WO2023019704A1 - 一种硒-水溶性高分子多糖水凝胶的制备及其在植物富硒方面的应用 - Google Patents

一种硒-水溶性高分子多糖水凝胶的制备及其在植物富硒方面的应用 Download PDF

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WO2023019704A1
WO2023019704A1 PCT/CN2021/123186 CN2021123186W WO2023019704A1 WO 2023019704 A1 WO2023019704 A1 WO 2023019704A1 CN 2021123186 W CN2021123186 W CN 2021123186W WO 2023019704 A1 WO2023019704 A1 WO 2023019704A1
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selenium
water
soluble polymer
hydrogel
polymer polysaccharide
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李娜
朱健
曹路
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/20—Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material
    • A01G24/22—Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material containing plant material
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    • C05G5/00—Fertilisers characterised by their form
    • C05G5/10—Solid or semi-solid fertilisers, e.g. powders
    • C05G5/18—Semi-solid fertilisers, e.g. foams or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/10—Growth substrates; Culture media; Apparatus or methods therefor based on or containing inorganic material
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/30—Growth substrates; Culture media; Apparatus or methods therefor based on or containing synthetic organic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/40—Growth substrates; Culture media; Apparatus or methods therefor characterised by their structure
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G31/00—Soilless cultivation, e.g. hydroponics
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00—Other organic fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00—Other organic fertilisers
    • C05F11/08—Organic fertilisers containing added bacterial cultures, mycelia or the like
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • 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
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • 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
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/12—Agar-agar; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/14—Measures for saving energy, e.g. in green houses

Definitions

  • the invention relates to the fields of polymer chemical synthesis and agriculture, in particular to the preparation of a selenium-water-soluble polymer polysaccharide hydrogel and its application in plant selenium enrichment.
  • Selenium is an essential trace element for the growth and development of humans and animals. It has many important functions such as scavenging free radicals, regulating redox state, preventing cancer and enhancing human immunity. The lack of selenium will interfere with the metabolism of protein, nucleic acid and polysaccharide, leading to cardiovascular and cerebrovascular diseases, Keshan disease and other diseases. However, the human body cannot synthesize and store selenium. At present, about 1 billion people in the world are deficient in selenium, including China, northwestern Europe, New Zealand, Australia and parts of the United States. In China, 70% of the places are selenium deficient, and 30% of them are seriously deficient in selenium. It is one of the internationally recognized major selenium deficient countries.
  • Selenium supplementation mainly includes dietary selenium supplementation, selenium nutrition enhancer supplementation, and drug selenium supplementation.
  • dietary selenium supplementation is the main source of selenium intake for the human body due to its wide range of sources, safety and convenience.
  • eating selenium-enriched agricultural products is a safe, effective and healthy method.
  • Natural selenium enrichment refers to the process of planting agricultural products in soil with high selenium content, plants absorb selenium in the soil, and convert inorganic selenium into organic selenium through their own biological functions.
  • the distribution of selenium in natural selenium-enriched soils is not uniform, mostly distributed in strips or dots, which causes problems such as low selenium content in some agricultural products and uneven selenium-enriched products.
  • Artificial selenium enrichment such as: foliar selenium application, basal fertilizer application, etc., refers to the production of selenium-enriched agricultural products through the addition of selenium from exogenous sources during the plant growth process.
  • the present invention provides a preparation of selenium-water-soluble polymer polysaccharide hydrogel and its application in plant selenium enrichment, by mixing water-soluble polymer polysaccharides and selenium-containing compounds in aqueous solution and polysaccharide Physical cross-linking forms selenium-water-soluble polymer polysaccharide hydrogel, which can be used to enrich selenium in plants, and the hydrogel can be recycled, avoiding the problems of low selenium content in agricultural products and selenium pollution caused by traditional selenium fertilizer application. Realize green selenium enrichment.
  • the first aspect of the present invention provides a kind of preparation method of selenium-water-soluble polymer polysaccharide hydrogel, comprising the following steps:
  • Step (1) adding water-soluble polymer polysaccharides and selenium-containing compounds into water, heating and stirring to dissolve, and obtaining a mixed solution;
  • Step (2) The mixed solution is left to cool and molded to obtain a selenium-water-soluble polymer polysaccharide hydrogel.
  • the water-soluble polymer polysaccharide is one or more of agarose, carrageenan, gelatin, konjac gum, and locust bean gum.
