Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostat...Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostate cancer cell line PC-3, and showed potent inhibiting activity at low micromolar concentrations (with an IC50 of approximately 45 μM).展开更多
A series of novel L-amino acid esters prodrugs of acyclic nucleoside phosphonates was synthesized and their anti-HBV activity was evaluated in HepG2 2.2.15 cells. Compound 1d exhibited more potent anti-HBV activity an...A series of novel L-amino acid esters prodrugs of acyclic nucleoside phosphonates was synthesized and their anti-HBV activity was evaluated in HepG2 2.2.15 cells. Compound 1d exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil with EC50 and CC50 values of 0.207 μmol/L and 2530 μmol/L, respectively.展开更多
Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyc...Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyclopropyl)methyl)phosphonate and various amines in the presence of Hunig’s base. Upon biological activity screening these compounds demonstrated encouraging anti-pancreatic cancer properties at low micromolar concentrations.展开更多
The doping of functionalized graphene oxide(GO)in the membranes becomes a promising method for improving the performance of high-temperature proton exchange membrane fuel cells(HT-PEMFC).Phosphonated graphene oxide(PG...The doping of functionalized graphene oxide(GO)in the membranes becomes a promising method for improving the performance of high-temperature proton exchange membrane fuel cells(HT-PEMFC).Phosphonated graphene oxide(PGO)with a P/O ratio of 8.5%was quickly synthesised by one-step electrochemical exfoliation based on a three-dimensiaonal(3D)printed reactor and natural graphite flakes.Compared with the GO prepared by the two-step electrochemical exfoliation method,the PGO synthesized by the one-step electrochemical exfoliation can better improve the performance of the membrane-electrode-assembly(MEA)based on the polybenzimidazole(PBI)membrane in the HTPEMFC.The doping of 1.5 wt%GO synthesised by electrochemical exfoliation with the 2-step method or reactor method in PBI increased the peak power density by 17.4%or 35.4%compared to MEA based on pure PBI membrane at 150℃,respectively.In addition,the doping of PGO in PBI improves its durability under accelerated stress test(AST).展开更多
A series of new type of germasesquioxides. germatranes, and β-trichlorogermylpropionic acid derivatives containing a-tmino group or a-aminophosphonyl group were synthesized by a convenient condensation reaction of ...A series of new type of germasesquioxides. germatranes, and β-trichlorogermylpropionic acid derivatives containing a-tmino group or a-aminophosphonyl group were synthesized by a convenient condensation reaction of β-trichlorogermyl propionyl chloride with a-amino acid esters or a-phosphonates in the presense of organic base. The mectures of products were detethened by 1HNMR 31PNMR MS, elemental analysis' and X-ray diffraction.展开更多
A novel organophosphorus compound containing the structure of bothβ-amino acid andβ-aminophosphonate is designed and synthesized.Arbuzov reaction with P(OEt)_3,the N-Boc protected iodide 3 cannot provide the desir...A novel organophosphorus compound containing the structure of bothβ-amino acid andβ-aminophosphonate is designed and synthesized.Arbuzov reaction with P(OEt)_3,the N-Boc protected iodide 3 cannot provide the desired product but 2-oxazolidinone 4 because of the neighboring-group participation of the Boc moiety.To avoid the intramolecular participation of the carbamates,the Ts protecting group is employed and the Ts-protected iodide 5 affords the target product successfully.展开更多
In this study, a series of flame-retardant polyisocyanurate-polyurethane (PIR-PUR) foams were prepared using various concentrations (0-25% by weight) of expandable graphite (EG) and dimethyl methyl phosphonate (DMMP) ...In this study, a series of flame-retardant polyisocyanurate-polyurethane (PIR-PUR) foams were prepared using various concentrations (0-25% by weight) of expandable graphite (EG) and dimethyl methyl phosphonate (DMMP) (0-7% by weight). The effect of these additives on the properties of the PIR-PUR foams, including physico-mechanical, morphological, flame retardancy, and thermal stability, was studied. Increasing amounts of EG in the PIR-PUR foam caused a significant drop in the compression strength. However, DMMP caused the mechanical properties of PIR-PUR foam to improve compared to foam filled with EG alone. The flame retardancy of PIR-PUR foams containing both EG and DMMP was enhanced significantly compared to EG filled foams. Thermogravimetric analysis (TGA) indicated that EG enhances the thermal stability of PIR-PUR foams but that DMMP decreased it. The morphology of the residual char provided conclusive evidence for the weak thermal stability of foams filled with DMMP.展开更多
