CN111205320B - Multinuclear organic-metal gold (I) supramolecular cluster compound and synthesis method and application thereof - Google Patents
Multinuclear organic-metal gold (I) supramolecular cluster compound and synthesis method and application thereof Download PDFInfo
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Abstract
The invention discloses a polynuclear organic-metal gold (I) supramolecular cluster compound which has the following structural general formula; the preparation method comprises the following steps: s1, coordination substitution reaction: 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate was added dropwise to Dppmau2Cl2Carrying out coordination substitution reaction to obtain a mixture; when 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate is mixed with the Dppmau2Cl2In a molar amount of 1: 1, obtaining the polynuclear organic-metal gold (I) supermolecular cluster compound; otherwise, proceeding to the following steps S2-S4; s2, adding inorganic salt to carry out displacement reaction to precipitate; s3, centrifuging, collecting and washing the precipitate; s4, dissolving and performing single crystal culture. The multinuclear organic-metal gold (I) supermolecular cluster compound prepared by the self-assembly synthesis method has high chemical stability, low cytotoxicity and good biocompatibility.
Description
Technical Field
The invention belongs to the technical field of coordinated supermolecules, relates to a series of gold (I) -based supermolecule cluster compounds, and particularly relates to a multinuclear organic-metal gold (I) supermolecule cluster compound and a synthesis method and application thereof.
Background
Gold affinity as an efficient non-covalent synthetic approach has been widely applied to the precise assembly of various gold (I) -containing supramolecular structures, including different multinuclear cluster structures, such as: metal ring structures, cage structures, catenane structures, and other structures. Polynuclear gold (I) clusters containing gold-philic bonds have gained considerable interest as one of the classical members of the gold (I) -based supramolecular family not only because of their attractive complex chemical structure but also because of their excellent physicochemical properties, such as: catalysis, photophysics, bioimaging properties, chiral sensing, and the like. From the current literature reports, most of gold (I) clusters are synthesized by a one-pot method of organic ligands and metal salts, and the synthesis method mainly has the following defects: (1) the separation and purification of a single product are difficult to realize in the synthesis reaction; (2) the chemical structure of the target product is difficult to predict; (3) the stability of the cluster compound is difficult to realize high-efficiency regulation and optimization; (4) real-time tracking and monitoring of the self-assembly process is difficult to achieve. In addition, the gold (I) -based supramolecular cluster compounds reported at present have poor chemical stability, and are often difficult to stably exist particularly in the case of responding to the complex heterocyclic environment in biological cells. The disadvantages of stability and biocompatibility must limit the application of gold (I) clusters in the fields related to biological cells.
Disclosure of Invention
The invention aims to overcome the defects of the traditional one-pot synthesis method, and the polynuclear organic-metallic gold (I) supermolecular cluster compound is prepared by a self-assembly synthesis method and has high chemical stability; the cell imaging result of the gold (I) supramolecular cluster compound and Hela cancer cells shows that the gold (I) supramolecular cluster compound also has good biological uptake capacity, so that the application of the gold (I) supramolecular cluster compound in cell imaging and the like is further widened.
In order to achieve the purpose, the invention is realized by the following scheme:
one of the objectives of the present invention is to provide a polynuclear organo-metallic gold (I) supramolecular cluster compound having the following structural formula:
wherein n may be selected from 0.5, 1 or 4;
the invention also aims to provide a method for synthesizing the polynuclear organic-metallic gold (I) supramolecular cluster compound, which comprises the following steps:
s1, coordination substitution reaction: 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate was added dropwise to Dppmau2Cl2Carrying out coordination substitution reaction to obtain a mixture; when 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate is mixed with the Dppmau2Cl2In a molar amount of 1: 1, obtaining the polynuclear organic-metal gold (I) supermolecular cluster compound; otherwise, proceeding to the following steps S2-S4;
s2, replacement reaction: stirring the obtained mixture at room temperature for a period of time, and adding inorganic salt to perform a displacement reaction to precipitate the inorganic salt;
s3, washing: centrifuging and collecting the precipitate, and washing to obtain yellow powder;
s4, dissolution and single crystal cultivation: dissolving the obtained yellow powder by using a solvent to obtain yellow precipitate, and diffusing diethyl ether into the yellow precipitate for a period of time to obtain the polynuclear organic-metallic gold (I) supramolecular cluster compound.