  • the selenium-containing compound is a water-soluble selenium-containing compound, preferably one of selenized carrageenan, sodium selenite and yeast selenium.
  • the mass ratio of the water-soluble polymer polysaccharide to water is 1-10:100.
  • the temperature of the heating and stirring is 80-100°C.
  • the heating and stirring time is 0.5-1 h.
  • cooling time is 12-24 hours.
  • the second aspect of the present invention provides a selenium-water-soluble polymer polysaccharide hydrogel prepared by the preparation method described in the first aspect.
  • the third aspect of the present invention provides the application of the selenium-water-soluble polymer polysaccharide hydrogel described in the second aspect in plant selenium enrichment.
  • plant seeds are sown on the surface of the selenium-water-soluble polymer polysaccharide hydrogel, and cultivated under the conditions of light, constant temperature and humidity, to obtain selenium-enriched plants.
  • the plant seeds include one or more of mung bean seeds, rape seeds and pea seeds.
  • the concentration of the selenium element in the selenium-water-soluble polymer polysaccharide hydrogel is 400-1600 ⁇ g/L.
  • the illumination is continuous illumination, and the intensity of illumination is 800-4000LX; the temperature of the constant temperature is 20-25°C; the humidity of the constant humidity is 70%-80%.
  • the cultivation time of the plant seeds is preferably 5-15 days.
  • the selenium-water-soluble polymer polysaccharide hydrogel is dissolved at high temperature and cooled to re-form a hydrogel of a certain shape, so as to recycle the selenium-water-soluble polymer polysaccharide hydrogel.
  • the present invention dissolves water-soluble polymer polysaccharides and selenium-containing compounds in an aqueous solution at high temperature to obtain a uniformly mixed solution. After lowering the temperature, the water-soluble polymer polysaccharides form selenium-water-soluble polymer polysaccharides through physical cross-linking.
  • Glue the preparation method is simple and easy to operate, and the water-soluble polymer polysaccharide as a carrier is a green and environmentally friendly polymer material with good biocompatibility and degradability.
  • the selenium-water-soluble polymer polysaccharide hydrogel prepared by the present invention can be applied to plant selenium enrichment, plant seeds are sown on the surface of the composite hydrogel, and selenium-enriched plants can be cultivated, which avoids the selenium-enrichment caused by traditional selenium-enrichment methods. Pollution problems, to achieve green selenium enrichment.
  • the selenium-water-soluble polysaccharide hydrogel After utilizing the selenium-water-soluble polymer polysaccharide hydrogel to cultivate plants, because the plant has limited absorption of selenium in the hydrogel, the hydrogel after use still contains a large amount of selenium.
  • the selenium-water-soluble polysaccharide of the present invention The permanent polymer polysaccharide hydrogel has the characteristics of solid-liquid phase transition, and can re-form a hydrogel with a fixed shape by dissolving at high temperature and then cooling down, and then recycle it to realize the efficient utilization of selenium in the hydrogel.
  • Fig. 1 is a diagram of plant selenium enrichment mechanism
  • Fig. 2 is the infrared spectrogram of SeCA, Agar (control), Agar/SeCA-Se (1200 ⁇ g/L), Agar/Selenite-Se (1200 ⁇ g/L) and Agar/Se yeast-Se (1200 ⁇ g/L);
  • Fig. 3 is the X-ray diffraction figure of SeCA, Agar (control), Agar/SeCA-Se (1200 ⁇ g/L), Agar/Selenite-Se (1200 ⁇ g/L) and Agar/Se yeast-Se (1200 ⁇ g/L);
  • Fig. 4 is the SEM figure of Agar (control), Agar/SeCA-Se (1200 ⁇ g/L), Agar/Selenite-Se (1200 ⁇ g/L) and Agar/Se yeast-Se (1200 ⁇ g/L);
  • Fig. 5 is the growth picture of mung bean sprouts cultivated on the surface of selenium-agarose hydrogel prepared by different forms and different concentrations of selenium compounds for seven days;
  • Figure 6 is a graph showing the growth height of mung bean sprouts cultivated on the surface of selenium-agarose hydrogel prepared by different forms and different concentrations of selenium compounds for seven days and the weight comparison after drying;
  • Figures a-c correspond to Agar/SeCA-Se respectively , Agar/Selenite-Se and Agar/Se yeast-Se;
  • Figure 7 is the influence of different forms of selenium and selenium concentration in selenium-agarose hydrogel on the accumulation of selenium in plants and the utilization rate of selenium:
  • Figure a-c is the effect of selenium concentration in different forms of selenium-agarose hydrogel on plant selenium The influence of content;
  • Figures d-f are respectively the influence of selenium concentration in different forms of selenium-agarose hydrogels on the utilization rate of selenium.
