The reaction of naphthalene with oxalyl chloride in the presence of anhydrous AlCl3 was investigated. The homolog of dinaphthyl methanone can be obtained mainly from this reaction. Naphthalene conversion does not have...The reaction of naphthalene with oxalyl chloride in the presence of anhydrous AlCl3 was investigated. The homolog of dinaphthyl methanone can be obtained mainly from this reaction. Naphthalene conversion does not have evident correlation with the amount of AlCl3. The results show that the reaction proceeds via carbon cation electrophilic substitution reaction-free radical substitution reaction pathway.展开更多
Oxalyl chloride is a highly toxic and caustic substance, which widely exists in human production and life as a kind of volatile organic compound. Based on the density functional theory B3 LYP at 6-311++G(d, p) level, ...Oxalyl chloride is a highly toxic and caustic substance, which widely exists in human production and life as a kind of volatile organic compound. Based on the density functional theory B3 LYP at 6-311++G(d, p) level, the influences of external electric field on the bond length, bond energy, dipole moment and dissociation mechanism are optimized. The results indicate that the C_1–Cl_3 bond length increases while the C_4–Cl_6 bond decreases. At the same time, the carbon-carbon bond length gradually increases with the increase of electric field. The total energy decreases while the dipole moment gradually increases with the increase of electric field. In the infrared spectra, the vibration frequency of the carbon-chlorine(C_4–Cl_6) bond decreases while the vibration frequency of the carbon-oxygen bond increases. In the ultraviolet-visible spectra, the wavelength of the strongest absorption peak increases as the external electric field increases and shows an observable red shift phenomenon. Additionally, single point energies of oxalyl chloride along the carbon-carbon bond are scanned with the equation-of-motion coupled cluster method restricted to single and double excitations(EOM-CCSD) method and the potential energy curves under different external electric fields are obtained. The dissociation barrier in potential energy curve decreases because of the breakage of carbon-carbon bond with the increase of external electric field. These results provide reference for further researches on the properties of oxalyl chloride and offer a theoretical basis for the study of oxalyl chloride degradation.展开更多
A rapid and simple method is presented for determining β-N-oxalyl-α. β- diaminopropionic acid (β -ODAP) and its much less toxic α -isomer (α -ODAP) in Lathyrus sativus. Seed and foliage extracts of Lathyrus sat...A rapid and simple method is presented for determining β-N-oxalyl-α. β- diaminopropionic acid (β -ODAP) and its much less toxic α -isomer (α -ODAP) in Lathyrus sativus. Seed and foliage extracts of Lathyrus sativus were treated with 1-fluoro-2,4-dinitrobenzene (FDNB) and a reversed-phase high-performance liquid chromatographic method for the separation of the derivatives in the pmol range is reported.展开更多
The multi-bond dissociation dynamics of oxalyl bromide ((BrCO)2) has been investigated by DFT and CIS calculations. Upon the results, conclusion could be drawn that dissociation of C-Br bond of oxalyl bromide at t...The multi-bond dissociation dynamics of oxalyl bromide ((BrCO)2) has been investigated by DFT and CIS calculations. Upon the results, conclusion could be drawn that dissociation of C-Br bond of oxalyl bromide at the ground state (So) is of barfierless. After the absorption of a photon, (BrCO)2 is excited to the first excited state and one of its C-Br bonds is broken to yield Br ·* and BrCOCO· * free radicals. In addition, BrCOCO · * with high energy is apt to release energy, and ultimately, turns into BrCOCO ·of the ground state. The energy is adequate for BrCOCO· to break down into Br · and 2CO; at the same time the C-C and C-Br bonds of BrCOCO · free radicals dissociate.展开更多
Background:Tauopathies comprise a family of neurodegenerative disorders including Alzheimer’s disease for which there is an urgent and unmet need for disease-modifying treatments.Tauopathies are characterized by path...Background:Tauopathies comprise a family of neurodegenerative disorders including Alzheimer’s disease for which there is an urgent and unmet need for disease-modifying treatments.Tauopathies are characterized by pathological tau hyperphosphorylation,which has been shown to correlate tightly with disease progression and memory loss in patients suffering from Alzheimer’s disease.We recently demonstrated an essential requirement for 3-O-sulfated heparan sulfate in pathological tau hyperphosphorylation in zebrafish,a prominent model organism for human drug discovery.Here,we investigated whether in vivo treatment with surfen or its derivatives oxalyl surfen and hemisurfen,small molecules with heparan