Specifically, the feeding ratio of the two reactants in the step S1 is divided into the following four cases:
A. if 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate is mixed with dppmaU2Cl2The molar ratio is 1: 1, directly synthesizing to obtain the polynuclear organic-metallic gold (I) supermolecular cluster compound 1 (binuclear Au) through the S1 coordination substitution reaction2) In the structural general formula, n is 0.5;
B. if 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate is mixed with dppmaU2Cl2The molar ratio is 1: 2, obtaining the polynuclear organic-metallic gold (I) supramolecular cluster compound 2 (tetranuclear Au) through the steps of S1-S44) In the structural general formula, n is 1;
C. if 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate is mixed with dppmaU2Cl2The molar ratio is 1: 3, obtaining the multinuclear organic-metallic gold (I) supramolecular cluster compound 3 (sixteen-nuclear Au) through the steps of S1-S416) In the structural general formula, n is 4;
D. if 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate anddppmAu2Cl2the molar ratio is 1: 2.5, obtaining the polynuclear organic-metallic gold (I) supramolecular cluster compound 4 (sixteen-nucleus Au) through the steps of S1-S416) In the structural general formula, n is 4.
The specific reaction process is shown in the following chart:
the relevant data for the crystal structure determination of the multinuclear organo-metallic gold (I) supramolecular cluster 2, 3, 4 are shown in table 1.
TABLE 1
Preferably, an organic solvent is further added in step S1, and the organic solvent includes one or more of dichloromethane and methanol, ethanol, isopropanol, isobutanol, acetonitrile, tetrahydrofuran, dioxane, chloroform, and carbon tetrachloride.
Preferably, the temperature of the coordination substitution reaction in the step S1 is 5-70 ℃.
Preferably, the inorganic salt in step S2 includes NaBF4、KPF6、NH4PF6、N(C2H5)4PF6、N(C4H9)4PF6、NaBPh4、K2HPO4、KH2PO4、KSCN,K2SO4、KOTs、KOTf、KTFA、KOAc、KCF3SO3、CF3COOK、KClO4Ac、KSiF6、KTcO4One or more of (a).
Preferably, the molar ratio of the inorganic salt added in the step S2 to the raw material 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate is 4-40: 1.
preferably, the stirring time in the step S2 is 6-36 h; the temperature of the anion displacement reaction is 5-70 ℃, and the reaction time is 8-48 h.
Preferably, in the step S3, a mixed solvent of water and methanol is adopted for washing, and the washing is performed for 2-5 times; the solvent used to dissolve the yellow powder in step S4 was an acetonitrile/dichloromethane solution.
The invention also aims to provide application of the gold (I) supramolecular cluster compound as a novel red light cell imaging reagent in biological fluorescence imaging.
Compared with the prior art, the invention has the beneficial effects that:
1. the synthesis method of the multi-core organic-metal gold (I) supramolecular cluster compound is prepared by a self-assembly synthesis method, and the synthesis strategy is characterized in that multi-component synergistic stepwise self-assembly of the supramolecular cluster compound and controllable growth of the cluster compound are realized by material control, and a binuclear gold (I) structural unit dppmAu is used2Cl2With trithiocyanate ligands Na containing soft S and hard N-donors3(tatt3-) Raw materials were mixed in different stoichiometric ratios (1: 1; 1: 2; 1: 2.5; 1: 3) then, the coordination exchange reactivity of sulfur-chlorine/phosphine atoms is activated in sequence, so that multiple components can be gathered together with high precision, and then the multi-component synergetic stepwise self-assembly of the supermolecular cluster and the controllable growth of the cluster are realized through simple material control. Specifically, when the material ratio of the heterocyclic bifunctional tripod ligand containing S, N to the binuclear gold (I) unit containing P is 1: 1, the heterocyclic bifunctional tripod ligand containing S, N and the binuclear gold (I) unit containing P can generate coordination exchange reaction, namely, the binuclear gold (I) cluster compound 1 is formed through S-Cl ligand exchange; continuing to increase the charge of 1 equivalent of metal units, another pair of synergistic [ S ]-⌒N]The donor is activated to form a planar tetranuclear gold (I) cluster 2; further adding an excessive amount of metal units, the double bridge angle [ (S) is trapped in the cluster 2-⌒S-)Au2]One of the coordinatively inert N donors is activated, thus by strong intermolecular and intramolecular AuI···AuIBond interaction driven spontaneous ligand displacement and conformational rearrangement gradually self-assemble to form a high-core number supramolecular gold (I) cluster. The method prepares a series of multinuclear gold (I) supermolecular clusters with different sizes and structures for the first time, including Au2、Au4、Au16And Au16@Cl2. Meanwhile, the configuration of the cluster compound and the metal-metal bonding action mode are regulated and controlled, so that the optimization of the optical performance and the chemical stability of the gold (I) supermolecule cluster compound is realized, and the cytotoxicity is effectively reduced. The self-assembly synthesis technology provides a new method and a synthesis way for accurately synthesizing the high-nuclear supermolecular cluster compound at the atomic level. Meanwhile, the synthesis method is simple, low in cost and high in yield.
