CN110669241A - Microbial cellulose membrane/nano precious metal composite material and preparation method and application thereof - Google Patents
Microbial cellulose membrane/nano precious metal composite material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Abstract
The invention discloses a microbial cellulose membrane/nano noble metal composite material and a preparation method and application thereof. The preparation process is safe, the conditions are mild, the operation is simple, the raw materials are cheap, and the prepared material can be used as a surface enhanced Raman substrate for rapid detection of protein biomacromolecules and has good application prospects.
Description
Technical Field
The invention relates to the technical field of spectroscopic analysis and detection, in particular to a microbial cellulose membrane/nano precious metal composite material with a surface enhanced Raman scattering effect and used for detecting protein, and a preparation method and application thereof.
Background
Raman spectroscopy is a scattering spectrum that was discovered by indian physicist Raman c.v. in 1982. The raman shift measured by raman spectroscopy is a physical quantity characterizing the vibration-rotation energy level characteristics of a substance molecule, and the information such as the structure, characteristics, change rule and the like of the substance can be known from the molecular level through raman spectroscopy analysis of the substance, so that the raman spectroscopy is widely applied to various fields. The protein is an important component for maintaining normal life activities of organisms, the structure of the protein is clarified to have important biological significance, the Raman spectrum is considered to be an effective analysis means for researching biomacromolecules such as the protein, the Raman spectrum technology can be used for samples in various forms from solid to dilute solution, and the like, and has no destructiveness to the samples (wood et al, optical scattering bulletin, 2005,17(2): 180-. However, the weak raman spectral intensity of proteins limits the application of raman spectroscopy in the field of protein research. Therefore, the study of the enhancement method of raman scattering signal is crucial to facilitate the application of raman spectroscopy.
The Surface Enhanced Raman Scattering (SERS) effect is one of the feasible methods for realizing the enhancement of the raman scattering signal, and is a surface detection spectroscopy technology with high sensitivity. In general, the SERS effect is a sharp increase in raman scattering caused by local amplification of the electromagnetic field occurring in the vicinity of the noble metal nanostructure material, which is caused by local surface plasmon resonance excitation, and these phenomena are generally achieved using SERS substrates composed of plasmonic nanoparticles made of noble metals. It has been found that the noble metal nanostructure materials with SERS effect are mainly nano silver, nano copper, nano platinum, nano palladium, nano rhodium, nano iridium, etc. (rhodamine, etc., spectroscopy and spectroscopy, 2018,38(10), 3112-3116; Kucheyev S.O., et al, Applied Physics Letters,2006,89(5): 053102; Markin A.V., et al, Tractrends in Analytical Chemistry,2018,108: 247-259; shinJ.H., et al, RSC adv.2016,6(75): 756-70762; Bhumana T, et al, Small (Weinheim and Bergstre, Germany),2008,4(5): 670; Li Y.Y., nal, Journal of Science, 35, 201423, 20145).
Conventional SERS substrate fabrication often requires expensive, time consuming and highly specialized fabrication techniques (erikar.s., et al, Advanced Optical Materials,2018,1800548), and also does not meet the requirements for fast, convenient sensing for field testing. Since most active layers with SERS effect are built on rigid substrates such as glass or silicon wafers, it is not possible to collect analytes directly from solid surfaces of different shapes and roughness. Because the flexible SERS substrate can be combined with various curved surfaces through contact deformation to collect analytes, and has a good application prospect (Cong W, et al., Talanta,2019,191: 241-. Related researchers have prepared a series of flexible SERS substrates, mainly comprising: (1) a SERS substrate prepared based on fiber paper; (2) SERS substrates prepared based on flexible polymers; (3) SERS substrate based on carbon nanotube and graphene preparation.
