CN106398680B - Oil-soluble blue light quantum dot and preparation method thereof - Google Patents
Oil-soluble blue light quantum dot and preparation method thereof Download PDFInfo
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Abstract
The invention provides an oil-soluble blue light quantum dot and a preparation method thereof. The oil-soluble blue light quantum dots comprise water-soluble blue light quantum dots, water-soluble metal nanoparticle layers wrapped on the surfaces of the water-soluble blue light quantum dots, and oil-soluble ligand layers formed on the surfaces of the water-soluble metal nanoparticle layers. The preparation method comprises the following steps: providing a mixed solution of water-soluble blue light quantum dots and water-soluble metal nanoparticles, adjusting the pH value to 7-10, stirring the mixed solution strongly, reacting at room temperature for 3-10h to obtain the water-soluble blue light quantum dots with the metal nanoparticles wrapped on the surfaces; providing an oil-soluble surface modifier containing sulfydryl, dissolving and mixing the water-soluble blue light quantum dots with the metal nanoparticles wrapped on the surfaces and the oil-soluble surface modifier containing sulfydryl, and then heating under inert atmosphere to obtain the oil-soluble quantum dots.
Description
Technical Field
The invention belongs to the technical field of quantum dot synthesis, and particularly relates to an oil-soluble blue light quantum dot and a preparation method thereof.
Background
Quantum dot display is receiving attention of people in the future display technology field, research enthusiasm of researchers is promoted due to the advantages of narrow half-peak width, high fluorescence intensity, good stability and the like, however, red, green and blue (RGB) three-color quantum dots need to be used as a next generation novel display material, and the red, green and blue (RGB) three-color quantum dots have good fluorescence intensity and stability and long service life.
The device efficiency and the service life of red light and green light in a quantum dot light emitting device (Q L ED) can meet the display requirement and are comparable to those of an organic light emitting diode (O L ED). however, the blue light quantum dot device does not have higher current efficiency and better device service life in the existing long wavelength band (458 + 465 nm). As for the blue light quantum dot material, higher fluorescence quantum yield and better fluorescence service life are also difficult to develop.
Disclosure of Invention
The invention aims to provide an oil-soluble blue light quantum dot and a preparation method thereof, and aims to solve the problems that the current efficiency of the existing blue light quantum dot in a long wave band (458-465nm) is low and the service life is short.
The oil-soluble blue light quantum dot comprises the water-soluble blue light quantum dot, a water-soluble metal nanoparticle layer wrapping the surface of the water-soluble blue light quantum dot, and an oil-soluble ligand layer formed on the surface of the water-soluble metal nanoparticle layer.
And the preparation method of the oil-soluble blue light quantum dot comprises the following steps:
providing a mixed solution of water-soluble blue light quantum dots and water-soluble metal nanoparticles, adjusting the pH value to 7-10, stirring the mixed solution strongly, reacting at room temperature for 3-10h to obtain the water-soluble blue light quantum dots with the metal nanoparticles wrapped on the surfaces;
providing an oil-soluble surface modifier containing sulfydryl, dissolving and mixing the water-soluble blue light quantum dots with the metal nanoparticles wrapped on the surfaces and the oil-soluble surface modifier containing sulfydryl, and then heating under inert atmosphere to obtain the oil-soluble quantum dots.
According to the oil-soluble blue light quantum dot and the preparation method thereof, after a layer of water-soluble metal nano-particles is modified at the tail end of a ligand of the water-phase blue light quantum dot, a layer of oleophylic ligand is modified on the surface of the water-soluble metal nano-particles, so that the oil-soluble blue light quantum dot is obtained. The obtained oil-soluble blue light quantum dot can enhance the fluorescence intensity and prolong the service life of the quantum dot, and solves the problems of low efficiency and short service life of a blue light device. In particular, the method comprises the following steps of,
firstly, since the water-soluble metal nanoparticles have the plasmon resonance effect and the conduction band and the valence band are separated, the size of the metal nanoparticles can be controlled to enable the metal nanoparticles to have a fluorescence peak in the 365-450nm wave band. The oil-soluble blue light quantum dot formed by the method can be used as a blue light display material, and when the oil-soluble blue light quantum dot is subjected to electro-excitation, the blue light quantum dot can receive energy from the electro-excitation and perform stimulated emission, and can also receive energy emitted by metal nanoparticles after absorbing the electro-excitation energy, so that the stimulated emission is further performed, and the fluorescence intensity is enhanced.
