CN102507952B - Method for detecting protein and metal ions - Google Patents
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- CN102507952B CN102507952B CN201110306635.0A CN201110306635A CN102507952B CN 102507952 B CN102507952 B CN 102507952B CN 201110306635 A CN201110306635 A CN 201110306635A CN 102507952 B CN102507952 B CN 102507952B
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Abstract
The invention relates to the field of biotechnology, and discloses a method for detecting protein and metal ions. The method comprises the following steps: providing a probe molecule with a reporter fluorophore and capable of specifically binding with a target; mixing the probe molecule with a nanoparticle solution rich in pi electrons; and adding the sample to be detected; and detecting fluorescence, wherein the nanoparticle rich in pi electrons is selected from conjugated polymer of phenylenediamine monomer, 3,4-ethylenedioxythiophene or styrene, Ag(I)-4,4'-bipyridyl, Cu(II)-4,4'-bipyridyl, 3,3',5,5'-tetramethylbenzidine chloroplatinate, p-phenylenediamine chloroplatinate or 4,4'-bipyridyl tetrachloroaurate coordination polymers, porphyrin cluster, mesoporous carbon and nano C60. The detection method provided by the invention has the advantages of low cost, simple operation, short detection time, high sensitivity and wide application range.
Description
Technical field
The present invention relates to biological technical field, relate to specifically a kind of method that detects protein and metallic ion.
Background technology
Protein is biomacromolecule important in human body, and it is not only very important and requisite for sustaining life, and meanwhile, it has substantial connection for copying of the transcribing of the translation of life genetic code, information, DNA etc.The content of protein in body fluid can be used as the important indicator of human nutrition health, medical diagnosis on disease, as the content of urinating albumen be diagnosis ephritis and diabetes according to one of, in normal person 24h urine, the content of protein is at 20～80mg, and having exceeded this limit is undesired value, is the sign of morbidity.If haemocyanin is the important living matter of one in human body, its content in body fluid can be used as the important indicator of human nutrition health, medical diagnosis on disease etc.And for example Alzheimer disease (AD) is one group of agnogenic central nervous system abiotrophic degeneration's disease, be still at present a kind of disease can not be cured, Tau albumen in quantitative determination cerebrospinal fluid may become a useful indicators of AD early diagnosis, biology is measured, as cerebrospinal fluid Tau protein determination, may help clinician to reach the object of early diagnosis and prevention AD.Therefore, can realize the early diagnosis of disease to the trace detection of specified protein, thereby treat ahead of time, extend patients ' lives.
Metallic ion is being played the part of important role at environment, biological and medical field, and its concentration, kind and valence state have material impact to vital movement and environment.Such as the metallic ions such as potassium, iron, zinc are the indispensable elements that life entity maintains normal physiological activity.And some heavy metal ion, owing to can not decomposing in environment and can, by food chain gradually in the enrichment of biologic chain upper strata, easily causing slow poisoning.According to " Beijing Youth Daily ": since 1974, Long Ling village, Hua County, Shaanxi is dead 58 people altogether, 29 people that die from cancer, 22 people that die from pulmonary heart disease, cerebrovascular disease, only 1 Genus Homo is in natural death.Mainly be subject to the pollution of plumbous and arsenic through looking into this ground soil, the edible flour of local villager is subject to the severe contamination of lead, arsenic, zinc, 4 kinds of elements of chromium, and in fresh kidney beans, cadmium, plumbous content are respectively 5.3 times and 2.55 times of standard value, the vegetables of genus severe contamination.Therefore, the detection of metallic ion is had great importance at the aspect such as environmental monitoring and medical diagnosis on disease.At present, mainly use the luminous and absorption spectrum of atom for metal ion detection, although the method has highly sensitive, accuracy advantages of higher need to be used large-scale instrument, testing cost is higher, is unfavorable for extensive popularization.Therefore, need exploitation a kind of simple, fast, high selectivity, highly sensitive metal ion inspection.
Summary of the invention
In view of this, the present invention seeks to the defect for existing detection method, a kind of simple to operate, highly sensitive, detection protein that selectivity is strong and the method for metallic ion are provided.
