CP Bond Research Articles

Features of electronic structure of (<i>η</i>⁵-C₅H₅)LuCl₂(THF)₃

For the first time, a topological analysis of the electron density distribution function in a crystal for an organolanthanide compound was carried out using the CpLuCl₂(THF)₃ complex as an example. The charges on atoms were determined. A predominantly ionic nature of the Lu–ligand bond was confirmed, but the essentially covalent nature of the Lu–Cp bond was discovered. The energies of the Lu–ligand bonds were determined.

Artificial light-harvesting system with sequential energy transfer in photocatalytic C[sbnd]P coupling based on supramolecular organic framework of triphenylamine

Porous structures exhibit an increased access surface area, thereby promoting the efficient transportation of active oxygen species. Reinforcing the development of artificial light-harvesting systems (LHSs) with porous structured supramolecular organic frameworks (SOFs) as the energy donor can significantly enhance its photocatalytic performance, thereby facilitating efficient organic transformation via photocatalysis. In this investigation, we have successfully fabricated a supramolecular organic framework (MT-SOF) composed of cucurbit[8]uril (CB[8]) and triphenylamine derivative (MeTPPA). Because of the framework structure and large ring restriction in MT-SOF, its fluorescence emission shows a significant increase when compared to that of the individual MeTPPA molecule. By harnessing the remarkable fluorescence emission characteristics of MT-SOF, it was employed as an energy donor in conjunction with Sulforhodamine 101 (SR101) and Cyanine 5 (Cy5) as acceptors to fabricate sequential energy transfer LHS. MT-SOF-SR101-Cy5 has the ability to act as a photosensitizer, facilitating the CP bond coupling with broad applicability. It is important to mention that when compared to MeTPPA, MT-SOF and MT-SOF-SR101, the photocatalytic performance of MT-SOF-SR101-Cy5, featuring continuous two-step energy transfer, shows significant improvement, which can be attributed to the porous structure of MT-SOF and the increased efficiency in generating superoxide anion radical (O2−)

Effect of nitrogen on the electrical properties and growth mechanism of phosphorus-doped diamonds

De‑nitrogen-doped phosphorus and nitrogen‑phosphorus co-doped diamond single crystals were synthesized using the high pressure and high-temperature (HPHT) method at 6.0 GPa and 1450–1510 °C. The synthesis process was catalyzed using Fe80Ni20 as the catalyst of choice. The optical, mechanical, and electrical properties of the crystals were characterized. The effect of nitrogen atoms inside the diamond on a phosphorus-doped diamond was explored. The color of the diamond gradually became lighter with increasing Ti content, while the color of the crystal changed from yellow to dark green with increasing NaN3 content, and a large number of growth stripes and pits appeared on the surface. The infrared test showed that the addition of Ti reduced the concentration of nitrogen atoms inside the diamond, and the concentration of nitrogen atoms gradually increased with the addition of NaN3. Raman tests showed that the addition of Ti and NaN3 negatively affected the crystal quality. The X-ray photoelectron spectroscopy showed that phosphorus was successfully introduced into the diamond lattice in the form of CP and PO bonds under the conditions of nitrogen removal and nitrogen doping. Electrical tests showed that an n-type semiconducting diamond was successfully synthesized. However, the increase in nitrogen negatively affected the n-type conductivity.

Thermolysis of Ru3(CO)10(µ-dppp): A new Ru4- cluster derived from 1,3-bis(diphenylphosphino)propane