2. The multinuclear organic-metal gold (I) supramolecular cluster compound provided by the invention is formed by strong intermolecular and intramolecular AuI···AuIForming a multinuclear gold (I) supermolecular cluster compound with unique crescent or layered sandwich structure and extremely stable physicochemical property by bonding interaction; the result of cytotoxicity experiments shows that the fluorogold (I) supramolecular cluster compounds 2 and 3 have good biocompatibility, and the cell imaging result of the fluorogold (I) supramolecular cluster compounds and Hela cancer cells shows that the fluorogold (I) supramolecular cluster compounds and Hela cancer cells also have good biological uptake capacity.
3. The multinuclear organic-metal gold (I) supermolecular cluster compound provided by the invention has high chemical stability; the fluorescent protein has low cytotoxicity and good biocompatibility, can be used as a novel red light cell imaging reagent to be applied to the aspects of biological fluorescence imaging and the like, and further widens the application of the gold (I) supermolecular cluster compound to the aspects of cell imaging and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a cluster compound 1 obtained in example 1 of the present invention;
FIG. 2 is a mass spectrum of cluster compound 1 prepared in example 1 of the present invention;
FIG. 3 is a NMR spectrum of cluster 2 obtained in example 2 of the present invention;
FIG. 4 is a mass spectrum of cluster 2 prepared in example 2 of the present invention;
FIG. 5 is a single crystal structural view of cluster compound 2 produced in example 2 of the present invention;
FIG. 6 is a NMR spectrum of cluster compound 3 obtained in example 3 of the present invention;
FIG. 7 is a mass spectrum of cluster compound 3 prepared in example 3 of the present invention;
FIG. 8 is a single crystal structural view of cluster compound 3 produced in example 3 of the present invention;
FIG. 9 is a NMR spectrum of cluster 4 obtained in example 4 of the present invention;
FIG. 10 is a mass spectrum of cluster 4 obtained in example 4 of the present invention;
FIG. 11 is a single crystal structural view of cluster compound 4 produced in example 4 of the present invention;
FIG. 12 is a graph summarizing cytotoxicity and cell imaging results in example 5 of the present invention; wherein FIGS. 12(a) - (c) are the cellular fluorescence imaging photographs of supramolecular cluster 2; FIGS. 12(d) - (f) are the fluorescence microscopy images of the cell of supramolecular cluster 3; FIG. 12(g) is the cytotoxicity results of supramolecular cluster 2; fig. 12(h) is the cytotoxicity results of supramolecular cluster 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention. The data given in the examples below include specific operating and reaction conditions and products. The purity of the product is identified by the analysis of nuclear magnetic resonance hydrogen spectrum and high resolution mass spectrum, and the compounds 2, 3 and 4 also obtain accurate structural information by an X-ray single crystal diffractometer.
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The experimental methods in the present invention are conventional methods unless otherwise specified. The experimental materials used in the present invention were all purchased from the market unless otherwise specified.
Example 1
Gold (I) cluster compound 1 (dppmAu)2(tatt3-) Synthesis of):
1, 3, 5-triazine-2, 4, 6-copper trisulfide trisodium salt hydrate (Na) at room temperature3(tatt3-) (7.32mg, 0.03mmol) was dissolved in about 3mL of methanol solution and slowly added to dppmAu dissolved in about 2mL of dichloromethane solution2Cl2(25.20mg, 0.03 mmol). The solution gradually changed from colorless to dark yellow, and the mixture instantly became a white suspension at the end of the reaction. The suspension was stirred at room temperature for an additional 12h and filtered to give a white solid powder (28.0mg, 0.029mmol, 96% yield).
