86119-84-8Relevant articles and documents
Regulating Higher-Order Organization through the Synergy of Two Self-Sorted Assemblies
Ji, Wei,Zhang, Shijin,Yukawa, Sachie,Onomura, Shogo,Sasaki, Toshio,Miyazawa, Kun'ichi,Zhang, Ye
, p. 3636 - 3640 (2018)
The extracellular matrix (ECM) is the natural fibrous scaffold that regulates cell behavior in a hierarchical manner. By mimicking the dynamic and reciprocal interactions between ECM and cells, higher-order molecular self-assembly (SA), mediated through the dynamic growth of scaffold-like nanostructures assembled by different molecular components, was developed. Designed and synthesized were two self-sorted coumarin-based gelators, a peptide molecule and a benzoate molecule, which self-assemble into nanofibers and nanobelts, respectively, with different dynamic profiles. Upon the dynamic growth of the fibrous scaffold assembled from peptide gelators, nanobelts assembled from benzoate gelators transform into a layer-by-layer nanosheet, reaching ninefold increase in height. By using light and an enzyme, the spatial–temporal growth of the scaffold can be modified, leading to in situ height regulation of the higher-order architecture.
Catalytic Photochemical Dehydrogenation of Organic Substrates by Polyoxometalates
Hill, Craig L.,Bouchard, Donald A.
, p. 5148 - 5157 (1985)
The photochemical behavior of the polyoxometalates based on W, Mo, V, Nb, and Ta in the presence of water or one of a variety of organic substrates including alcohols, amides, ethers, aldehydes, carboxylic acids, nitriles, ketones, and ureas is examined.Irradiation of the charge-transfer bands of polyoxometalates dissolved in organic media at 25 deg C leads in most cases to the oxidation of the organic substrate and reduction of the polyoxometalate.The polyoxometalates fall into three categories defined by their thermal and photochemical redox chemistry in the presence of organic substrates.Type I complexes exemplified by those of Nb and Ta do not appear to photooxidize any organic substrate upon iradiation.Type II complexes, exemplified by decavanadate and most heteropoly- and isopolymolybdates, and type III complexes, exemplified by most heteropoly- and isopolytungstates, do oxidize a wide range of organic substrates upon irradiation.Reoxidation of the reduced forms of the type II complexes either by reaction with O2 or by evolution of H2 is kinetically or thermodynamically unfavorable; reoxidation of the reduced forms of the type III complexes either by reaction with O2 or by evolution of H2 is not.Several factors affecting the quantum yields for production of reduced polyoxometalates are outlined, and the energetic features regarding hydrogen evolution are discussed.The infrared, electronic, 31P NMR, 183W NMR, and 17O NMR spectral properties of α-H3PW12O40*6H2O, 1, and other polyoxometalates remain the same before and after catalytic photochemical dehydrogenation of representative alcohol, ether, or amide substrates.These results indicate that little if any polyoxometalate decomposition occurs during the photoredox chemistry.Interactions between organic substrates and polyoxometalates have profound effects on the electronic structure of the polyoxometalates.The charge-transfer transitions of polyoxometalate 1 display different sensitivities to medium in the low-energy (λ>300 nm) vs. the high-energy region of the ultraviolet-visible spectral range.The highest sensitivities of the quantum yields for photoredox chemistry involving organic substrates and 1 to medium are observed in the low-energy or absorption tail region of the spectrum.One possible model explaining the wavelength dependence of the absorption and photochemical action spectra is discussed.A general mechanism in agreement with all the experimental data is proposed for organic substrate oxidation and the effective capture of light energy in these polyoxometalate-organic substrate systems.
Efficient hydrolytic cleavage of phosphodiester with a lanthanide-based metal-organic framework
Dong, Yunhui,Dou, Yong,Qin, Lan,Yang, Lu,Zhang, Daopeng,Zhou, Zhen
, (2020/11/09)
Hydrolysis of phosphate diesters has attracted substantial research efforts, not only in bio-organic chemistry, but also in inorganic chemistry. Herein, a lanthanide-based metal-organic framework was synthesized by incorporating a tetraphenylethylene moiety as the four-point connected node, Ce-TCPE (noted as 1). The structural analyses indicate that 1 exhibits 3D framework connected by the sharing carboxylate groups with two kinds of 1D rhombic channels when viewed along the c direction. Hydrolytic cleavage catalysis have been performed and showed that 1 could act as efficient heterogeneous catalyst for the hydrolytic cleavage of the phosphodiester BNPP (bis(p-nitrophenyl)phosphate) with the high activity and hydrolytic stability in a pseudo-first-order rate. DFT studies has also gain an insight analysis to elucidate the cleavage process.
