CN104387790A - Benzindole salt dye containing thiophene group and preparation method and application of benzindole salt dye - Google Patents
Benzindole salt dye containing thiophene group and preparation method and application of benzindole salt dye Download PDFInfo
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Abstract
The invention relates to a benzindole salt dye containing a thiophene group, which is as shown in formula (1) and has a relatively strong surface-enhanced Raman scattering (SERS) effect, and a preparation method and application of the benzindole salt dye. Cations of a benzindole salt are of a D-pi-A structure, dialkylamino is taken as an electron donor, nitrogen-containing heterocyclic benzindole cations are taken as electron acceptors, and thiophene vinyl is taken as a conjugated bridge respectively. Dye molecules with the structure can be compounded with nano-gold or silver particles to form an SERS marker for surface-enhanced Raman spectral detection, the SERS intensity is high, and the reaction is sensitive; and the absorption wavelength of the dye is controllable by regulating and controlling the length of a molecular conjugated chain, and the SERS dye molecules are expected to be applied in the field of biomedical spectral detection.
Description
Technical field
The invention belongs to organic materials, Raman spectrum analysis field, be specifically related to benzindole salt dyestuff of a class thienyl-containing group and its production and use.
Background technology
The SERS technology of high speed development drastically increases the sensitivity of Raman spectrum detection, can overcome the congenital defect of raman spectrum strength aspect, adding Raman spectrum can provide the advantage enriching structural information to make SERS technology become an important research means gradually in biochemical analysis research field.
SERS probe technique is the emerging method detected for immunity, DNA and cell bacterial.Nie group (Qian X, Peng X, Nie S, et al.Nature Biotechnology, 2008,26 (1): 83-90) devise the gold nano grain SERS marker (see accompanying drawing 1) that a kind of sulfhydrylation PEG embeds, be referred to as third generation SERS marker, it is the nanometer gold of 60nm, raman active molecule and sulfhydrylation PEG tri-part composition primarily of particle diameter.SERS dyestuff (raman active molecule) is its important integral part, and exploitation has large SERS effect concurrently and maximum absorption wavelength is significant at the SERS dyestuff of Photobiology scope.
In infrared 630nm to 785nm region, the natural chromophoric group in organism and the absorption of water minimum, be called as biomedical spectral window.Thiophene is excellent conjugation linking group, the molecule containing phenyl ring that structure compared is similar, and the maximum absorption wavelength containing the molecule of thiphene ring is larger, is more easily absorbed at the novel material in biomedical spectral window region.
Summary of the invention
The object of the present invention is to provide D-π-A type benzindole salt dyestuff of a class thienyl-containing group and its production and use.Product is organic ion type compound, has water-soluble preferably; Changing the absorbing wavelength of dye molecule by changing thienyl conjugated chain length, making chromophoric group natural in organism and water affect less on absorbing wavelength; Meanwhile, the change of its concentration of SERS intensity of product is sensitiveer, is expected to be applied in SERS marker.
A benzindole salt dyestuff for thienyl-containing group, is characterized in that utilizing double bond to be connected from different thienyl groups by benzindole salt, and as the passage of Charger transfer therebetween, the SERS dye composition of formation D-π-A structure.(1) be the general structure of the benzindole salt of thienyl-containing group:
Wherein
R
1, R
2and R
3be C1-C4 straight or branched alkyl independently of one another, preferred C1-C2 alkyl, is more preferably methyl;
X is F, Cl, Br or I, is preferably Br or I, more preferably I;
N is the integer of 2-5, is preferably 2 or 3.
Most preferably, the benzindole salt of described thienyl-containing group is following compound:
According to a further aspect in the invention, provide a kind of preparation method of benzindole salt of described thienyl-containing group, the method is as follows:
Specifically comprise the steps:
(1) end 5 is that substituent n bithiophene and dialkylamine aqueous solution back flow reaction generate with end 5 dialkyl aminos and formaldehyde with bromine and formaldehyde is respectively substituent n bithiophene;
(2) benzindole and haloalkane in ethanol back flow reaction generate benzindole salt;
(3) end 5 respectively with dialkyl amino and formaldehyde for substituent n bithiophene and benzindole reactant salt generate described in the benzindole salt rolled into a ball of thienyl-containing.