The prepared substances were characterized by a nuclear magnetic resonance hydrogen spectrometer and a high resolution mass spectrometer with the following results:
cluster 1:
1H NMR(500MHz,DMSO-d6298K) δ 7.76(bs,8H), 7.60-7.42 (m,4H),7.38(d, J ═ 19.4Hz,8H),4.67(s,2H), the detailed nmr hydrogen spectrum is shown in fig. 1.
ESI-MS(MeCN,m/z)：[1-Na+2H]+,calcd for C28H22Au2N3P2S3 +(ii) a 953.97 found,953.99, detailed mass spectrogram see FIG. 2.
Example 2
Gold (I) Cluster 2([ (dppmAu)2)2(tatt3-)]·BF4 -) The synthesis of (2):
(1) 1, 3, 5-triazine-2, 4, 6-copper trisulfide trisodium salt hydrate (Na)3(tatt3-) (3.66mg, 0.015mmol) solution in methanol (4mL) was slowly added dropwise to a binuclear angle dppmAu in dichloromethane (2mL)2Cl2(25.20mg, 0.03mmol) in water. The mixture turned from colorless to light yellow and then to a clear solution of bright yellow.
(2) The mixture was stirred at room temperature for 24 hours. Then excess 10 times of NaBF was added4Adding intoTo a yellow solution. After stirring for a further 24 hours, the crude cluster 2 was completely precipitated.
(3) The yellow precipitate was collected by centrifugation, washed with copious amounts of water and methanol to give a yellow powder (27.24mg, 0.014mmol, 96% yield).
(4) Slow diffusion into acetonitrile/dichloromethane solution (v/v, 2: 1) with ether gave after 48h supramolecular cluster 2 yellow bulk single crystals (15mg, 0.008mmol) suitable for X-ray diffraction analysis.
The prepared substances are characterized by a nuclear magnetic resonance hydrogen spectrometer, a high-resolution mass spectrometer and an X-ray single crystal diffractometer, and the results are as follows:
cluster 2:
1H NMR(400MHz，DMSO-d6298K, ppm) δ 7.75(m, 7.5Hz, 16H), 7.47(t, J ═ 7.3Hz, 8H), 7.39(t, J ═ 7.2Hz, 16H), 4.89-4.58 (m,4H), and the specific nmr hydrogen spectrum is shown in fig. 3.
ESI-MS(MeCN，m/z)：[2]+，calcd for C53H44Au4N3P4S3 +(ii) a 1730.04 found, 1730.03, see FIG. 4 for the mass spectrum.
Single crystal structure: specifically, the structure diagram of the single crystal is shown in FIG. 5a, the three-dimensional molecular stacking diagram is shown in FIG. 5b, the data table of the crystal structure measurement and the like is shown in Table 1, and the data of the bond angle of part of the bond length is shown in Table 2.
TABLE 2-data Table of key angles of major bond lengths of single crystal of cluster compound 2 prepared in example 2 of the present invention
As can be seen from the above, the single crystal structure of cluster 2 is monoclinic system, space group P21C, molecular formula is [ Au4(dppm)2(tatt3-)]·BF4 -. Two dppmAu2The angle is bridged by a tricyanate ligand to form a planar tetranuclear crescent gold (I) supramolecular cluster. Two dppmAu2The horns are coordinated with one set of bidentate bridged donor S, N atoms and the other set of S, S atoms in the tricyanate ligand, respectively, the former being short intramolecular AuI…AuIA working distance of
(Au1 to Au3). In the latter, two gold atoms (Au)2And Au4) Coordinated to the two P atoms of the terminal dppm ligand and to the two S atoms located at the 3, 5 positions of the tricyanate, respectively. Au coating2…Au4Atomic distance of (2)
Slightly larger than the sum of their van der Waals radii, indicating Au between the two metalsI…AuIThe interaction is very weak.
Example 3
Gold (I) Cluster 3([ (dppmAu)2)6Au4(tatt3-)4]·4BF4 -) The synthesis of (2):
the synthesis step and the post-treatment were the same as those of cluster 2 except that Na was used3(tatt3-) The amount used was (2.44mg, 0.01mmol), and substitution, centrifugation and washing gave a yellow powder (53.18mg, 0.009mmol, 90% yield). Slow diffusion with ether afforded cluster 3 as a yellow massive single crystal (25mg, 0.004 mmol).