  • Figure 8 is the effect of different forms of selenium in selenium-agarose hydrogel on the kinetics of selenium accumulation in plants:
  • Figure a is the growth picture of mung bean sprouts; Line graph of selenium content and cultivation time of mung bean sprouts;
  • Figure 9 is the recycling use of selenized carrageenan-agarose hydrogel on plant selenium enrichment:
  • Figure a is a picture of selenized carrageenan-agarose hydrogel that has been cycled 1 to 4 times to cultivate mung bean sprouts;
  • Figure b is The impact of the number of cycles on the growth height and weight of the cultivated mung bean sprouts;
  • Figure c is the effect of the number of cycles on the selenium content in the cultivated mung bean sprouts.
  • Embodiment 1 Selenized carrageenan-agarose hydrogel
  • Hydrogels with different selenium concentrations were named Agar(control), Agar/SeCA-Se(400 ⁇ g/L), Agar/SeCA-Se(800g/L), Agar/SeCA-Se(1200 ⁇ g/L), Agar/SeCA-Se -Se (1600 ⁇ g/L).
  • Embodiment 2 sodium selenite-agarose hydrogel
  • Hydrogels with different selenium concentrations were named Agar(control), Agar/Selenite-Se(400 ⁇ g/L), Agar/Selenite-Se(800 ⁇ g/L), Agar/Selenite-Se(1200 ⁇ g/L), Agar/Selenite -Se (1600 ⁇ g/L).
  • Embodiment 3 yeast selenium-agarose hydrogel
  • Hydrogels with different selenium concentrations were named Agar (control), Agar/Se yeast-Se (400 ⁇ g/L), Agar/Se yeast-Se (800 ⁇ g/L), Agar/Se yeast-Se (1200 ⁇ g/L), Agar/Se yeast-Se (1600 ⁇ g/L).
  • Figures 2-4 are the infrared spectra of SeCA, Agar (control), Agar/SeCA-Se (1200g/L), Agar/Selenite-Se (1200 ⁇ g/L) and Agar/Se yeast-Se (1200 ⁇ g/L) respectively , X-ray diffraction pattern and SEM image of the cross section.
  • the test results show that the FTIR spectra and XRPD patterns of agarose hydrogel and different forms of selenium-agarose composite hydrogel are very similar, so it is speculated that the introduction of different forms of selenium did not chemically modify the polymer polysaccharide.
  • SEM image of Figure 4 it can be seen from the SEM image of Figure 4 that both the agarose hydrogel and the selenium-agarose composite hydrogel have abundant pore structures.
  • the cultivation conditions LED with an intensity of 800LX Light source, 25°C, 80% humidity. After seven days of cultivation, the mung bean sprouts were harvested, the biomass of the plants was measured, and then placed in an oven at 80° C. to dry to constant weight, and the selenium content was measured.
  • the mung bean sprouts cultivated with different hydrogels for seven days are shown in Figure 5, and the plant height and dried quality of the corresponding mung bean sprouts are shown in Figure 6: 6a-c are the selenized A comparison chart of plant height and dried quality of mung bean sprouts cultivated with carrageenan-agarose hydrogel, sodium selenite-agarose hydrogel, and yeast selenium-agarose hydrogel for seven days.
  • mung bean sprouts can absorb selenium carrageenan and sodium selenite in the hydrogel better than yeast selenium; and it can be seen from Figure 7d-f that in different forms of selenium- Agarose hydrogels have a high utilization rate of selenium at a lower selenium concentration of 400 ⁇ g/L; mung bean sprouts cultivated with different forms of selenium-agarose hydrogels with different selenium concentrations (400-1600 ⁇ g/L) The selenium content in the vegetable is much higher than that of the mung bean sprouts cultivated by pure agarose hydrogel, and the selenium-enriched mung bean sprouts are obtained.
