CN110698499A - Chiral silver nanocluster and preparation and application thereof - Google Patents
Chiral silver nanocluster and preparation and application thereof Download PDFInfo
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- CN110698499A CN110698499A CN201911014977.8A CN201911014977A CN110698499A CN 110698499 A CN110698499 A CN 110698499A CN 201911014977 A CN201911014977 A CN 201911014977A CN 110698499 A CN110698499 A CN 110698499A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 35
- 239000004332 silver Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003814 drug Substances 0.000 claims abstract description 60
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 54
- 229940079593 drug Drugs 0.000 claims abstract description 33
- 229960002009 naproxen Drugs 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 claims abstract description 9
- 229960000310 isoleucine Drugs 0.000 claims abstract description 9
- UIYKSYBJKIMANV-UHFFFAOYSA-N (4-tert-butylphenyl)methanethiol Chemical group CC(C)(C)C1=CC=C(CS)C=C1 UIYKSYBJKIMANV-UHFFFAOYSA-N 0.000 claims abstract description 8
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229960001680 ibuprofen Drugs 0.000 claims abstract description 3
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 claims abstract description 3
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 137
- 239000000243 solution Substances 0.000 claims description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000001514 detection method Methods 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 7
- 229940071536 silver acetate Drugs 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- -1 sodium triacetoxyborohydride Chemical compound 0.000 claims description 3
- 239000012321 sodium triacetoxyborohydride Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000001142 circular dichroism spectrum Methods 0.000 description 34
- 238000002983 circular dichroism Methods 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 11
- GAWAYYRQGQZKCR-UWTATZPHSA-N (2r)-2-chloropropanoic acid Chemical compound C[C@@H](Cl)C(O)=O GAWAYYRQGQZKCR-UWTATZPHSA-N 0.000 description 10
- 101100163901 Rattus norvegicus Asic2 gene Proteins 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000003446 ligand Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229930182844 L-isoleucine Natural products 0.000 description 6
- HEFNNWSXXWATRW-SNVBAGLBSA-N levibuprofen Chemical compound CC(C)CC1=CC=C([C@@H](C)C(O)=O)C=C1 HEFNNWSXXWATRW-SNVBAGLBSA-N 0.000 description 6
- AGPKZVBTJJNPAG-RFZPGFLSSA-N D-Isoleucine Chemical compound CC[C@@H](C)[C@@H](N)C(O)=O AGPKZVBTJJNPAG-RFZPGFLSSA-N 0.000 description 5
- 229930182845 D-isoleucine Natural products 0.000 description 5
- HEFNNWSXXWATRW-JTQLQIEISA-N dexibuprofen Chemical compound CC(C)CC1=CC=C([C@H](C)C(O)=O)C=C1 HEFNNWSXXWATRW-JTQLQIEISA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DKYWVDODHFEZIM-LLVKDONJSA-N (2r)-2-(3-benzoylphenyl)propanoic acid Chemical compound OC(=O)[C@H](C)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 DKYWVDODHFEZIM-LLVKDONJSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- WTDRDQBEARUVNC-ZCFIWIBFSA-N D-DOPA Chemical compound OC(=O)[C@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-ZCFIWIBFSA-N 0.000 description 1
- 206010013709 Drug ineffective Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical class [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- GSDSWSVVBLHKDQ-SNVBAGLBSA-N dextrofloxacin Chemical compound C([C@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-SNVBAGLBSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 210000000224 granular leucocyte Anatomy 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 229960000991 ketoprofen Drugs 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 208000028169 periodontal disease Diseases 0.000 description 1
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- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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Abstract
The invention discloses a chiral silver nanocluster and preparation and application thereof, wherein the molecular formula of the chiral silver nanocluster is as follows: ag40(TBBM)22(CH3COO)10Abbreviated as Ag40Wherein TBBM is p-tert-butyl benzyl mercaptan. Ag of the present invention40The nanoclusters can react with chiral carboxylic acid drugs (such as 2-chloropropionic acid, ibuprofen, naproxen, isoleucine and the like) sensitively, quickly and quantitatively, so that chiral signals of the chiral carboxylic acid drugs are transmitted to Ag40The nanoclusters are convenient for measuring the content and the chiral e.e. value of the chiral carboxylic acid drugs, the reaction condition is mild, the operation is simple, the substrate can be recycled, and the universality is wide.