sulfate antagonist properties,could mitigate tau hyperphosphorylation and neuronal deficits in a zebrafish model of tauopathies.Results:In vivo treatment of Tg[HuC::hTau^(P301L);DsRed]embryos for 2 days with surfen or oxalyl surfen significantly reduced the accumulation of the pThr181 tau phospho-epitope measured by ELISA by 30%and 51%,respectively.Western blot analysis also showed a significant decrease of pThr181 and pSer396/pSer404 in embryos treated with surfen or oxalyl surfen.Immunohistochemical analysis further confirmed that treatment with surfen or oxalyl surfen significantly decreased the AT8 tau epitope in spinal motoneurons.In addition,in vivo treatment of Tg[HuC::hTau^(P301L);DsRed]embryos with surfen or oxalyl surfen significantly rescued spinal motoneuron axon-branching defects and,as a likely consequence,the impaired stereotypical touch-evoked escape response.Importantly,treatment with hemisurfen,a surfen derivative devoid of heparan sulfate antagonist activity,does not affect tau hyperphosphorylation,nor neuronal or behavioural deficits in Tg[HuC::hTau^(P301L);DsRed]embryos.Conclusion:Our findings demonstrate for the first time that surfen,a well-tolerated molecule in clinical settings,and its derivative,oxalyl surfen,could mitigate or delay neuronal defects in tauopathies,including Alzheimer’s disease.展开更多
A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The metho...A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The method offers several advantages including high yields of products and performing reaction under solvent-free conditions.展开更多
The multi-bond dissociation dynamics of oxalyl chloride ((ClCO)2) is investigated by ab initio calculation. Dissociation of C-Cl bond of oxalyl chloride in the ground state is of barrierless. After the absorption of a...The multi-bond dissociation dynamics of oxalyl chloride ((ClCO)2) is investigated by ab initio calculation. Dissociation of C-Cl bond of oxalyl chloride in the ground state is of barrierless. After the absorption of a photon, (ClCO)2 is excited to the first excited state and one of its C-Cl bonds is broken to yield Cl and ClCOCO* free radicals. In addition, ClCOCO* with high energy is prone to release energy (Q), and to turn into ClCOCO in the ground state. The energy (Q) is ade-quate for ClCOCO to break down into ClCO and CO, and even for ClCO into Cl and CO. The result is consistent with the experimental data that Kong reported.展开更多
基金Supported by the National Nature Science Foundation of China ( 2 96 76 0 45 )
文摘The reaction of naphthalene with oxalyl chloride in the presence of anhydrous AlCl3 was investigated. The homolog of dinaphthyl methanone can be obtained mainly from this reaction. Naphthalene conversion does not have evident correlation with the amount of AlCl3. The results show that the reaction proceeds via carbon cation electrophilic substitution reaction-free radical substitution reaction pathway.
基金This project was supported by the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province of China(No.18KJA140002)National Natural Science Foundation of China(Nos.11564040,21763027)+1 种基金Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX18_1015)Undergraduate Training Program for Innovation and Entrepreneurship(Nos.201710762008,201710762055)
文摘Oxalyl chloride is a highly toxic and caustic substance, which widely exists in human production and life as a kind of volatile organic compound. Based on the density functional theory B3 LYP at 6-311++G(d, p) level, the influences of external electric field on the bond length, bond energy, dipole moment and dissociation mechanism are optimized. The results indicate that the C_1–Cl_3 bond length increases while the C_4–Cl_6 bond decreases. At the same time, the carbon-carbon bond length gradually increases with the increase of electric field. The total energy decreases while the dipole moment gradually increases with the increase of electric field. In the infrared spectra, the vibration frequency of the carbon-chlorine(C_4–Cl_6) bond decreases while the vibration frequency of the carbon-oxygen bond increases. In the ultraviolet-visible spectra, the wavelength of the strongest absorption peak increases as the external electric field increases and shows an observable red shift phenomenon. Additionally, single point energies of oxalyl chloride along the carbon-carbon bond are scanned with the equation-of-motion coupled cluster method restricted to single and double excitations(EOM-CCSD) method and the potential energy curves under different external electric fields are obtained. The dissociation barrier in potential energy curve decreases because of the breakage of carbon-carbon bond with the increase of external electric field. These results provide reference for further researches on the properties of oxalyl chloride and offer a theoretical basis for the study of oxalyl chloride degradation.