The prepared substances are characterized by a nuclear magnetic resonance hydrogen spectrometer, a high-resolution mass spectrometer and an X-ray single crystal diffractometer, and the results are as follows:
cluster 3:
1H NMR(500MHz,DMSO-d6,298K,ppm)：δ7.70(m,8H),7.48(m,4H),7.20(m,8H),5.53(d,J＝17.8Hz,2H) 4.90(bs,2H), detailed NMR spectrum of FIG. 6.
MALDI-TOF-MS(MeCN，m/z)：[3·2BF4 -]2+，calcd for；2079.63，found，2080.30；[3·BF4 -]3+，calcd for C162H132Au16N12P12S12BF43 +(ii) a 3163.95 found, 3163.95, see FIG. 7 for the mass spectrum.
Single crystal structure: specifically, the structure diagram of the single crystal is shown in FIG. 8a, the three-dimensional molecular stacking diagram is shown in FIG. 8b, the data table of the crystal structure measurement and the like is shown in Table 1, and the data of the bond angle of part of the bond length is shown in Table 3.
TABLE 3
The single crystal structure of cluster 3 is also monoclinic, space group P21C, molecular formula is [ Au16(dppm)8(tatt3-)4]·4BF4 -. All three N donors at positions 2, 4, 6 in the thiocyanate ligands are activated driven by exchange and rearrangement of the ligands. In the S-shaped three-layer structure, two coplanar four-core gold (I) coordination units [ (dppmAu)2)2(tatt3-)]Respectively arranged on the upper layer and the lower layer of the sandwich layer structure with the layer interval of
(distance between top and bottom planes). The middle layer is an eight-core gold (I) cluster motif [ (dppmAu [)2)Au2(tatt3-)]2 2-Bridging two coplanar quad-cluster units located at the top and bottom layers of the overall three-layer layered structure. Different from two Au in cluster 2, 34Module [ (dppmAu)2)Au2(tatt3-)]-Inseparably interweaved together to form a square-ring Au4Core unit (made of Au)11，Au12,Au13And Au16Composition) of Au4The centers are connected together by six groups of S-Au-P bonds and two groups of N-Au-P bonds. Au related to intramolecular metallophilic interaction in the two groups of N-Au-P bondsI…AuIA distance of
Example 4
Gold (I) Cluster 4([ (dppmAu)2)6Au4(tatt3-)Cl2]·2BF4 -) The synthesis of (2):
the synthesis procedure and the post-treatment were the same as for cluster 2, except that dppmAu was used2Cl2The amount used was (31.50mg, 0.0375mmol), and substitution, centrifugation and washing gave a yellow powder (232.17mg, 0.0346mmol, 92% yield). Slow diffusion with ether gave cluster 4 as a green bulk single crystal (20mg, 0.003 mml).
The prepared substances are characterized by a nuclear magnetic resonance hydrogen spectrometer, a high-resolution mass spectrometer and an X-ray single crystal diffractometer, and the results are as follows:
cluster 4:
1H NMR(400MHz,DMSO-d6298K, ppm): δ 7.76(m,8H),7.50(m,4H),7.38(m,4H),5.26(d,1H),4.66(m,1H), and the specific nmr hydrogen spectrum is shown in fig. 9.
MALDI-TOF-MS(MeCN,m/z)：[4-Cl]3+,calcd for C162H132Au16ClN12P12S12 3+；2062.96,found,2063.29；[4]2+,calcd for C162H132Au16Cl2N12P12S12 2+3112.17 found,3112.44, see FIG. 10 for the mass spectrum.
Single crystal structure: specifically, the structure diagram of the single crystal is shown in FIG. 11a, the three-dimensional molecular stacking diagram is shown in FIG. 11b, the data table of the crystal structure measurement and the like is shown in Table 1, and the data of the bond angle of part of the bond length is shown in Table 4.
TABLE 4
The structure is similar to cluster 3, except that the tetranuclear gold (I) unit in the upper and lower layers is changed into two monothiocoordinated binuclear motifs [ S ]-Au(P⌒P)AuCl-]I.e. the terminal 2 Cl atoms are not completely substituted by the ligand.