Description
Technical Field
The invention relates to a chiral detection agent, in particular to a chiral silver nanocluster, and preparation and application thereof, which are used for detecting the concentration and the e.e. value of chiral carboxylic acid drugs.
Background
Drugs, particularly chiral drugs with chiral configuration orientation, are ubiquitous in the fields of life sciences, disease treatment, and the like. The physical properties of chiral drugs are basically the same, but the chemical and biological properties of the chiral drugs are often different, for example, S-ofloxacin can play the role of resisting bacteria and diminishing inflammation, while R-ofloxacin has no drug effect; s-ketoprofen can be used for treating rheumatism, and R-ketoprofen is used for preventing and treating periodontal diseases; s-dopa is the first choice drug for treating Parkinson' S disease, but R-dopa causes granular leukocyte reduction and endangers human life. In order to avoid the influence of chiral enantiomers, chiral detection of drugs plays a very important role.
The current chiral detection mainly comprises direct circular dichroism detection spectroscopy and a chiral high performance liquid chromatography column separation method, wherein the former has the defects of high instrument requirement, large error and the like due to the fact that luminescent signals of chiral drugs are generally in ultraviolet or deep ultraviolet regions (chem.Soc.Rev.2013,42, 5408-doped 5424.); the chiral high performance liquid chromatography column separation method has the defects of difficult condition screening, poor separation effect and the like due to the complex preparation process, high use cost, few varieties and the like of various commercial chiral columns at present. Therefore, the invention discloses a stable chiral detection agent with the functions of prolonging and enlarging chiral signals, so that the identification and detection of chiral enantiomers are very important.
The noble metal nanoclusters have good stability, surface activity, optical properties and the like, and are used for chiral drug binding reactions. The Wanquanming group in 2013 proves that the material is Au6Ag2(C) Cluster ligand modification can be used to detect e.e. value (j.am. chem. soc.2013,135,16184) of chiral amine drug, and the reaction requires 1.5h to reach equilibrium. Two full-group discovery of zang in 2018 (CO)3)@Ag20Nitrates and carboxylates on the nanoclusters may be substituted with chiral carboxylic drugs to exhibit chiral circular dichromatic signals in the visible region (j.am. chem. soc.2018,140, 594). The above examples all illustrate that the noble metal nanoclusters have a great application prospect in the field of chiral detection.
Disclosure of Invention
The invention aims to provide a chiral silver nanocluster and preparation and application thereof, so as to realize high-sensitivity, rapid and quantitative detection of concentration and e.e. value of chiral carboxylic acid drugs under mild conditions.
The molecular formula of the chiral silver nanocluster is as follows: ag40(TBBM)22(CH3COO)10Abbreviated as Ag40Wherein TBBM is p-tert-butyl benzyl mercaptan.
The preparation method of the chiral silver nanocluster comprises the following steps:
adding 600mg of silver acetate and 50mL of methanol into a three-neck flask, stirring until the silver acetate and the methanol are uniformly dispersed, then adding 0.4mL of p-tert-butyl benzyl mercaptan, reacting for 30min until the solution is light yellow and turbid, then adding 20mL of methanol or tetrahydrofuran solution dissolved with 1.5g of sodium triacetoxyborohydride, and reacting for 20h at room temperature; centrifuging after the reaction is finished, pouring out supernatant, dissolving the precipitate with 50mL of dichloromethane, centrifuging, evaporating the supernatant of the dichloromethane with a rotary evaporator to remove the solvent, drying, dissolving with 50mL of n-hexane, centrifuging, evaporating the supernatant of the n-hexane with a rotary evaporator to remove the solvent, and drying to obtain a crude product; the crude product was purified with dichloromethane: recrystallizing acetonitrile at 1:2(v/v) to obtain black rhombus or long-strip crystal as the target product, 225mg and 30% of yield.