  • Figure 8b-d are respectively the pictures of mung bean sprouts cultivated on different forms of selenium-agarose hydrogels for the 5th to 9th days The content value of selenium measured in days; As can be seen from the test results, with the prolongation of cultivation time, at the 9th day, the selenium content of the mung bean sprouts cultivated by Agar/Selenite-Se is the highest, followed by Agar/SeCA-Se, However, the mung bean sprouts grown on Agar/Se yeast-Se had the lowest selenium content and the selenium content did not change much during the 5th to 9th day of measurement.
  • Fig. 9 shows the selenium-enriched plants cultivated for 1 to 4 times and the values of plant height, weight and selenium content of Agar/SeCA-Se (1200 ⁇ g/L) composite hydrogel.
  • Figure 9a shows the mung bean sprouts cultivated by composite hydrogels with different recycling times. It can be seen from the figure that the selenium-agarose hydrogel after recycling can still support plant growth, and the composite hydrogels with different recycling times can still support plant growth. Mung bean sprouts cultivated with glue were tested for plant height, plant weight and selenium content on the seventh day of cultivation. The absorption of selenium in the hydrogel is limited, and the selenium content in the hydrogel after repeated use can still meet the needs of selenium enrichment in plants. The efficient utilization of selenium in the hydrogel can be realized through the recycling of the hydrogel .
  • mung bean sprouts cultivated through selenium-water-soluble polymer polysaccharide hydrogel can obtain selenium-enriched mung bean sprouts.
  • the absorption of selenium by plants is related to the type and concentration of selenium compounds.