Secondly, the water-soluble metal nanoparticles such as gold nanoparticles have high stability and are not easily oxidized, so that the stability of the quantum dots wrapped by the water-soluble metal nanoparticles is further improved.
In addition, after the blue light quantum dots are prepared into a Q L ED device, generally, when the current efficiency is the maximum, the electric field intensity of the quantum dots is larger than that of red and green quantum dots, which is not beneficial to prolonging the service life of the Q L ED device.
Drawings
Fig. 1 is a flow chart of a preparation method of oil-soluble blue light quantum dots provided by an embodiment of the invention;
fig. 2 is a diagram illustrating the effect of the steps of preparing the oil-soluble blue light quantum dot provided in embodiment 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. 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 embodiment of the invention provides an oil-soluble blue light quantum dot, which is prepared by the method and comprises the water-soluble blue light quantum dot, a water-soluble metal nanoparticle layer wrapped on the surface of the water-soluble blue light quantum dot and an oil-soluble ligand layer formed on the surface of the water-soluble metal nanoparticle layer.
Specifically, the water-soluble blue light quantum dot comprises a quantum dot and a surface ligand with an amphiphilic effect, wherein the quantum dot is a binary phase quantum dot, a ternary phase quantum dot or a quaternary phase quantum dot, the binary phase quantum dot comprises but is not limited to at least one of CdS, CdSe, CdTe, InP, AgS, PbS, PbSe and HgS, and the ternary phase quantum dot comprises but is not limited to ZnXCd1-XS、CuXIn1-XS、ZnXCd1-XSe、ZnXSe1-XS、ZnXCd1-XTe、PbSeXS1-XIncluding but not limited to ZnXCd1-XS/ZnSe、CuXIn1-XS/ZnS、ZnXCd1-XSe/ZnS、CuInSeS、ZnXCd1- XTe/ZnS、PbSeXS1-XAt least one of/ZnS wherein 0<X<1; the surface ligand comprises at least one of thioglycolic acid (TGA), mercaptopropionic acid (MPA), mercaptohexanoic acid (MHA), mercaptooctanoic acid (MOA), mercaptoundecanoic acid (MUA), 2-mercapto-5-benzimidazole carboxylic acid (MBIA) and 4-mercaptobenzoic acid (4-MBA).
Preferably, the metal nanoparticles used in the embodiments of the present invention should have water-solubility characteristics, so as to have good compatibility with the water-soluble metal nanoparticles, thereby facilitating the reaction. Furthermore, the water-soluble metal nanoparticles provided by the embodiment of the invention have a fluorescence peak at the wavelength band of 300-450nm, so that energy is generated after electro-stimulation, the stimulated emission of blue light quantum dots is further promoted, and the fluorescence intensity is increased. Preferably, the water-soluble metal nanoparticles are at least one of gold nanoparticles, silver nanoparticles and copper nanoparticles. Further, the embodiments of the present invention satisfy the above requirements by adjusting the particle size of the water-soluble metal nanoparticles. Specifically, the particle size of the water-soluble metal nanoparticles is 1-3 nm.
The oil-soluble blue light quantum dot provided by the embodiment of the invention can be prepared by the following method.
The embodiment of the invention also provides a preparation method of the oil-soluble blue light quantum dot, which comprises the following steps, and the flow chart is shown in figure 1:
s01, providing a mixed solution of water-soluble blue light quantum dots and water-soluble metal nano-particles, adjusting the pH value to 7-10, stirring the mixed solution strongly, reacting at room temperature for 3-10h to obtain the water-soluble blue light quantum dots with the metal nano-particles wrapped on the surfaces;
s02, providing an oil-soluble surface modifier containing sulfydryl, dissolving and mixing the water-soluble blue light quantum dots with the surfaces coated with the metal nano particles and the oil-soluble surface modifier containing sulfydryl, and then heating in an inert atmosphere to obtain the oil-soluble quantum dots.
