CN113321747A - Antibacterial component containing quaternary phosphonium salt modified locust bean gum - Google Patents
Antibacterial component containing quaternary phosphonium salt modified locust bean gum Download PDFInfo
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- CN113321747A CN113321747A CN202110562640.1A CN202110562640A CN113321747A CN 113321747 A CN113321747 A CN 113321747A CN 202110562640 A CN202110562640 A CN 202110562640A CN 113321747 A CN113321747 A CN 113321747A
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- Prior art keywords
- locust bean
- bean gum
- phosphonium salt
- quaternary phosphonium
- lbg
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0093—Locust bean gum, i.e. carob bean gum, with (beta-1,4)-D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from the seeds of carob tree or Ceratonia siliqua; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
Abstract
The invention relates to an antibacterial component of a quaternary phosphonium salt modified locust bean gum, which is prepared by an oxidation method and an amidation method, wherein sodium periodate is utilized to oxidize and open the galactomannan chain C2 and C3 in natural locust bean gum to obtain a dialdehyde structure, and the dialdehyde structure and an amine compound generate Schiff base to obtain an intermediate containing terminal amino, and the intermediate and the quaternary phosphonium salt are further amidated under the condition of an initiator; the obtained quaternary phosphonium salt modified locust bean gum has high antibacterial activity and can be used as a flocculating agent antibacterial component for sewage treatment.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an antibacterial component of a quaternary phosphonium salt modified locust bean gum.
Technical Field
The quaternary ammonium salt modified natural degradable biological material is one of the commonly used antibacterial material modification means at present, but the antibacterial duration is short, the medicinal dosage is large, however, the drug resistance is easy to generate along with the mass use of the quaternary ammonium salt antibacterial agent, and the antibacterial effect is gradually weakened. The quaternary phosphonium salt which is a product of the same family has weaker electronegativity, is easier to form cations, can easily act on cell walls and cell membranes of bacteria with negative electricity, destroys the membrane integrity of the bacteria and promotes the death of the bacteria, and has the advantages of good chemical stability, wide pH application range and the like compared with the quaternary ammonium salt quaternary phosphonium salt. At present, the modification and application of cellulose are the most extensive in natural degradable biological materials, but the crystallinity is extremely high, the water solubility is poor, and the biodegradability is poor, so that the natural locust bean gum which is a material with a large molecular weight, almost no crystal region and high biodegradability can be endowed with antibacterial activity after being modified by quaternary phosphonium salt, and meanwhile, the natural locust bean gum keeps good biodegradability and has wide application value.
Disclosure of Invention
In order to solve the above-mentioned problems, an object of the present invention is to provide a structure of a quaternary phosphonium salt-modified locust bean gum, and another object is to provide a method for preparing an antibacterial component of a quaternary phosphonium salt-modified locust bean gum.
The structural formula of the quaternary phosphonium salt modified locust bean gum is shown as the following (I):
wherein R is
m＝3～5。
The preparation method of the locust bean gum modified by the quaternary phosphonium salt comprises the following steps:
1) preparation of O-LBG
Adding 0.1-1.0 g of natural locust bean gum and 0.5-2.0 g of sodium periodate into 10% (w/v) sodium hydroxide and 5% (w/v) urea solution, reacting in a round-bottom flask, wrapping with tinfoil paper to shield light, avoiding the decomposition of the sodium periodate, and magnetically stirring at room temperature for 3-5 hours; adding ethylene glycol into the mixed solution, and stirring for 0.5-1.0 h to eliminate unreacted sodium periodate to obtain O-LBG;
2) preparation of quaternary phosphonium salt modified locust bean gum
Adding 30mL of dimethyl sulfoxide aqueous solution into a flask, weighing 0.5-1.0 g O-LBG and 1-hydroxybenzotriazole initiator, sequentially adding the weighed materials into the DMSO aqueous solution, stirring and hydrating at room temperature, adjusting the pH to 4.8-5.5, continuing to stir for 30min, dropwise adding a quaternary phosphonium salt (0.12-0.20M) dissolved in 10mL of the DMSO aqueous solution, stirring for 30min, slowly dropwise adding 9mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloric acid DMSO aqueous solution, continuing to stir and react for 12-48 h, pouring acetone/ether mixed solution after the reaction is finished for precipitation, centrifuging, and vacuum-drying a solid product overnight to obtain a compound (I);
the total reaction scheme is shown as (II):
wherein R is
m is 3-5, and X is halogen.
