluoroacetone is highly dependent on the P-substituent as fluoride substitution occurred in the case of R = CPh3 and C5Me5via a radical pathway, whereas for R = CH(SiMe3)2 a complex having a novel 1,2-diol-type P-ligand was obtained via a closed-shell pathway. DFT calculations reveal a new SET pathway starting with a noncovalent π-hole complex between the phosphinidenoid anion and hexafluoroacetone followed by an elimination of LiF. The second, closed-shell reaction course is strongly influenced by a noncovalent OSi interaction established after the initial nucleophilic attack.

ChemInform Abstract: Recent Advances in H‐Phosphonate Chemistry. Part 1. H‐Phosphonate Esters: Synthesis and Basic Reactions

AbstractReview: 233 refs.

A spectroscopic case for SPSi detection: The third-row in a single molecule.

In moving beyond the second row of the periodic table for molecules of astronomical and atmospheric significance, the exploration of sulfur and phosphorus chemistry is essential. Additionally, silicon is abundant in most astrophysical environments and is a major component of most rocky bodies. The triatomic molecule composed of each of these atoms is therefore a tantalizing candidate for spectroscopic characterization for astrophysical reasons as well as gaining further understanding into the chemical physics of molecules that are not carbon-based. The current work employs high-level quantum chemical techniques to provide new insights into this simplest of heterogeneous third-row atom systems. The fundamental vibrational frequencies are all within the 350-600 cm-1 range and do not demonstrate strong anharmonicities. These frequencies, rotational constants, vibrationally excited state spectroscopic data, and related isotopic substitution information produced will aid in laboratory experimentation and, even potentially, telescopic observation since modern instruments possess the power to resolve extremely fine details.

Surface chemistry of black phosphorus under a controlled oxidative environment

Black phosphorus (BP), the bulk counterpart of monolayer phosphorene, is a relatively stable phosphorus allotrope at room temperature. However, monolayer phosphorene and ultra-thin BP layers degrade in ambient atmosphere. In this paper, we report the investigation of BP oxidation and discuss the reaction mechanism based on the x-ray photoelectron spectroscopy (XPS) data. The kinetics of BP oxidation was examined under various well-controlled conditions, namely in 5% O2/Ar, 2.3% H2O/Ar, and 5% O2 and 2.3% H2O/Ar. At room temperature, the BP surface is demonstrated not to be oxidized at a high oxidation rate in 5% O2/Ar nor in 2.3% H2O/Ar, according to XPS, with the thickness of the oxidized phosphorus layer <5 Å for 5 h. On the other hand, in the O2/H2O mixture, a 30 Å thickness oxide layer was detected already after 2 h of the treatment. This result points to a synergetic effect of water and oxygen in the BP oxidation. The oxidation effect was also studied in applications to the electrical measurements of BP field-effect transistors (FETs) with or without passivation. The electrical performance of BP FETs with atomic layer deposition (ALD) dielectric passivation or h-BN passivation formed in a glove-box environment are also presented.

NbCl5 as an Expeditious Catalyst for the Synthesis of Quinoxalinyl and Dibenzodioxepinyl Phosphonates/Phosphinates via Michaelis-Arbuzov Reaction and their Biological Evaluation

Background: Michaelis-Arbuzov reaction is one of the well studied reaction in phosphorus chemistry and used for the synthesis of phosphonates, phosphinates and phosphine oxides. Phosphonates are not only versatile intermediates in synthetic organic chemistry but also plays a vital role in biological activity. The usage of niobium(V) chloride as a catalyst has attracted the considerable attention due to its low hygroscopic character, high stability, cost effective, low loading and ease of handling. Methods: The present study describes the synthesis of a series of various aryl/heterocyclic substituted phosphonates/ phosphinates of 2-chloroquinoxaline 3(a-e) and 6-iododibenzo[d,f][1,3]dioxepine 5(a-e) using an expeditious catalyst, niobium(V) chloride by Michaelis-Arbuzov reaction and evaluated their antimicrobial and antioxidant activities. Results: A simple, efficient and new synthetic protocol was developed for the synthesis of quinoxalinyl and dibenzodioxepinyl phosphonate/phosphinate derivatives (3a-e/5a-e) in good yields using niobium(V) chloride as a catalyst. Biological data revealed that compound 5c exhibited potent antimicrobial activity and the compounds 3e and 5e good antioxidant activity. Conclusion: From the results it was concluded that niobium(V) chloride was an efficient catalyst for the synthesis of quinoxalinyl and dibenzodioxepinyl phosphonate/phosphinate derivatives and also exhibited good antimicrobial and antioxidant activities. Keywords: 2-chloroquinoxaline, 6-iododibenzo[d, f][1, 3]dioxepine, antimicrobial activity, antioxidant activity, aryl/heterocylic phosphonates, Michaelis-Arbuzov reaction, niobium(V) chloride catalyst.

