N-亚硝基吲哚系列化合物及其自由基负离子在乙腈介质中N—NO键断裂能的测定

利用滴定量热技术并结合适当的热力学循环测定了乙腈溶液中7个取代的N-亚硝基吲哚化合物中N—NO键的异裂能和均裂能,能量范围分别为206.1～246.2 kJ/mol和119.1～124.6 kJ/mol.表明N-亚硝基吲哚均裂释放NO自由基（NO.）比异裂释放NO正离子（NO^＋）要容易得多,通过热力学循环得到的相应自由基负离子中N—NO键的异裂能和均裂能的能量范围分别为25.5～34.4和5.0～40.5 kJ/mol,表明所研究化合物的自由基负离子在室温下很不稳定.

S-亚硝基-N-乙酰基-D,L-青霉胺二肽分子中S—NO键断裂能的测定

利用滴定量热技术并结合适当的热力学循环测定了乙腈溶液中7个S-亚硝基-N-乙酰基-D，L-青霉胺二肽化合物中S—NO键的异裂能和均裂能，其能量范围分别为234．5～246．2kJ／mol和101．6～122．1kJ/mol. 结果表明，所研究的亚硝基硫醇化合物更容易通过S—NO键的均裂释放NO自由基（NO）．通过热力学循环对7个亚硝基硫醇化合物自由基负离子中S—NO键的异裂能和均裂能进行估算，能量范围分别为19．2～35．5kJ／mol和～4．2～22．6kJ／mol，表明这些自由基负离子在室温下不稳定，容易通过S—NO键的异裂释放出NO^-．

基于平均影响值的反向传播神经网络方法用于提高密度泛函理论计算Y-NO键均裂能精度

将基于平均影响值(Mean impact value,MIV)的反向传播神经网络(Back propagation neural netowrk,BPNN)(MIV-BPNN)方法用于提高密度泛函理论(Density functional theory,DFT)计算Y—NO(Y=N,S,O及C)键均裂能的精度.利用量子化学计算和MIV-BPNN联合方法计算92个含Y—NO键的有机分子体系的均裂能.结果表明,相对于单一的密度泛函理论B3LYP/6-31G(d)方法,利用全参数下的BPNN方法计算92个有机分子均裂能的均方根误差从22.25 kJ/mol减少到1.84 kJ/mol,而MIV-BPNN方法使均方根误差减少到1.36 kJ/mol,可见B3LYP/6-31G(d)和MIV-BPNN联合方法可以提高均裂能的量子化学计算精度,并可预测实验上无法获取的均裂能值.

乙腈溶液中亚硝酸苄(醇)酯系列化合物NO化学亲和势的测定

There is an increasing interest for the study of NO affinity of organic nitrite,for the biological and physiological effects of organic nitrites seem to be due to their ability releasing NO.In this paper,NO chemical affinities of ten benzyl nitrites were determined respectively by titration calorimetry and from a thermodynamic cycle in acetonitrile solution.The results show that ΔHhet of O—NO in the O-nitroso compounds were substantially larger than the corresponding ΔHhomo of O—NO in the same compounds,suggesting that these O-nitroso compounds were much easier release NO radical by the O—NO bond homolytic cleavage.It is believed that the structural and energetic information disclosed in this work should be useful in understanding chemical and biological functions of organic nitrites.