Surface-Enhanced Raman Scattering Spectroscopic Analysis Of Compatibility Of Lupus Ⅱ Prescription

Objective(1)The SERS spectroscopy of Lupus Ⅱ prescription was tested and analyzed,to reveal the relationship between single drug decoction and groud drug decoction,groud drug decoction and Lupus Ⅱ decoction,and to reveal the rule and correlation between Lupus Ⅱ decoction and the single drug decoction or groud drug decoction,for providing guidance of clinical medication.(2)The SERS spectral characteristics of different preparations of Lupus II prescription were explored,for expounding the differences chemical components of different preparations,for realizing the evaluation and identification of new traditional Chinese herbal compounds.Methods(1)The Raman spectroscopy and SERS spectroscopy techniques were used to detect Lupus II decoction,and the SERS experimental conditions were evaluated,such as the state of the combination of silver nanoparticles and the drug solution,the best combination ratio,etc.(2)The Lupus Ⅱ decoction was divided into five drug group in prescription according to the own drug efficay of TCM.Which was divided as follow:Bu-Gan-Shen-Yin drug group decoction(BGSYDGD),Qing-Re-Liang-Xue drug group decoction(QRLXDGD)、Tiao-He drug group decoction(THDGD)、Bu-Shen-Se-Jing drug group decoction(BSSJDGD)and Zi-Yin-Xie-Zhuodrug group decoction(ZYXZDGD).The SERS spectroscopy was used to detect all single medicines and drug group decoctions,and the correlation coefficient was calculatted,and also,the characteristics Raman bands of all decot ions were analyzed.(3)The SERS spectroscopy combined with the second derivative was used to analyze the spectrum of different Lupus II preparations,and the correlation coefficients was used to evaluate the relationship between the overall composition of different preparations and Lupus II decoction.Results(1)Regular Raman spectroscopy found:due to the strong fluorescence effect of the sample of the Chinese medicine compound prescription decoction,the regular Raman signal of the decoction of Lupus Ⅱ prescription only detected the individual Raman signals of samples.SERS spectrometric detect found:The elargol basement has a certain effect of quenching fluorescence,the elargol 1:1 liquid direct mixing which can better enhance the Raman signal and improve the signal-to-noise ratio.There are ten Raman signal peaks in the decoction of Lupus II prescription was detected out by SERS spectrometric technology:176、310、428、592、710、825、1320、1455、1542 and 1657cm-1.And among the Raman peaks,there have 176、313、428 and 1542cm-1 are belong to carbohydrate structure,428cm-1 the Raman signal tell us that the Lupus II prescription decoction have amylose,592、710、825、1455 and 1657cm-1 Raman peaks are belong to amino acid structure;1320cm-1 Raman peak is belong to deoxynucleotide 1-Methylimidazole ring stretching vibration;825 and 1657cm-1 Raman signal point the exist of the terpenoids;592、1542 and 1657cm-1 Raman signal point the exist of the flavonoids;No Raman response at 2000～3000cm-1 wave band,it point no the lipids and the fatty acids included in the Lupus II prescription decoction.(2)The Lupus II prescription and single drug decoction 600～1800cm-1 wave band SERS spectrometric detection:The Lupus Ⅱ prescription decoction have six spectral peaks(710、825、1320、1455、1542 and 1657cm-1),the cornus officinalis Decoction have five spectral peaks(704、825、1201、1320 and 1691cm-1),The Rehmanniaglutinosa decoction have six spectral peaks(704、825、1024、1320、1440 and 1648cm-1),Cortex moutan have nine spectral peaks(704、825、977、1092、1176、1320、1558、1648 and 1778cm-1),Poria cocos have 13 spectral peaks(704、825、943、1024、1126、1173、1201、1275、1320、1440、1595、1648 and 1691cm-1),Alisma Orientale have five spectral peaks(704、825、1320,1440 and 1648cm-1),Artemisia apiacea have eight spectral peaks(704、825、943、1024、1201、1320、1595 and 1648cm-1),liquiritia glycyrrhiza have seven spectral peaks(704、825、1024、1320、1558、1648 and 1778cm-1).After compared the Lupus Ⅱ prescription and single decoction spectral peaks found that the ingredients of the Lupus Ⅱ prescription decoction is closer to the ingredients of Shengdi decoction,Alisma Orientale decoction and liquiritia glycyrrhiza decoction.The single medicine in the compatibility and co-decocting adds the common ingredients of the single medicine and produces a new ingredients that won’t have in the single medicine;The spectral peaks of superimposed components are at 704,825,1320 and 1455cm-1 Raman shifts,and the spectral peaks of vanished ingredients are at 900～1200cm-1 wave band,the spectral peaks of new produced ingredients are at 1542cm-1 Raman shifts.The single medicine and the drug group Decoction 600～1800cm-1 wave band SERS spectrometric detection:Represented by the "Replenishing and Reducing"compatibility medicine team,the medicine team of Rehmanniaglutinosa and Alisma Oriental decoction have five Raman peaks(710、825、1320、1455 and 1570cm-1),Rehmanniaglutinosa decoction have six Raman peaks(704、825、1024、1320、1440 and 1648cm-1),Alisma Oriental decoction have five Raman peaks(704、825、1320、1440 and 1648cm-1).The spectrum analysis and discovery of the decoction of Shengdi and Alisma orientalis and its compatible drugs,the trend of