More specifically comprise the steps:
(1) end 5 is the synthesis of substituent n bithiophene respectively with dialkyl amino and formaldehyde: in round-bottomed flask, add end 5 with the mol ratio of 1:4 is substituent n bithiophene and the dialkylamine aqueous solution with bromine and formaldehyde respectively, reacting by heating under catalyzer (such as 4-toluene sulfonic acide, bi triphenyl phosphine nickelous chloride etc.) effect, reaction process midpoint board following response process.The organic amines such as dialkylamine are volatile, supplement a certain amount of dialkylamine aqueous solution every 6 hours, and (end 5 be respectively substituent n bithiophene with bromine and formaldehyde) reacts completely until raw material.Reaction terminates the rear method of column chromatography that utilizes and obtains target product;
(2) synthesis of benzindole salt: add haloalkane and 1 with the mol ratio of 1:1 in round-bottomed flask, 1,2-trimethylammonium-1H-benzo [e] indoles, and add appropriate dehydrated alcohol, reflux 6 hours, is cooled to room temperature, filters out solid, vacuum-drying, finally obtains light blue benzindole salt;
(3) synthesis of bithiophene benzindole salt: be that substituent n bithiophene and benzindole salt join in dehydrated alcohol with the mol ratio of 1.1:1 with dialkyl amino and formaldehyde respectively by end 5, drip 2 ~ 3 piperidines as catalyzer, 85 DEG C of back flow reaction 12 hours; Be cooled to room temperature after reaction terminates, revolve and steam the most of solvent of removing.Then pour precipitating in ether into, filter and obtain crude product, by the method separating-purifying of column chromatography, obtain target product.
According to a further aspect in the invention, the benzindole salt providing described thienyl-containing group in Surface Enhanced Raman Scattering Spectrum is analyzed as the application of the raman active molecule of SERS marker.First test dye molecule maximum absorption wavelength in aqueous, then carries out surface enhanced Raman scattering strength test to dye molecule.The dye molecule of gained all shows certain surface reinforced Raman active in surface enhanced Raman scattering strength test, wherein bithiophene benzindole salt compounded of iodine just has stronger response when concentration is very little, and increase rapidly along with the increase of concentration, be quick on the draw, the commercial label dyestuff QSY (3 that its SERS signal intensity ratio is respond well, 6-bis-(2, 3-dihydro-1H-indoles-1-base)-9-[2-[[4-[[(2, 5-dioxo-1-pyrrolidyl) oxygen] carbonyl]-piperidino] alkylsulfonyl] phenyl]-chlorination xanthene (Xanthylium, 3, 6-bis (2, 3-dihydro-1H-indol-1-yl)-9-[2-[[4-[[(2, 5-dioxo-1-pyrrolidinyl) oxy] carbonyl]-1-piperidinyl] sulfonyl] phenyl]-, chloride)) large more than 10 times.
In a word, main advantage of the present invention is: utilize simple liquid phase reaction to prepare D-π-A type dye, saved cost; Have and be easy to preparation, the advantages such as material cost is cheap, and surface-enhanced Raman intensity is sensitive.By the change of thiophene conjugated chain length, achieve the adjustment of the near infrared absorption of material, add the controllability of absorbed wavelength, contribute to the application in biomedical context of detection.
Accompanying drawing explanation
Fig. 1 shows the gold nano grain SERS marker that a kind of sulfhydrylation PEG of the prior art embeds.
Fig. 2 is the benzindole salt compounded of iodine uv-visible absorption spectra in aqueous containing bithiophene group in embodiment 1.
Fig. 3 be in embodiment 1 containing the benzindole salt compounded of iodine surface-enhanced Raman intensity in aqueous of bithiophene group to the spectrogram of strength of solution.
Fig. 4 is bithiophene benzindole salt compounded of iodine and the respond well surface-enhanced Raman effectiveness comparison of commercial label dyestuff QSY under same experiment condition in embodiment 1.
Fig. 5 is the uv-visible absorption spectra in aqueous containing the benzindole salt compounded of iodine of terthienyl group in embodiment 2.
Fig. 6 be in embodiment 2 containing the benzindole salt compounded of iodine surface-enhanced Raman intensity in aqueous of terthienyl group to the spectrogram of strength of solution.
Fig. 7 is the application example of bithiophene benzindole salt in cancer cells context of detection.
Fig. 8 is the general structure of the benzindole salt dyestuff of thienyl-containing group.
Specific embodiments
Below in conjunction with specific embodiment, technical scheme of the present invention is described in further details, but the present invention is not limited thereto.