Since the water-soluble quantum dots are not suitable for display materials such as Q L ED luminescent materials, and the conventional blue quantum dots have the disadvantages of low fluorescence efficiency and short lifetime, the water-soluble blue quantum dots need to be modified.
Specifically, in step S01, after the water-soluble blue light quantum dot and the water-soluble metal nanoparticle are mixed under an alkaline condition, the water-soluble blue light quantum dot with the metal nanoparticle coated on the surface thereof can be generated at room temperature.
In the embodiment of the invention, the water-soluble metal nanoparticles are bonded with polar groups such as carboxyl on the surface of the water-soluble blue light quantum dots under an alkaline condition, and specifically, the pH value under the alkaline condition is in a range of 7-10. If the pH value is too low, an acid environment is formed, and a corresponding reaction cannot occur; if the alkalinity is too strong, the metal nanoparticles and the basic groups generate side reactions, and the reaction efficiency and the product purity are influenced. In order to improve the reaction efficiency, the reaction is carried out under the condition of strong stirring, and the reaction lasts for 3-10 hours at room temperature, so as to ensure that the ligand on the water-soluble blue light quantum dot is fully combined with the water-soluble metal nano-particles.
Further preferably, in the step of coating the water-soluble blue light quantum dots with the metal nanoparticles on the surface, the ratio of the water-soluble blue light quantum dots to the water-soluble metal nanoparticles is 1 g: 15-30 mmol. The optimal proportion can avoid the increase of production cost caused by the waste of a large amount of raw materials on the premise of improving the reaction efficiency.
In the step S02, an oil-soluble surface modifier is bonded to the water-soluble blue light quantum dot coated with the metal nanoparticles, so as to finally obtain the oil-soluble blue light quantum dot.
In order to ensure the stability of the obtained oil-soluble blue light quantum dots, the oil-soluble surface modifier containing sulfydryl is selected, and the sulfydryl has strong binding capacity with the nano metal particles and is not easy to fall off, so that the stability of the product is ensured. In the step, when the number of sulfydryl groups in the molecular structure of the oil-soluble surface modifier containing sulfydryl groups is large, the molecular structure is complex, and one oil-soluble surface modifier containing sulfydryl groups can be combined with a plurality of metal nano-particles, so that the content of the oil-soluble surface modifier bonded on the surface of the blue light quantum dot is relatively reduced, and the oil solubility of the obtained product is influenced. Preferably, the oil-soluble surface modifier containing a sulfhydryl group is a straight-chain molecule, and the molecular structure contains only one sulfhydryl group. In order to ensure oil solubility, the number of carbon atoms in the molecule of the oil-soluble surface modifier containing sulfydryl is more than or equal to 8. Further, in the oil-soluble surface modifier containing a mercapto group, the mercapto group is a terminal mercapto group. Therefore, the steric hindrance of the oil-soluble surface modification containing the sulfydryl can be reduced, the reaction difficulty is further reduced, and the phenomenon of insufficient surface ligand combination is avoided.
Particularly preferably, the oil-soluble surface modifier containing a mercapto group includes, but is not limited to, octathiol { CH3(CH2)7HS }, dodecanethiol { CH }, dodecanethiol }3(CH2)11HS, octadecanethiol { CH }3(CH2)17HS }, tetradecanethiol { CH }3(CH2)13HS, decanethiol { CH }3(CH2)9HS.
In the above steps, the temperature of the heating treatment is 60-150 ℃, and the heating time is 1-5 h. If the temperature is too low or the heating time is too short, the reaction is insufficient, and the oil solubility of the blue light quantum dots is limited; if the temperature is too high or the heating time is too long, the ligand bound to the blue light quantum dot is likely to fall off.
In order to improve the reaction efficiency, it is preferable that, in the step of preparing the oil-soluble quantum dot, the mass ratio of the water-soluble blue quantum dot with the surface coated with the metal nanoparticle to the oil-soluble surface modifier containing a thiol group is 1: 50-100.
To avoid side reactions, the steps of the embodiments of the present invention are preferably performed under an inert atmosphere, including but not limited to argon, nitrogen, helium.