Synthesis of Organic Compounds Containing Phosphorus Using Ultra sounds

The technique involving ultrasound is a very modern and versatile method used in the last decades for the synthesis of organic compounds containing phosphorus. The use of ultrasonication in phosphorus chemistry was described in many scientific papers in last years. Nowadays this method is still developing. Until now, it was used for transesterification reactions, coupling reaction, production of nanocomposites, synthesis of different compounds for anticorrosion coatings, synthesis of polycyclic phosphonate resins and so on. This technique is of great interest, because first of all, it is a green method. As we will describe further in this review, in some cases the ultrasonication also improved the products yield, in comparison with the classical approaches. Keywords: Green chemistry, phosphorus organic compounds, polycyclic phosphonates, transesterification, ultrasonication, ultrasounds.

Phosphorus dynamics in Swedish agricultural soils as influenced by fertilization and mineralogical properties: Insights gained from batch experiments and XANES spectroscopy

The soil chemistry of phosphorus (P) is important for understanding the processes governing plant availability as well as the risk of environmental losses of P. The objective of this research was to investigate both the speciation and the pH-dependent solubility patterns of P in clayey agricultural soils in relation to soil mineralogy and fertilization history. The study focused on soil samples from six fields that were subjected to different P fertilization regimes for periods of 45 to 57years. Soil P speciation was analyzed by P K-edge XANES spectroscopy and chemical fractionation, sorption isotherms were constructed, and dissolved P was measured as a function of pH. The XANES fitting results showed that organic P and P adsorbed to Fe and Al (hydr)oxides were common P constituents in all soils. Calcium phosphates were identified in five of six soil samples. The XANES results also indicated an increase in P adsorbed to Al and to a lesser extent Fe (hydr)oxides as a result of fertilization. Moreover, the fluorescence intensity from the P K-edge XANES analysis was most strongly correlated with HCl-digestible P (r=0.81***). Consistent with the XANES analysis, laboratory sorption isotherm models showed that the Freundlich sorption coefficient (KF) was most closely related to oxalate-extractable Al. Greater proportions of Ca phosphate in two of the heavily fertilized soils in combination with enhanced PO4 solubilization upon sample acidification indicated neoformation of Ca-phosphate precipitates. The results for the unfertilized soil samples generally showed a minimum in dissolved PO4 between pH6.5 and 7.5, with increases particularly at lower pH. This behavior can be explained either by the dissolution of Al-hydroxide-type sorbents or Ca phosphates at lower pH. In fertilized soils, there was no consistent trend in pH-dependent solubilization of P, with a complex relationship to solid-phase speciation. To conclude, inorganic P species changed most dynamically in agricultural clay soils over a period of several decades, and the role of pH in the solubilization of P depended mainly on P fertilization history and the content of reactive Ca phosphates.

Changes in soil phosphorus fractions across a toposequence in the estuary plains of Pakistan

ABSTRACTUnderstanding the regional dynamics of soil phosphorus (P) chemistry is essential for developing the best fertilizer management practices aimed at enhancing P use efficiency in cropping systems. The soil content of apatite, an important P-containing lithogenic mineral, can be influenced by its position in the local relief of a landscape. The objective of this study was to determine quantitative distribution of various P-forms in estuary plains of southern Pakistan in relation to soil genesis. Soils at different positions within the estuary plain were sampled at various genetic horizons. Apatite-P was the most abundant inorganic P constituent (380-590 mg kg−1) in all cases, followed in decreasing abundance by iron oxides surfaces adsorbed phosphorus (Fe-P), octacalcium phosphates (Ca8-P), aluminum oxides with surface bound P (Al-P) and the least abundant was the phosphorus occluded in iron oxides mineral (Occl-P). The abundance of apatite-P and these other forms of secondary phosphate varied for the soils at different relief positions in these estuary plain landscapes.