Raw material used in the specific embodiment of the invention and reagent are common commercially available acquisition.Adopt the ultra-violet absorption spectrum of JASCO V-570 type ultraviolet spectrometer to dye molecule to measure, wavelength region is 400 ~ 800nm; Adopt the chemical structure of Bruker DMX-500 type nuclear magnetic resonance spectrometer to intermediate and product to characterize, solvent is CDCl
3or DMSO; The compound system of DeltaNu NIR Raman spectrometer to dye molecule and nano particle is adopted to carry out surface-enhanced Raman strength test (laser excitation wavelength is 785nm).
Embodiment 1
Containing the synthesis of the benzindole salt compounded of iodine of bithiophene
The synthesis of A5-(dimethylamino)-2,2'-bis-thiophene-5'-formaldehyde:
1) synthesis of 2,2'-bithiophenes: by two for the 10mol% of 1.8g (triphenyl phosphorus) nickelous chloride (II) [(PPh
3)
2niCl
2], the 20mol% triphenylphosphine of 1.45g, the zinc powder of 1.81g (2.76mmol) and the dry DMF solution of 55mL join in the there-necked flask of 100mL, and mixture stirs 0.5 hour under room temperature under nitrogen protection, and the color of solution becomes reddish-brown from bluish-green; Then, add 4.5g2-bromothiophene (27.6mmol), stir 12 hours at 60 DEG C; After reaction terminates, with diatomite filtration several; Add 50mL water, with 50mL dichloromethane extraction 3 times, merge organic phase, use anhydrous sodium sulfate drying 24 hours; Revolve and boil off except most of solvent, the oily matter obtained, by the method separating-purifying of 2 column chromatographies, first time sherwood oil do eluent, second time hexane does eluent, obtains glaucous crystal, productive rate 92%.
1H NMR(400MHz,CDCl
3-d6)：δ＝7.19(q,J＝4.5Hz,4H),7.01(t,J＝4.2Hz,2H)。
2) 2, the synthesis of 2'-bithiophene-5-acetaldehyde: 0.33g bithiophene (2.0mmol) and 18mL anhydrous ether solution are joined in the there-necked flask of 50mL, at 0 DEG C, under nitrogen protection, slowly drip in above-mentioned solution by the hexane solution minute hand head of 1.6mL2.5M n-Butyl Lithium (4.0mmol), adition process agitator constantly stirs; Mixture stirs 1 hour at 0 DEG C afterwards, and solution becomes faint yellow; After room temperature stops 15 minutes, add 2.4mmol (0.18g) DMF with syringe and be dissolved in the solution of 2mL anhydrous diethyl ether, then reflux 2 hours; Be cooled to room temperature after reaction terminates, mixture poured in 20mL water, with 50mL extraction into ethyl acetate three times; Organic extracts washed with water (100mL) washing merged, with anhydrous sodium sulfate drying, be spin-dried for and obtain crude product, by the method separating-purifying of 2 column chromatographies, eluent: sherwood oil: ethyl acetate=8:1, obtains pink crystal, productive rate 45%.
1H NMR(400MHz,CDCl
3-d6)：δ＝7.08(,J＝4.3Hz,1H),7.25(d,J＝3.8Hz,1H),7.36(d,J＝4.3Hz,2H),7.67(d,J＝3.8Hz,1H),9.86(s,1H)。
3) synthesis of bromo-2, the 2'-bis-thiophene-5'-formaldehyde of 5-:
By 2 of 0.8g, 2'-bithiophene-5-acetaldehyde (4.1mmol) is dissolved in the solution of 1 ~ 2mL DMF and is placed in 25mL flask, drip the solution that 4.1mmol (0.73g) N-bromo-succinimide is dissolved in 2 ~ 3mL DMF, after dripping, cover ground glass stopper, wrap up lucifuge with tinfoil, stirring is spent the night; After reaction terminates, reaction solution is poured in appropriate frozen water, organic phase is merged for several times by 10mL extracted with diethyl ether, with 10mL water washing once, with anhydrous sodium sulfate drying, be spin-dried for and obtain crude product, by the method separating-purifying of column chromatography, eluent: ethyl acetate: sherwood oil=1:20, obtains dark yellow powder, productive rate 81%.