基金Tshe prOject!(39770469) supported by the National Natural Science Foundation of China.
文摘A rapid and simple method is presented for determining β-N-oxalyl-α. β- diaminopropionic acid (β -ODAP) and its much less toxic α -isomer (α -ODAP) in Lathyrus sativus. Seed and foliage extracts of Lathyrus sativus were treated with 1-fluoro-2,4-dinitrobenzene (FDNB) and a reversed-phase high-performance liquid chromatographic method for the separation of the derivatives in the pmol range is reported.
基金This research was financially supported by the Key Laboratory Foundation of Polymer Materials of Gansu Province
文摘The multi-bond dissociation dynamics of oxalyl bromide ((BrCO)2) has been investigated by DFT and CIS calculations. Upon the results, conclusion could be drawn that dissociation of C-Br bond of oxalyl bromide at the ground state (So) is of barfierless. After the absorption of a photon, (BrCO)2 is excited to the first excited state and one of its C-Br bonds is broken to yield Br ·* and BrCOCO· * free radicals. In addition, BrCOCO · * with high energy is apt to release energy, and ultimately, turns into BrCOCO ·of the ground state. The energy is adequate for BrCOCO· to break down into Br · and 2CO; at the same time the C-C and C-Br bonds of BrCOCO · free radicals dissociate.
基金This work was supported by Institut National de la Santéet la Recherche Médicale(INSE RM),the French National Research Agency(ANR-16-CE18–0010)Fondation NRJ(Institut de France)to NSY and grants CA46462 and CA112278 from the National Institute of Health to JDE and YT.
文摘Background:Tauopathies comprise a family of neurodegenerative disorders including Alzheimer’s disease for which there is an urgent and unmet need for disease-modifying treatments.Tauopathies are characterized by pathological tau hyperphosphorylation,which has been shown to correlate tightly with disease progression and memory loss in patients suffering from Alzheimer’s disease.We recently demonstrated an essential requirement for 3-O-sulfated heparan sulfate in pathological tau hyperphosphorylation in zebrafish,a prominent model organism for human drug discovery.Here,we investigated whether in vivo treatment with surfen or its derivatives oxalyl surfen and hemisurfen,small molecules with heparan sulfate antagonist properties,could mitigate tau hyperphosphorylation and neuronal deficits in a zebrafish model of tauopathies.Results:In vivo treatment of Tg[HuC::hTau^(P301L);DsRed]embryos for 2 days with surfen or oxalyl surfen significantly reduced the accumulation of the pThr181 tau phospho-epitope measured by ELISA by 30%and 51%,respectively.Western blot analysis also showed a significant decrease of pThr181 and pSer396/pSer404 in embryos treated with surfen or oxalyl surfen.Immunohistochemical analysis further confirmed that treatment with surfen or oxalyl surfen significantly decreased the AT8 tau epitope in spinal motoneurons.In addition,in vivo treatment of Tg[HuC::hTau^(P301L);DsRed]embryos with surfen or oxalyl surfen significantly rescued spinal motoneuron axon-branching defects and,as a likely consequence,the impaired stereotypical touch-evoked escape response.Importantly,treatment with hemisurfen,a surfen derivative devoid of heparan sulfate antagonist activity,does not affect tau hyperphosphorylation,nor neuronal or behavioural deficits in Tg[HuC::hTau^(P301L);DsRed]embryos.Conclusion:Our findings demonstrate for the first time that surfen,a well-tolerated molecule in clinical settings,and its derivative,oxalyl surfen,could mitigate or delay neuronal defects in tauopathies,including Alzheimer’s disease.
文摘A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The method offers several advantages including high yields of products and performing reaction under solvent-free conditions.
基金The authors would like to thank professor Fang D. C. for his helpful discussion. This work was supported by the National Natural Science Foundation of China (Grant No. 29713007).
文摘The multi-bond dissociation dynamics of oxalyl chloride ((ClCO)2) is investigated by ab initio calculation. Dissociation of C-Cl bond of oxalyl chloride in the ground state is of barrierless. After the absorption of a photon, (ClCO)2 is excited to the first excited state and one of its C-Cl bonds is broken to yield Cl and ClCOCO* free radicals. In addition, ClCOCO* with high energy is prone to release energy (Q), and to turn into ClCOCO in the ground state. The energy (Q) is ade-quate for ClCOCO to break down into ClCO and CO, and even for ClCO into Cl and CO. The result is consistent with the experimental data that Kong reported.