Example 5 application of gold (I) supramolecular clusters 2 and 3 cellular imaging
1. Cell culture
HeLa cells (cervical cancer cells) were purchased from Saibuximab (Shanghai, China) Biotech Co., Ltd, cultured in Dulbecco's modified Eagle Medium (DMEM, HyClone), and then supplemented with 10% v/v Fetal Bovine Serum (FBS), 100U penicillin and 100. mu.g/mL streptomycin in a humidified incubator. HeLa cells at 37 ℃ with 5% CO2And 95% humus until use.
2. Gold (I) supramolecular cluster 2 and 3 cytotoxicity assays
The killing effect of gold (I) supermolecular clusters 2 and 3 on Hela cells was studied by the CCK-8 method. Stock solutions with medium concentrations of 0.1-100. mu.M were prepared using mixed solvents (PBS/DMSO, 99: 1, v/v). Cells grown in protoplast phase were seeded at a density of 10000 cells/well in 96-well plates (Gray Biotech, Flikenhausen, Germany) and then incubated at 37 ℃ with 5% CO2And incubated for 24 hours. Different concentrations (1.6, 3.2, 6.4, 12.5, 25, 50, 100 μ M) of cluster 2 or 3(100 μ L/well) were added to the experimental groups. The same amount of mixed solvent (PBS/DMSO, 100. mu.L/well) was also added to the control group. For each sample, 5 parallel multiple wells were prepared at different concentrations and were incubated at 37 ℃ in 5% CO2The cells were incubated for 24 hours. Next, 10. mu.L of CCK-8 reagent was added to each well of all the above plates and incubation was continued at 37 ℃ for 4 hours in a 5% carbon dioxide atmosphere. Before reading the plates, care was taken to gently mix the plates to be tested on an orbital shaker for 1 minute to ensure uniform distribution of color. OD570 (absorbance value) was measured at 450nm for each well with an enzyme-linked immunosorbent assay (Dr-200Bs, Delron). We calculated the specific cell viability (%) (all experimental and control absorbance values should be subtracted by the blank in the absence of any cells) according to the following formula:
3. cell staining and microscopic imaging experiments
1mM of 2 or 3 clusters were prepared in dimethyl sulfoxide (DMSO) and diluted to 10. mu.M in PBS. Hela cells grown in the medium were observed under a microscope, washed 3 times with PBS, and allowed to react with clusters 2 or 3 in a PBS/DMSO (99: 1, v/v, pH 7.4) solution for 10 min. Then, the PBS/DMSO solution was removed and washed with PBS. Finally, the cell samples should be stored at 4 ℃ prior to the intracellular fluorescence imaging experiment.
4. Results
FIG. 12(g) is the cytotoxicity results of supramolecular cluster 2; FIG. 12(h) shows the cytotoxicity results of supramolecular cluster 3, and FIGS. 12(a) - (c) show the fluorescence imaging photographs of cell of supramolecular cluster 2; FIGS. 12(d) - (f) are the fluorescence microscopy images of the cell of supramolecular cluster 3; these results indicate that these fluorogold (I) supramolecular clusters 2 and 3 have good biocompatibility, and cellular imaging results with Hela cancer cells indicate that they also have good bioabsorption capability.
It should be noted that the above embodiments belong to the same inventive concept, and the description of each embodiment has a different emphasis, and reference may be made to the description in other embodiments where the description in individual embodiments is not detailed.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. Multinuclear organo-metallic gold (I) supramolecular cluster selected from the group consisting of:
2. a method for the synthesis of multinuclear organo-metallic gold (I) supramolecular clusters as claimed in claim 1, characterized in that it comprises the following steps:
and (3) coordination substitution reaction: 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate was added dropwise to Dppmau2Cl2Carrying out coordination substitution reaction to obtain the polynuclear organic-metallic gold (I) supramolecular cluster compound 1; the 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate and the Dppmau2Cl2In a molar amount of 1: 1.