1H NMR(400MHz,CDCl
3-d6)：δ＝7.02(d,J＝3.9Hz,1H)，7.09(d,J＝3.9Hz,1H),7.17(d,J＝3.9Hz,1H),7.65(d,J＝3.9Hz,1H),9.84(s,1H)。
4) synthesis of 5-(dimethylamino)-2,2'-bis-thiophene-5'-formaldehyde:
By 100mg5 '-bromo-2,2 '-bis-thiophene-5-formaldehyde (0.37mmol), 1g dimethylamine (the aqueous solution of 40%, 8.9mmol), 13.9mg cuprous iodide (0.073mmol), 4.7mg copper powder (0.074mmol), the DMF of 155.4mg potassiumphosphate (0.73mmol) and 1mL joins in high-pressure reaction vessel, mixture was 80 DEG C of reactions 87 hours, and in reaction process, solution colour reddens; Be cooled to room temperature after reaction terminates, filter with short silicagel column, use ethyl acetate drip washing; Be spin-dried for and obtain crude product, by the method separating-purifying of column chromatography, eluent: methylene dichloride (product is dissolved in methylene dichloride and presents intense green fluorescence), obtains orange solid, productive rate 37%.
1H NMR(400MHz,CDCl
3-d
6)：δ＝3.00(s,6H),5.81(d,J＝4.0Hz,1H),6.95(d,J＝4.0Hz,1H),7.13(d,J＝4.0Hz,1H),7.57(d,J＝4.0Hz,1H),9.75(s,1H)。
The synthesis of B benzindole salt compounded of iodine: add 20mL dehydrated alcohol, 2.5g methyl iodide (17.6mmol) and 3.7g1 in round-bottomed flask, 1,2-trimethylammonium-1H-benzo [e] indoles (17.6mmol), reflux 6 hours, be cooled to room temperature, filter out solid, vacuum-drying, finally obtain light blue benzindole salt compounded of iodine, productive rate is about 87%.
1HNMR(DMSO,400MHz)：δ＝8.25～8.27(d,1H,C
10H
6),8.04～8.11(m,2H,C
10H
6),7.79～7.77(d,1H,C
10H
6),7.66～7.69(m,1H,C
10H
6),7.51～7.54(m,1H,C
10H
6),3.79(s,3H,CH
3),2.61(s,3H,CH
3)1.93(s,6H,CH
3)。
The synthesis of C bithiophene benzindole salt compounded of iodine: get 20mg5-(dimethylamino)-2,2'-bis-thiophene-5'-formaldehyde and 27mg1,1,2-trimethylammonium-1H-benzo [e] indoles salt compounded of iodine join in 5mL dehydrated alcohol, drip 1 piperidines as catalyzer, 85 DEG C of back flow reaction 12 hours; Be cooled to room temperature after reaction terminates, revolve and steam the most of solvent of removing.Then pour precipitating in ether into, filter and obtain crude product, the method separating-purifying of bithiophene benzindole salt compounded of iodine column chromatography, eluent: methylene dichloride: methyl alcohol=15:1, product is blue solid, productive rate 46%.
1H NMR(DMSO,500MHz)：δ＝8.61～8.64(d,1H,C
10H
6),8.36～8.38(d,1H,C
10H
6),8.21～8.23(d,1H,C
2H
2),8.15～8.17(d,1H,C
10H
6),8.04～8.05(d,1H,C
4H
2S),7.97～7.99(1,H,C
2H
2),7.74～7.77(m,1H,C
10H
6),7.63～7.66(m,1H,C
10H
6),7.56～7.57(d,1H,C
4H
2S),7.37～7.38(d,1H,C
4H
2S),6.84～6.87(d,1H,C
10H
6),6.16～6.17(d,1H,C
4H
2S),4.05(s,3H,CH
3),3.08(s,6H,CH
3),1.98(s,6H,CH
3)。
Accompanying drawing 2 is the uv-visible absorption spectra that bithiophene benzindole salt compounded of iodine records in aqueous, and which show bithiophene benzindole salt compounded of iodine maximum absorption wavelength is in aqueous 686nm.
Accompanying drawing 3 is the change of bithiophene benzindole salt compounded of iodine surface enhanced Raman scattering intensity concentration in aqueous, which show bithiophene benzindole salt compounded of iodine and just have stronger response when concentration is very little, and increase rapidly along with the increase of concentration, be quick on the draw.
Accompanying drawing 4 is bithiophene benzindole salt compounded of iodine (dotted line) and the respond well surface-enhanced Raman effectiveness comparison of commercial label dyestuff QSY (solid line) under same experiment condition, can find out large more than 10 times of the SERS signal intensity ratio QSY of bithiophene benzindole salt.