The reaction of Ru3(CO)12 and dppp [dppp = 1,3-bis(diphenylphosphino)propane/Ph2P(CH2)3PPh2] in the presence of benzophenone ketyl radical anion afforded [Ru3(CO)11]2(µ-dppp) (1) Ru3(CO)10(µ-dppp) (2), Ru3(CO)9(µ-dppp)(ƞ1-dppp) (3) and Ru3(CO)8(µ-dppp)2 (4). Refluxing 2 in octane yields new triruthenium clusters Ru3(CO)9(μ3-PPh(CH2)3PPh(C6H4)) (5) and Ru4(CO)9(µ-CO){µ4-η2-P(CH2)3PPh2}(µ4-η4-C6H4) (6), as a result of CH and CP bond activation involving the Ph2P(CH2)3PPh2 ligand. Compounds 2 and 6 have been structurally determined by the single crystal X-ray diffraction. As expected, the Ph2PCH2CH2CH2PPh2 ligand in 2 is equatorially bonded to Ru–Ru bond in µ2-η2 mode. In contrast, the X-ray structure of 6 shows an µ4-η2-PCH2CH2CH2PPh2 and a benzyne group coordinated to a square of Ru atoms. A rotation of benzyne group on a square of Ru atoms was supported by variable temperature NMR studies. The topological analysis was performed on 6 to further elucidate their chemical bond properties.

Full carbon upcycling of organophosphorus wastewater enabled by interface photolysis

The key of wastewater treatment is to reduce the toxicity of organic pollutants and ideally undergo mineralization, typically accompanying the formation of greenhouse gas CO2 in large amounts. Here, a full carbon upcycling strategy for efficient valorization of organic phosphorus (OPs) contaminants enabled by interface photolysis was developed, in which the van der Waals interface effect based on the interfacial heterojunction interaction could efficiently regulate the electron density of the UCN/CdS NPs photocatalyst interface to benefit the construction of the interface-orienteering electron pump and edge active sites. The synergistic catalysis of ·OH on the C sites and holes on the Cd sites at the photocatalyst interface edge could realize the complete photodegradation of glyphosate wastewater in 2 h to exclusively afford gas fuel CO (4124 μmol g−1) and glycine (86 %), which was likewise applicable to an extensive scope of OPs for nigh quantitative carbon upcycling. Quantum calculations elaborated that the Cd edge sites with the ability to enrich holes induced by the van der Waals interface effect could reduce the activation energy of CP bond cleavage of glyphosate activated by ·OH, resulting in CP bond scission selectivity of ca. 91.5 %, which is vital to full carbon upcycling. The oriented interface engineering offers a more eco-friendly photocatalytic protocol to facilitate both wastewater treatment and carbon resource recovery.

Dipeptide-catalysed Michael reaction under physiological conditions: Examination of potential bioorthogonality

Reactions for drug synthesis under cell-like conditions or even inside living cells can potentially be used e.g., to minimize toxic side effects, to maximize bioactive compound efficacy and/or to address drug delivery problems. Those reactions should be bioorthogonal to enable the generation of drug-like compounds with sufficiently good yields. In the known bioorthogonal Michael reactions, using thiols and phosphines as nucleophiles (e.g., in CS and CP bond formation reactions) is very common. No bioorthogonal Michael addition with a carbon nucleophile is known yet. Therefore, the development of such a reaction might be interesting for future drug discovery research. In this work, the metal-free Michael addition between cyclohexanone and various trans-β-nitrostyrenes (CC bond formation reaction), catalysed by a dipeptide salt H-Pro-Phe-O-Na+, was investigated for the first time in the presence of glutathione (GSH) and in phosphate-buffered saline (PBS). We demonstrated that with electron-withdrawing substituents on the aromatic ring and in β-position of the trans-β-nitrostyrene yields up to 64% can be obtained under physiological conditions, indicating a potential bioorthogonality of the studied Michael reaction. In addition, the selected Michael products demonstrated activity against human ovarian cancer cells A2780. This study opens up a new vista for forming bioactive compounds via CC bond formation Michael reactions under physiological (cell-like) conditions.