In the chiral silver nanocluster of the present invention, 10 carboxylic acid ligands are in two states, wherein 7 carboxylic acid ligands are located on three Ag7 chains (3+2+2) at the periphery of the silver nanocluster, the other 3 carboxylic acid ligands are located on three Ag2 chains (1+1+1) at the periphery of the silver nanocluster, three Ag7 chains are spirally twisted along the same direction, one Ag2 chain having the same spiral direction exists between every two Ag7 chains, 20 thiol ligands are connected between the Ag7 chains and between the Ag7 chain and the Ag2 chain, the remaining 2 thiol ligands are located on three Ag7 chains (0+1+1), three ligands (thiol ligands or carboxylic acid ligands) are located on each Ag7 chain, the three spiral Ag7 chains and three Ag2 chains having the same spiral direction cause chirality of the cluster, the chiral silver nanocluster inner core is a core-shell structure of Ag12 composed of 13 silver atoms, and the chiral silver nanocluster is uncharged, the specific structure is shown in figure 1.
The application of the chiral silver nanocluster is that the chiral silver nanocluster is used as a reaction substrate and reacts with chiral carboxylic acid drugs to transmit chiral signals, and then the content and the chiral e.e. value of the chiral carboxylic acid drugs are measured. The method specifically comprises the following steps:
step 1: preparation of chiral silver nanocluster standard solution
Dissolving 10mg of chiral silver nanocluster in 10mL of organic solvent to obtain a standard solution of the chiral silver nanocluster, wherein the concentration of the standard solution is 1.16x10-7mol/mL; the organic solvent is selected from toluene, dichloromethane, n-hexane or diethyl ether.
Step 2: preparation of chiral carboxylic acid medicine gradient concentration
Dissolving chiral carboxylic acid medicine in organic solvent to prepare 1.16x10-7To 1.16x10-6Different gradient concentration chiral carboxylic acid medicine solution of mol/mL. The organic solvent is dichloromethane or ethanol.
And step 3: preparation of gradient e.e. value of chiral carboxylic acid medicine
Chiral carboxylic acid drugs with different e.e. values are dissolved in an organic solvent to prepare the chiral carboxylic acid drugs with the concentration of 1.16x10-6Chiral carboxylic acid medicine solution with different e.e. values of mol/mL. The organic solvent is dichloromethane or ethanol.
And 4, step 4: determination of working curve for detecting concentration of chiral carboxylic acid drugs by chiral silver nanocluster
Respectively taking 1mL of the chiral nanocluster solution obtained in the step 1 and 1mL of the chiral carboxylic acid drug solution obtained in the step 2, mixing, and testing a circular dichroism spectrum signal on a circular dichroism spectrometer by using an ultraviolet dish of 1x10x40mm, wherein the concentrations of the circular dichroism spectrum signal and the chiral carboxylic acid drug are 1.16x10-7To 1.16x10-6mol/mL is linear.
And 5: determination of e.e. value working curve of chiral carboxylic acid drug detected by chiral silver nanocluster
And (3) mixing 1mL of each chiral nanocluster solution obtained in the step (1) and 1mL of chiral carboxylic acid drug solution obtained in the step (3), and testing a circular dichroism spectrum signal on a circular dichroism spectrometer by using an ultraviolet dish of 1x10x40mm, wherein the circular dichroism spectrum signal and the e.e. value of the chiral carboxylic acid drug are in a linear relation of 100% -0% (S) and 0% -100% (R).
Step 6: preparation of chiral carboxylic acid drug solution to be detected
Weighing 10mg chiral carboxylic acid drugs to be detected, dissolving in organic solvent to prepare 10mL solution with concentration of C1(ii) a Taking 5mL of C1Adding an organic solvent to dilute the solution to 10mL to obtain a solution with a concentration of C2The solution of (1); taking 5mL of C2Adding an organic solvent to dilute the solution to 10mL to obtain a solution with a concentration of C3The solution of (1); … … Take 5mL of CnAdding an organic solvent to dilute the solution to 10mL to obtain a solution with a concentration of Cn+1The solution of (1). The organic solvent is dichloromethane or ethanol. Wherein, the concentration CnThe calculation formula of (a) is as follows:
Cn＝nn/Vn＝mn/(M·Vn)＝1/(2n-1·103·M)mol/mL(n＝1，2，3……)
in the formula:
Cnthe preparation concentration of the nth chiral carboxylic acid drug solution to be detected;
nnthe quantity of the preparation substance of the nth part of chiral carboxylic acid drug solute to be detected;
mnthe preparation quality of the nth part of chiral carboxylic acid drug solute to be detected;
m is the molar mass of the chiral carboxylic acid medicament;
Vnis the preparation volume of the nth chiral carboxylic acid drug solution to be detected.