Embodiment 2
Containing the synthesis of the benzindole salt compounded of iodine of terthienyl
A5 "-(dimethylamino)-bromo-2; 2':5'; 2 " the synthesis of-terthienyl-5-formaldehyde: by 100mg5 "-bromo-2; 2':5'; 2 "-terthienyl-5-formaldehyde (0.28mmol), 1g dimethylamine (the aqueous solution of 40%, 8.9mmol), 13.9mg cuprous iodide (0.073mmol), 4.7mg copper powder (0.074mmol), 155.4mg potassiumphosphate (0.73mmol), and 1mL DMF joins in high-pressure reaction vessel, mixture is the reaction 159 hours of 80 DEG C, and in reaction process, solution colour reddens; Be cooled to room temperature after reaction terminates, filter with short silicagel column, use ethyl acetate drip washing; Be spin-dried for and obtain crude product, by the method separating-purifying of column chromatography, eluent: methylene dichloride (product is dissolved in methylene dichloride and presents intense green fluorescence), obtains orange solid, productive rate 20%.
1H NMR(400MHz,CDCl
3-d6)：δ＝3.33(s,6H),5.77(d,J＝4.0Hz,1H),6.83(d,J＝3.6Hz,1H)，6.94(d,J＝4.0Hz,1H),7.15(d,J＝4.0Hz,1H),7.21(d,J＝3.6Hz,1H)，7.64(d,J＝4.0Hz,1H),9.82(s,1H)。
The synthesis of B benzindole salt compounded of iodine: add 20mL dehydrated alcohol, 2.5g methyl iodide (17.6mmol) and 3.7g1 in round-bottomed flask, 1,2-trimethylammonium-1H-benzo [e] indoles (17.6mmol), reflux 6 hours, be cooled to room temperature, filter out solid, vacuum-drying, finally obtain light blue benzindole salt compounded of iodine, productive rate is about 87%.
1HNMR(DMSO,400MHz)：δ＝8.25～8.27(d,1H,C
10H
6),8.04～8.11(m,2H,C
10H
6),7.79～7.77(d,1H,C
10H
6),7.66～7.69(m,1H,C
10H
6),7.51～7.54(m,1H,C
10H
6),3.79(s,3H,CH
3),2.61(s,3H,CH
3)1.93(s,6H,CH
3)。
The synthesis of C terthienyl benzindole salt compounded of iodine: "-(dimethylamino)-2; 2':5'; 2 of getting 10mg5 " 1 of-terthienyl-5-formaldehyde and 9.6mg, 1,2,3-tetramethyl-benzene diindyl salt compounded of iodine (both ratios are 1.1:1) joins in 5mL dehydrated alcohol, drips 1 piperidines as catalyzer, 85 DEG C of back flow reaction 12 hours; Be cooled to room temperature after reaction terminates, revolve and steam the most of solvent of removing.Then pour precipitating in ether into, filter and obtain crude product, by the method separating-purifying of column chromatography, eluent: methylene dichloride: methyl alcohol=15:1, product is blue solid, productive rate 34%.
1H NMR(DMSO,500MHz)：δ＝8.67～8.71(d,1H,C
9H
6N),8.39～8.41(d,1H,C
9H
6N),8.24～8.26(d,1H,C
9H
6N),8.17～8.19(d,1H,C
2H
2),8.11～8.2(d,1H,C
4H
2S),8.03～8.05(d,H,C
9H
6N),7.76～7.80(m,1H,C
9H
6N),7.67～7.71(d,1H,C
9H
6N),7.57～7.58(d,1H,C
4H
2S),5.54～6.55(d,1H,C
4H
2S),7.15～7.19(d,2H,C
4H
2S+C
2H
2),7.09～7.10(d,1H,C
4H
2S),5.93～5.94(d,1H,C
4H
2S),4.16(s,3H,CH
3),2.94(s,6H,CH
3),1.98(s,6H,CH
3)。
Accompanying drawing 5 is the benzindole salt compounded of iodine uv-visible absorption spectra in aqueous containing terthienyl group, and its maximum absorption wavelength demonstrating terthienyl benzindole salt compounded of iodine is at 608nm.
Accompanying drawing 6 is the change of terthienyl benzindole salt compounded of iodine surface enhanced Raman scattering efficiency in aqueous with strength of solution, it demonstrates terthienyl benzindole salt compounded of iodine and has certain surface enhanced Raman scattering performance, is tending towards saturated in concentration more than 2000nM.