The development of high-efficiency and low-cost catalysts is very crucial for the MeerweinPonndorf-Verley (MPV) reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF). In this ...The development of high-efficiency and low-cost catalysts is very crucial for the MeerweinPonndorf-Verley (MPV) reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF). In this work, an amorphous and mesoporous zirconium phosphonate catalyst (Zr-DTMP), which is a zirconium-containing organic-inorganic nanohybrid, was successfully designed and synthesized by the simple assembly of zirconium tetrachloride (ZrCl4) and diethylene triaminepenta(methylene phosphonic acid)(DTMP). Satisfactorily, when Zr-DTMP was employed for the MPV reduction of HMF in the presence of 2-butanol (secBuOH), DHMF yield could be achieved as 96.5% in 3 h under a relatively mild reaction temperature of 140℃. Systematic investigations indicated that this high catalytic activity should be mainly due to the cooperative role of enhancive Lewis acid site (Zr4+) and Lewis base site (O2-) in activating the carbonyl group of HMF and dissociating the hydroxyl group of secBuOH, respectively. Additionally, Zr-DTMP showed excellent catalytic stability, when it was successively used 5 recycles, its surface characteristics and textural properties still remained almost unchanged, and so, the catalytic activity was not obviously affected. More interestingly, Zr-DTMP could also be applied for the selective reduction of other biomass-derived carbonyl compounds, such as 5-methylfurfural (MF), furfural (FF), levulinic acid (LA), ethyl levulinate (EL) and cyclohexanone (CHN), into the corresponding products with high yields, which is beneficial to the effective synthesis of various valuable bio-based chemicals.展开更多
A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1?-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform...A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1?-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra(FTIR), circular dichroism(CD) and thermogravimetric analyses(TGA). Two neighboring Mn ions are linked by two carboxylate groups and one phosphate group to form a di-manganese unit [Mn2] and each [Mn2] cluster in 1 is linked by five ligands, generating a 3D network with fns topology. In addition, the photoluminescence properties of 1 and H4 L were investigated.展开更多
A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yie...A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylene phosphonate) oligomers is over 85% by using hexadecyltrimethylammoniun bromide as phase transfer catalyst (PTC) at 0 'C . The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270 °C and the resulting polymer had a Mw, of 8 × 103 with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.展开更多
The present study focuses on the evaluation of the potential applicability of Ultra Stable Y(USY) and phosphonated USY(1 wt%-4 wt%phosphorous loading) as heterogeneous catalysts for biodiesel(methyl acetate) pro...The present study focuses on the evaluation of the potential applicability of Ultra Stable Y(USY) and phosphonated USY(1 wt%-4 wt%phosphorous loading) as heterogeneous catalysts for biodiesel(methyl acetate) production.The synthesized catalysts were characterized by powder X-ray diffraction(XRD),Brunaer-Emmett-Teller(BET) surface area,total acidity by temperature-programmed desorption of ammonia(TPD-NH3) and Fourier Transform Infrared(FTIR) spectra.The performances of catalysts were evaluated for the transesterification of butyl acetate with methanol(a model reaction in biodiesel production).In view to obtain a maximum yield of methyl acetate,the optimization of process parameters such as reactant molar ratio,catalyst loading,reaction temperature and reaction time was performed.All the phosphonated USY catalysts showed higher catalytic activity than the parent USY,which can be attributed to the increase of total acidity due to phosphonation.2 wt% P/USY(2% phosphorous loaded on USY) exhibited 92% methyl acetate yield with 100% selectivity,which was proved to be a potential catalyst for biodiesel production.The invented catalyst was found to be stable and reusable for five catalytic cycles,demonstrating that it might be a environmentally benign catalytic process.展开更多
