光谱学与光谱分析
光譜學與光譜分析
광보학여광보분석
SPECTROSCOPY AND SPECTRAL ANALYSIS
2014年
8期
2122-2125
,共4页
李涛%唐延林%凌智刚%隆正文
李濤%唐延林%凌智剛%隆正文
리도%당연림%릉지강%륭정문
黄曲霉素B1%Raman光谱%分子前线轨道%DFT
黃麯黴素B1%Raman光譜%分子前線軌道%DFT
황곡매소B1%Raman광보%분자전선궤도%DFT
Aflatoxin B1%Raman spectrum%Molecular frontier orbital%DFT
采用B3LYP混合泛函和6-311＋g（d，p）基组，利用DFT密度泛函理论优化得到了黄曲霉素Afla-toxin B1（cis）（AFB1（cis））及其反式异构体分子AFB1（trans）的稳定结构，通过单点能计算和几何结构分析，其顺式结构比反式结构更加稳定；计算了两种分子的Raman光谱，并与AFB1（c）粉末的实验Raman光谱进行比较，吻合较好。把最强的三个峰1582，3065和1626 cm-1指认为顺式结构的特征峰，把1616，3065和1659 cm-1指认为反式结构的特征峰；在优化计算的基础上采用Hirshfeld原子划分方法结合Multiwfn软件分析了前线轨道成分，两种分子的亲电能力明显强于其亲核能力，通过计算C1原子在LUMO 轨道中的占据权重分别为21．48％和20．62％，预测出C1原子是这两种顺反异构分子夺走DNA中的电子致癌的最主要位点。结果对该类顺反异构分子的检测、转化以及毒性抑制方面具有一定的理论指导意义。
採用B3LYP混閤汎函和6-311＋g（d，p）基組，利用DFT密度汎函理論優化得到瞭黃麯黴素Afla-toxin B1（cis）（AFB1（cis））及其反式異構體分子AFB1（trans）的穩定結構，通過單點能計算和幾何結構分析，其順式結構比反式結構更加穩定；計算瞭兩種分子的Raman光譜，併與AFB1（c）粉末的實驗Raman光譜進行比較，吻閤較好。把最彊的三箇峰1582，3065和1626 cm-1指認為順式結構的特徵峰，把1616，3065和1659 cm-1指認為反式結構的特徵峰；在優化計算的基礎上採用Hirshfeld原子劃分方法結閤Multiwfn軟件分析瞭前線軌道成分，兩種分子的親電能力明顯彊于其親覈能力，通過計算C1原子在LUMO 軌道中的佔據權重分彆為21．48％和20．62％，預測齣C1原子是這兩種順反異構分子奪走DNA中的電子緻癌的最主要位點。結果對該類順反異構分子的檢測、轉化以及毒性抑製方麵具有一定的理論指導意義。
채용B3LYP혼합범함화6-311＋g（d，p）기조，이용DFT밀도범함이론우화득도료황곡매소Afla-toxin B1（cis）（AFB1（cis））급기반식이구체분자AFB1（trans）적은정결구，통과단점능계산화궤하결구분석，기순식결구비반식결구경가은정；계산료량충분자적Raman광보，병여AFB1（c）분말적실험Raman광보진행비교，문합교호。파최강적삼개봉1582，3065화1626 cm-1지인위순식결구적특정봉，파1616，3065화1659 cm-1지인위반식결구적특정봉；재우화계산적기출상채용Hirshfeld원자화분방법결합Multiwfn연건분석료전선궤도성분，량충분자적친전능력명현강우기친핵능력，통과계산C1원자재LUMO 궤도중적점거권중분별위21．48％화20．62％，예측출C1원자시저량충순반이구분자탈주DNA중적전자치암적최주요위점。결과대해류순반이구분자적검측、전화이급독성억제방면구유일정적이론지도의의。
Through computation,this paper obtained Aflatoxin B1 and its trans-isomer molecules stable structure which was rarely reported by the density functional theory(DFT)with B3LYP complex function and 6-311+g(d,p)basis set.Through a single point calculations and geometry analysis,we know that the cis-structure is more stable than trans-structure.On the basis of this,Raman spectra of two molecules are calculated by the same method and basis set.compared with the Aflatoxin B1 cis-structure powder experimental Raman spectra,it was informed that numerical results with experimental results combined with a better.While 1 582,3 065,1 626 means to take the strongest of the three peaks of cis-structure raman characteristics,1 616, 3 065,1 659 cm-1 is indicated for the strongest of the three peaks of trans-structure raman characteristics.Use the Hirshfeld at-om division method combined with Multiwfn software to analyze the composition of frontier orbital based on optimization calcula-tion,and it was informed that the electrophilic ability of two m on olecules was stronger than the nucleophilic ability.The pro-portion of C1 atoms in LUMO orbital are respectively 21.48 percent,20.62 percent by calculating,thus it is predicted that C1 atom is most main position spot depriving of the electronic in DNA to cause cancer.The above-mentioned research has certain theoretical directive significance in detection,transformation and toxicity inhibition of the cis-trans isomers.