Preliminary validation of a sequential fractionation method to study phosphorus chemistry in a calcareous soil

A sequential fractionation method proposed by Jiang and Gu (1989) distinguished three types of calcium phosphates (Ca-P) according to their different plant availabilities. Three extractants, NaHCO3, NH4Ac, and H2SO4 were used to extract Ca2-P, Ca8-P, and Ca10-P types, respectively, from soil. This sequential fractionation method was tested and modified for analyzing the P chemistry of a calcareous soil. The solubility test and the model diagrams of the stability of the major Ca-P minerals showed that NaHCO3 was able to extract brushite (Ca2-P type), and NH4Ac extracted brushite and β-tricalcium P (Ca8-P type) as well as hydroxyapatite (Ca10-P type). Therefore the P forms targeted by extraction with NH4Ac should include both Ca8-and Ca10-P types. The sum of the P extracted by all extractants in the sequential fractionation method in the calcareous soil was in agreement with the total P measured by the perchloric acid digestion method. A proportion of organic P measured by the sequential fractionation method was in agreement with the result from solution 31P NMR spectroscopy. This study showed that the modified sequential fractionation method and its target P forms would be useful for quantifying and characterizing inorganic and organic P in a calcareous soil, even though it should be used in combination with other techniques, such as solution 31P NMR spectroscopy.

ChemInform Abstract: Recent Highlights in Mixed‐Coordinate Oligophosphorus Chemistry

AbstractReview: [167 refs.

Low‐Coordinate Phosphorus Chemistry Has Come a Long Way

AbstractEditor Karen Hindson highlights the importance of low‐coordinate phosphorus chemistry and tells the story of this Cluster Issue on the fiftieth anniversary of the synthesis of the first stable low‐coordinate phosphorus compound.

Consuming Ocean Island: Stories of People and Phosphate from Banaba by Katerina Martina Teaiwa