And 7: detection of chiral carboxylic acid drugs to be detected
Respectively mixing 1mL of the chiral nanocluster solution obtained in the step 1 and 1mL of the chiral carboxylic acid drug solution to be detected prepared in the step 6, testing a circular dichroism spectrum signal on a circular dichroism spectrometer by using an ultraviolet dish of 1x10x40mm, and testing to obtain a concentration Cn-1When the corresponding circular dichroism spectrum signal is less than the concentration CnAt 2 times the corresponding value of the circular dichroism spectrum signal and at a concentration of Cn+1The corresponding circular dichroism spectrum signal is the concentration CnTime corresponding circular dichroism spectrum signal value1/2 at a concentration of Cn-1The chiral carboxylic acid drug is in a saturated state after reacting with the chiral nanocluster, the circular dichroism spectrum signal of the chiral carboxylic acid drug is only in direct proportion to the e.e. value and is irrelevant to the purity of the chiral carboxylic acid drug, and the concentration of the chiral carboxylic acid drug is CnThe chiral carboxylic acid drugs are in an unsaturated state after reacting with the chiral nanoclusters, and the circular dichroism spectrum signals of the chiral carboxylic acid drugs are in direct proportion to the purity and the e.e. value of the chiral carboxylic acid drugs. To a concentration of Cn-1And (3) comparing the corresponding circular dichroism spectrum signal with the linear relation graph of the e.e. value of the chiral carboxylic acid drugs obtained in the step (5) between 100 percent and 0 percent (S) and 0 percent to 100 percent (R) to obtain the e.e. value of the chiral carboxylic acid drugs to be detected, wherein the e.e. value is Z percent. To a concentration of CnThe actual concentration C of the chiral carboxylic acid drugs to be detected with the e.e. value of Z% can be measured by comparing the corresponding circular dichroism spectrum signals with the linear relation graph of the chiral carboxylic acid drug concentration obtained in the step 4ZThe purity (p) of the sample to be tested is calculated using the following formula:
p＝CZ/(Z·Cn)＝(2n-1·103·M·CZ)/Z(n＝2，3，4……)
in the formula:
p is the purity of the chiral carboxylic acid drug to be detected;
CZthe measured concentration of the n part of chiral carboxylic acid medicine solution to be measured corresponding to the e.e. value linear relation graph of the chiral carboxylic acid medicine;
z is the e.e. value of the chiral carboxylic acid drugs;
Cnthe preparation concentration of the nth chiral carboxylic acid drug solution to be detected;
m is the molar mass of the chiral carboxylic acid medicament.
The chiral carboxylic acid drugs comprise 2-chloropropionic acid, ibuprofen, naproxen, isoleucine and the like.
The chiral detection signal range of the chiral silver nanocluster is 250-800 nm.
The chiral detection concentration range of the chiral silver nanocluster is 12.59-125.88 micrograms/milliliter, and the ratio of the object to be detected to the chiral silver nanocluster is 1:1-10:1, so that a good linear relation is presented.
The chiral detection of the chiral silver nanocluster of the present invention has: the reaction time is short, the chiral signal can be prepared at present, and the chiral signal does not change along with the increase of time, and the like, thereby being convenient for tracking and detection.
Compared with the prior art, the invention has the following advantages:
1. silver acetate is used as a silver source, and the raw materials are easily obtained; acetic acid and p-tert-butyl benzyl mercaptan are used as ligands, so that the raw material cost is low.