According to the preparation method of the oil-soluble blue light quantum dot, provided by the embodiment of the invention, after a layer of water-soluble metal nano-particles is modified at the tail end of a ligand of the water-phase blue light quantum dot, a layer of oleophylic ligand is modified on the surface of the water-soluble metal nano-particles, so that the oil-soluble blue light quantum dot is obtained. The obtained oil-soluble blue light quantum dot can enhance the fluorescence intensity and prolong the service life of the quantum dot, and solves the problems of low efficiency and short service life of a blue light device. In particular, the method comprises the following steps of,
firstly, since the water-soluble metal nanoparticles have the plasmon resonance effect and the conduction band and the valence band are separated, the size of the metal nanoparticles can be controlled to enable the metal nanoparticles to have a fluorescence peak in the 365-450nm wave band. The oil-soluble blue light quantum dot formed by the method can be used as a blue light display material, and when the oil-soluble blue light quantum dot is subjected to electro-excitation, the blue light quantum dot can receive energy from the electro-excitation and perform stimulated emission, and can also receive energy emitted by metal nanoparticles after absorbing the electro-excitation energy, so that the stimulated emission is further performed, and the fluorescence intensity is enhanced.
Secondly, the water-soluble metal nanoparticles such as gold nanoparticles have high stability and are not easily oxidized, so that the stability of the quantum dots wrapped by the water-soluble metal nanoparticles is further improved.
In addition, after the blue light quantum dots are prepared into a Q L ED device, generally, when the current efficiency is the maximum, the electric field intensity of the quantum dots is larger than that of red and green quantum dots, which is not beneficial to prolonging the service life of the Q L ED device.
The following description will be given with reference to specific examples.
Example 1
A preparation method of oil-soluble blue light quantum dots comprises the following steps, and a flow chart of the method is shown in figure 1:
s11, 20ul of blue light (ZnCdS/ZnS) water-soluble quantum dots (30mg/ml) with thioglycolic acid on the surfaces and 3ml of water-soluble gold (Au) nanoparticles (10mg/ml) are added into a 50ml three-neck flask, argon is introduced for protection, after stirring for 10min at normal temperature, NaHCO3 aqueous solution is added into the mixed solution dropwise to adjust the pH value of the mixed solution, and the dropwise addition is stopped until the pH value is 9. Then, strongly stirring the mixed solution for 3 hours until the gold nanoparticles are fully mixed with carboxyl ions (-COO) on the surfaces of the quantum dots-) After the quantum dots are combined into (-COOAu) in an ionic bond mode, adding ethyl acetate into the quantum dot mixed solution, carrying out high-speed centrifugation to obtain the blue light quantum dots with the single-layer gold (Au) nanoparticles wrapped on the periphery, and then centrifuging for later use.
Wherein, the gold nanoparticles can be prepared by the following method: to a 100ml three-necked flask, 60ml of water and 1ml of 1% HAuCl hydrate were added under oil bath conditions4·3H2And O, fully stirring under the protection of argon. After 1min, 1ml of 1% sodium citrate hydrate was added. After 1min of addition, 1ml of 0.075% NaBH was added4Mixing the solution withStirring is stopped for 5min, the obtained gold nanoparticles are screened out by adopting a size selection method, the gold nanoparticles with the size of about 1nm and the emission peak in the range of (365-.
S12, adding 30ml of the prepared water-soluble blue light quantum dots wrapped with the single-layer gold nanoparticles and 20ml of n-hexane solution dissolved with dodecanethiol into a 100ml three-neck flask, introducing argon for protection, heating the mixed solution to 60 ℃, rapidly stirring the mixed solution until the mixed solution is obviously layered, and then stirring for 1h to fully combine the dodecanethiol with the gold (Au) nanoparticles to realize phase conversion, wherein the effect diagram of each step of the embodiment of the invention is shown in FIG. 2.
Example 2
S21, 20ul of blue light (ZnCdS/ZnS) water-soluble quantum dots (30mg/ml) with thioglycolic acid on the surface and 5ml of water-soluble silver (Ag) nanoparticles (10mg/ml) are taken and added into a 50ml three-neck flask, argon is introduced for protection, the mixture is stirred at normal temperature for 10min, and NaHCO is dropwise added into the mixed solution3The pH value of the mixed solution is adjusted by the aqueous solution, and the dropwise addition is stopped until the pH value is 9. Then, strongly stirring the mixed solution for 3 hours until the gold nanoparticles are fully mixed with carboxyl ions (-COO) on the surfaces of the quantum dots-) After the ionic bond is combined into (-COOAg), ethyl acetate is added into the quantum dot mixed solution for high-speed centrifugation to obtain the blue light quantum dot with the periphery wrapped by the single-layer silver (Ag) nano particles, and then the blue light quantum dot is centrifuged for later use.
