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制备具有荧光示踪功能的硼掺杂银杏叶碳量子点木材防腐剂

花匠小妙招
2025-01-13 08:46

摘要:

目的

环境友好型木材防腐剂的开发中，示踪功能对于木材防腐效果的评价研究具有重要意义。为充分发挥银杏叶的抗菌性能、硼砂的阻燃性能以及碳量子点的荧光示踪功能，制备一种新型硼掺杂银杏叶碳量子点（B-CQDs）木材防腐剂，以丰富环境友好型木材防腐剂体系，拓宽碳量子点抗菌性和荧光示踪应用。

方法

以绿色生物质银杏叶为碳源，硼砂为硼元素掺杂剂，通过水热法一步合成B-CQDs木材防腐剂，进行单因素实验探究最优制备工艺。采用荧光光谱、紫外可见光光谱、透射电子显微镜（TEM）、傅里叶变换红外光谱（FTIR）、X-射线光电子能谱（XPS）等测试方法对其性能进行表征。以白腐菌彩绒革盖菌和褐腐菌密黏褶菌作为供试菌种，通过抑菌圈试验对不同质量分数的B-CQDs木材防腐剂抑菌效果进行综合评价。

结果

以荧光强度为参考指标，B-CQDs木材防腐剂最佳制备条件：水热反应时间3.0 h，水热反应温度180 ℃，银杏叶用量0.5 g，银杏叶与硼砂质量比5∶1。B-CQDs呈类球状，平均粒径为2.41 nm，分散性较好。B-CQDs木材防腐剂具有激发波长依赖性和荧光稳定性，在365 nm紫外光照射下发出明亮蓝色荧光。FTIR与XPS分析的元素组成和官能团信息一致，表明硼元素成功掺入碳量子点。木材腐朽真菌抑菌圈试验结果表明：随着B-CQDs木材防腐剂质量分数的增加，其对2种木材腐朽真菌的抑制效果逐渐增强，B-CQDs木材防腐剂抑制效果优于未掺杂的碳量子点木材防腐剂。当B-CQDs木材防腐剂的质量分数为0.80%时，彩绒革盖菌和密黏褶菌的抑菌圈直径均达到最大值，分别为54.15和63.59 mm。

结论

本研究成功制备了B-CQDs木材防腐剂。该防腐剂具有光致发光特性和荧光示踪功能，且对彩绒革盖菌和密黏褶菌2种常见的木腐真菌均有较好的抑制作用，具备作为环境友好型荧光示踪木材防腐剂的潜力。

关键词: 木材防腐 / 荧光 / 示踪 / 碳量子点 / 银杏叶 / 硼掺杂 / 木腐菌

Abstract:

Objective

In the development of environment-friendly wood preservatives, its tracer function is of great significance to the evaluation of wood preservative effect. A new type of wood preservative based on boron doping Ginkgo biloba leaf carbon quantum dots (B-CQDs) was prepared, aiming to make full use of antifungal properties of Ginkgo biloba leaves, the flame retardant properties of borax and the fluorescent tracer function of carbon quantum dots. B-CQDs will enrich the environment-friendly wood preservative system, and broaden the antifungal properties and fluorescent tracer applications of carbon quantum dots.

Method

The wood preservative of B-CQDs was one-step hydrothermal synthesized by green biomass Ginkgo biloba leaves as carbon source and borax as boron dopant. The optimum preparation process was investigated by single factor experiment. It was characterized by fluorescence spectrum, UV-visible spectrum, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The antifungal effects with different mass fractions of B-CQDs were evaluated by antifungal zone test with white rot fungi Trametes versicolor and brown rot fungi Gloeophyllum trabeum as the tested fungi.

Result

Taking the fluorescence intensity as the test index, the optimum preparation conditions of B-CQDs were hydrothermal reaction time 3.0 h, hydrothermal reaction temperature 180 ℃, dosage of Ginkgo biloba 0.5 g, and mass ratio of Ginkgo biloba leaves to borax 5∶1. B-CQDs were semispherical with better dispersion. The average particle size was 2.41 nm. B-CQDs wood preservatives had excitation wavelength dependence and fluorescence stability, emitting bright blue fluorescence under ultraviolet light at 365 nm. The element composition and functional group information analyzed by FTIR and XPS were consistent, which indicated that boron elements were successfully incorporated into carbon quantum dots. The results of antifungal zone test of wood rot fungi showed that with the increase of mass fraction of B-CQDs, the control effect against two kinds of wood rot fungi had gradually improved. Among them, the antifungal effect of B-CQDs wood preservatives was better than non-doped carbon quantum dot wood preservatives. When the mass fraction of B-CQDs increased to 0.80%, the diameter of antifungal zone of the two groups reached the maximum, which were 54.15 and 63.59 mm, respectively.