the three spectral lines is basically the same.The main peak 1320 and 1440cm-1 strength is the strongest in the medicine team of Rehmanniaglutinosa decoction and Alisma Oriental decoction.It showed that the main ingredients of the decoction ofRehmanniaglutinosa and Alisma orientalis are the superposition of ingredients of Rehmanniaglutinosa and Alisma,and the compatibility of Rehmanniaglutinosa and Alisma is mainly synergistic.The cornus officinalis and cortex moutan drug group have ten Raman peaks(642、825、977、1176、1185、1320、1455、1558、1620、1691 and 1778cm-1),the cornus officinalis have five Raman peaks(704、825、1201、1320 and 1691cm-1),the cortex moutan have nine Raman peaks(704、825、977、1092、1176、1320、1558、1648 and 1778cm-1).The spectrum analysis and discovery of the decoction of cornus officinalis and cortex moutan and its compatible drugs,the main peaks of 825 and 1320cm-1 peak intensity and peak area fit are superimposed.It shows that the compatibility of cornus officinalis and cortex moutan have a synergistic effect.But the spectral trend of the cornus officinalis and the peony medicine team decoction are similar with the cortex mountan decoction.The cornus officinalis have 825,1320 and 1691cm-1 three Raman signals are appeared in the medicine team decoction of the cornus officinalis and the cortex mountan.The cortex mountan decoction have seven Raman peaks of 704、825、977、1176、1320、1558 and 1778cm-1 are appeared in the medicine team decoction of the cornus officinalis and the cortex mountan.The SERS spectral correlation coefficients separately among both and the cornus officinalis&the cortex mountan medicine team are 0.69,0.88,it shows the medicine team decoction of the cornus officinalis&the cortex mountan have more ingredients of cortex mountan decoction.However,the ingredients of the cornus officinalis decoction have more changes.The compatibility of the cornus officinalis and the cortex mountan is mainly antagonistic,which is consistent with the theory that "The cortex mountan can make the cornus officinalis mild and astringent".The Lupus II prescription and the drug group decoction 600～1800cm-1 wave band SERS spectrometric detection:The BGSYDGD have five spectral peaks(825、1176、1320、1455 and 1657cm-1),the QRLXDGD have seven spectral peaks(825、940、1011、1320、1455、1657 and 1691cm-1),the THDGD have five spectral peaks(825、1011、1320、1455 and 1691cm-1),the BSSJDGD have ten spectral peaks(624、825、977、1176、1190、1320、1455、1620、1691 and 1778cm-1),the ZYXZDGD have five spectral peaks(710、825、1320、1455 and 1570cm-1).By the compared the spectral peaks of The Lupus II prescription and the drug group decoction and found that the ingredients of the Lupus II prescription decoction is closer to the ingredients of the THDGD(Artemisia apiacea+liquiritia glycyrrhiza).After the codecocting with the compatibility of the drug group decoction,it not only have the superimposed ingredients of the drug group decoction,but also many ingredients are transformed or disappeared during the decoction process,and some new ingredients are generated.The spectral peaks of the superimposed ingredients are at 825、1320 and 1455cm-1 Raman shifts,and the spectral peaks of the vanished ingredients are at 900～1200cm-1 wave band,and the spectral peak of new produced ingredients are at 710cm-1 Raman shifts.(3)The results of SERS spectra of different preparations of the Lupus II prescription combined with the second derivative showed that the ingredients of the Lupus II prescription decoction have little difference with the ingredients of the decoction I(The correlation coefficient is 0.971).The Lupus II prescription decoction have the ingredient of Artemisinin,which is consistent with the experimental result of "the ingredients of artemisinin can be preserved after the Artemisia apiacea";The capsule preparation of the Lupus Ⅱ have big difference with the ingredients of particles,and it’s also different on pharmaceutical excipients.But The capsule preparation of the Lupus Ⅱ is closer to the ingredients of the prescription decoction I of Lupus Ⅱ(the correlation coefficient is 0.894),the chemical ingredients of particles of Lupus Ⅱ have big difference with the decoction I(the correlation coefficient is 0.771),it shows the difference among ingredients of different preparation.ConclusionIt points the Lupus Ⅱ prescription decoction have multiple chemical components such as carbohydrate,amylose,protein,amino acid,DNA hydrolyzate,terpenoids and flavonoids.The Lupus II prescription chemical compositions were more similar to Rehmanniaglutinosa,Alisma,Artemisia annua and THDGD.Medical ingredients in the Lupus II decoction were not the simple addition of all single drug decotion,and not the simple addition of BGSYDGD,QRLXDGD,THDGD,BSSJDGD and ZYXZDGD.The synergistic and antagonistic effects of the ingredients during the compatibility process make the main same ingredients superimpose,and at the same time make individual ingredients Transformation or disappearance occurs,producing new chemical components.SERS spectroscopy technology has great potential for providing a novle method for simply,quickly,effectivelly and accurately studying the compatibility rules and the overall quality assessment of chinese herbal compounds.