Two novel transition metal phosphonate compounds, [Co(H2BDPP)(phen)]n 1 (BDPP = p-O3PCH2(C6H4)CH2PO3, phen = 1,10-phenanthroline) and [Pb3(BCP)2]n 2 (BCP = OOC(C6H4)CH2PO3), have been synthesized and str...Two novel transition metal phosphonate compounds, [Co(H2BDPP)(phen)]n 1 (BDPP = p-O3PCH2(C6H4)CH2PO3, phen = 1,10-phenanthroline) and [Pb3(BCP)2]n 2 (BCP = OOC(C6H4)CH2PO3), have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169(4), b = 12.001(2), c = 7.6211(15)A, β = 98.03(3)°, V= 1917.2(6)A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F(000) = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections (I 〉 2σ(I). Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167(9), b = 18.753(2), c = 22.781(3)A, β = 91.07(3)°, V= 2014.7(14)A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F(000) = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections (I 〉 2σ(I). In compound 1, the 1D chain running along the c axis is bridged by four ligands (trans- HO3PCH2C6H4CH2PO3H) in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb(II) displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb(II) cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered (LC) transition.展开更多
The extraction of Eu(Ⅲ) with β-diketone, HA, and monodentate or bidentate Lewis bases, B, into chloroform and the luminescence properties of the extracted species were studied. Pivaloyltrifluoroacetone, Hpta, and ...The extraction of Eu(Ⅲ) with β-diketone, HA, and monodentate or bidentate Lewis bases, B, into chloroform and the luminescence properties of the extracted species were studied. Pivaloyltrifluoroacetone, Hpta, and 2-thenoyltfifluoroacetone, Htta, were used as the β-diketones. The Lewis bases, B, were tetraethyl methylene diphosphonate, POPO, which was bidentate, and diethyl benzylphosphonate, PhPO which was monodentate. Based on the extraction data, the stability constants, log β, of the first complexes between tfis(β-diketonato)Eu(Ⅲ) and the phosphonate, EuA3B, were determined to be 6.0 for the POPO complex and 3.40 for the PhPO complex. The Eu(Ⅲ) luminescence intensity in the EuA3POPO was larger than EuA3 where A was either pta or tta at similar concentrations of Eu(Ⅲ), while that in Eu(pta)3PhPO was stronger than EuA3; however, in Eu(tta)3PhPO, it was weaker than Eu(tta)3. The POPO functions as a sensitizer, and the PhPO functions as a quencher for the tta chelate and as a sensitizer for the pta chelate. From the lifetime and quantum yield, φ, of the Eu(Ⅲ) luminescence in the complexes as well as the observation of the extractability of Eu(Ⅲ) with the Hpta and the phosphonates and of the luminescence spectra of the complexes, it was confirmed that the extraction of Eu(Ⅲ) was remarkably enhanced with a β-diketonate and a strong Lewis base, and also the ternary complex that was formed as the extracted species, showed luminescence enhancement. This phenomenon may be due the formation of a strong bond between the Eu(Ⅲ) and the strong Lewis base leading to more hydrophobicity in the extracted species and also to more effective energy transfer from the Lewis base to the Eu(Ⅲ). It was not significant whether the donor atoms were N or O.展开更多
A new crystal of 2-methylpropan-2-aminium methyl ((4-fluorobenzamido)(4- fluorophenyl)methyl)phosphonate has been prepared at room temperature and characterized by ZH- NMR, 13C NMR, IR, MS, elemental analysis an...A new crystal of 2-methylpropan-2-aminium methyl ((4-fluorobenzamido)(4- fluorophenyl)methyl)phosphonate has been prepared at room temperature and characterized by ZH- NMR, 13C NMR, IR, MS, elemental analysis and X-ray single-crystal determination. The compound crystallizes in monoclinic space, group C2/c with a = 20.719(2), b = 11.8559(13), c = 18.176(2) A,β = 94.434(2)°, V= 4451.4(9) A3, Dc = 1.317 Mg/m3, Z= 8, F(000) = 1864 and μ= 0.174 mm-1. The crystal packing is stabilized by intermolecular N-H……O and O-H……O hydrogen bonds, as well as by weak π-π stacking interactions.展开更多