2. Has a definite structure, and the purity of the product is easy to detect.
3. The optical property is excellent, and all can have circular dichroism spectral signal from ultraviolet ray to ruddiness, can carry out the multiple spot and measure, and the precision is high.
4. The invention has high yield, and the yield can reach more than 30 percent by silver. The reaction can be carried out at room temperature, the repeatability is good, the preparation can be carried out in a magnification mode, and the method is particularly suitable for large-scale production.
5. The reaction is rapid, the on-site measurement and on-site preparation can be realized, and the tracking detection is convenient.
Drawings
FIG. 1 is Ag40Crystal structure and resolution. Wherein a is M13A kernel; b is three chain Ag7Protecting groups comprising one Ag strand7(CH3COO)3And two Ag strands7(CH3COO)2(TBBM); c is three lines of Ag2(CH3COO)(TBBM)4A protecting group; d is Ag40An overall top view; e is Ag40And (6) overall front view.
FIG. 2 is Ag40Stability test of (2).
FIG. 3 is Ag40Is/are as follows1H NMR spectrum.
FIG. 4 is Ag40Comparison with the UV-visible absorption spectrum (a) and the circular dichroism spectrum (b) of the chiral acid reaction.
FIG. 5 is Ag40The concentration of the chiral acid (a) and the e.e. value (b) were detected and a curve was fitted.
Detailed Description
The invention is further described below with reference to specific examples.
Hand of the inventionSilver nanoclusters having the formula: ag40(TBBM)22(CH3COO)10Abbreviated as Ag40Wherein TBBM is p-tert-butyl benzyl mercaptan.
The preparation method of the chiral silver nanocluster comprises the following steps:
adding 600mg of silver acetate and 50mL of methanol into a three-neck flask, stirring until the silver acetate and the methanol are uniformly dispersed, then adding 0.4mL of p-tert-butyl benzyl mercaptan, reacting for 30min until the solution is light yellow and turbid, then adding 20mL of methanol or tetrahydrofuran solution dissolved with 1.5g of sodium triacetoxyborohydride, and reacting for 20h at room temperature; centrifuging after the reaction is finished, pouring out supernatant, dissolving the precipitate with 50mL of dichloromethane, centrifuging, evaporating the supernatant of the dichloromethane with a rotary evaporator to remove the solvent, drying, dissolving with 50mL of n-hexane, centrifuging, evaporating the supernatant of the n-hexane with a rotary evaporator to remove the solvent, and drying to obtain a crude product; the crude product was purified with dichloromethane: recrystallizing acetonitrile at 1:2(v/v) to obtain black rhombus or long-strip crystal as the target product, 225mg and 30% of yield.
Example 1: ag40Concentration detection of a dichloromethane solution of R-2-chloropropionic acid in a dichloromethane solution
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) with 1mL of a solution of R-2-chloropropionic acid in methylene chloride (concentration from 1.16X10-7mol/mL to 1.16x10-6mol/mL) were mixed homogeneously and tested using a circular dichroism spectrometer. The results show that: the concentration of R-2-chloropropionic acid is 1.16x10-7mol/mL to 1.16x10-6In the mol/mL range, the circular dichroism spectrum signal has a linear relation with the concentration of R-2-chloropropionic acid, and the linear equation is that y is-2.0423 x107C +0.07009, coefficient of linear correlation R20.99976, wherein y is the absorption at 331nm on a circular dichroism spectrum in mdeg and C is the concentration of R-2-chloropropionic acid in mol/mL.
Example 2: ag40Detection of e.e. value of a dichloromethane solution of R-2-chloropropionic acid in a dichloromethane solution
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) with 1mL of a solution of R-2-chloropropionic acid in methylene chloride (concentration 1.16X10-6mol/mL, e.e. values from 0% to 100%) were mixed homogeneously and tested using a circular dichroism spectrometer. The results show that: the e.e. value of R-2-chloropropionic acid ranges from 0% to 100%, the circular dichroism spectrum signal and the e.e. value of R-2-chloropropionic acid have a linear relation, the linear equation is that y is-0.24382C +0.46794, and the linear correlation coefficient R is20.99949 where y is the absorption at 331nm in mdeg on a circular dichroism spectrum and C is the e.e. value for R-2-chloropropionic acid in%.