For realizing object of the present invention, the present invention adopts following technical scheme:
Detect a method for protein and metallic ion,
Provide band report fluorophor can with the probe molecule of target specific binding;
Described probe molecule is mixed with the nano material solution that is rich in pi-electron, then add testing sample, detect fluorescence;
Wherein, described target is protein and metallic ion, it is phenylenediamine, 3,4-rthylene dioxythiophene or cinnamic conjugated polymer that the described nano material that is rich in pi-electron is selected from monomer, silver (I)-4,4 '-dipyridine, copper (II)-4,4 '-dipyridine, chloroplatinic acid-3,3 ', 5,5 '-tetramethyl biphenyl diamines, chloroplatinic acid-p-phenylenediamine (PPD) or tetrachloro alloy acid-4,4'-Bipyridine coordination polymer, porphyrin bunch collective, mesoporous carbon and nanometer C
60.
Along with the development of the external evolution technology of DNA, the screening of DNA probe molecular sequences and synthetic cost are more and more lower, and therefore the detection platform based on DNA molecular has broad application prospects.The specific recognition effect of DNA molecular and protein is study hotspot in recent years, be widely used in identification and the detection of specific protein, as the people such as the Landegren at the biomedical center of Uppsala, SWE detect by high sensitivity and high selectivity that DNA has realized PDGF albumen as probe, its minimal detectable concentration is 40 × 10
-21mol[Fredriksson, S.Gullberg, M.; Jarvius, J.; Olsson, C.; Pietras, K.; Gustafsdottir, S.M.; Ostman, A.; Landegren, U., Nat.Biotechnol, 2002,20,473-477].The DNA sequence dna of special screening can form stable complex with metallic ion, shows the specificity of effect, as a kind of Hg
2+the colorimetric detection method of ion, utilizes Hg
2+the effect of T base in ion and DNA sequence dna AGR0100, detects and is limited to 50nM[Li, T.; Dong, S.J.; Wang, E.K., Anal Chem, 2009,81,2144-2149].Through the DNA molecular of external evolution screening, can with the effect of organic molecule generation specific recognition, thereby the conversion of inducing DNA molecular conformation, as the people such as the Liu of NUS utilize the selection effect of fluorescently-labeled DNA and ATP, realize the selectivity of ATP has been detected, its detection is limited to 20 μ M[Wang, Y.; Liu, B., Analyst, 2008,133,1593-1598].
The present invention detects the method for protein and metallic ion and utilizes π-π to interact, to be adsorbed on the nano-material surface that is rich in pi-electron with the probe molecule of target specific binding, the fluorescence of quenching probes molecule, then probe molecule mixes with testing sample, probe molecule is combined with target, probe molecule is departed from from nano-material surface, and fluorescent quenching effect disappears, and realizes the detection to testing sample by detecting fluorescence signal.And according to fluorescence intensity change, also can determine the content of target in testing sample.The method of detection protein of the present invention and metallic ion is with low cost, described in to be rich in the preparation method of nano material of pi-electron simple, the prices of raw and semifnished materials are cheap, and can prepare on a large scale; Simple to operate, in testing process, only the nano material, probe molecule and the testing sample that are rich in pi-electron need to be mixed, use simple fluoroscopic examination instrument to detect fluorescence, do not need to use expensive large-sized analytic instrument; Detect excellent performance, detection time is short, highly sensitive, be a kind of easy, quick, cost is low, the detection protein of applied range and the method for metallic ion.
Accompanying drawing explanation
Fig. 1 shows the principle schematic of detection method of the present invention, and wherein, the nano material of pi-electron is rich in spherical representative, does not show that material is originally as spherical, and target comprises protein and metallic ion; DNA probe is folding represents that its conformation changes, but is not limited only to fold;
Fig. 2 shows that poly m-phenylene diamine nanometer rods detects the result figure of fibrin ferment albumen.A is DNA probe (20nMT
a) fluorescence emission spectrum; B is DNA probe (20nM T
a)+target protein (100nM T
b) fluorescence emission spectrum; C is DNA probe (20nM T
a)+target protein (100nM T
bthe fluorescence emission spectrum of)+PMPD nanometer rods; D is DNA probe (20nM T
athe fluorescence emission spectrum of)+PMPD nanometer rods; E is the fluorescence emission spectrum of PMPD nanometer rods self;
Fig. 3 shows the specificity selection result figure of poly m-phenylene diamine nanometer rods to fibrin ferment; Other two kinds of immunoglobulin (Ig)s (IgG) that disturb albumen to be respectively bovine serum albumin(BSA) (BSA) and people, concentration is 100nM.