A new crystal of O,Oˊ-dipropyl-α-(2,4-dichlorolphenoxyacylamido)-α-(4-methoxyphenyl) methylphosphonates has been prepared at room temperature and characterized by elemental analysis and IR,MS,1H NMR spectra,13C...A new crystal of O,Oˊ-dipropyl-α-(2,4-dichlorolphenoxyacylamido)-α-(4-methoxyphenyl) methylphosphonates has been prepared at room temperature and characterized by elemental analysis and IR,MS,1H NMR spectra,13C NMR spectra and X-ray single-crystal determination.The complex crystallizes in triclinic,space group P1 with a = 7.858(2),b = 12.621(4),c = 12.621(4),α = 96.17(3),β = 90.960(3),γ = 90.960(3)°,V = 1243.9(7)3,Dc = 1.346 Mg/m3,Z = 2,μ = 0.362 mm-1and F(000) = 528.展开更多
Metal organophosphonates have been explored in energy-related fields due to their high chemical and thermal stability as a type of uniformly precursor,but only few of pristine metal organophosphonate are directly used...Metal organophosphonates have been explored in energy-related fields due to their high chemical and thermal stability as a type of uniformly precursor,but only few of pristine metal organophosphonate are directly used for oxygen evolution reaction(OER)catalysts.Here,a mixedvalence iron phosphonate(Fe_(3)-ppat)has been constructed and applied to OER catalysis considered the potential active sites in pillars Fe^(Ⅱ)(-H_(2)O)_(4)(COO)_(2)and inorganic layers Fe^(Ⅲ)(μ_(2)–OH)PO_(3).Specifically,isostructural trimetallic framework Fe_(1.7)Co_(0.3)Ni_(1.0)-ppat possesses a minimum overpotential(291 mV),small Tafel slope(91.65 mV dec^(-1)),and high stability up to 83 h.The enhanced catalytic performance could be mainly ascribed to the synergistic effect of Ni^(Ⅱ)equivalent occupancy in pillars and Co/Fe^(Ⅲ)in layers.展开更多
Titanium phosphonate adsorbent materials with hierarchically porous structure were fabricated using the hydrolysis of tetrabutyl titanate in different organophosphonic acids solutions. Based on the macroporous structu...Titanium phosphonate adsorbent materials with hierarchically porous structure were fabricated using the hydrolysis of tetrabutyl titanate in different organophosphonic acids solutions. Based on the macroporous structure of 100-2000 nm in size, a worm-hole like mesostructure was in the macropore walls, which was supported by the scanning electron microscopy(SEM), transmission electron microscopy(TEM), and N2 sorption analysis. Fourier transform infrared spectroscopy(FT-IR) data indicated the organic groups inside the solid materials framework. NH3 adsorption detection was performed using titanium phosphonate adsorbent materials and some significant results were obtained. The adsorption mechanism was also discussed in this study. Large adsorption amount(75.2 mg/g) was mainly attributed to the acid site via acid-base reactions and the physical adsorption site via Van der Waals forces. Resultant materials could effectively restrain the desorption of adsorbent NH3 back into air causing secondary pollution, so it could make a promising potential use in decontamination of gas pollutants in the future.展开更多
Theoretical insights elucidate a series of active phosphonate esters application in preparation of Cephalosporin antibiotics’ intermediate. The B3LYP/6-311+G(d,p) method was employed to obtain the stable equilibrium ...Theoretical insights elucidate a series of active phosphonate esters application in preparation of Cephalosporin antibiotics’ intermediate. The B3LYP/6-311+G(d,p) method was employed to obtain the stable equilibrium geometries including comparing to the AE-active ester. It was found that the Ethyl-aminothiazoly Loximate (AT) molecule fragment is almost planar sheet, but it is almost perpendicular to the plane of phosphoryl ester. Moreover, the calculated Mulliken atomic charge distribution and frontier molecular orbital analysis of these esters showed that the amino N atom connected to the Thiazole ring of the AT had the maximum negative charge, which suggested that this area had high molecular activity. The value of ΔEL-H was energy gap between EHOMO and ELUMO and indicated that compound 6a had high reaction activity. The theory calculation results can explain the reaction mechanism well and predict that the novel active phosphonate ester has a hopeful application prospect in preparation of Cephalosporin antibiotics’ intermediate.展开更多
文摘Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostate cancer cell line PC-3, and showed potent inhibiting activity at low micromolar concentrations (with an IC50 of approximately 45 μM).