The quaternary phosphonium salt in the step (2) is one of 2-carboxyethyl triphenyl phosphonium bromide, 3-carboxypropyl triphenyl phosphonium bromide and 4-carboxybutyl triphenyl phosphonium bromide;
the adding amount ratio of the natural locust bean gum, the sodium periodate and the urea in the step (1) can be 0.5-2.5: 3:3, and preferably 2:3: 3;
preferably, the quaternary phosphonium salt is added in the step (2) at a concentration of 0.16M.
Compared with the prior art, the invention has the following beneficial effects:
the O-LBG and the quaternary phosphonium salt modified locust bean gum have antibacterial activity, wherein the inhibition zones of the quaternary phosphonium salt modified locust bean gum to gram-negative bacteria and gram-positive bacteria respectively reach 12.5mm and 16.5mm, which shows that the O-LBG and the quaternary phosphonium salt modified locust bean gum can well inhibit the growth of bacteria.
Drawings
FIG. 1 is a Fourier infrared spectrum of 3-carboxypropyltriphenylphosphonium bromide modified locust bean gum, 3-carboxypropyltriphenylphosphonium bromide, natural Locust Bean Gum (LBG).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
EXAMPLE 1 preparation of O-LBG
1) Mixing 0.1-1.0 g natural Locust Bean Gum (LBG) and 0.5-2.0 g NaIO4Adding 10% (w/v) sodium hydroxide and 5% (w/v) urea solutionReacting in a round-bottom flask, wrapping with tin foil paper to shield light, avoiding the decomposition of sodium periodate, and magnetically stirring at room temperature for 3-5 h; adding ethylene glycol into the mixed solution, and stirring for 0.5-1.0 h to eliminate unreacted sodium periodate to obtain O-LBG;
wherein LBG and NaIO4The addition amount ratio of the urea is 0.5-2.5: 3:3, and the specific addition amount is shown in table 1;
table 1 shows LBG and NaIO4And the amount of urea added
The weight gain (%) and the antibacterial effect were measured for five groups of samples of the above example 1 and LBG as a blank under the following conditions:
1) weight gain (%): wg is the weight gain (%) and W is0Mass (g) before reaction, W1The mass (g) after the reaction was calculated by the following formula (1):
2) the antibacterial effect is as follows: the bacteria are tested to be escherichia coli, staphylococcus aureus and candida albicans by adopting a bacteriostatic circle method, and the method comprises the following steps: preparing LB culture solution and LB culture medium, recovering strains, preparing bacterial suspension (106CFU/mL), weighing 5mg of each sample in examples 1-2 respectively, performing ultraviolet sterilization treatment, uniformly coating 200 microliter of the prepared bacterial suspension on the LB culture medium, placing the prepared samples on the culture medium coated with bacteria and fungi at equal intervals, placing a blank group (LBG) and three test samples (five groups of samples in examples 1 and 2) in each culture medium, placing the culture dish upside down in a constant-temperature incubator at 37 ℃, performing bacterial culture for 18 hours, performing fungal culture for 42 hours, taking out the culture dish, taking a picture, measuring the diameter of a bacteriostatic circle by using a vernier caliper, continuously culturing for 36 hours respectively, recording the measurement again, and recording the result;
according to the relevant standard, the diameter of the inhibition zone is larger than 7mm, which indicates that the antibacterial effect is achieved.
The results obtained by the above-mentioned measurement method are shown in Table 2;
table 2: LBG, NaIO4The influence of the addition amount of urea on the weight gain rate and the inhibition zone (mm) of O-LBG
The results in Table 2 show that LBG has no antibacterial activity, O-LBG has antibacterial activity against bacteria, and the main reason is that Schiff base is generated by the reaction, contains a large amount of imine and imide structure, has antibacterial property, but has weak fungal inhibition effect, wherein LBG and NaIO4The addition amount ratio of urea to LBG is 0.5-2.5: 3:3, and the results of the measurement shown in Table 2 show that as the ratio of LBG to the oxidizing agent is decreased, the weight gain rate is increased, and the degree of oxidation is increased, the antibacterial activity of the obtained O-LBG is improved, and when the ratio is 2:3:3, the optimal addition ratio is reached, and further reduction of the addition amount of the oxidizing agent causes incomplete oxidation reaction and reduction of the antibacterial activity.
