辣椒叶片表观表面自由能的计算方法
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摘要
【目的】农用化学品叶面喷雾的效率与植物叶面理化性能的复杂性密切相关。为了更好地理解农用化学品喷雾液与植物叶面内在结构的界面互作效应,本研究以辣椒叶片为例从热力学角度出发寻求其内在的关联性,以期为植株上农药的高效使用提供依据。【方法】以水(W)、丙三醇(G)和二碘甲烷(DM)为检测液,借助接触角测量仪测定其在3种辣椒叶片上的稳定接触角后,分别采用Wu调和平均数法(HM)、Owens-Wendt-Rabel-Kaelble法(OWRK)、Van-Oss-Chaudhury-Good法(OCG)以及ZDY法计算叶片的表面自由能及其分量并进行比较,同时对辣椒叶面的溶解度系数进行分析。【结果】水在苏紫1号和GR甜椒叶片上表现出较好的润湿性(θ<90°),而在苏椒13叶片上的润湿性一般(θ>90°)。在估测辣椒叶片表面表观自由能的4种方法中,OCG法采用3种检测液进行分析,较其他方法获得的辣椒叶面特征物理量较多,3种辣椒叶片表观表面自由能的非极性分量所占百分率(>85%)均高于极性分量(<15%)。采用2种检测液的方法为HM法和OWRK法,当2种检测液均为极性(W-G)时,辣椒叶片表观表面自由能的非极性分量和极性分量所占百分率变化较大,甚至相反;当2种检测液为极性和非极性组合(W-DM或G-DM)时,以OCG法计算获得辣椒叶面表观表面自由能的数值为基准,OWRK法计算获得的数值比HM法获得的数值偏差要小。采用1种检测液的方法为ZDY法,计算获得辣椒叶面表观表面自由能的数值远高于其他3种方法,比OCG法获得辣椒叶面表观表面自由能的数值偏差均>100%。以OCG法为基准,偏差在10%以内,苏紫1号辣椒叶面表观表面自由能为37.72—43.11 m J·m~(-2),溶解度系数为18.89—22.77 m J1/2·m-3/2;GR甜椒叶面表观表面自由能为37.53—40.95 m J·m~(-2),溶解度系数为18.81—20.09 m J1/2·m-3/2;苏椒13号辣椒叶面表观表面自由能为33.21—36.92 m J·m~(-2),溶解度系数为17.17—18.58 m J1/2·m-3/2。【结论】以水、丙三醇和二碘甲烷为检测液,ZDY法不适用计算辣椒叶片表观表面自由能;HM法、OWRK法、OCG法可用来计算辣椒叶片表观表面自由能,其中HM法和OWRK法应注重选择检测液组合的极性问题。同时,3种辣椒叶面表面自由能的非极性分量的比率均高于极性分量的比率。
【Objective】The efficiency of foliar-applied agrochemicals is closely related to the complexity of physicochemical properties of plant leaf surfaces.For better understanding the interfacial interaction between agrochemical spray liquids and plant leaf surfaces,the internal relation would be seek from the thermodynamic point based on pepper leaf surfaces.This will provide a basis for efficient use of pesticides on plants.【Method】Three test liquids were water(W),glycerol(G) and diiodomethane(DM).Their static contact angles of a single droplet on the pepper leaf surfaces of different varieties were determined by contact angle meter.Then the total surface free energy(SFE) and its components were evaluated by Harmonic mean(HM) method,Owens-Wendt-RabelKaelble(OWRK) method,Van-Oss-Chaudhury-Good(OCG) method and ZDY method.Accordingly,solubility parameter(δ) of pepper leaf surfaces was calculated.【Result】The leaves of Suzi-1 and GR pepper were wettable(θ<90°) for W and Sujiao-13 pepper leaves were unwettable(θ>90°) for W.Among the 4 methods,more physical characteristic information was obtained by the OCG method with 3 test liquids(W-G-DM) and calculated percentages of non-polar components of the SFE of pepper leaf surfaces(>85%) were higher than the polar components(<15%).The HM and OWRK methods based on 2 test liquids.When the 2 test liquids were polar(i.e.W-G),the percentages of non-polar or polar component of the SFE of the pepper leaf surface varied greatly,or even the opposite to the percentage obtained in the OCG method.When the 2 test liquids were polar and non-polar combination(i.e.W-DM or G-DM),the deviation of the SFE values calculated by OWRK method was lower than that by HM method based on the OCG method.The SFE values calculated by ZDY method with 1 test liquid were much higher than that of the other three methods.Compared with OCG method,the deviation of the SFE of pepper leaf surfaces was >100%.Based on the deviation from the OCG method within 10% of the SFE,SFE of Suzi-1 leaf surface was 37.72-43.11 m J·m~(-2) and solubility parameter was 18.89-22.77 m J1/2·m-3/2.SFE of GR leaf surface was 37.53-40.95 m J·m~(-2) and solubility parameter was 18.81-20.09 m J1/2·m-3/2.SFE of Sujiao-13 leaf surface was 33.21-36.92 m J·m~(-2) and solubility parameter was 17.17-18.58 m J1/2·m-3/2.【Conclusion】Using water(W),glycerol(G) and diiodomethane(DM) as the test liquid,ZDY method is not suitable for calculating the SFE of pepper leaf surfaces and the rest methods(HM,OWRK,OCG) can be used to calculate the SFE.Among them,the HM or OWRK method should be paid more attention to the polarity of selecting test liquid combination.Meanwhile,the percentage of non-polar component of the SFE of 3 kinds of pepper is higher than that of the polar component.