Reviewed by: Consuming Ocean Island: Stories of People and Phosphate from Banaba by Katerina Martina Teaiwa Anne Perez Hattori Consuming Ocean Island: Stories of People and Phosphate from Banaba, by Katerina Martina Teaiwa. Bloomington: Indiana University Press, 2015. isbn cloth, 978-0-253-01444-3; paper, 978-0-253-01452-8; e-book, 978-0-253-01460-3; xvii + 202 pages, notes, bibliography, index. Cloth, us $80.00; paper, us $28.00; e-book, us $27.99. Pacific Islands studies, long the domain of Euro-American writers and researchers, has for decades challenged its practitioners to tell different kinds of stories—localized stories that shed light on the daily lives of its native inhabitants—while at the same time remaining mindful of the global contexts of these local experiences. How to achieve this, given the dearth of written accounts that convey Islander perspectives, has itself been a topic of thoughtful commentary and lingers as a worthy and worthwhile goal. In Consuming Ocean Island: Stories of People and Phosphate from Banaba, Katerina Martina Teaiwa displays artfully the powerful potential of interdisciplinarity as an approach toward gaining a richer and deeper understanding of Pacific pasts and peoples. She matches her deep digs into the historical archives with a reflexive and reflective care of collected oral testimonies, as well as a nuanced treatment of a variety of films, poems, songs, dances, photographs, and memoirs. A chapter on the chemistry and history of phosphorus perhaps best exemplifies this work’s interdisciplinarity, spanning centuries and continents to reveal an interwoven mix of scientific, agricultural, geological, and cultural issues before firmly grounding the narrative on the two-and-a-half square mile island of Banaba. At the most basic level, Consuming Ocean Island tells the history from 1900 to 1980 of the land and people of Banaba, formerly part of the British Gilbert and Ellice Islands colony and presently within the national boundary of the Republic of Kiribati. Named Ocean Island by early nineteenth-century European voyagers, Banaba was profoundly exploited by Australian, New Zealand, and British mining companies for its 22 million tons of phosphate reserves. As an essential ingredient in fertilizer, phosphates played a key role in the success of Australia’s and New Zealand’s agricultural industries, while at the same time their extraction destroyed the land from which they were mined. Teaiwa’s account of Banaban history includes the oft-repeated, almost comical story of a large rock that was being used as a doorstop in the Sydney office of Albert Ellis. An official in the Pacific Islands Company, Ellis and company manager Henry Denson tested the rock in 1899 and found it to be made of pure phosphate. Because the rock had been procured from Nauru, then a German territory beyond the reach of his mining company, Ellis headed out to Banaba, a nearby island, which he thought would be of similar geological formation. Consuming Ocean Island retells the history of Ellis’s Banaba negotiations and of questionable contracts and other egregious misdeeds by colluding mining and colonial officials from Australia, New Zealand, and Great Britain. The forced relocation of Banabans to Rabi after World War II is but briefly described, as are details [End Page 492] of the court cases heard in London, lodged by the Banaban people against the British Empire. The work continues to present-day Rabi, a contested space because of two peoples who call it home—the displaced Banabans and the indigenous Fijian Rabeans who had lost their island in a regional war involving Tongan chief Ma‘afu several decades prior to Banaban settlement there (18). This is a story of the political and corporate machinations that fueled the mining project, a story of lucrative profit making alongside ecological destruction, and cultural resilience and revitalization amid oppressive dispossession and grief. Yet, as Teaiwa notes, much of the earlier scholarship on mining in Banaba reads like a “celebratory account” of the British Phosphate Commissioners, with much less attention given to Pacific Islander actors, particularly after the phosphate supply ran out. While never losing sight of the histories and identities of Banabans, the author also attends to a plethora of other actors and their contributions to the “multiple...

ChemInform Abstract: A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, Arsenic, Antimony and Bismuth

AbstractReview: 100 refs.

Adding a new dimension to the chemistry of phosphorus and arsenic.

The recently discovered phosphorenes are emerging as promising 2D materials for nanoelectronics. Novel structures and topologies can produce new properties and functionalities, and pave the way for potential new applications. For the first time, we predict two novel highly stable free-standing 2D monolayers of P and As with exotic hypercoordination motifs. This is the first hexacoordinate P and planar hexacoordinate As extended sheet. Ab initio calculations and molecular dynamics simulations demonstrate that these new Cu2X (X = P/As) materials are highly stable and are diamagnetic and metallic. Cu2P is slightly buckled without magnetism. For Cu2As, the exactly planar motif is the ground state. We observe an interesting phenomenon, i.e., buckling quenching of the magnetism in a 2D crystal. To our knowledge, this is the first example of buckling quenching of the magnetism in a 2D crystal. These results add a new dimension to the chemistry of phosphorus and arsenic.

Phosphorus in Environmental Technology: Principles and Applications

Phosphorus in Environmental Technology: Principles and Applications, provides a definitive and detailed presentation of state-of-the-art knowledge on the environmental behaviour of phosphorus and its applications to the treatment of waters and soils. Special attention is given to phosphorus removal for recovery technologies, a concept that has emerged over the past 5-6 years. The book features an all-encompassing approach: the fundamental science of phosphorus (chemistry, geochemistry, mineralogy, biology), key aspects of its environmental behaviour and mobility, industrial applications (treatment, removal, recovery) and the principles behind such applications, novel biotechnologies and, importantly, it also addresses socio-economic issues which often influence implementation and the ultimate success of any new technology. A detailed subject index helps the reader to find their way through the different scientific and technological aspects covered, making it an invaluable reference work for students, professionals and consultants dealing with phosphorus-related environmental technologies. State-of-the-art knowledge on the behaviour of phosphorus and its applications to environmental science and technology. Covers all aspects of phosphorus in the environment, engineered and biological systems; an interdisciplinary text.