Conclusion

The preparation of B-CQDs wood preservative is studied successfully. It has photoluminescence characteristics and fluorescent tracer function. The preservative has good antifungal effect on two kinds of common wood rot fungi (Trametes versicolor and Gloeophyllum trabeum). It has the potential to be used as environment-friendly wood preservative with the function of fluorescent tracer.

图 1 B-CQDs 制备路线

λex、λem 分别代表溶液的激发波长和发射波长。黄褐色溶液为自然光下的B-CQDs溶液，蓝色溶液对应365 nm紫外照射下的B-CQDs溶液。

Figure 1. Preparation route of B-CQDs

图 2 水热反应时间（a）、水热反应温度（b）和银杏叶用量（c）对B-CQDs荧光强度的影响（λex = 358 nm）

Figure 2. Effects of hydrothermal reaction time (a), hydrothermal reaction temperature (b) and dosage of Ginkgo biloba leaves (c) on fluorescence intensity of B-CQDs (λex = 358 nm)

图 3 pH（a）、NaCl浓度（b）、紫外激发时间（c）对B-CQDs相对荧光强度的影响（λex = 358 nm）

I1F0、I2F0、I3F0分别为不同条件下的溶液荧光强度，I1F为pH值为7的溶液荧光强度，I2F为含有0 mmol/L NaCl混合液的荧光强度，I3F为紫外光激发照射时间为0 min的溶液荧光强度。

Figure 3. Effects of pH (a), concentration of NaCl (b), ultraviolet excitation time (c) on relative fluorescence intensity of B-CQDs (λex = 358 nm)

图 4 B-CQDs在不同激发波长下的发射光谱（a）、紫外–可见吸收光谱和荧光光谱（b）

插图为B-CQDs水溶液在自然光（左）和紫外光365 nm（右）照射下的图像。Abs代表紫外光谱吸光度，em是荧光发射光谱，ex是荧光激发光谱。

Figure 4. Emission spectra of B-CQDS at different excitation wavelengths (a), UV-VIS absorption spectra and fluorescence spectra of B-CQDs (b)

图 5 B-CQDs的TEM图像（a）和粒径分布（b）

Figure 5. TEM image (a) and particle size distribution (b) of B-CQDs

图 6 B-CQDs、CQDs、GB和BX的FTIR图

Figure 6. FTIR spectra of B-CQDs, CQDs, GB and BX

图 7 B-CQDs的XPS谱图

Figure 7. XPS spectra of B-CQDs

图 8 CQDs的XPS谱图

Figure 8. XPS spectra of CQDs

图 9 彩绒革盖菌的抑菌试验照片

Figure 9. Antifungal activity test photos of Trametes versicolor

图 10 密黏褶菌的抑菌试验照片

Figure 10. Antifungal activity test photos of Gloeophyllum trabeum

表 1 不同质量分数试剂的木腐菌抑菌圈平均直径

Table 1 Average diameter of inhibition zone of different mass fractions of reagents against wood rot fungi mm

试剂抑菌圈平均直径彩绒革盖菌密黏褶菌无菌水 0 0 0.50%GB 0 0 0.10%BX 0 0 0.10%CQDs 20.64 ± 0.19 21.80 ± 0.32 0.20%CQDs 28.56 ± 0.37 28.11 ± 0.48 0.40%CQDs 34.45 ± 0.46 32.06 ± 0.46 0.60%CQDs 37.83 ± 0.76 39.79 ± 0.59 0.80%CQDs 41.41 ± 0.51 51.18 ± 0.68 0.10%B-CQDs 30.93 ± 0.24 31.51 ± 0.08 0.20%B-CQDs 38.71 ± 0.48 39.98 ± 0.32 0.40%B-CQDs 41.51 ± 0.45 54.59 ± 0.40 0.60%B-CQDs 47.03 ± 0.45 56.91 ± 0.73 0.80%B-CQDs 54.15 ± 0.90 63.59 ± 0.62 [1] 葛晓雯, 王立海, 侯捷建, 等. 褐腐杨木微观结构、力学性能与化学成分的关系研究[J]. 北京林业大学学报, 2016, 38(10): 112−122.

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