  • mung bean sprouts The absorption of selenium carrageenan and sodium selenite in the hydrogel is better than that of yeast selenium; in addition, the selenium-water-soluble polymer polysaccharide hydrogel of the present invention can be dissolved at high temperature and solidified by cooling For recycling, the composite hydrogel recycled 4 times can still support plant growth and realize plant selenium enrichment.

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Abstract

硒-水溶性高分子多糖水凝胶的制备及其在植物富硒方面的应用。其制备方法包括以下步骤：(1)将水溶性高分子多糖及含硒化合物加入水中，加热搅拌溶解，得到混合溶液；(2)将混合溶液静置冷却成型，得到硒-水溶性高分子多糖复合水凝胶。上述制备方法简单、反应物及反应过程绿色环保，将植物种子播撒在该复合水凝胶的表面，进行培养可获得富硒植物，且使用后的水凝胶可通过高温溶解重新形成形状可控的水凝胶，可循环使用以实现水凝胶中硒元素的高效利用。与传统富硒方法相比，利用含硒水凝胶培育植物，避免了硒肥施用造成硒污染的问题，实现绿色富硒。

Description

一种硒-水溶性高分子多糖水凝胶的制备及其在植物富硒方面的应用 技术领域
本发明涉及高分子化学合成与农业领域，具体涉及一种硒-水溶性高分子多糖水凝胶的制备及其在植物富硒方面的应用。
背景技术
硒是人类和动物生长发育必需的微量元素，具有清除自由基、氧化还原状态调节、预防癌症以及增强人体免疫力等多种重要功能。硒的缺乏会干扰蛋白质、核酸和多糖的代谢，导致心脑血管疾病、克山病等疾病。但是，人体不能合成和存储硒。目前，全球大约有10亿人缺硒，包括中国、欧洲西北部、新西兰、澳大利亚以及美国的部分地区。在中国，70％的地方缺硒，其中30％为严重缺硒地区，是国际公认的缺硒大国之一。我国人均膳食中硒的摄入量仅为14-21微克，与人体正常硒的需求量差距很大(中国营养学会推荐：成人日摄取硒的标准应为50-250微克)，造成了7000多万中国人的健康问题。
硒的补充方式主要有膳食补硒、硒营养强化剂补硒和药物补硒等、其中膳食补硒由于来源广泛、安全便捷、是人体摄入硒的主要来源。为提高人体的摄硒量，食用富硒农产品是一种安全、有效、健康的方法。如富硒萝卜、富硒水稻等。
植物富硒的方式主要有两种：天然富硒和人工富硒。天然富硒是指将农产品种植在硒含量较高的土壤中，植物吸收土壤中的硒，通过自身的生物作用将无机硒转化为有机硒的过程。但是，天然富硒土壤中硒的分布并不均匀，多成条状或者点状分布，因此造成部分农产品硒含量低以及产品富硒不均衡等问题。而人工富硒，如：叶面施硒、施用基肥等，是指在植物生长过程中通过外源添 加硒，生产富硒农产品。人工喷硒能够显著地提高农产品的硒含量。但是在人工喷施硒时，利用率不高，持续性不好。而且传统的硒肥会随着雨水而流失，容易造成硒污染，给环境、植物以及人体带来安全隐患。因此，迫切需要探索一种绿色、有效的植物富硒方式。
发明内容
为解决上述问题，本发明提供了一种硒-水溶性高分子多糖水凝胶的制备及其在植物富硒方面的应用，通过水溶性高分子多糖及含硒化合物在水溶液中混合及多糖的物理交联形成硒-水溶性高分子多糖水凝胶，可应用于植物富硒，且该水凝胶可循环使用，避免了农产品中硒含量低以及传统硒肥施用造成的硒污染等问题，实现绿色富硒。
本发明第一方面提供了一种硒-水溶性高分子多糖水凝胶的制备方法，包括以下步骤：
步骤(1)：将水溶性高分子多糖及含硒化合物加入水中，加热搅拌溶解，得到混合溶液；
步骤(2)：将混合溶液静置冷却成型，得到硒-水溶性高分子多糖水凝胶。
进一步地，所述水溶性高分子多糖为琼脂糖、卡拉胶、明胶、魔芋胶、刺槐豆胶中的一种或多种。
进一步地，所述含硒化合物为水溶性含硒化合物，优选硒化卡拉胶、亚硒酸钠和酵母硒中的一种。
进一步地，所述水溶性高分子多糖与水的质量比为1～10:100。
进一步地，所述加热搅拌的温度为80～100℃。
进一步地，所述加热搅拌的时间为0.5～1h。
进一步地，所述冷却的时间为12～24h。
本发明第二方面提供了由第一方面所述制备方法制备得到的一种硒-水溶性高分子多糖水凝胶。