Fig. 4 shows the result of fibrin ferment in mesoporous carbon detection of particulates human serum sample;
Fig. 5 shows nanometer C
60(nano-C
60) to metallic ion Hg
2+testing result figure, DNA probe (P
h, 100nM) and fluorescence emission spectrum under different condition: (a) P
h, (b) P
h+ Hg
2+(8 μ M), (c) P
h+ nano-C60, (d) P
h+ nano-C
60+ Hg
2+(8 μ M);
Fig. 6 shows nano-C
60to metallic ion Hg
2+selectivity result figure.Wherein, Hg
2+concentration is that the concentration of other interfering ion in 8 μ M figure A is 5 μ M, and in figure B, the concentration of other interfering ion is 50 μ M;
Fig. 7 shows nano-C
60detect metallic ion Hg in lake water
2+result figure.A is the fluorescence emission spectrum of lake water, and b is lake water+30nM Hg
2+fluorescence emission spectrum.
Embodiment
The embodiment of the invention discloses a kind of method that detects protein and metallic ion.Those skilled in the art can use for reference content herein, suitably improve technological parameter and realize.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are all deemed to be included in the present invention.Method of the present invention is described by preferred embodiment, and related personnel obviously can change method as herein described in content of the present invention, spirit and scope or suitably change and combination not departing from, and realizes and apply the technology of the present invention.
For realizing object of the present invention, the present invention adopts following technical scheme:
Provide band report fluorophor can with the probe molecule of target specific binding;
Described probe molecule is mixed with the nano material solution that is rich in pi-electron, then add testing sample, detect fluorescence;
Wherein, described target is protein and metallic ion, it is phenylenediamine, 3,4-rthylene dioxythiophene or cinnamic conjugated polymer that the described nano material that is rich in pi-electron is selected from monomer, silver (I)-4,4 '-dipyridine, copper (II)-4,4 '-dipyridine, chloroplatinic acid-3,3 ', 5,5 '-tetramethyl biphenyl diamines, chloroplatinic acid-p-phenylenediamine (PPD) or tetrachloro alloy acid-4,4'-Bipyridine coordination polymer, porphyrin bunch collective, mesoporous carbon and nanometer C
60.
The method of detection protein of the present invention and metallic ion will be mixed with the nano material that is rich in pi-electron with the probe molecule of target specific binding, because π-π interacts, probe molecule is adsorbed on material surface, reports that afterwards between the same nano material that is rich in pi-electron of fluorophor, energy occurring shifts the fluorescent quenching that fluorophor can be launched on probe molecule.Add after testing sample, the target in testing sample is combined with probe molecule, and probe molecule is departed from from nano-material surface, and fluorescent quenching effect disappears, and probe molecule recovers fluorescence, realizes the detection to testing sample by detecting fluorescence signal.And according to fluorescence intensity change, also can determine the content of target in testing sample.
Probe molecule of the present invention, with report fluorophor, can be held or 5 ' end mark report fluorophor at probe molecule 3 ', also can report fluorophor with tense marker at 3 ' end and 5 ' end, to improve fluorescence intensity, improves the sensitivity detecting.The report fluorophor of probe mark includes but not limited to following fluorescent material: FAM, TET, JOE, VIC, HEX, ROX, TAMRA, CY3, CY3.5, CY5, CY5.5, Oregon Green, CAL Red, Red640 and Texas Red.
It is phenylenediamine, 3,4-rthylene dioxythiophene or cinnamic conjugated polymer that the nano material that is rich in pi-electron of the present invention is selected from monomer.Wherein, the preparation method of described conjugated polymer mixes the solution of monomer and oxygenant according to mol ratio 1: 0.1～20, place 1min～24h, makes.Described monomer is phenylenediamine, 3,4-rthylene dioxythiophene or styrene, and described oxygenant is preferably ammonium persulfate or ferric trichloride.