Wherein, the silver nano-particles can be prepared by the following method: to a 100ml three-necked flask, 20ml of ethyl acetate and 1ml of 0.01mmol of Ag (NO) were added under oil bath conditions3)2Then, the mixture was stirred sufficiently for 60 minutes under heating at 50 ℃. Until a yellow solution appeared indicating that Ag nanoparticles began to form gradually. The obtained sample was stored at low temperature (about 4 ℃) in the dark.
S22, adding 30ml of the prepared water-soluble blue light quantum dots wrapped with the single-layer silver nanoparticles and 20ml of n-hexane solution dissolved with dodecanethiol into a 100ml three-neck flask, introducing argon for protection, heating the mixed solution to 60 ℃, rapidly stirring the mixed solution until the mixed solution is obviously layered, and then stirring for 1h to fully combine the dodecanethiol with the silver (Ag) nanoparticles so as to realize phase conversion.
Example 3
S31, 20ul of blue light (ZnCdS/ZnS) water-soluble quantum dots (30mg/ml) with thioglycolic acid on the surface and 8ml of water-soluble copper (Cu) nanoparticles (10mg/ml) are added into a 50ml three-neck flask, argon is introduced for protection, the mixture is stirred at normal temperature for 10min, and NaHCO is dropwise added into the mixed solution3The pH value of the mixed solution is adjusted by the aqueous solution, and the dropwise addition is stopped until the pH value is 9. Then, strongly stirring the mixed solution for 3 hours until the gold nanoparticles are fully mixed with carboxyl ions (-COO) on the surfaces of the quantum dots-) After the quantum dots are combined into (-COOCu) in an ionic bond mode, adding ethyl acetate into the quantum dot mixed solution, carrying out high-speed centrifugation to obtain the blue light quantum dots with the single-layer copper (Cu) nanoparticles wrapped on the periphery, and then centrifuging for later use.
Respectively preparing 5 mmol/L of copper acetate aqueous solution, 50 mmol/L of hydrazine hydrate aqueous solution and 15 mmol/L of (O, O') -bis-n-hexadecyl dithiophosphate benzene solution (extracting agent), quickly adding the equal-volume copper acetate aqueous solution into the hydrazine hydrate aqueous solution at room temperature, strongly stirring, reacting for 1 minute, adding the equal-volume extracting agent into the reaction system, stirring for 1 hour at room temperature, standing for 4 hours, separating an organic phase, filtering, evaporating the solvent at 90 ℃, adding 200ml of acetone, stirring, generating a large amount of brown precipitate, aging for 24 hours, filtering, washing with 100ml of acetone for three times, drying, and storing the obtained sample in a dark low temperature (about 4 ℃) mode.
S32, adding 30ml of the prepared water-soluble blue light quantum dots wrapped with the single-layer copper nanoparticles and 20ml of n-hexane solution dissolved with dodecanethiol into a 100ml three-neck flask, introducing argon for protection, heating the mixed solution to 60 ℃, rapidly stirring the mixed solution until the mixed solution is obviously layered, and then stirring for 1h to fully combine the dodecanethiol with the copper (Cu) nanoparticles so as to realize phase conversion.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The oil-soluble blue light quantum dot is characterized by comprising a water-soluble blue light quantum dot, a water-soluble metal nanoparticle layer wrapping the surface of the water-soluble blue light quantum dot and an oil-soluble ligand layer formed on the surface of the water-soluble metal nanoparticle layer, wherein the particle size of the water-soluble metal nanoparticle is 1-3nm, and the water-soluble metal nanoparticle is selected from at least one of gold nanoparticles, silver nanoparticles and copper nanoparticles with a fluorescence peak in a wave band of 300-450 nm; the water-soluble blue light quantum dot comprises a quantum dot and a surface ligand with an amphiphilic effect.