Example 3: ag40Concentration detection of dichloromethane solution of S-2-chloropropionic acid in dichloromethane solution
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) with 1mL of a solution of S-2-chloropropionic acid in methylene chloride (concentration from 1.16X10-7mol/mL to 1.16x10-6mol/mL) were mixed homogeneously and tested using a circular dichroism spectrometer. The results show that: the concentration of S-2-chloropropionic acid is 1.16x10-7mol/mL to 1.16x10-6In the mol/mL range, the circular dichroism spectrum signal has a linear relation with the concentration of S-2-chloropropionic acid, and the linear equation is that y is 2.0426x 107C +0.07119, coefficient of linear correlation R20.99908, wherein y is the absorption at 331nm on a circular dichroism spectrum in mdeg and C is the concentration of S-2-chloropropionic acid in mol/mL.
Example 4: ag40Detection of e.e. value of a dichloromethane solution of S-2-chloropropionic acid in a dichloromethane solution
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) with 1mL of a solution of S-2-chloropropionic acid in methylene chloride (concentration 1.16X10-6mol/mL, e.e. values from 0% to 100%) were mixed homogeneously and tested using a circular dichroism spectrometer. The results show that: the e.e. value of S-2-chloropropionic acid ranges from 0% to 100%, the circular dichroism spectrum signal and the e.e. value of S-2-chloropropionic acid have a linear relation, the linear equation is that y is 0.23285C +0.34423, and the linear correlation coefficient R is20.99898 where y is the absorption at 331nm in mdeg on a circular dichroism spectrum and C is the e.e. value for S-2-chloropropionic acid in%.
Example 5: ag40Detection of e.e. value of a solution of R-ibuprofen in dichloromethane
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) with 1mL of R-ibuprofen in methylene chloride (concentration 1.16X10-6mol/mL, e.e. values from 0% to 100%) were mixed homogeneously and tested using a circular dichroism spectrometer. The results show that: the e.e. value of the R-ibuprofen ranges from 0% to 100%, the circular dichroism spectrum signal of the R-ibuprofen ranges from the e.e. value to the e.e. value of the R-ibuprofen, the linear equation is that y is 0.07691C-0.1761, and the linear correlation coefficient R is20.99514 where y is the absorption at 325nm in mdeg on a circular dichroism spectrum and C is the e.e. value for R-ibuprofen in%.
Example 6: ag40Detection of e.e. value of S-ibuprofen in dichloromethane solution
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) with 1mL of S-ibuprofen in dichloromethane (1.16X 10 concentration)-6mol/mL, e.e. values from 0% to 100%) were mixed homogeneously and tested using a circular dichroism spectrometer. The results show that: the e.e. value of S-ibuprofen ranges from 0% to 100%, the circular dichroism spectrum signal and the S-ibuprofen e.e. value form a linear relation, the linear equation is that y is-0.07157C +0.07093, and the linear correlation coefficient R is20.99879 where y is the absorption at 325nm in mdeg on a circular dichroism spectrum and C is the e.e. value for S-ibuprofen in%.
Example 7: ag40E.e. value detection of dichloromethane solution of R-naproxen in dichloromethane solution
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) with 1mL of a solution of R-naproxen in methylene chloride (concentration 1.16X10-6mol/mL, e.e. values from 0% to 100%) were mixed homogeneously and tested using a circular dichroism spectrometer. The results show that: the e.e. value of R-naproxen ranges from 0% to 100%, the circular dichroism spectrum signal and the E.e. value of R-naproxen have linear relation, and the linear equation is that y is 0.23767C-1.22368 coefficient of linear correlation R20.99659 where y is the absorption at 325nm in mdeg on a circular dichroism spectrum and C is the e.e. value for R-naproxen in%.