Microbial Cellulose (also called Bacterial Cellulose (BC for short) is synthesized by fermenting microorganisms such as Acetobacter, Rhizobium, Sarcina, Pseudomonas, Azotobacter, Aerobacter and Alcaligenes, and is a linear polysaccharide connected by beta and nitrogen-fixed glycosidic bonds. The microbial cellulose membrane not only has high elastic modulus (up to tens of times of elastic modulus compared with common plant cellulose), high tensile strength and excellent shape maintenance capability, but also has a special three-dimensional network structure, so that nano-scale holes exist in the microbial cellulose membrane, and the microbial cellulose membrane has high void ratio and high specific surface area (Czaja W.K., et al, Biomacromolecules,2007,8(1): 1-12). However, at present, no report is found for preparing a flexible SERS substrate material by using a microbial cellulose membrane.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a microbial cellulose membrane/nano precious metal composite material with a surface enhanced Raman scattering effect and used for detecting protein. The nano-noble metal particle is prepared by growing nano-noble metal particles in situ in a nano-fiber network structure of a microbial cellulose membrane by using noble metal salt and a reducing agent and dehydrating the nano-noble metal particles. The preparation method is green and safe, mild in condition and simple in operation.
The invention also aims to provide the microbial cellulose membrane/nano noble metal composite material with the surface enhanced Raman scattering effect prepared by the method.
The invention further aims to provide the application of the microbial cellulose membrane/nano noble metal composite material with the surface enhanced Raman scattering effect in protein Raman enhanced spectroscopy.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a microbial cellulose membrane/nano precious metal composite material with a surface enhanced Raman scattering effect comprises the following steps:
s1, soaking a microbial cellulose membrane in a sodium hydroxide solution, then soaking in water, repeating for a plurality of times, and removing impurities (mainly a culture medium or thalli) in the microbial cellulose membrane; then repeatedly oscillating and cleaning with water until the cleaning solution is neutral; at the moment, the surface of the bacterial cellulose is smooth and is in a milk white semitransparent gel state;
s2, soaking the microbial cellulose membrane purified in the step S1 in 0.01-0.2 mol/L noble metal salt solution at 30-60 ℃ in a dark place for 2-24 h;
s3, separating the microbial cellulose membrane soaked in the step S2, washing the surface for a plurality of times by using water to remove the non-bonded precious metal ions on the surface, soaking the microbial cellulose membrane in 0.01-0.2 mol/L reducing agent solution, and soaking for 6-48 h at 30-100 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and carrying out vibration cleaning by using water until the cleaning solution does not contain precious metal ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 to obtain the microbial cellulose membrane/nano precious metal composite material with the surface enhanced Raman scattering effect.
The microbial cellulose membrane is a natural flexible high polymer, has excellent physicochemical properties, and has a unique three-dimensional network structure, so that nano-scale holes exist in the microbial cellulose membrane. According to the invention, noble metal salt and a reducing agent are used for growing noble metal nanoparticles in situ in a nanofiber network structure of a microbial cellulose membrane, the superfine three-dimensional network structure of the microbial cellulose membrane is used for limiting the growth of the noble metal nanoparticles, so that the formed noble metal nanoparticles are uniformly distributed in nano-scale holes of the microbial cellulose membrane and are adhered to a fiber bundle, and finally, the surface-enhanced Raman scattering substrate with a good surface-enhanced Raman spectrum scattering effect is obtained through dehydration and drying treatment.
Preferably, step S1 is to soak the microbial cellulose membrane in 0.5-2% sodium hydroxide solution, treat for 0.5-6 h at 25-100 ℃, then soak the microbial cellulose membrane in water, treat for 0.5-2 h at 20-100 ℃, repeat for 1-5 times, and remove impurities in the microbial cellulose membrane; then repeatedly oscillating and cleaning with water until the cleaning solution is neutral.
Preferably, the microbial cellulose membrane of S1 has a thickness of 1mm, 3mm, 8mm, 10mm or 15 mm.
Preferably, the microbial cellulose membrane of S1 is derived from acetobacter, agrobacterium, sarcina, rhizobium, pseudomonas, or azotobacter, among others.
Preferably, the water of the present invention is distilled water, deionized water, pure water or high purity water.
Preferably, the noble metal salt in S2 is a soluble salt of a noble metal such as silver, copper, platinum, palladium, rhodium, iridium, and the like.
Preferably, the reducing agent in S3 is a reducing saccharide (saccharide containing hemiacetal group) including galactose, mannose, teraose, glucose, fructose, lactose, maltose, isomaltose, cellobiose, fucose, gentiobiose, melibiose, maltotriose, maltotetraose, maltopentaose, maltohexaose, maltoheptaose, etc., and sodium citrate, sodium borohydride, sodium cyanoborohydride, ascorbic acid, ethylene glycol, hydrazine hydrate or formaldehyde.