2. The oil-soluble blue quantum dot of claim 1, wherein the quantum dot is a binary phase quantum dot, a ternary phase quantum dot, or a quaternary phase quantum dot, wherein the binary phase quantum dot comprises at least one of CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS, and the ternary phase quantum dot comprises ZnXCd1-XS、CuXIn1-XS、ZnXCd1-XSe、ZnXSe1-XS、ZnXCd1-XTe、PbSeXS1-XThe quaternary phase quantum dots comprise ZnXCd1-XS/ZnSe、CuXIn1-XS/ZnS、ZnXCd1-XSe/ZnS、CuInSeS、ZnXCd1-XTe/ZnS、PbSeXS1-XAt least one of/ZnS wherein 0<X<1；
The surface ligand comprises at least one of thioglycolic acid, mercaptopropionic acid, mercaptohexanoic acid, mercaptooctanoic acid, mercaptoundecanoic acid, 2-mercapto-5-benzimidazole carboxylic acid and 4-mercaptobenzoic acid.
3. A preparation method of oil-soluble blue light quantum dots is characterized by comprising the following steps:
providing a mixed solution of water-soluble blue light quantum dots and water-soluble metal nanoparticles, adjusting the pH value to 7-10, stirring the mixed solution with strong force, reacting at room temperature for 3-10h to obtain the water-soluble blue light quantum dots with the metal nanoparticles wrapped on the surfaces, wherein the water-soluble blue light quantum dots comprise quantum dots and surface ligands with an amphiphilic effect, the particle size of the water-soluble metal nanoparticles is 1-3nm, and the water-soluble metal nanoparticles are selected from at least one of gold nanoparticles, silver nanoparticles and copper nanoparticles with a fluorescence peak at a wave band of 300-450 nm;
providing an oil-soluble surface modifier containing sulfydryl, dissolving and mixing the water-soluble blue light quantum dots with the metal nanoparticles wrapped on the surfaces and the oil-soluble surface modifier containing sulfydryl, and then heating under inert atmosphere to obtain the oil-soluble quantum dots.
4. The method of claim 3, wherein the oil-soluble surface modifier containing thiol groups is a linear molecule and has a molecular structure containing only one thiol group.
5. The method for preparing the oil-soluble blue light quantum dot according to claim 4, wherein the mercapto group is a terminal mercapto group in the oil-soluble surface modifier containing a mercapto group.
6. The method of claim 4, wherein the thiol-group-containing oil-soluble surface modifier comprises at least one of octathiol, dodecanethiol, octadecathiol, tetradecanethiol, and decanethiol.
7. The method for preparing the oil-soluble blue light quantum dot of claim 3, wherein the temperature of the heating treatment is 60-150 ℃ and the heating time is 1-5 h.
8. The method for preparing the oil-soluble blue light quantum dot according to claim 3, wherein in the step of coating the water-soluble blue light quantum dot with the metal nanoparticles on the surface, the ratio of the water-soluble blue light quantum dot to the water-soluble metal nanoparticles is 1 g: 15-30 mmol; and/or
In the step of preparing the oil-soluble quantum dots, the mass ratio of the water-soluble blue light quantum dots with the metal nanoparticles wrapped on the surfaces to the oil-soluble surface modifier containing sulfydryl is 1: 50-100.
9. The method of claim 3, wherein the quantum dot is a binary phase quantum dot, a ternary phase quantum dot, or a quaternary phase quantum dot, wherein the binary phase quantum dot comprises at least one of CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS, and the ternary phase quantum dot comprises ZnXCd1-XS、CuXIn1-XS、ZnXCd1- XSe、ZnXSe1-XS、ZnXCd1-XTe、PbSeXS1-XThe quaternary phase quantum dots comprise ZnXCd1-XS/ZnSe、CuXIn1-XS/ZnS、ZnXCd1-XSe/ZnS、CuInSeS、ZnXCd1-XTe/ZnS、PbSeXS1-XAt least one of/ZnS wherein 0<X<1；
The surface ligand comprises at least one of thioglycolic acid, mercaptopropionic acid, mercaptohexanoic acid, mercaptooctanoic acid, mercaptoundecanoic acid, 2-mercapto-5-benzimidazole carboxylic acid and 4-mercaptobenzoic acid.
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