Example 2 preparation of locust Bean Gum modified with Quaternary phosphonium salt
Adding 30mL of dimethyl sulfoxide aqueous solution into a flask, weighing 0.57g O-LBG (1-4 in example 1) and 1-hydroxybenzotriazole initiator, sequentially adding the initiators into the DMSO aqueous solution, stirring and hydrating at room temperature, adjusting the pH to 4.8-5.5, then continuing to stir for 30min, dropwise adding 3-carboxypropyltriphenylphosphonium bromide (the concentrations of which are respectively 0.12M, 0.14M, 0.16M, 0.18M and 0.20M and are recorded as 2-1, 2-2, 2-3, 2-4 and 2-5) dissolved in 10mL of the DMSO aqueous solution, stirring for 30min, then slowly dropwise adding 9mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloric acid DMSO aqueous solution, continuing to stir for reaction for 12-48 h, pouring acetone/diethyl ether mixed solution for precipitation after the reaction is finished, centrifuging, vacuum-drying a solid product overnight, to obtain a compound (I);
the weight gain (%) and the antibacterial effect of the five groups of samples of the above example 2 were measured under the same conditions as those of example 1, and the results are shown in Table 3;
table 3: influence of 3-carboxypropyltriphenylphosphonium bromide addition on weight gain rate and inhibition zone (mm) of antibacterial component
As can be seen from the inhibition zone results in Table 3, the inhibition zones of the antibacterial component are both greater than 7mm, which shows that the antibacterial component has antibacterial activity on both bacteria and fungi, and the inhibition zones of gram-negative bacteria and gram-positive bacteria respectively reach 12.5mm and 16.5mm, which shows that the antibacterial component can well inhibit the growth of bacteria, and the inhibition rate of fungi is low, so that the quaternary phosphonium salt modified locust bean gum can be used as a good antibacterial component.
Example 3 FT-IR structural analysis
The samples of example 2(2-4) were subjected to qualitative analysis of structure by means of Fourier IR spectroscopy under the following conditions: freeze-drying, grinding and tabletting by potassium bromide, wherein the wavelength scanning range is 4000-400 cm-1；
As can be seen from the infrared spectrum of FIG. 1, the length of the 3-carboxypropyltriphenylphosphonium bromide modified locust bean gum is 1535cm-1A new absorption peak appears, which corresponds to the C ═ C skeleton vibration characteristic peak of the benzene ring on the 3-carboxypropyl triphenyl phosphonium bromide; in addition, the quaternary phosphonium salt introduced has a large amount of C-H stretching vibration, so that the length of the quaternary phosphonium salt is 2900cm-1The absorption peak intensity is obviously increased, and the quaternary phosphonium salt is successfully grafted.
Claims (5)
1. An antibacterial component of a quaternary phosphonium salt modified locust bean gum is characterized in that the structural formula of the quaternary phosphonium salt modified locust bean gum is shown as (I):
wherein R is
m＝3～5。
2. The preparation method of the antibacterial component of the locust bean gum modified by the quaternary phosphonium salt is characterized by comprising the following steps:
1) preparation of O-LBG
Adding 0.1-1.0 g of natural locust bean gum and 0.5-2.0 g of sodium periodate into 10% (w/v) sodium hydroxide and 5% (w/v) urea solution, reacting in a round-bottom flask, wrapping with tinfoil paper to shield light, avoiding the decomposition of the sodium periodate, and magnetically stirring at room temperature for 3-5 hours; adding ethylene glycol into the mixed solution, and stirring for 0.5-1.0 h to eliminate unreacted sodium periodate to obtain a locust bean gum intermediate O-LBG;
2) preparation of quaternary phosphonium salt modified locust bean gum
Adding 30mL of dimethyl sulfoxide aqueous solution into a flask, weighing 0.5-1.0 g of O-LBG and 1-hydroxybenzotriazole initiator, sequentially adding the O-LBG and 1-hydroxybenzotriazole initiator into the DMSO aqueous solution, stirring and hydrating at room temperature, adjusting the pH to 4.8-5.5, then continuing stirring for 30min, dropwise adding 9mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloric acid DMSO aqueous solution after stirring for 30min, slowly dropwise adding 9mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloric acid DMSO aqueous solution, continuing stirring and reacting for 12-48 h, pouring acetone/diethyl ether mixed solution for precipitation after the reaction is finished, centrifuging, and drying the solid product in vacuum overnight to obtain a compound (I);
the total reaction scheme is shown as (II):
wherein R is
m is 3-5, and X is Br.