Preferably, when the noble metal salt is silver salt and the reducing agent is glucose at S2; step S2, soaking the purified microbial cellulose membrane in 0.01-0.1 mol/L silver nitrate solution, and soaking for 6-12 h at 30-50 ℃ in a dark place; and step S3, separating the microbial cellulose membrane soaked in the S2, washing the surface with deionized water for 5 times to remove silver ions which are not combined on the surface, soaking the microbial cellulose membrane in 0.05-0.2 mol/L glucose solution, and soaking for 24-48 h at 30-60 ℃ in a dark place.
Preferably, the freeze drying in the step S5 is carried out at-20 to-80 ℃ for 0.5 to 5 days.
The invention also claims a microbial cellulose membrane/nano precious metal composite material with a surface enhanced Raman spectrum scattering effect, which is prepared by any one of the preparation methods.
The microbial cellulose membrane/nano precious metal composite material prepared by the invention can be used as a flexible substrate with surface enhanced Raman scattering for analyzing and detecting protein biological macromolecules.
Therefore, the invention also claims the application of the microbial cellulose membrane/nano precious metal composite material in the preparation or serving as a flexible substrate with the surface enhanced Raman scattering effect; and the application of the microbial cellulose membrane/nano noble metal composite material with the surface enhanced Raman scattering effect in protein analysis and detection is protected.
Compared with the prior art, the invention has the following beneficial effects:
the prepared microbial cellulose membrane/nano precious metal composite material can limit the growth of precious metal particles by utilizing the hyperfine three-dimensional network structure of the microbial cellulose membrane, so that the formed precious metal nanoparticles are uniformly distributed in nano-scale holes of the microbial cellulose membrane and are adhered to fiber bundles, the composite material has a good surface enhanced Raman scattering effect, and the composite material has the surface enhanced Raman scattering effect and can be used for analyzing and detecting protein biological macromolecules. Meanwhile, the preparation process is safe, mild in condition, simple to operate and low in raw material cost.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the present invention.
FIG. 2 is an X-ray diffraction pattern of a lyophilized sample prepared according to the present invention: (A) a microbial cellulose membrane raw material, and (B) a microbial cellulose membrane/nano silver composite material.
FIG. 3 is a UV-VIS absorption spectrum of a lyophilized sample prepared according to the present invention: (A) a microbial cellulose membrane raw material, and (B) a microbial cellulose membrane/nano silver composite material.
FIG. 4 is a scanning electron micrograph of a lyophilized sample prepared according to the present invention: (A) a microbial cellulose membrane raw material, and (B) a microbial cellulose membrane/nano silver composite material.
FIG. 5 is a Raman spectrum of a lyophilized sample prepared according to the present invention: (A) a microbial cellulose membrane raw material, (B) a microbial cellulose membrane/nano silver composite material, and (C) a microbial cellulose membrane/nano silver composite material/bovine serum albumin.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
S1, soaking a microbial cellulose membrane which is fermented and synthesized by Acetobacter and has the thickness of 1mm in a 0.5% sodium hydroxide solution, treating the microbial cellulose membrane at 100 ℃ for 2 hours, then soaking the microbial cellulose membrane in deionized water at 100 ℃ for 2 hours, and repeating the step for 1 time to remove impurities in the microbial cellulose membrane. Then repeatedly oscillating and cleaning with deionized water until the cleaning solution is neutral;
s2, soaking the microbial cellulose membrane purified by the S1 in 0.01mol/L silver nitrate solution at 30 ℃ in a dark place for 12 hours;
s3, separating the microbial cellulose membrane soaked in the S2, washing the surface for 5 times by using deionized water to remove silver ions which are not combined on the surface, soaking the microbial cellulose membrane in 0.05mol/L glucose solution, and soaking for 48 hours at 30 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and performing oscillation cleaning by using deionized water until the cleaning solution does not contain silver ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 at the temperature of-20 ℃ for 0.5 day to obtain the microbial cellulose membrane/nano-silver composite material with the surface enhanced Raman scattering effect.