Coordination polymer of the present invention is silver (I)-4,4 '-dipyridine, copper (II)-4,4 '-dipyridine, chloroplatinic acid-3,3 ', 5,5 '-tetramethyl biphenyl diamines, chloroplatinic acid-p-phenylenediamine (PPD) or tetrachloro alloy acid-4,4 '-dipyridine coordination polymer, by containing the 4,4'-Bipyridine of pi-electron and tetramethyl biphenyl two amine molecules as monomer, transition metal ion silver, copper, platinum or gold, as initiating agent, are polymerized.The preparation method of described coordination polymer mixes according to mol ratio 1: 0.1～20 by transition metal ion with containing the solution of the organic molecule of pi-electron, places 1min～24h, makes.
Organic molecule bunch collective is in the mixed system of water or water and organic solvent, and organic molecule is under hydrophobic lipotropism drives, mutually near the simple molecules aggregate forming.Porphyrin of the present invention bunch collective is formed near a bunch collection in the mixed solution of water and organic solvent mutually by the Porphyrin Molecule containing pi-electron.Wherein, the preparation method of described porphyrin bunch collective is that the Porphyrin Molecule containing pi-electron is dissolved in and in organic solvent, obtains the solution that concentration is 1mmol/L～0.5mol/L, is then with water to mix at 0.001～1: 1 according to volume ratio, and placement 1min～24h, makes.Wherein, described organic solvent is preferably methyl alcohol, ethanol, propyl alcohol, ethylene glycol, dimethyl sulfoxide (DMSO), tetrahydrofuran or 1-METHYLPYRROLIDONE.
Mesoporous carbon of the present invention and nanometer C
60all belong to material with carbon element, wherein, the preparation method of described mesoporous carbon introduces carbon source precursor in the duct of mesopore silicon oxide by infusion process, under acid catalysis, make precursor thermal decomposition and be deposited in the duct of template mesoporous material, calcining carbonization makes carbon-silicon compound, then remove silicon template, make mesoporous carbon.Wherein, described carbon source precursor is preferably glucose, sucrose acetylene, mesophase pitch, furancarbinol, phenol/formaldehyde resins.Nanometer C of the present invention
60preparation method be by C
60powder dissolution, in acetone, then mixes with acetonitrile, collects khaki precipitation, is then dispersed in water and makes.
In order further to understand the present invention, below in conjunction with embodiment, the present invention is described in detail.
Wherein, the present invention target protein (T take human thrombin albumen as detecting in an embodiment
b), what fluorophore (FAM) was modified has the single stranded DNA sequence of specific recognition capability as the fluorescence probe (T of fluoroscopic examination albumen to human thrombin albumen
a).In an embodiment with Hg
2+and Ag
+respectively as detect metal target ion, by fluorophore (FAM) modify be rich in T base to Hg
2+there is the single stranded DNA sequence of specific binding capacity as fluoroscopic examination Hg
2+dNA probe (P
h), by fluorophore (FAM) modify be rich in C base to Ag
+there is the single stranded DNA sequence of specific binding capacity as fluoroscopic examination Ag
+dNA probe (P
ag).Each probe sequence refers to table 1.
Table 1 probe sequence of being correlated with
Embodiment 1: the preparation of the nanometer rods of poly m-phenylene diamine (PMPD) and detection albumen
Material preparation and processing: under room temperature, the ammonium persulfate aqueous solution that is 0.5M by 0.06mL concentration mixes with 0.84mL water, then adding 0.1mL concentration is aqueous solution the vibration of 0.1M m-phenylene diamine, the nanosphere precipitation of visible poly m-phenylene diamines in a large number occurs afterwards.Intermediate water for gained precipitation is rinsed and centrifugal, repeatable operation several times, and then is dispersed in water, and makes poly m-phenylene diamine (PMPD) nanometer rods, and 4 ℃ store for future use.