Efficient degradation and detoxification of antibiotic Fosfomycin by UV irradiation in the presence of persulfate

Fosfomycin (FOS) as a widely used antibiotic has been found in abundance throughout the environment, but little effort has been devoted to its treatment. In this study, we systemically looked into the degradation of FOS by ultraviolet-activated persulfate (UV/PS) in aqueous solutions. Our findings demonstrated that FOS can be degraded efficiently under the UV/PS, e.g., >90 % of FOS was degraded with 19,200 mJ cm−2 of UV irradiance and 20 μM of PS. HO was the dominant radical responsible for FOS degradation. FOS degradation increased as PS dosage increased, and higher degradation efficiency was observed at neutral pH. Natural water constitutes either promoted (e.g., Cu2+, Fe3+, and SO42−) or inhibited (e.g., humic acid, HCO3−, and CO32−) FOS degradation to varying degrees. Hydroxyl substitution, CP bond cleavage, and coupling reactions were the major degradation pathways for FOS degradation. Finally, the toxicity evaluation revealed that FOS was toxic to E. coli and S. aureus, but the toxicity of the intermediate products of FOS to E. coli and S. aureus rapidly decreased over time after UV/PS treatment. Therefore, these findings provided a fundamental understanding of the transformation process of FOS and supplied useful information for the environmental elimination of FOS contamination and its toxicity.

3-Ferrocenyl-estra-1,3,5 (10)-triene-17-one: Synthesis, Crystal Structure, Hirshfeld Surface Analysis, DFT Studies, and Its Binding to Human Serum Albumin Studied through Fluorescence Quenching and In Silico Docking Studies.

3-ferrocenyl-estra-1,3,5 (10)-triene-17-one (2), [Fe(C5H5)(C24H25O3)], crystallizes in the monoclinic space group C2. The cyclopentadienyl (Cp) rings adopt a nearly eclipsed conformation, and the Cp plane is tilted by 87.66° with respect to the substituted phenyl plane. An average Fe-C(Cp) bond length of 2.040(13) Å was determined, similar to the one reported for ferrocene. Hirshfeld surfaces and two-dimensional fingerprint plots were generated to analyze weak intermolecular C-H···π and C-H···O interactions. Density functional theory studies revealed a 1.15 kcal/mol rotational barrier for the C3-O1 single bound. Fluorescence quenching studies and in silico docking studies suggest that human serum albumin forms a complex with 2 via a static mechanism dominated by van der Waals interactions and hydrogen bonding interactions.

Chemical mechanical polishing for potassium dihydrogen phosphate using four kinds of green developed slurries

Due to the soft-brittle, deliquescent, and temperature-sensitive nature, potassium dihydrogen phosphate (KDP) has become one of the most difficult-to-process materials. Nonetheless, high-performance devices strictly require the surface roughness of KDP less than 1 nm, which is a great challenge for the ultraprecision machining field. To overcome this challenge, four kinds of green slurries were developed. For instance, ceria and graphene oxide were selected as abrasives, sodium carboxymethylcellulose was used as thickener, fatty alcohol-polyoxyethylene ether was employed as emulgator, sodium carbonate was proposed as a pH regulator, and tiny water was applied to dissolving agent. Four kinds of various base solutions, such as corn oil, glycol, polyethylene glycol and glycerol, form four varieties of green slurries for the chemical mechanical polishing (CMP) of KDP. After CMP, the surface roughness Sa is 0.562 nm with a scanning area of 50 × 50 μm2, using the glycol slurry. Until now, to the best of our knowledge, this is the lowest surface roughness at a such large measurement area. X-ray photoelectron spectroscopy and infrared Fourier transformation confirm that CP bonds were generated between graphene oxide and KDP, resulting in the breaking away of H2PO4− from KDP. A soft layer was produced by the tiny water. CO32− reacts with H2PO4−, forming CO2 gas and protecting the concave area on the surface of KDP. The soft layer was removed by the synergistic effect among abrasives, thickener and a polishing pad. The developed green slurries suggest new insights to achieve sub-nanometer surfaces on KDP with uniquely physical nature, for the potential use in laser systems.