Hydrolysis of element (White) phosphorus under the action of heterometallic cubane-type cluster {mo3pds4}
Babaev, Vasily M.,Gushchin, Artem L.,Khayarov, Khasan R.,Kuchkaev, Aidar M.,Kuchkaev, Airat M.,Shmelev, Nikita Y.,Sinyashin, Oleg G.,Sokolov, Maxim N.,Sukhov, Aleksandr V.,Yakhvarov, Dmitry G.
, (2021/05/28)
Reaction of heterometallic cubane-type cluster complexes—[Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6, [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl and [Mo3{Pd(dba)}S4/s
Synthesis, Stability, and Kinetics of Hydrogen Sulfide Release of Dithiophosphates
Bowden, Ned B.,Brown, Eric M.,Paudel, Arjun,Ranasinghe Arachchige, Nimesh P. R.
, p. 12900 - 12908 (2021/11/17)
The development of chemicals to slowly release hydrogen sulfide would aid the survival of plants under environmental stressors as well as increase harvest yields. We report a series of dialkyldithiophosphates and disulfidedithiophosphates that slowly degrade to release hydrogen sulfide in the presence of water. Kinetics of the degradation of these chemicals were obtained at 85 °C and room temperature, and it was shown that the identity of the alkyl or sulfide group had a large impact on the rate of hydrolysis, and the rate constant varied by more than 104×. For example, using tert-butanol as the nucleophile yielded a dithiophosphate (8) that hydrolyzed 13,750× faster than the dithiophosphate synthesized from n-butanol (1), indicating that the rate of hydrolysis is structure-dependent. The rates of hydrolysis at 85 °C varied from a low value of 6.9 × 10-4 h-1 to a high value of 14.1 h-1. Hydrogen sulfide release in water was also quantified using a hydrogen sulfide-sensitive electrode. Corn was grown on an industrial scale and dosed with dibutyldithiophosphate to show that these dithiophosphates have potential applications in agriculture. At a loading of 2 kg per acre, a 6.4% increase in the harvest yield of corn was observed.
Synthesis, crystal structure, IR, Raman spectroscopy, and DFT computation of metacarboxyphenyl ammonium dihydrogenomonophosphate (C7H4NH3OOH) H2PO4(m-C AMP)
Belaaouad, Said,Chtita, Samir,El Makhloufy, Smail,Majdi, El Mehdi
, (2021/08/12)
The metacarboxyphenyl ammonium dihydrogenomonophosphate (C7H4NH3OOH) H2PO4 was synthesized and studied by a combination of single-crystal X-ray diffraction analysis, infrared, Raman vibrational spectroscopy, and density functional computation (DFT) calculation. This compound crystallizes in the monoclinic system, with the central space group P21/c. Its unit-cell dimensions are a = 12.9361 (7) (?), b = 11.7735 (6) (?), c = 6.5764 (4) (?), β = 102.668° (2), and V = 977.22 (9) ?3.The structure determined gives a clear description of the hydrogen bonds connecting the hydrogen phosphate H2PO4– with the organic matrix. The atomic arrangement of this compound is built up by symmetric (H4P2O8)2– dimers anions formed by two (H2PO4)– via hydrogen bonding O1—H…O3. Each (H2PO4)– aggregates with cation through hydrogen bond interactions of O–H…O(P) and N–H…O(P) types. The bands observed in the infrared and Raman spectra of (C7H4NH3OOH) H2PO4 are assigned based on the results obtained in the literature and based on the computational group analyses performed in the factor group C2h. Besides, the optimal molecular geometry, harmonic vibration frequencies, infrared intensities, and Raman scattering activities were calculated using the DFT approach performed with the Gaussian 09 program using the hybrid function B3LYP combining the three Becke parameters and the Lee-Yang-Parr exchange-correlation function using the 6-311 + G(d,p) base set. The highest occupied molecular orbital–lowest unoccupied molecular orbital properties and geometries of this compound were determined and discussed. The results of the calculated structural parameters are generally in agreement with the experimental investigations. The computational infrared and Raman spectra of the reference compound have been constructed.