本发明第三方面提供了第二方面所述的一种硒-水溶性高分子多糖水凝胶在植物富硒方面的应用。
进一步地，所述植物富硒的具体操作为：将植物种子撒播在硒-水溶性高分子多糖水凝胶的表面，在光照、恒温恒湿的条件下培养，获得富硒植物。
进一步地，所述植物种子包括绿豆种子、油菜种子及豌豆种子中的一种或多种。
进一步地，所述硒-水溶性高分子多糖水凝胶中的硒元素的浓度为400～1600μg/L。
进一步地，所述光照为持续光照，光照的强度为800～4000LX；所述恒温的温度为20～25℃；所述恒湿的湿度为70％～80％。
进一步地，植物种子的培养时间优选为5～15天。
进一步地，植物富硒培养结束后，硒-水溶性高分子多糖水凝胶通过高温溶解、冷却重新形成一定形状的水凝胶，以循环利用所述硒-水溶性高分子多糖水凝胶。
与现有技术相比，本发明的有益效果至少有以下几点：
1.本发明通过水溶性高分子多糖与含硒化合物在水溶液中，高温下溶解得到混合均匀的溶液，降低温度后由于水溶性高分子多糖通过物理交联形成硒-水溶性高分子多糖水凝胶，制备方法简单、易操作，且作为载体的水溶性高分子多糖为一种绿色环保的高分子材料，具有良好的生物相容性和可降解性。
2.本发明制备的硒-水溶性高分子多糖水凝胶可应用于植物富硒，将植物种子播撒在复合水凝胶表面，可培育出富硒植物，避免了传统富硒方法造成的硒污染问题，实现绿色富硒。
3.利用硒-水溶性高分子多糖水凝胶培育植物结束后，由于植物对于水凝胶中的硒元素吸收有限，使用后的水凝胶中仍含有大量硒元素，本发明的硒-水溶性高分子多糖水凝胶具有固液相转变的特性，可通过高温溶解再降温的方式重新形成具有固定形状的水凝胶，进而循环使用以实现水凝胶中硒元素的高效利用。
附图说明
图1为植物富硒机制图；
图2为SeCA、Agar(control)、Agar/SeCA-Se(1200μg/L)、Agar/Selenite-Se(1200μg/L)和Agar/Se yeast-Se(1200μg/L)的红外光谱图；
图3为SeCA、Agar(control)、Agar/SeCA-Se(1200μg/L)、Agar/Selenite-Se(1200μg/L)和Agar/Se yeast-Se(1200μg/L)的X射线衍射图；
图4为Agar(control)、Agar/SeCA-Se(1200μg/L)、Agar/Selenite-Se(1200μg/L)和Agar/Se yeast-Se(1200μg/L)的SEM图；
图5为绿豆芽苗菜在不同形式、不同浓度的硒化合物制备的硒-琼脂糖水凝胶表面上培育七天的生长图片；
图6为绿豆芽苗菜在不同形式、不同浓度的硒化合物制备的硒-琼脂糖水凝胶表面上培育七天的植物生长高度以及烘干后的重量对比图；图a-c分别对应Agar/SeCA-Se、Agar/Selenite-Se及Agar/Se yeast-Se；
图7为硒-琼脂糖水凝胶中不同形式的硒及硒浓度对植物内硒的积累以及硒的利用率的影响：图a-c分别为不同形式的硒-琼脂糖水凝胶中硒浓度对植物硒含量的影响；图d-f分别为不同形式的硒-琼脂糖水凝胶中硒浓度对硒的利用率 的影响。
图8为硒-琼脂糖水凝胶中不同形式的硒对植物硒积累动力学的影响：图a为绿豆芽苗菜的生长图片；图b～d分别为不同形式硒-琼脂糖水凝胶培育的绿豆芽苗菜的硒含量与培育时间的变化折线图；
图9为硒化卡拉胶-琼脂糖水凝胶在植物富硒上的循环使用：图a为循环1～4次的硒化卡拉胶-琼脂糖水凝胶培育绿豆芽苗菜的图片；图b为循环次数对培育的绿豆芽苗菜的生长高度以及重量的影响；图c为循环次数对培育的绿豆芽苗菜中硒含量的影响。
具体实施；
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1：硒化卡拉胶-琼脂糖水凝胶
取1g琼脂糖(Agar)、100mL去离子水分别与不同含量(0、400、800、1200、1600μg/L)的硒化卡拉胶(SeCA)加入相应的500mL平底烧瓶中，各放入温度为95℃的油浴锅中，搅拌0.5h后溶液澄清透明，此时琼脂糖基本完全溶解。将硒与琼脂糖混合溶液倒入圆柱形模具中，自然冷却后，即可形成不同硒浓度的硒-琼脂糖复合水凝胶。不同硒浓度水凝胶被命名为Agar(control)，Agar/SeCA-Se(400μg/L)，Agar/SeCA-Se(800g/L)，Agar/SeCA-Se(1200μg/L)， Agar/SeCA-Se(1600μg/L)。