3. The method for preparing a quaternary phosphonium salt modified locust bean gum antibacterial ingredient as claimed in claim 2, wherein the quaternary phosphonium salt in the step (2) is one of 2-carboxyethyl triphenyl phosphonium bromide, 3-carboxypropyl triphenyl phosphonium bromide and 4-carboxybutyl triphenyl phosphonium bromide.
4. The method for preparing the antibacterial component of locust bean gum modified by quaternary phosphonium salt according to claim 2, wherein the adding amount ratio of the natural locust bean gum, the sodium periodate and the urea in the step (1) is 0.5-2.5: 3: 3.
5. The method for preparing a quaternary phosphonium salt modified locust bean gum antibacterial ingredient as claimed in claim 2, wherein the quaternary phosphonium salt is added in the concentration of 0.16M in the step (2).
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| CN202110562640.1A CN113321747A (en) | 2021-05-24 | 2021-05-24 | Antibacterial component containing quaternary phosphonium salt modified locust bean gum |
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|---|---|---|---|---|
| JP2006241082A (en) * | 2005-03-03 | 2006-09-14 | Toho Chem Ind Co Ltd | Cation-modified pure locust bean gum and cosmetic composition containing the substance |
| CN101649007A (en) * | 2009-09-30 | 2010-02-17 | 上海交通大学 | Chitosan quaternary phosphonium salt derivative and preparation method thereof |
| CN102976463A (en) * | 2012-11-19 | 2013-03-20 | 沈阳工业大学 | Crosslinked cation locust bean gum flocculant and preparation method thereof |
| US20130274225A1 (en) * | 2010-07-19 | 2013-10-17 | Actamax Surgical Materials, Llc | Method for making a polysaccharide dialdehyde having high purity |
| CN103709267A (en) * | 2013-11-28 | 2014-04-09 | 江南大学 | Preparation method of dialdehyde carboxymethyl chitosan |
| CN103980367A (en) * | 2014-05-19 | 2014-08-13 | 浙江理工大学 | Method for preparing carboxyl cellulose flocculant |
| CN104974267A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Etherification-modified locust bean gum and preparation method thereof, water-base gel fracturing fluid containing the locust bean gum and application thereof |
| CN106947095A (en) * | 2017-03-29 | 2017-07-14 | 邱发龙 | A kind of preparation method for wound healing antibacterial type hydrogel |
| CN110747534A (en) * | 2019-11-18 | 2020-02-04 | 东北师范大学 | Antibacterial polysaccharide fiber material and preparation method thereof |
| CN112300449A (en) * | 2020-11-03 | 2021-02-02 | 赵书敏 | Modified locust bean gum-kappa carrageenan gel and preparation method thereof |
-
2021
- 2021-05-24 CN CN202110562640.1A patent/CN113321747A/en not_active Withdrawn
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006241082A (en) * | 2005-03-03 | 2006-09-14 | Toho Chem Ind Co Ltd | Cation-modified pure locust bean gum and cosmetic composition containing the substance |
| CN101649007A (en) * | 2009-09-30 | 2010-02-17 | 上海交通大学 | Chitosan quaternary phosphonium salt derivative and preparation method thereof |
| US20130274225A1 (en) * | 2010-07-19 | 2013-10-17 | Actamax Surgical Materials, Llc | Method for making a polysaccharide dialdehyde having high purity |
| CN102976463A (en) * | 2012-11-19 | 2013-03-20 | 沈阳工业大学 | Crosslinked cation locust bean gum flocculant and preparation method thereof |
| CN103709267A (en) * | 2013-11-28 | 2014-04-09 | 江南大学 | Preparation method of dialdehyde carboxymethyl chitosan |
| CN104974267A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Etherification-modified locust bean gum and preparation method thereof, water-base gel fracturing fluid containing the locust bean gum and application thereof |
| CN103980367A (en) * | 2014-05-19 | 2014-08-13 | 浙江理工大学 | Method for preparing carboxyl cellulose flocculant |
| CN106947095A (en) * | 2017-03-29 | 2017-07-14 | 邱发龙 | A kind of preparation method for wound healing antibacterial type hydrogel |
| CN110747534A (en) * | 2019-11-18 | 2020-02-04 | 东北师范大学 | Antibacterial polysaccharide fiber material and preparation method thereof |
| CN112300449A (en) * | 2020-11-03 | 2021-02-02 | 赵书敏 | Modified locust bean gum-kappa carrageenan gel and preparation method thereof |
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Application publication date: 20210831 |