Holistic and parametric optimization study on Cr(VI) removal using acid-treated coco peat biochar adsorbent

This study presents the use of H3PO4 surface-modified coco peat biochar (PSMCB), as an effective adsorbent to remove Cr (VI) from aqueous and real systems. Microstructure and adsorption mechanisms were analysed via pre- and post-adsorption characterization techniques, with experimental results demonstrating PSMCB capacities of 122.5 mg/g and 149.25 mg/g in batch and column studies, respectively. XPS analysis revealed the significant contribution of PO, CP, and CO bonds to the adsorption of Cr (VI), with reduction, complexation, and electrostatic interaction influencing the adsorption process. The removal efficiency of PSMCB in binary, ternary, and real systems exceeded 90 %. PSMCB was found stable upto 4 cycles, with a maximum desorption of 97.4 %. Spent biochar was successfully demonstrated as an effective bio-fertilizer. Cost analysis revealed that PSMCB is highly cost-effective (Rs 164.7 INR/kg or 2.03 USD/kg) indicating that it has a great promise for industrial applications.

Insight into the mechanism and toxicity assessment of a novel Co3O4/BiOBr p-n heterojunction driven by sunlight for efficient degradation of glyphosate

The environmental stresses posed by glyphosate, an organic phosphorus herbicide with inert CP and CN bonds, necessitate its effective degradation. Herein, we present a novel p-type Co3O4/n-type BiOBr heterojunction (COBB) photocatalyst as an efficient solution for this challenge. Owing to the built-in electric field as well as the synergistic matching band potentials of the p-Co3O4 and n-BiOBr, the COBB considerably enhances the separation efficiency and transfer rates of photogenerated carriers. As a result, it displays remarkable activity in degrading 16.9 mg/L of glyphosate under simulated sunlight with 88.5 % efficiency, outperforming both the pure Co3O4 and BiOBr by 51.8 and 3.3 times, respectively. In addition, COBB also demonstrates promising performance under natural sunlight and maintains a high level of stability in four cycles. Furthermore, intermediate product and toxicity analyses illustrate that the toxicity of glyphosate is greatly reduced in the COBB system. Altogether, this study provides renewed opportunities for the use of heterojunction photocatalysts in natural environments.

Microbial biotransformation mechanisms of PFPiAs in soil unveiled by metagenomic analysis

As alternatives of long-chain PFASs (Poly- and perfluoroalkyl substances), perfluoroalkyl phosphinic acids (PFPiAs) are increasingly observed in the environment, but their environmental behaviors have not been well understood. Here, the microbial biotransformation of C6/C6 and C8/C8 PFPiA in two soils (Soil N and Y) was investigated. After 252 d and 330 d of incubation with PFPiAs in Soil N and Y respectively, the levels of PFPiAs decreased distinctly, accompanied by the increasing perfluorohexaphosphonic acid (PFHxPA) or perfluorooctanophosphonic acid (PFOPA) formation, magnifying PFPiAs were susceptible to C-P cleavage, which was also confirmed by the density functional theory calculations. The half-lives of the PFPiAs were longer than one year, while generally shorter in Soil N than in Soil Y and that of C6/C6 was shorter than C8/C8 PFPiA (392 d and 746 d in Soil N, and 603 and 1155 d in Soil Y, respectively). Metagenomic sequencing analysis revealed that Proteobacteria as the primary host of the potential functional genes related to CP bond cleavage might be the crucial phyla contributing to the biotransformation of PFPiAs. Meanwhile, the more intensive interactions between the microbes in Soil N consistently contribute to its greater capacity for transforming PFPiAs.