Detect albumen: what fluorophore (FAM) was modified has the single stranded DNA sequence of specific recognition capability as the fluorescence probe (T that detects albumen to human thrombin albumen
a), the target protein (T take human thrombin albumen as detecting
b).Detection method: first PMPD nanometer rods is joined to fluorescence probe (50nM T
a) solution in, the DNA probe of strand is adsorbed onto the surface of PMPD nanometer rods, causes fluorescent quenching.Through one period of reaction time (60min), fluorescent quenching reaches balance (98%).Add human thrombin albumen (100nM T
b),, due to the existence of albumen, the cancellation of fluorescence is suppressed, and only has 50% cancellation generation (60min reaches balance).Testing result is shown in Fig. 2.Result demonstration, the detection method detectability based on PMPD nanometer rods can reach 100pM.When adding other albumen (100nM bovine serum albumin BSA or people's immunoglobulin (Ig) 100nM IgG) to fluorescence probe (50nM T
a) solution in after, then add PMPD nanometer rods, the results are shown in Figure 3.Fluorescent quenching is not suppressed as seen from Figure 3, and BSA and the IgG fluorescence intensity contrast T while existing
bthe ratio of the fluorescence intensity while existence is 10.6% and 8.6%, and therefore the detection method based on PMPD nanometer rods has very high specific detection ability to human thrombin albumen.
Embodiment 2:nano-C
60preparation and detect albumen and metallic ion
Material preparation and processing: by the C of 2.5mg
60be dissolved in 2mL acetone, be then added dropwise to while stirring 12mL acetonitrile, next a large amount of khaki precipitations occur.To precipitate and rinse and centrifugal with acetonitrile, several times, more ultrasonic 30min makes the Nano-C obtaining to repeatable operation
60be dispersed in 8mL water for subsequent use.
The detection of albumen: what fluorophore (FAM) was modified has the single stranded DNA sequence of specific recognition capability as the fluorescence probe (T of fluoroscopic examination albumen to human thrombin albumen
a), the target protein (T take human thrombin albumen as detecting
b).First by nano-C
60join fluorescence probe (50nMT
a) solution in, the DNA probe of strand can be adsorbed onto nano-C
60surface, cause fluorescent quenching.Through one period of reaction time (60min), fluorescent quenching reaches balance (86%).Add human thrombin albumen (100nM T
b), then add nano-C
60,, due to the existence of albumen, the cancellation of fluorescence is suppressed, and only has 60% cancellation generation (60min reaches balance).Based on nano-C
60detection method detectability can reach 1nM.When adding other albumen (100nM bovine serum albumin BSA or people's immunoglobulin (Ig) 100nM IgG) to fluorescence probe (50nM T
a) solution in after, then add nano-C
60, fluorescent quenching is not suppressed, and BSA and the IgG fluorescence intensity contrast T while existing
bthe ratio of the fluorescence intensity while existence is 27.3% and 29.3%, therefore based on nano-C
60detection method human thrombin albumen is had to very high specific detection ability.
Metallic ion (Hg
2+, Ag
+) detection: by fluorophore (FAM) modify be rich in T base to Hg
2+there is the single stranded DNA sequence of specific binding capacity as the fluorescence probe (P of fluoroscopic examination
h), with Hg
2+for the metal target ion detecting.First by nano-C
60join fluorescence probe (50nM P
h) solution in, the DNA probe of strand can be adsorbed onto nano-C
60surface, cause 88% fluorescent quenching.And at Hg
2+under the condition existing, due to T-Hg
2+the formation of the caused foldable structure of-T, the cancellation of fluorescence is suppressed, and fluorescence intensity is now without Hg
2+while existence 6 times.By above process, based on nano-C
60detection Hg
2+the method of ion, detectability can be low to moderate 500pM.The results are shown in Figure 5 and Fig. 6.In the time adding other metallic ion, this detection method also has very high selectivity, and the method can detect in actual sample lake water, the results are shown in Figure 7.In addition, the method can be applicable to Ag
+detect, detectability reaches 1nM.
Embodiment 3: the preparation of mesoporous silicon and detection albumen and metallic ion
Material preparation and processing: the mesoporous silicon of 1g (MS) is added in 5g water, then add 1.25 glucose and 0.14g 98%H
2sO
4, under room temperature, stir after 5h, allow gained potpourri react respectively 6h at 100 ℃ and 160 ℃.Afterwards, reaction mixture is added in 5g water, then adds 0.75g sugar and 0.09g 98%H
2sO
4.Stirring after 12h, by reaction mixture dry 6h at 160 ℃.Finally, at 800 ℃ of N
2under protective condition, calcine 4h, complete carbonization process.1M NaOH (water/alcohol mixeding liquid) for the carbon-silicon compound of gained is rinsed to 12h and remove silicon template, under room temperature, be dried afterwards, obtain the particulate of mesoporous carbon (MC).