3. a method for the synthesis of multinuclear organo-metallic gold (I) supramolecular clusters as claimed in claim 1, characterized in that it comprises the following steps:
s1, coordination substitution reaction: 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate was added dropwise to Dppmau2Cl2Carrying out coordination substitution reaction to obtain a mixture;
s2, replacement reaction: stirring the obtained mixture at room temperature for a period of time, and adding inorganic salt to perform a displacement reaction to precipitate the inorganic salt;
s3, washing: centrifuging and collecting the precipitate, and washing to obtain yellow powder;
s4, dissolution and single crystal cultivation: dissolving the obtained yellow powder with a solvent to obtain yellow precipitate, and diffusing diethyl ether into the yellow precipitate for a period of time to obtain the polynuclear organic-metallic gold (I) supramolecular cluster compound;
the 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate and the Dppmau2Cl2In a molar amount of 1: 2 obtaining the polynuclear organic-metal gold (I) supramolecular cluster compound 2;
the 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate and the Dppmau2Cl2In a molar amount of 1: 3 obtaining the polynuclear organic-metallic gold (I) supramolecular cluster compound 3;
the 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate and the Dppmau2Cl2In a molar amount of 1: 2.5 obtaining the polynuclear organic-metallic gold (I) supramolecular cluster compound 4.
4. The method for synthesizing multinuclear organo-metallic gold (I) supramolecular cluster compounds according to claim 2 or 3, characterized in that an organic solvent is further added in the coordination substitution reaction, wherein the organic solvent is selected from one or more of dichloromethane, methanol, ethanol, isopropanol, isobutanol, acetonitrile, tetrahydrofuran, dioxane, chloroform and carbon tetrachloride.
5. The method for synthesizing multinuclear organo-metallic gold (I) supramolecular cluster compounds according to claim 2 or 3, wherein the temperature of coordination substitution reaction is 5-70 ℃.
6. The method for synthesizing multinuclear organo-metallic gold (I) supramolecular cluster compound as claimed in claim 3, wherein the inorganic salt in step S2 comprises NaBF4、KPF6、NH4PF6、N(C2H5)4PF6、N(C4H9)4PF6、NaBPh4、K2HPO4、KH2PO4、KSCN,K2SO4、KOTs、KOTf、KTFA、KOAc、KCF3SO3、CF3COOK、KClO4Ac、KSiF6、KTcO4One or more of (a).
7. The method for synthesizing multinuclear organo-metallic gold (I) supramolecular cluster compounds as claimed in claim 3, wherein the molar ratio of inorganic salt added in the step S2 to the raw material 1, 3, 5-triazine-2, 4, 6-trithione trisodium salt hydrate is 4-40: 1.
8. the method for synthesizing a polynuclear organo-metallic gold (I) supramolecular cluster compound according to claim 3, wherein the stirring time in the step S2 is 6-36 h; the temperature of the displacement reaction is 5-70 ℃, and the reaction time is 8-48 h.
9. The method for synthesizing a polynuclear organo-metallic gold (I) supramolecular cluster compound according to claim 3, wherein the washing in step S3 is performed 2-5 times by using a mixed solvent of water and methanol; the solvent used to dissolve the yellow powder in step S4 was an acetonitrile/dichloromethane solution.
10. The use of the multinuclear organo-metallic gold (I) supramolecular cluster compounds as claimed in claim 1 as a class of red light cell imaging agents for non-disease diagnostic and therapeutic purposes in bioluminescence imaging.
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| CN109134517A (en) * | 2018-09-30 | 2019-01-04 | 苏州大学 | 14 core gold phosphine sulfur clusters and its preparation method and application |
| TR201816596A2 (en) * | 2018-11-05 | 2019-07-22 | Karadeniz Teknik Ueniversitesi | Recovery of gold and silver from thiosulfate leach solutions by precipitation with trimercapto-s-triazine (tmt). |
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| US6423481B1 (en) * | 2001-01-23 | 2002-07-23 | Eastman Kodak Company | High speed photothermographic materials with combined chemical sensitizers and methods of using same |
| CN109134517A (en) * | 2018-09-30 | 2019-01-04 | 苏州大学 | 14 core gold phosphine sulfur clusters and its preparation method and application |
| TR201816596A2 (en) * | 2018-11-05 | 2019-07-22 | Karadeniz Teknik Ueniversitesi | Recovery of gold and silver from thiosulfate leach solutions by precipitation with trimercapto-s-triazine (tmt). |
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| (4,6-Dimercapto-1,3,5-triazine-2-thiolato-S2)tris(triphenylphosphine- P)gold(I) dimethylformamide solvate;Zhao, Yingjun等;《Acta Crystallographica, Section C: Crystal Structure Communications》;20001231;第C56(8)卷;E331-E332 * |
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