Возможная роль представителей кишечного микробиома в биотрансформации арил-, пиридилсодержащих фосфинов и их производных (по данным спектроскопии ЯМР 31Р)

Organophosphorus compounds (OPCs) are used in many areas of human activity. Unique physicochemical properties and high biological activity not only determine the applied value of OPCs but also give them the properties of xenobiotics that are harmful to human health, which largely depend on the state of the endogenous microbiota. The purpose of this work is to assess the effect of pyridyl- and aryl-containing phosphines, their oxides, and sulfides on the growth of Bifidobacterium bifidum and Escherichia coli and to identify possible patterns of biotransformation of OPCs using 31P NMR spectroscopy. Bacteria were cultivated in thioglycollate medium containing the tested phosphorus compounds. At the stationary growth phase was determined the cell concentration and were recorded spectra 31P NMR. It was shown that the most reliable (p<0,05) and opposite effect on the growth dynamics of both species of bacteria was exhibited by phosphine sulfides 1 and 3: PS1 (pyridyl) reduced the population reproduction rate by 35–40%, and PS3 (aryl) increased it by 45–60%. At the same time, OPCs themselves were most likely not metabolized. Phosphine oxides reduced the average titer of bacteria compared to the control, and PO3 caused complete cell elimination after 24 hours cultivation. In the medium with PO2 was identified PS2 appeared, which may be caused by the biologically mediated process of oxide-to-sulfide conversion. All phosphines are chemically labile and they were oxidized abiotically to oxides and sulfides. Formed sulfides could be the reason for a significant increase (to 35%) in the growth rate bacteria population both species. Five new unidentified organophosphorus compounds (UPC) were recorded on medias with B. bifidum, some of which may belong to the products of biotransformation of the original OPCs. Some organic phosphates, homologous to the phosphine oxides tested, have a δp value neighboring to the taken NMR spectra. This may indicate the way of their biological transformation: oxidation of the CP bond in the phosphine oxides to an ester bond of organic phosphates. This ability of bifidobacteria to metabolize OPCs will make it possible to develop a therapeutic strategy based on the use of B. bifidum as a microorganism that degrades phosphorus-containing xenobiotics.

The effects of doped phosphorus on the electrochemical performance of hard carbon anode for lithium ion capacitors

Heteroatom is a practical tactic to improve the ability of carbon materials to store lithium ions. In this research, a series of hard carbon with different phosphorus species and contents were simply prepared by annealing the mixture of phytic acid and starch. By studying the phosphorus functional groups species and electrochemical performance of phosphorus-doped carbon, the relation of phosphorus species, phosphorus atoms contents and the Li-storage performance of samples have been closely related. In this context, the high content of phosphorus atoms not means a high specific capacity and the phosphorus-doped hard carbon will produce a higher specific capacity when the doping content of phosphorus atoms ranges around 1.8 %. As to the effect of phosphorus functional groups species on the electrochemical performance of hard carbon, the Li-ions may be stored more efficiently with the higher proportion of CP bonds in phosphorus functional groups species. In this regard, the understanding of how phosphorus functional groups species affect electrochemical performance on hard carbon will help better understand the effect of phosphorus doping on hard carbon anode for lithium ion storage. Meanwhile, it also will provide some insights and support for the application of phosphorus-doped electrodes.

Enhancing flame retardant property of graphene oxide via phosphorus and nitrogen co-doping

A simple and versatile method has been developed to efficiently enhance the flame retardant of graphene oxide (GO) by adding ammonium phosphate (AP) into GO. The as-made GO/AP exhibits excellent flame retardant properties, which emits some smoke at the beginning without catching any fire and any observable shrinkage. In contrast, the GO catches fire within several seconds and completely burns out. The improvement of flame retardancy can be attributed to the formation of CP and CN bonds with heat. This simple and effective technique of the introduction of P and N can be adopted for inexpensive mass production of GO/AP for many practical applications such as sensors, energy-storing materials, and nanomaterial electronics.