Example 8: ag40E.e. value detection of dichloromethane solution of S-naproxen in dichloromethane solution
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) with 1mL of a solution of S-naproxen in methylene chloride (concentration 1.16X10-6mol/mL, e.e. values from 0% to 100%) were mixed homogeneously and tested using a circular dichroism spectrometer. The results show that: the e.e. value of S-naproxen is in the range of 0% to 100%, the circular dichroism spectrum signal and the E.e. value of S-naproxen are in linear relation, the linear equation is that y is-0.25526C-1.92022, and the linear correlation coefficient R is20.99584 where y is the absorption at 325nm in mdeg on a circular dichroism spectrum and C is the e.e. value for S-naproxen in%.
Example 9: ag40E.e. value detection of a dichloromethane solution of L-isoleucine in a dichloromethane solution
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) was mixed homogeneously with 1mL of an ethanol-saturated solution of L-isoleucine (e.e. values from 0% to 100%) and tested using a circular dichroism spectrometer. The results show that: the e.e. value of the L-isoleucine ranges from 0% to 100%, the circular dichroism spectrum signal of the L-isoleucine is in linear relation with the e.e. value of the L-isoleucine, the linear equation is that y is 0.22638C +1.89319, and the linear correlation coefficient R is20.98522 where y is the absorption at 325nm in mdeg on a circular dichroism spectrum and C is the e.e. value for L-isoleucine in%.
Example 10: ag40E.e. value detection of a dichloromethane solution of D-isoleucine in a dichloromethane solution
1mL of Ag40Dichloromethane solution (concentration 1.16x 10)-7mol/mL) was mixed homogeneously with 1mL of an ethanol-saturated solution of D-isoleucine (e.e. values from 0% to 100%) and tested using a circular dichroism spectrometer. The results show that: e.e. value of D-isoleucine from 0% to 100In the% range, the circular dichroism spectrum signal and the D-isoleucine e.e. value are in a linear relation, the linear equation is that y is-0.19157C +0.44447, and the linear correlation coefficient R is20.98111 where y is the absorption at 325nm in mdeg on a circular dichroism spectrum and C is the e.e. value for D-isoleucine in%.
Claims (7)
1. A chiral silver nanocluster characterized by:
the molecular formula of the chiral silver nanocluster is as follows: ag40(TBBM)22(CH3COO)10Abbreviated as Ag40Wherein TBBM is p-tert-butyl benzyl mercaptan.
2. A method for preparing the chiral silver nanocluster of claim 1, comprising the steps of:
adding 600mg of silver acetate and methanol into a three-neck flask, stirring until the silver acetate and the methanol are uniformly dispersed, then adding 0.4mL of p-tert-butyl benzyl mercaptan, reacting for 30min until the solution is light yellow and turbid, then adding 20mL of methanol or tetrahydrofuran solution dissolved with 1.5g of sodium triacetoxyborohydride, and reacting for 20h at room temperature; and after the reaction is finished, centrifuging, pouring out supernatant, dissolving the precipitate with dichloromethane, centrifuging, evaporating the supernatant of the dichloromethane by using a rotary evaporator to remove the solvent, drying, dissolving with n-hexane, centrifuging, evaporating the supernatant of the n-hexane by using the rotary evaporator to remove the solvent, and drying to obtain a crude product.
3. The preparation method according to claim 2, characterized in that:
and recrystallizing the obtained crude product by using a mixed solution of dichloromethane and acetonitrile in a volume ratio of 1:2 to obtain black rhombus or long-strip crystal, namely the target product.
4. Use of chiral silver nanoclusters according to claim 1, wherein:
the chiral silver nanoclusters are used as reaction substrates and react with chiral carboxylic acid drugs to transmit chiral signals, and then the content and the chiral e.e. value of the chiral carboxylic acid drugs are measured.
5. Use according to claim 4, characterized in that:
the chiral carboxylic acid drugs comprise 2-chloropropionic acid, ibuprofen, naproxen, isoleucine and the like.
6. Use according to claim 4, characterized in that:
the chiral detection signal range of the chiral silver nanocluster is 250-800 nm.
7. Use according to claim 4, characterized in that:
the chiral detection concentration range of the chiral silver nanocluster is 12.59-125.88 micrograms/milliliter, and the ratio of the object to be detected to the chiral silver nanocluster is 1:1-10:1 and shows a linear relationship.
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