文摘A series of novel L-amino acid esters prodrugs of acyclic nucleoside phosphonates was synthesized and their anti-HBV activity was evaluated in HepG2 2.2.15 cells. Compound 1d exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil with EC50 and CC50 values of 0.207 μmol/L and 2530 μmol/L, respectively.
文摘Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyclopropyl)methyl)phosphonate and various amines in the presence of Hunig’s base. Upon biological activity screening these compounds demonstrated encouraging anti-pancreatic cancer properties at low micromolar concentrations.
基金financially supported by the UK Research Council EPSRC EP/009050/1。
文摘The doping of functionalized graphene oxide(GO)in the membranes becomes a promising method for improving the performance of high-temperature proton exchange membrane fuel cells(HT-PEMFC).Phosphonated graphene oxide(PGO)with a P/O ratio of 8.5%was quickly synthesised by one-step electrochemical exfoliation based on a three-dimensiaonal(3D)printed reactor and natural graphite flakes.Compared with the GO prepared by the two-step electrochemical exfoliation method,the PGO synthesized by the one-step electrochemical exfoliation can better improve the performance of the membrane-electrode-assembly(MEA)based on the polybenzimidazole(PBI)membrane in the HTPEMFC.The doping of 1.5 wt%GO synthesised by electrochemical exfoliation with the 2-step method or reactor method in PBI increased the peak power density by 17.4%or 35.4%compared to MEA based on pure PBI membrane at 150℃,respectively.In addition,the doping of PGO in PBI improves its durability under accelerated stress test(AST).
文摘A series of new type of germasesquioxides. germatranes, and β-trichlorogermylpropionic acid derivatives containing a-tmino group or a-aminophosphonyl group were synthesized by a convenient condensation reaction of β-trichlorogermyl propionyl chloride with a-amino acid esters or a-phosphonates in the presense of organic base. The mectures of products were detethened by 1HNMR 31PNMR MS, elemental analysis' and X-ray diffraction.
文摘A novel organophosphorus compound containing the structure of bothβ-amino acid andβ-aminophosphonate is designed and synthesized.Arbuzov reaction with P(OEt)_3,the N-Boc protected iodide 3 cannot provide the desired product but 2-oxazolidinone 4 because of the neighboring-group participation of the Boc moiety.To avoid the intramolecular participation of the carbamates,the Ts protecting group is employed and the Ts-protected iodide 5 affords the target product successfully.
基金supported by the State Key Program of Coal Joint Funds of National Natural Science Foundation of China (No.51134020)the Natural Science Foundation of Shandong Province(No. ZR2011EL036)the High School Science & Technology Fund Planning Project of Shandong Province (No. JIILD53)
文摘In this study, a series of flame-retardant polyisocyanurate-polyurethane (PIR-PUR) foams were prepared using various concentrations (0-25% by weight) of expandable graphite (EG) and dimethyl methyl phosphonate (DMMP) (0-7% by weight). The effect of these additives on the properties of the PIR-PUR foams, including physico-mechanical, morphological, flame retardancy, and thermal stability, was studied. Increasing amounts of EG in the PIR-PUR foam caused a significant drop in the compression strength. However, DMMP caused the mechanical properties of PIR-PUR foam to improve compared to foam filled with EG alone. The flame retardancy of PIR-PUR foams containing both EG and DMMP was enhanced significantly compared to EG filled foams. Thermogravimetric analysis (TGA) indicated that EG enhances the thermal stability of PIR-PUR foams but that DMMP decreased it. The morphology of the residual char provided conclusive evidence for the weak thermal stability of foams filled with DMMP.