Electrochemical functionalization at anodic conditions of multi-walled carbon nanotubes with chlorodiphenylphosphine

Covalent functionalization of multi-walled carbon nanotubes (MWCNTs) and oxidized MWCNTs (o-MWCNTs) with chlorodiphenylphosphine (Ph2PCl) has been studied by cyclic voltammetry in organic medium. Depending the upper potential limit used in the electrochemical functionalization, different amount of phosphorus incorporation n is obtained, as result of the formation of radical species during the electrochemical oxidation of the Ph2PCl. The electrochemical oxidation of Ph2PCl promotes the covalent attachment of diphenylphosphine-like structure on the carbon nanotube surface. At the same time, the incorporation of Cl on the carbon nanotubes is observed during the functionalization. Furthermore, the presence of oxygen surface groups on the MWCNTs provides a favorable attachment of the Ph2P∙+ species, which has promoted preferentially the formation of CP bonds, whereas the amount of Cl is reduced.

Flower-like composites of black phosphorus and reduced graphene oxide: Its synergistic energy storage performance

Composite of black phosphorus and graphene is a promising energy storage material and rarely used in supercapacitor. Here, composites of black phosphorus and reduced graphene oxide (BP/rGO) were prepared by solvothermal method and oil bath method for contrast, respectively. BP/rGO prepared by solvothermal method (S-BP/rGO) shows block morphology with thickness of 20 μm. BP/rGO prepared by oil bath method (O-BP/rGO) shows flower-like morphology with BP quantum dots evenly dispersed on rGO flakes. O-BP/rGO has a better energy storage performance with specific capacitance of 143 F/g at 1 A/g, and a retention rate of 96.8% after 10,000 cycles. The flower-like structure allows for efficient charge storage and the CP bond between BP and graphene can enhance ion transport, which results in synergistic energy storage performance.

Enhancing fluorescence and lowering the optical gap through C[dbnd]P doping of a [formula omitted]-conjugated molecular backbone: A computational-based design approach

Design principles of organic fluorescent materials are investigated at the molecular level using a first-principles-based computational approach. The design approach incorporates hetero atoms into a conjugated cyclic skeleton by introducing CP bonds. In particular we report the design of a molecular system of an extended conjugation system that maintains its planarity across the full system, achieving low lying electronic excited states of large oscillator strengths. We also present calculations that confirm the competing process of internal system crossing to be too slow for affecting the actual relaxation following photexcitation.

New Trends in the Development of C-P Bond Forming Reactions

This account reviews some innovative (“non-classical”) synthetic strategies for the formation of CP bonds developed during the last decades. It provides examples of the most important milestones in this field, highlighting the state-of-art of functional phosphoruscontaining molecules. Among these are the direct functionalization of organic substrates through chlorine-free reactions with elemental phosphorus, syntheses based on phosphinidene (RP) transfer, phosphorylating methodology employing multiple bonds containing P(III) compounds, reactions with stable heterocyclic carbenes, and synthetic approaches using phosphaethynolate and bis(trichlorosilyl)phosphide salts.

Ultraviolet photodissociation of gas-phase transition metal complexes: dicarbonylcyclopentadienyliodoiron(II)

The ultraviolet photodissociation of the prototypical organometallic half-sandwich compound dicarbonylcyclopentadienyliodoiron(II) [η 5-CpFe(CO)2I] has been studied in the gas phase across the wavelength range 260 ≤ λ ≤ 310 nm using multi-mass velocity-map ion imaging with photoproducts detected using both resonance enhanced multiphoton and vacuum ultraviolet (λ = 118.2 nm) single photon ionisation methods. Ion images recorded for the atomic iodine and the cyclopentadienyl photoproducts reveal fast, anisotropic components to their recoil velocity distributions. The experimental work is supported by multi-reference (spin–orbit averaged) electronic structure calculations that suffice to illustrate the high electronic state density in such transition metal complexes and provide insights into the rival fragmentation dynamics. The ground state parent molecule has singlet spin multiplicity, but the product energy disposal measured following Fe–Cp bond fission shows the involvement of nominally spin-forbidden transitions. The Fe–I and Fe–Cp bond fissions should both be viewed as homolytic and occurring on excited state potentials that are dissociative in the relevant ligand elimination coordinate.