实施例2：亚硒酸钠-琼脂糖水凝胶
取1g琼脂糖(Agar)、100mL去离子水分别与不同含量(0、400、800、1200、1600μg/L)的亚硒酸钠(Selenite)加入相应的500mL平底烧瓶中，各放入温度为95℃的油浴锅中，搅拌0.5h后溶液澄清透明，此时琼脂糖基本完全溶解。将硒与琼脂糖混合溶液倒入圆柱形模具中，自然冷却后，即可形成不同硒浓度的硒-琼脂糖复合水凝胶。不同硒浓度水凝胶被命名为Agar(control)，Agar/Selenite-Se(400μg/L)，Agar/Selenite-Se(800μg/L)，Agar/Selenite-Se(1200μg/L)，Agar/Selenite-Se(1600μg/L)。
实施例3：酵母硒-琼脂糖水凝胶
取1g琼脂糖(Agar)、100mL去离子水分别与不同含量(0、400、800、1200、1600μg/L)的酵母硒(Se yeast)加入相应的500mL平底烧瓶中，各放入温度为95℃的油浴锅中，搅拌0.5h后溶液澄清透明，此时琼脂糖基本完全溶解。将硒与琼脂糖混合溶液倒入圆柱形模具中，自然冷却后，即可形成不同硒浓度的硒-琼脂糖复合水凝胶。不同硒浓度水凝胶被命名为Agar(control)，Agar/Se yeast-Se(400μg/L)，Agar/Se yeast-Se(800μg/L)，Agar/Se yeast-Se(1200μg/L)，Agar/Se yeast-Se(1600μg/L)。
样品表征
将上述实施例中硒-琼脂糖复合水凝胶置于冷冻干燥机中冻干，取样进行傅里叶红外变换光谱(FT-TR)和X射线衍射(XRPD)测试；将冻干后的样品在液氮中脆断后进行扫描电子显微镜(SEM)测试。
图2-4分别为SeCA、Agar(control)、Agar/SeCA-Se(1200g/L)、Agar/Selenite-Se(1200μg/L)和Agar/Se yeast-Se(1200μg/L)的红外光谱图、X射线衍射图以及横截面的SEM图。测试结果显示：琼脂糖水凝胶与不同形式的硒-琼脂糖复合水凝胶的FTIR谱图以及XRPD图均非常相似，因此推测引入不同 形式的硒未对高分子多糖进行化学修饰。此外，由图4的SEM图可以看出，琼脂糖水凝胶和硒-琼脂糖复合水凝胶均具有丰富的孔道结构。
植物富硒的应用
将绿豆种子均匀撒播在实施例1～3中制备的琼脂糖水凝胶以及不同形式、浓度的硒-琼脂糖复合水凝胶的表面，在光照培养箱中培养，培养条件：强度为800LX的LED光源、25℃、80％的湿度。培育七天后，收获绿豆芽苗菜，测定植株生物量，再置于80℃烘箱中干燥至恒重，进行硒含量的测定。
用不同水凝胶培育七天的绿豆芽苗菜如图5所示，相应的绿豆芽苗菜的株高以及干燥后的质量如图6所示：其中6a-c分别为不同硒浓度的硒化卡拉胶-琼脂糖水凝胶、亚硒酸钠-琼脂糖水凝胶、酵母硒-琼脂糖水凝胶培育七天的绿豆芽苗菜的株高以及干燥后的质量的对比图。由图中对比结果可知，硒化卡拉胶-琼脂糖水凝胶及酵母硒-琼脂糖水凝胶中硒的浓度对绿豆芽苗菜的生长并无显著的影响；而亚硒酸钠-琼脂糖水凝胶在硒浓度为0-800μg/L时，对绿豆芽苗菜的生长起到一定的促进作用，但随着硒浓度增加至1600μg/L时，对绿豆芽苗菜的生长反而起到一定的抑制作用。
此外，通过电感耦合等离子体质谱仪(ICP-MS)对绿豆芽苗菜中的硒含量进行测定，测试结果如图7所示：其中7a-c分别为不同硒浓度的硒化卡拉胶-琼脂糖水凝胶、亚硒酸钠-琼脂糖水凝胶、酵母硒-琼脂糖水凝胶培育七天的绿豆芽苗菜中硒的含量(测试每千克干燥后的绿豆芽苗菜中硒的质量)；7d-f分别为不同硒浓度的硒化卡拉胶-琼脂糖水凝胶、亚硒酸钠-琼脂糖水凝胶、酵母硒-琼脂糖水凝胶培育七天的绿豆芽苗菜中硒的含量与相应水凝胶中硒的含量的比值(每1kg干燥后的植物含硒的量与水凝胶中硒的总量的比值)。由图可知，绿豆芽苗菜对于水凝胶中硒化卡拉胶以及亚硒酸钠形式的硒的吸收要优于酵母硒；且从图7d-f中可以看出，在不同形式的硒-琼脂糖水凝胶，均在较低硒浓度400μg/L的情况下，硒的利用率高；以不同形式、不同硒浓度(400～1600μg/L)的硒-琼脂糖水凝胶培育的绿豆芽苗菜中的硒含量均远高于纯琼脂糖水凝 胶培育的绿豆芽苗菜，得到富硒绿豆芽苗菜。