基金financially supported by the National Natural Science Foundation of China (21506071)the Special Foundation of Jiangsu Collaborative Innovation Center of Regional Modern Agriculture and Environmental Protection (HSXT2-316)
文摘The development of high-efficiency and low-cost catalysts is very crucial for the MeerweinPonndorf-Verley (MPV) reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF). In this work, an amorphous and mesoporous zirconium phosphonate catalyst (Zr-DTMP), which is a zirconium-containing organic-inorganic nanohybrid, was successfully designed and synthesized by the simple assembly of zirconium tetrachloride (ZrCl4) and diethylene triaminepenta(methylene phosphonic acid)(DTMP). Satisfactorily, when Zr-DTMP was employed for the MPV reduction of HMF in the presence of 2-butanol (secBuOH), DHMF yield could be achieved as 96.5% in 3 h under a relatively mild reaction temperature of 140℃. Systematic investigations indicated that this high catalytic activity should be mainly due to the cooperative role of enhancive Lewis acid site (Zr4+) and Lewis base site (O2-) in activating the carbonyl group of HMF and dissociating the hydroxyl group of secBuOH, respectively. Additionally, Zr-DTMP showed excellent catalytic stability, when it was successively used 5 recycles, its surface characteristics and textural properties still remained almost unchanged, and so, the catalytic activity was not obviously affected. More interestingly, Zr-DTMP could also be applied for the selective reduction of other biomass-derived carbonyl compounds, such as 5-methylfurfural (MF), furfural (FF), levulinic acid (LA), ethyl levulinate (EL) and cyclohexanone (CHN), into the corresponding products with high yields, which is beneficial to the effective synthesis of various valuable bio-based chemicals.
基金Supported by NSFC(No.21431004,21522104 and 21620102001)“973”Program(No.2014CB932102 and 2016YFA0203400)+1 种基金the Shanghai“Eastern Scholar”Program SSTC-14YF1401300the Key Project of Basic Research of Shanghai(17JC1403100)
文摘A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1?-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra(FTIR), circular dichroism(CD) and thermogravimetric analyses(TGA). Two neighboring Mn ions are linked by two carboxylate groups and one phosphate group to form a di-manganese unit [Mn2] and each [Mn2] cluster in 1 is linked by five ligands, generating a 3D network with fns topology. In addition, the photoluminescence properties of 1 and H4 L were investigated.
基金This project was supported by the National Natural Science Foundation of China (No. 20084001).
文摘A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylene phosphonate) oligomers is over 85% by using hexadecyltrimethylammoniun bromide as phase transfer catalyst (PTC) at 0 'C . The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270 °C and the resulting polymer had a Mw, of 8 × 103 with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.
文摘The present study focuses on the evaluation of the potential applicability of Ultra Stable Y(USY) and phosphonated USY(1 wt%-4 wt%phosphorous loading) as heterogeneous catalysts for biodiesel(methyl acetate) production.The synthesized catalysts were characterized by powder X-ray diffraction(XRD),Brunaer-Emmett-Teller(BET) surface area,total acidity by temperature-programmed desorption of ammonia(TPD-NH3) and Fourier Transform Infrared(FTIR) spectra.The performances of catalysts were evaluated for the transesterification of butyl acetate with methanol(a model reaction in biodiesel production).In view to obtain a maximum yield of methyl acetate,the optimization of process parameters such as reactant molar ratio,catalyst loading,reaction temperature and reaction time was performed.All the phosphonated USY catalysts showed higher catalytic activity than the parent USY,which can be attributed to the increase of total acidity due to phosphonation.2 wt% P/USY(2% phosphorous loaded on USY) exhibited 92% methyl acetate yield with 100% selectivity,which was proved to be a potential catalyst for biodiesel production.The invented catalyst was found to be stable and reusable for five catalytic cycles,demonstrating that it might be a environmentally benign catalytic process.