FIG. 2 is an X-ray diffraction pattern of the freeze-dried sample for preparing the microbial cellulose membrane/nano-silver composite material, wherein the X-ray diffraction pattern of the raw material of the microbial cellulose membrane shows characteristic peaks (FIG. 2A) of microbial cellulose crystals, namely (111), (1 ī 0) and (200) crystal faces. In the X-ray diffraction pattern of the microbial cellulose film/nano silver composite sample (fig. 2B), in addition to the above-described characteristic peaks of microbial cellulose crystals, characteristic peaks of elemental silver crystals, i.e., (111), (200), (220), and (311) crystal planes, appear. The results show that a microbial cellulose membrane containing elemental silver was prepared.
Fig. 3 is an ultraviolet-visible light absorption spectrum of the freeze-dried sample for preparing the microbial cellulose membrane/nano silver composite material, wherein the microbial cellulose membrane has no absorption peak (fig. 3A), and the microbial cellulose membrane/nano silver composite material has a characteristic absorption peak of silver (fig. 3B) at about 420nm, which further proves that the silver grows in situ in the structure of the microbial cellulose membrane, and the microbial cellulose membrane/silver composite material is prepared.
Fig. 4 is a scanning electron micrograph of the freeze-dried sample for preparing the microbial cellulose membrane/nano silver composite material, and both the microbial cellulose membrane raw material and the micro-topography of the freeze-dried microbial cellulose membrane/nano silver composite material sample show a nanofiber network structure. In addition, the micro-topography of the microbial cellulose membrane/nano-silver composite material sample can clearly see that nano-scale silver particles are attached to the nano-fibers of the microbial cellulose membrane (fig. 4B), which indicates that the microbial cellulose membrane containing nano-silver is prepared.
The prepared microbial cellulose membrane/nano-silver is researched by taking bovine serum albumin as a model proteinThe surface enhanced Raman scattering effect of the composite material. FIG. 5 is a Raman spectrum of the freeze-dried sample of the microbial cellulose membrane/nano-silver composite material prepared as described above, wherein a Raman signal (FIG. 5A) of the microbial cellulose appears in the Raman spectrum of the raw material of the microbial cellulose membrane, i.e., 439cm-1And 460cm-1Peaks, 1097cm, produced by bending vibrations of C-O, C-C-C, C-O-C, O-C-O and C-C-O appeared-1And 1125cm-1A peak of 1339cm was observed due to stretching vibration of C-C and C-O-1And 1378cm-1Is represented by C-C-H, O-C-H, C-O-H, H-C-H and CH2Peaks due to bending vibrations. In the Raman spectrogram of the microbial cellulose membrane/nano silver composite material sample (FIG. 5B), the Raman peak of the microbial cellulose is weakened, and the Raman peak is at 1500cm-1To 1600cm-1A new peak appears and is attributed to the Raman signal of the nano-silver. In the Raman spectrogram (FIG. 5C) of lyophilized microorganism cellulose membrane/nano-silver composite material/bovine serum albumin sample, the Raman characteristic peaks (such as tryptophan and phenylalanine residue Raman peaks) (1003 cm) of bovine serum albumin amino acid residue with stronger signal appear-1) Raman peak of tryptophanyl residue Ring (1450 cm)-1) Amide I band Raman peak (1648 cm)-1). The result proves that the microbial cellulose membrane/nano silver composite material has good surface enhanced Raman scattering effect on bovine serum albumin.
Example 2
S1, soaking a microbial cellulose membrane which is fermented and synthesized by Acetobacter and has the thickness of 1mm in a 0.5% sodium hydroxide solution, treating the microbial cellulose membrane at 100 ℃ for 2 hours, then soaking the microbial cellulose membrane in deionized water at 100 ℃ for 2 hours, and repeating the step for 1 time to remove impurities in the microbial cellulose membrane. Then repeatedly oscillating and cleaning with deionized water until the cleaning solution is neutral;
s2, soaking the microbial cellulose membrane purified by the S1 in 0.1mol/L silver nitrate solution at 40 ℃ in a dark place for 6 hours;
s3, separating the microbial cellulose membrane soaked in the S2, washing the surface for 5 times by using deionized water to remove silver ions which are not combined on the surface, soaking the microbial cellulose membrane in 0.2mol/L glucose solution, and soaking for 24 hours at 60 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and performing oscillation cleaning by using deionized water until the cleaning solution does not contain silver ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 at the temperature of-20 ℃ for 0.5 day to obtain the microbial cellulose membrane/nano-silver composite material with the surface enhanced Raman scattering effect.