Embodiment 3
The bithiophene benzindole salt compounded of iodine that the present inventor uses embodiment 2 to prepare is to detect tumour cell, the SERS signal contrast of the cancer cells Tu212 adopting it to locate and normal white cell (WBC) is strong, and this shows that bithiophene benzindole salt compounded of iodine may be used for biological detection aspect as raman active molecule.
Accompanying drawing 7 is the application example of bithiophene benzindole salt compounded of iodine in cancer cells context of detection.
Claims (7)
1. a benzindole salt dyestuff for thienyl-containing group, is characterized in that this benzindole salt dyestuff general structure is for shown in (1):
Wherein
R
1, R
2and R
3be C1-C4 straight or branched alkyl independently of one another,
X is F, Cl, Br or I;
N is the integer of 2-5.
2. the benzindole salt dyestuff of thienyl-containing group according to claim 1, is characterized in that in general structure, R
1, R
2and R
3be C1-C2 alkyl independently of one another;
X is Br or I;
N is 2 or 3.
3. the benzindole salt dyestuff of thienyl-containing group according to claim 1, is characterized in that R in general structure
1, R
2and R
3be methyl;
X is I;
N is 2 or 3.
4. the benzindole salt dyestuff of thienyl-containing group according to claim 1, is characterized in that this benzindole salt dyestuff structural formula is:
5. a preparation method for the benzindole salt-dye of the thienyl-containing group according to any one of claim 1-4, is characterized in that comprising following step:
A. end 5 is that substituent n bithiophene and dialkylamine aqueous solution back flow reaction generate with end 5 dialkyl aminos and formaldehyde with bromine and formaldehyde is respectively substituent n bithiophene;
B. benzindole and haloalkane in ethanol back flow reaction generate benzindole salt;
C. end 5 respectively with dialkyl amino and formaldehyde for substituent n bithiophene and benzindole reactant salt generate described in the benzindole salt rolled into a ball of thienyl-containing.
6. the preparation method of the benzindole salt-dye of thienyl-containing group as claimed in claim 5, is characterized in that concrete preparation process is as follows:
(1) end 5 is the synthesis of substituent n bithiophene respectively with dialkyl amino and formaldehyde: adding end 5 with the mol ratio of 1:4 is in a reservoir substituent n bithiophene and the dialkylamine aqueous solution with bromine and formaldehyde respectively, reacting by heating under catalyst action, reaction process midpoint board following response process; A certain amount of dialkylamine aqueous solution is supplemented, until end 5 is that the raw material reaction of substituent n bithiophene is complete with bromine and formaldehyde respectively every 6 hours; Reaction terminates the rear method of column chromatography that utilizes and obtains target product;
(2) synthesis of benzindole salt: add haloalkane and 1 with the mol ratio of 1:1 in a reservoir, 1,2-trimethylammonium-1H-benzo [e] indoles, and add appropriate dehydrated alcohol, reflux 6 hours, is cooled to room temperature, filters out solid, vacuum-drying, finally obtains light blue benzindole salt;
(3) synthesis of bithiophene benzindole salt: be that substituent n bithiophene and benzindole salt join in dehydrated alcohol with the mol ratio of 1.1:1 with dialkyl amino and formaldehyde respectively by end 5, drip 2 ~ 3 piperidines as catalyzer, 85 DEG C of back flow reaction 12 hours; Be cooled to room temperature after reaction terminates, revolve and steam the most of solvent of removing, then pour precipitating in ether into, filter and obtain crude product, by the method separating-purifying of column chromatography, obtain target product.
7. the benzindole salt of the thienyl-containing group according to any one of claim 1-4 in Surface Enhanced Raman Scattering Spectrum is analyzed as the application of raman active molecule.
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| CN105199422A (en) * | 2015-10-20 | 2015-12-30 | 北京科技大学 | Sulfhydryl group-containing bithiophene benzoindoles dye as well as preparation method and application thereof |
| CN107090190A (en) * | 2017-04-24 | 2017-08-25 | 北京科技大学 | One class acridine salt dyestuff and its preparation method and application |
| US10392598B2 (en) | 2015-06-19 | 2019-08-27 | Emory University | Methods of measuring cell purity for making quality control determinations and related compositions |
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| CN107090190A (en) * | 2017-04-24 | 2017-08-25 | 北京科技大学 | One class acridine salt dyestuff and its preparation method and application |
| CN107090190B (en) * | 2017-04-24 | 2019-09-06 | 北京科技大学 | A kind of acridine salt dyestuff and its preparation method and application |
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