基金supported by the State Key Laboratory of Structural Chemistry, National Natural Science Foundation of China (20873021)the Young Talent Programmed of Fujian Province (No. 2006F3072)
文摘Two novel transition metal phosphonate compounds, [Co(H2BDPP)(phen)]n 1 (BDPP = p-O3PCH2(C6H4)CH2PO3, phen = 1,10-phenanthroline) and [Pb3(BCP)2]n 2 (BCP = OOC(C6H4)CH2PO3), have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169(4), b = 12.001(2), c = 7.6211(15)A, β = 98.03(3)°, V= 1917.2(6)A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F(000) = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections (I 〉 2σ(I). Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167(9), b = 18.753(2), c = 22.781(3)A, β = 91.07(3)°, V= 2014.7(14)A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F(000) = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections (I 〉 2σ(I). In compound 1, the 1D chain running along the c axis is bridged by four ligands (trans- HO3PCH2C6H4CH2PO3H) in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb(II) displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb(II) cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered (LC) transition.
基金a Grant-in-Aid for Scientific Research(C), (No19550096) from the Ministry of Education, Science, Sports, and Culture, Japan
文摘The extraction of Eu(Ⅲ) with β-diketone, HA, and monodentate or bidentate Lewis bases, B, into chloroform and the luminescence properties of the extracted species were studied. Pivaloyltrifluoroacetone, Hpta, and 2-thenoyltfifluoroacetone, Htta, were used as the β-diketones. The Lewis bases, B, were tetraethyl methylene diphosphonate, POPO, which was bidentate, and diethyl benzylphosphonate, PhPO which was monodentate. Based on the extraction data, the stability constants, log β, of the first complexes between tfis(β-diketonato)Eu(Ⅲ) and the phosphonate, EuA3B, were determined to be 6.0 for the POPO complex and 3.40 for the PhPO complex. The Eu(Ⅲ) luminescence intensity in the EuA3POPO was larger than EuA3 where A was either pta or tta at similar concentrations of Eu(Ⅲ), while that in Eu(pta)3PhPO was stronger than EuA3; however, in Eu(tta)3PhPO, it was weaker than Eu(tta)3. The POPO functions as a sensitizer, and the PhPO functions as a quencher for the tta chelate and as a sensitizer for the pta chelate. From the lifetime and quantum yield, φ, of the Eu(Ⅲ) luminescence in the complexes as well as the observation of the extractability of Eu(Ⅲ) with the Hpta and the phosphonates and of the luminescence spectra of the complexes, it was confirmed that the extraction of Eu(Ⅲ) was remarkably enhanced with a β-diketonate and a strong Lewis base, and also the ternary complex that was formed as the extracted species, showed luminescence enhancement. This phenomenon may be due the formation of a strong bond between the Eu(Ⅲ) and the strong Lewis base leading to more hydrophobicity in the extracted species and also to more effective energy transfer from the Lewis base to the Eu(Ⅲ). It was not significant whether the donor atoms were N or O.
基金supported by the National Basic Research Program of China(2010CB126100)the National Natural Science Foundation of China(21002037 and 21172090)The research was supported in part by the PCSIRT(No.IRT0953)
文摘A new crystal of 2-methylpropan-2-aminium methyl ((4-fluorobenzamido)(4- fluorophenyl)methyl)phosphonate has been prepared at room temperature and characterized by ZH- NMR, 13C NMR, IR, MS, elemental analysis and X-ray single-crystal determination. The compound crystallizes in monoclinic space, group C2/c with a = 20.719(2), b = 11.8559(13), c = 18.176(2) A,β = 94.434(2)°, V= 4451.4(9) A3, Dc = 1.317 Mg/m3, Z= 8, F(000) = 1864 and μ= 0.174 mm-1. The crystal packing is stabilized by intermolecular N-H……O and O-H……O hydrogen bonds, as well as by weak π-π stacking interactions.