Example 3
S1, soaking a microbial cellulose membrane which is fermented and synthesized by Acetobacter and has the thickness of 1mm in a 0.5% sodium hydroxide solution, treating the microbial cellulose membrane at 100 ℃ for 2 hours, then soaking the microbial cellulose membrane in deionized water at 100 ℃ for 2 hours, and repeating the step for 1 time to remove impurities in the microbial cellulose membrane. Then repeatedly oscillating and cleaning with deionized water until the cleaning solution is neutral;
s2, soaking the microbial cellulose membrane purified by the S1 in 0.05mol/L silver nitrate solution at 50 ℃ in a dark place for 12 hours;
s3, separating the microbial cellulose membrane soaked in the S2, washing the surface for 5 times by using deionized water to remove silver ions which are not combined on the surface, soaking the microbial cellulose membrane in 0.1mol/L glucose solution, and soaking for 36 hours at 40 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and performing oscillation cleaning by using deionized water until the cleaning solution does not contain silver ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 at the temperature of-20 ℃ for 0.5 day to obtain the microbial cellulose membrane/nano-silver composite material with the surface enhanced Raman scattering effect.
Example 4
S1, soaking a microbial cellulose membrane which is formed by rhizobium fermentation and has the thickness of 10mm in a 2% sodium hydroxide solution, treating for 6 hours at 25 ℃, then soaking the microbial cellulose membrane in high-purity water for 2 hours at 20 ℃, and repeating the step for 5 times to remove impurities in the microbial cellulose membrane. Then repeatedly oscillating and cleaning with high-purity water until the cleaning solution is neutral;
s2, soaking the microbial cellulose membrane purified by the S1 in 0.1mol/L copper sulfate solution at 40 ℃ in a dark place for 24 hours;
s3, separating the microbial cellulose membrane soaked in the S2, washing the surface for 1 time by using high-purity water to remove the copper ions which are not combined on the surface, soaking the microbial cellulose membrane in 0.2mol/L hydrazine hydrate solution, and soaking for 6 hours at 40 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and performing oscillation cleaning by using high-purity water until the cleaning solution does not contain copper ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 at-60 ℃ for 2 days to obtain the microbial cellulose membrane/nano copper composite material with the surface enhanced Raman scattering effect. The microbial cellulose membrane/nano silver composite material has a good surface enhanced Raman scattering effect on bovine serum albumin.
Example 5
S1, soaking a microbial cellulose membrane which is fermented and synthesized by sarcina and has the thickness of 3mm in a 2% sodium hydroxide solution, treating for 6 hours at 80 ℃, then soaking the microbial cellulose membrane in distilled water for 2 hours at 80 ℃, and repeating the step for 3 times to remove impurities in the microbial cellulose membrane. Then repeatedly oscillating and cleaning by using distilled water until the cleaning solution is neutral;
s2, soaking the microbial cellulose membrane purified by the S1 in a 0.01mol/L chloroplatinic acid solution at 40 ℃ in a dark place for 24 hours;
s3, separating the microbial cellulose membrane soaked in the S2, washing the surface for 1 time by using distilled water to remove the unconjugated chloroplatinic acid radical ions on the surface, soaking the microbial cellulose membrane in 0.01mol/L sodium borohydride solution, and soaking for 6 hours at 40 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and oscillating and cleaning the microbial cellulose membrane by using distilled water until the cleaning solution does not contain chloroplatinic acid radical ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 at-60 ℃ for 1 day to obtain the microbial cellulose membrane/nano platinum composite material with the surface enhanced Raman scattering effect. The microbial cellulose membrane/nano silver composite material has a good surface enhanced Raman scattering effect on bovine serum albumin.