进一步探究硒-琼脂糖水凝胶中不同形式的硒对于所培育的绿豆芽苗菜中硒积累动力学的影响，研究硒浓度均为1200μg/L的Agar/SeCA-Se、Agar/Selenite-Se、Agar/Se yeast-Se复合水凝胶培育的绿豆芽苗菜在第5-9天时积累的硒的含量，绿豆芽苗菜生长变化以及硒的积累量如图8所示：图8a为绿豆芽苗菜分别在不同形式的硒-琼脂糖水凝胶上培育第5～9天时的图片，图8b～d分别为绿豆芽苗菜分别在不同形式的硒-琼脂糖水凝胶上培育第5～9天时测定的硒的含量值；由测试结果可知，随着培育时间的延长，在第9天时，通过Agar/Selenite-Se培育的绿豆芽苗菜的硒含量最高，其次为Agar/SeCA-Se，而Agar/Se yeast-Se上生长的绿豆芽苗菜的硒含量最低且在测定的第5～9天内硒含量的变化不大。
硒-水溶性高分子多糖水凝胶的循环使用
将使用过的1200μg/L的Agar/SeCA-Se复合水凝胶加入500mL平底烧瓶中，放入温度为95℃的油浴锅中，搅拌0.5h后呈澄清透明溶液状，将溶液倒入圆柱形模具中，自然冷却后，形成硒化卡拉胶-琼脂糖复合水凝胶，所得复合水凝胶仍可应用于植物富硒培养。
图9为Agar/SeCA-Se(1200μg/L)复合水凝胶循环使用1～4次培养的富硒植物及其植株高度、重量、硒含量的值。图9a为不同循环使用次数的复合水凝胶培育的绿豆芽苗菜，由图中可以看出，循环使用后的硒-琼脂糖水凝胶仍可支撑植物生长，不同循环使用次数的复合水凝胶培育的绿豆芽苗菜，在培育的第七天，对植株高度、植株重量以及硒含量进行测定，结果如图9b、9c所示，各参数的含量并无明显变化，这是由于植物对于水凝胶中的硒元素吸收有限，循环多次使用后的水凝胶中的含硒量仍满足植物富硒的需求，通过水凝胶的循环使用可以实现水凝胶中硒元素的高效利用。
综上所述，通过硒-水溶性高分子多糖水凝胶培育的绿豆芽苗菜，可得到富 硒绿豆芽苗菜，植物对硒的吸收与硒化合物种类以及浓度有关，其中绿豆芽苗菜对于水凝胶中硒化卡拉胶以及亚硒酸钠形式的硒的吸收要优于酵母硒；此外，本发明的硒-水溶性高分子多糖水凝胶可通过高温溶解、降温凝固成型的方式进行循环使用，循环使用4次的复合水凝胶仍可支撑植物生长，实现植物富硒。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (10)

  1. 一种硒-水溶性高分子多糖水凝胶的制备方法，其特征在于，包括以下步骤：
    步骤(1)：将水溶性高分子多糖及含硒化合物加入水中，加热搅拌溶解，得到混合溶液；
    步骤(2)：将混合溶液静置冷却成型，得到硒-水溶性高分子多糖水凝胶。
  2. 根据权利要求1所述的一种硒-水溶性高分子多糖水凝胶的制备方法，其特征在于，所述水溶性高分子多糖为琼脂糖、卡拉胶、明胶、魔芋胶、刺槐豆胶中的一种或多种；所述水溶性高分子多糖与水的质量比为1～10:100。
  3. 根据权利要求1所述的一种硒-水溶性高分子多糖水凝胶的制备方法，其特征在于，所述含硒化合物为硒化卡拉胶、亚硒酸钠和酵母硒中的一种。
  4. 根据权利要求1所述的一种硒-水溶性高分子多糖水凝胶的制备方法，其特征在于，所述加热搅拌的温度为80～100℃；所述加热搅拌的时间为0.5～1h。
  5. 根据权利要求1所述的一种硒-水溶性高分子多糖水凝胶的制备方法，其特征在于，所述冷却的时间为12～24h。
  6. 一种硒-水溶性高分子多糖水凝胶，其特征在于，由权利要求1～5任一项所述制备方法制备得到。
  7. 权利要求6所述的一种硒-水溶性高分子多糖水凝胶在植物富硒方面的应用。
  8. 根据权利要求7所述的应用，其特征在于，所述植物富硒的具体操作为：将植物种子撒播在硒-水溶性高分子多糖水凝胶的表面，在光照、恒温恒湿的条件下培养，获得富硒植物。
  9. 根据权利要求8所述的应用，其特征在于，所述植物种子包括绿豆种子、油菜种子、豌豆种子中的一种或多种；所述硒-水溶性高分子多糖水凝胶中的硒元素的浓度为400～1600μg/L；所述光照为持续光照，光照的强度为800～4000LX；所述恒温的温度为20～25℃；所述恒湿的湿度为70％～80％。
  10. 根据权利要求7所述的应用，其特征在于，植物富硒培养结束后，硒-水溶性高分子多糖水凝胶通过高温溶解、冷却重新形成一定形状的水凝胶，以循环利用所述硒-水溶性高分子多糖水凝胶。
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