Tunable pH-sensitive 2-carboxybenzyl phosphoramidate cleavable linkers
Backer, Brian S.,Berkman, Clifford E.,Browne, Zachery S.,Choy, Cindy J.,Davis, Austen L.
supporting information, (2020/02/15)
We previously described a pH-sensitive phosphoramidate linker scaffold that can be tuned to release amine-containing drugs at various pH values. In these previous studies it was determined that the tunability of this linker was dependent upon the proximity of an acidic group (e.g., carboxylic acid or pyridinium). In this study, we confirmed that the tunability of pH-triggered amine-release was also dependent upon the pKa of the proximal acidic group. A series of 2-carboxybenzyl phosphoramidates was prepared in which the pKa of the proximal benzoic acid was predictably attenuated by substituents on the benzoate ring consistent with their σ-values.
PROCESS FOR RECOVERING PHOSPHORIC ACID FROM SOLID PHOSPHORUS SOURCES
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Page/Page column 10-12; 14-17, (2020/09/08)
The invention pertains to a process for preparing phosphoric acid from a solid phosphorus-containing material, comprising the steps of: - reacting a solid phosphorus-containing material with strong acid in an amount of 1.0-15 mole acid, calculated as protons, per mole of phosphorus (calculated as P) in the solid phosphorus-containing material in a monophasic reaction medium comprising an organic solvent, to form a solution of phosphoric acid in organic solvent and remaining solid material, - separating the solution of phosphoric acid in organic solvent from the remaining solid material. It has been found that phosphoric acid can be recovered from a solid phosphorus-containing material in high purity and efficiency via a solid-state rearrangement/elution process. The process according to the invention does not require the use of the large amounts of water required by the conventional dissolution/extraction processes known in the art. The solution of phosphoric acid in organic solvent can be used as a starting material for further processes.
Degradation of tri(2-chloroisopropyl) phosphate by the UV/H2O2 system: Kinetics, mechanisms and toxicity evaluation
He, Huan,Ji, Qiuyi,Gao, Zhanqi,Yang, Shaogui,Sun, Cheng,Li, Shiyin,Zhang, Limin
, (2019/07/31)
A photodegradation technology based on the combination of ultraviolet radiation with H2O2 (UV/H2O2) for degrading tri(chloroisopropyl) phosphate (TCPP) was developed. In ultrapure water, a pseudo-first order reaction was observed, and the degradation rate constant reached 0.0035 min?1 (R2 = 0.9871) for 5 mg L?1 TCPP using 250 W UV light irradiation with 50 mg L?1 H2O2. In detail, the yield rates of Cl? and PO43? reached 0.19 mg L?1 and 0.58 mg L?1, respectively. The total organic carbon (TOC) removal rate was 43.02%. The pH value of the TCPP solution after the reaction was 3.46. The mass spectrometric detection data showed a partial transformation of TCPP into a series of hydroxylated and dechlorinated products. Based on the luminescent bacteria experimental data, the toxicity of TCPP products increased obviously as the reaction proceeded. In conclusion, degradation of high concentration TCPP in UV/H2O2 systems may result in more toxic substances, but its potential application for real wastewater is promising in the future after appropriate optimization, domestication and evaluation.
Mechanism of methylphosphonic acid photo-degradation based on phosphate oxygen isotopes and density functional theory
Xia, Congcong,Geng, Huanhuan,Li, Xiaobao,Zhang, Yiyue,Wang, Fei,Tang, Xiaowen,Blake,Li, Hui,Chang, Sae Jung,Yu, Chan
, p. 31325 - 31332 (2019/10/19)
Methylphosphonic acid (MPn) is an intermediate in the synthesis of the phosphorus-containing nerve agents, such as sarin and VX, and a biosynthesis product of marine microbes with ramifications to global climate change and eutrophication. Here, we applied the multi-labeled water isotope probing (MLWIP) approach to investigate the C-P bond cleavage mechanism of MPn under UV irradiation and density functional theory (DFT) to simulate the photo-oxidation reaction process involving reactive oxygen species (ROS). The results contrasted with those of the addition of the ROS-quenching compounds, 2-propanol and NaN3. The degradation kinetics results indicated that the extent of MPn degradation was more under alkaline conditions and that the degradation process was more rapid at the initial stage of the reaction. The phosphate oxygen isotope data confirmed that one exogenous oxygen atom was incorporated into the product orthophosphate (PO4) following the C-P bond cleavage, and the oxygen isotopic composition of this free PO4 was found to vary with pH. The combined results of the ROS-quenching experiments and DFT indicate that the C-P bond was cleaved by OH-/OH and not by other reactive oxygen species. Based on these results, we have established a mechanistic model for the photolysis of MPn, which provides new insights into the fate of MPn and other phosphonate/organophosphate compounds in the environment.