Example 6
S1, soaking a microbial cellulose membrane which is fermented and synthesized by azotobacter and has the thickness of 8mm in a 2% sodium hydroxide solution, treating at 80 ℃ for 0.5h, then soaking the microbial cellulose membrane in deionized water at 80 ℃ for 0.5h, and repeating the step for 5 times to remove impurities in the microbial cellulose membrane. Then repeatedly oscillating and cleaning with deionized water until the cleaning solution is neutral;
s2, soaking the microbial cellulose membrane purified by the S1 in 0.1mol/L chloropalladate solution at 40 ℃ in a dark place for 2 hours;
s3, separating the microbial cellulose membrane soaked in the S2, washing the surface for 1 time by using deionized water to remove the chlorine palladate ions which are not combined on the surface, soaking the microbial cellulose membrane in 0.1mol/L formaldehyde solution, and soaking for 6 hours at 40 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and performing oscillation cleaning by using deionized water until the cleaning solution does not contain chloropalladate ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 at-60 ℃ for 2 days to obtain the microbial cellulose membrane/nano-palladium composite material with the surface enhanced Raman scattering effect. The microbial cellulose membrane/nano silver composite material has a good surface enhanced Raman scattering effect on bovine serum albumin.
Example 7
S1, soaking a microbial cellulose membrane which is fermented and synthesized by agrobacterium and has the thickness of 15mm in a 1% sodium hydroxide solution, treating for 6 hours at 80 ℃, then soaking the microbial cellulose membrane in deionized water at 80 ℃ for 2 hours, and repeating the step for 5 times to remove impurities in the microbial cellulose membrane. Then repeatedly oscillating and cleaning with deionized water until the cleaning solution is neutral;
s2, soaking the microbial cellulose membrane purified by the S1 in a 0.2mol/L rhodium chloride solution at 60 ℃ in a dark place for 6 hours;
s3, separating the microbial cellulose membrane soaked in the S2, washing the surface for 5 times by using deionized water to remove rhodium ions which are not combined on the surface, soaking the microbial cellulose membrane in 0.2mol/L glycol solution, and soaking for 6 hours at 100 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and performing oscillation cleaning by using deionized water until the cleaning solution does not contain rhodium ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 at-80 ℃ for 5 days to obtain the microbial cellulose membrane/nano rhodium composite material with the surface enhanced Raman scattering effect.
Example 8
S1, soaking a microbial cellulose membrane which is fermented and synthesized by pseudomonas and has the thickness of 8mm in a 2% sodium hydroxide solution, treating the microbial cellulose membrane for 2 hours at 80 ℃, then soaking the microbial cellulose membrane in pure water for 2 hours at 80 ℃, and repeating the step for 3 times to remove impurities in the microbial cellulose membrane. Then repeatedly oscillating and cleaning with pure water until the cleaning solution is neutral;
s2, soaking the microbial cellulose membrane purified by the S1 in 0.1mol/L iridium chloride solution at 60 ℃ in a dark place for 6 hours;
s3, separating the microbial cellulose membrane soaked in the S2, washing the surface for 1 time by using pure water to remove iridium ions which are not combined on the surface, soaking the microbial cellulose membrane in 0.1mol/L sodium borohydride solution, and soaking for 12 hours at 80 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and carrying out oscillation cleaning by using pure water until the cleaning solution does not contain iridium ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 at-60 ℃ for 2 days to obtain the microbial cellulose membrane/nano iridium composite material with the surface enhanced Raman scattering effect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a microbial cellulose membrane/nano precious metal composite material is characterized by comprising the following steps:
s1, soaking a microbial cellulose membrane in a sodium hydroxide solution, then soaking in water, repeating the soaking treatment for a plurality of times, and removing impurities in the microbial cellulose membrane; then repeatedly oscillating and cleaning with water until the cleaning solution is neutral;
s2, soaking the microbial cellulose membrane purified in the step S1 in 0.01-0.2 mol/L noble metal salt solution at 30-60 ℃ in a dark place for 2-24 h;
s3, separating the microbial cellulose membrane soaked in the step S2, washing the surface for a plurality of times by using water to remove the non-bonded precious metal ions on the surface, soaking the microbial cellulose membrane in 0.01-0.2 mol/L reducing agent solution, and soaking for 6-48 h at 30-100 ℃ in a dark place;
s4, separating the microbial cellulose membrane soaked in the S3, and carrying out vibration cleaning by using water until the cleaning solution does not contain precious metal ions;
s5, freeze-drying the microbial cellulose membrane treated by the S4 to obtain the microbial cellulose membrane/nano precious metal composite material with the surface enhanced Raman scattering effect.