The detection of albumen: what fluorophore (FAM) was modified has the single stranded DNA sequence of specific recognition capability as the fluorescence probe (T of fluoroscopic examination albumen to human thrombin albumen
a), the target protein (T take human thrombin albumen as detecting
b).First MC is joined to fluorescence probe (50nM T
a) solution in, the DNA probe of strand can be adsorbed onto the surface of MC, causes fluorescent quenching.Through one period of reaction time (60min), fluorescent quenching reaches balance (97%).Add human thrombin albumen (100nM T
b), then add MC,, due to the existence of albumen, the cancellation of fluorescence is suppressed, and only has 38% cancellation generation (60min reaches balance), the results are shown in Figure 4.Result demonstration, the detection method detectability based on MC can be low to moderate 250pM.When adding other albumen (100nM bovine serum albumin BSA or people's immunoglobulin (Ig) 100nM IgG) to fluorescence probe (50nM T
a) solution in after, then add MC, fluorescent quenching is not suppressed, and BSA and the IgG fluorescence intensity contrast T while existing
bthe ratio of the fluorescence intensity while existence is 6.2% and 7.4%, and therefore this detection method based on MC has very high specific detection ability to human thrombin albumen.
The detection of metallic ion: by fluorophore (FAM) modify be rich in C base to Ag
+there is the single stranded DNA sequence of specific binding capacity as the fluorescence probe (P of fluoroscopic examination
ag), with Ag
+for the metal target ion detecting.First MC is joined to fluorescence probe (50nM P
ag) solution in, the DNA probe of strand can be adsorbed onto the surface of MC, causes 84% fluorescent quenching.And at Ag
+under the condition existing, due to C-Ag
+the formation of the caused foldable structure of-C, the cancellation of fluorescence is suppressed, and fluorescence intensity is now without Ag
+while existence 4 times.Result demonstration, the detection method detectability based on MC can be low to moderate 500pM.In the time adding other metallic ion, this detection method also has very high selectivity, and the method can detect in actual sample lake water.In addition, the method can be used for Hg
2+detection, detectability can reach 10nM.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (1)
1. a method that detects protein or metallic ion, is characterized in that,
Provide band report fluorophor can with the probe molecule of target specific binding;
Described probe molecule is mixed with the nano material solution that is rich in pi-electron, then add testing sample, detect fluorescence;
Wherein, described target is protein or metallic ion, described in be rich in pi-electron nano material monomer be copper (II)-4,4'-Bipyridine.
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| CN103487416B (en) * | 2013-03-06 | 2016-01-20 | 中北大学 | A kind of based on the fluorescent optical sensor of asymmetrical porphyrin fluorescence than detection zinc ion |
| CN107044961A (en) * | 2017-03-24 | 2017-08-15 | 福建工程学院 | A kind of method of spectrophotometry silver ion |
| CN108732348B (en) * | 2017-04-19 | 2022-07-08 | 复旦大学 | Construction method of ligand-gated diagnosis and treatment system and application of ligand-gated diagnosis and treatment system in tumor real-time response |
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| Production of stable aqueous dispersion of poly(3,4-ethylenedioxythiophene) nanorods using graphene oxide as a stabilizing agent and their application for nitrite detection;Sen Liu et al.;《Analyst》;20111006;第136卷(第23期);第4898－4902页 * |
| Sen Liu et al..A new application of mesoporous carbon microparticles to nucleic acid detection.《J. Mater. Chem》.2010,第21卷第339-341页. |
| SenLiuetal..Productionofstableaqueousdispersionofpoly(3 4-ethylenedioxythiophene) nanorods using graphene oxide as a stabilizing agent and their application for nitrite detection.《Analyst》.2011 |
| Yingwei Zhang et al..Poly(m-Phenylenediamine) Nanospheres and Nanorods: Selective Synthesis and Their Application for Multiplex Nucleic Acid Detection.《PLoS ONE》.2011,第6卷(第6期),第1-11页. |
| Yonglan Luo et al..Coordination polymer nanobelts for nucleic acid detection.《Nanotechnology》.2011,第22卷(第19期),第1-6页. |
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