基金supported by the National Basic Research Program of China(2010CB126100)
文摘A new crystal of O,Oˊ-dipropyl-α-(2,4-dichlorolphenoxyacylamido)-α-(4-methoxyphenyl) methylphosphonates has been prepared at room temperature and characterized by elemental analysis and IR,MS,1H NMR spectra,13C NMR spectra and X-ray single-crystal determination.The complex crystallizes in triclinic,space group P1 with a = 7.858(2),b = 12.621(4),c = 12.621(4),α = 96.17(3),β = 90.960(3),γ = 90.960(3)°,V = 1243.9(7)3,Dc = 1.346 Mg/m3,Z = 2,μ = 0.362 mm-1and F(000) = 528.
基金supported by the National Natural Science Foundation of China(NSFC 21871167)the National Natural Science Fund for Young Scholars of China(NSFC 21201114)+2 种基金the 1331 Engineering of Shanxi ProvinceScientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2019L0464)Shanxi Province Science Foundation for Youths(201901D211391)。
文摘Metal organophosphonates have been explored in energy-related fields due to their high chemical and thermal stability as a type of uniformly precursor,but only few of pristine metal organophosphonate are directly used for oxygen evolution reaction(OER)catalysts.Here,a mixedvalence iron phosphonate(Fe_(3)-ppat)has been constructed and applied to OER catalysis considered the potential active sites in pillars Fe^(Ⅱ)(-H_(2)O)_(4)(COO)_(2)and inorganic layers Fe^(Ⅲ)(μ_(2)–OH)PO_(3).Specifically,isostructural trimetallic framework Fe_(1.7)Co_(0.3)Ni_(1.0)-ppat possesses a minimum overpotential(291 mV),small Tafel slope(91.65 mV dec^(-1)),and high stability up to 83 h.The enhanced catalytic performance could be mainly ascribed to the synergistic effect of Ni^(Ⅱ)equivalent occupancy in pillars and Co/Fe^(Ⅲ)in layers.
基金Funded by the National Science&Technology Pillar Program during the Twelfth Five-year Plan Period(2011BAK03B07)the Specialized Research Fund for the Technology Research Program of Ministry of Public Security(2014JSYJA024)the Specialized Research Fund for the Applications Innovation Program of Ministry of Public Security(2011YYCXWJXY131)
文摘Titanium phosphonate adsorbent materials with hierarchically porous structure were fabricated using the hydrolysis of tetrabutyl titanate in different organophosphonic acids solutions. Based on the macroporous structure of 100-2000 nm in size, a worm-hole like mesostructure was in the macropore walls, which was supported by the scanning electron microscopy(SEM), transmission electron microscopy(TEM), and N2 sorption analysis. Fourier transform infrared spectroscopy(FT-IR) data indicated the organic groups inside the solid materials framework. NH3 adsorption detection was performed using titanium phosphonate adsorbent materials and some significant results were obtained. The adsorption mechanism was also discussed in this study. Large adsorption amount(75.2 mg/g) was mainly attributed to the acid site via acid-base reactions and the physical adsorption site via Van der Waals forces. Resultant materials could effectively restrain the desorption of adsorbent NH3 back into air causing secondary pollution, so it could make a promising potential use in decontamination of gas pollutants in the future.
文摘Theoretical insights elucidate a series of active phosphonate esters application in preparation of Cephalosporin antibiotics’ intermediate. The B3LYP/6-311+G(d,p) method was employed to obtain the stable equilibrium geometries including comparing to the AE-active ester. It was found that the Ethyl-aminothiazoly Loximate (AT) molecule fragment is almost planar sheet, but it is almost perpendicular to the plane of phosphoryl ester. Moreover, the calculated Mulliken atomic charge distribution and frontier molecular orbital analysis of these esters showed that the amino N atom connected to the Thiazole ring of the AT had the maximum negative charge, which suggested that this area had high molecular activity. The value of ΔEL-H was energy gap between EHOMO and ELUMO and indicated that compound 6a had high reaction activity. The theory calculation results can explain the reaction mechanism well and predict that the novel active phosphonate ester has a hopeful application prospect in preparation of Cephalosporin antibiotics’ intermediate.