2. The method according to claim 1, wherein the thickness of the microbial cellulose membrane of step S1 is 1mm, 3mm, 8mm, 10mm or 15 mm.
3. The method according to claim 1 or 2, wherein the microbial cellulose membrane obtained in step S1 is derived from the genus Acetobacter, Agrobacterium, Sarcina, Rhizobium, Pseudomonas or Azotobacter.
4. The preparation method according to claim 1, wherein the step S1 is to soak the microbial cellulose membrane in 0.5-2% sodium hydroxide solution, treat the microbial cellulose membrane at 25-100 ℃ for 0.5-6 h, then soak the microbial cellulose membrane in water, treat the microbial cellulose membrane at 20-100 ℃ for 0.5-2 h, repeat the treatment for 1-5 times, and remove impurities in the microbial cellulose membrane; then repeatedly oscillating and cleaning with water until the cleaning solution is neutral.
5. The method according to claim 1, wherein the noble metal salt in step S2 is a soluble salt of a noble metal selected from silver, copper, platinum, palladium, rhodium and iridium.
6. The method according to claim 1, wherein the reducing agent in step S3 is a reducing saccharide, sodium citrate, sodium borohydride, sodium cyanoborohydride, ascorbic acid, ethylene glycol, hydrazine hydrate, or formaldehyde.
7. The method according to claim 6, wherein the reducing saccharide substance of S3 is galactose, mannose, teraose, glucose, fructose, lactose, maltose, isomaltose, cellobiose, fucose, gentiobiose, melibiose, maltotriose, maltotetraose, maltopentaose, maltohexaose, or maltoheptaose.
8. The method according to claim 1, wherein the freeze-drying in step S5 is carried out at-20 to-80 ℃ for 0.5 to 5 days.
9. The microbial cellulose membrane/nano precious metal composite material prepared by the method of any one of claims 1 to 8.
10. Use of the microbial cellulose membrane/nano precious metal composite of claim 9 in protein analysis and detection.
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| CN112471173A (en) * | 2020-11-26 | 2021-03-12 | 中国科学院合肥物质科学研究院 | Preparation method of graphene antibacterial composite membrane and prepared antibacterial composite membrane |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112471173A (en) * | 2020-11-26 | 2021-03-12 | 中国科学院合肥物质科学研究院 | Preparation method of graphene antibacterial composite membrane and prepared antibacterial composite membrane |
| CN112471173B (en) * | 2020-11-26 | 2022-02-11 | 中国科学院合肥物质科学研究院 | Preparation method of graphene antibacterial composite membrane and prepared antibacterial composite membrane |
| CN113604039A (en) * | 2021-08-31 | 2021-11-05 | 中山大学 | Flexible cationic hyperbranched polymer/noble metal nanoparticle composite material for protein surface enhanced Raman spectroscopy |
| CN113877643A (en) * | 2021-09-18 | 2022-01-04 | 重庆市益康环保工程有限公司 | Cellulose 3D enhanced Raman spectrum microfluidic chip for detecting water pollution and application thereof |
| CN113877643B (en) * | 2021-09-18 | 2022-09-13 | 重庆市益康环保工程有限公司 | Cellulose 3D enhanced Raman spectrum microfluidic chip for detecting water pollution and application thereof |
| CN114437389A (en) * | 2022-03-02 | 2022-05-06 | 五邑大学 | Ordered nano-folded cellulose composite membrane with high surface Raman enhancement effect and preparation method thereof |
| CN114437389B (en) * | 2022-03-02 | 2023-11-07 | 五邑大学 | Ordered nano-pleated cellulose composite membrane with high surface Raman enhancement effect and preparation method thereof |
| CN116162277A (en) * | 2023-04-24 | 2023-05-26 | 北京市农林科学院智能装备技术研究中心 | Method for rapidly measuring phosphate radical in water |
| CN116380876A (en) * | 2023-05-26 | 2023-07-04 | 北京市农林科学院智能装备技术研究中心 | Method for detecting content of phosphorus element in water body |
| CN116380876B (en) * | 2023-05-26 | 2023-09-19 | 北京市农林科学院智能装备技术研究中心 | Method for detecting content of phosphorus element in water body |
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