【Objective】The efficiency of foliar-applied agrochemicals is closely related to the complexity of physicochemical properties of plant leaf surfaces.For better understanding the interfacial interaction between agrochemical spray liquids and plant leaf surfaces,the internal relation would be seek from the thermodynamic point based on pepper leaf surfaces.This will provide a basis for efficient use of pesticides on plants.【Method】Three test liquids were water(W),glycerol(G) and diiodomethane(DM).Their static contact angles of a single droplet on the pepper leaf surfaces of different varieties were determined by contact angle meter.Then the total surface free energy(SFE) and its components were evaluated by Harmonic mean(HM) method,Owens-Wendt-RabelKaelble(OWRK) method,Van-Oss-Chaudhury-Good(OCG) method and ZDY method.Accordingly,solubility parameter(δ) of pepper leaf surfaces was calculated.【Result】The leaves of Suzi-1 and GR pepper were wettable(θ<90°) for W and Sujiao-13 pepper leaves were unwettable(θ>90°) for W.Among the 4 methods,more physical characteristic information was obtained by the OCG method with 3 test liquids(W-G-DM) and calculated percentages of non-polar components of the SFE of pepper leaf surfaces(>85%) were higher than the polar components(<15%).The HM and OWRK methods based on 2 test liquids.When the 2 test liquids were polar(i.e.W-G),the percentages of non-polar or polar component of the SFE of the pepper leaf surface varied greatly,or even the opposite to the percentage obtained in the OCG method.When the 2 test liquids were polar and non-polar combination(i.e.W-DM or G-DM),the deviation of the SFE values calculated by OWRK method was lower than that by HM method based on the OCG method.The SFE values calculated by ZDY method with 1 test liquid were much higher than that of the other three methods.Compared with OCG method,the deviation of the SFE of pepper leaf surfaces was >100%.Based on the deviation from the OCG method within 10% of the SFE,SFE of Suzi-1 leaf surface was 37.72-43.11 m J·m~(-2) and solubility parameter was 18.89-22.77 m J1/2·m-3/2.SFE of GR leaf surface was 37.53-40.95 m J·m~(-2) and solubility parameter was 18.81-20.09 m J1/2·m-3/2.SFE of Sujiao-13 leaf surface was 33.21-36.92 m J·m~(-2) and solubility parameter was 17.17-18.58 m J1/2·m-3/2.【Conclusion】Using water(W),glycerol(G) and diiodomethane(DM) as the test liquid,ZDY method is not suitable for calculating the SFE of pepper leaf surfaces and the rest methods(HM,OWRK,OCG) can be used to calculate the SFE.Among them,the HM or OWRK method should be paid more attention to the polarity of selecting test liquid combination.Meanwhile,the percentage of non-polar component of the SFE of 3 kinds of pepper is higher than that of the polar component.
引文
[1]PUENTE D W,BAUR P.Wettability of soybean(Glycine max L.)leaves by foliar sprays with respect to developmental changes.Pest Management Science,2011,67(7):798-806.
[2]TAYLOR P.The wetting of leaf surface.Current Opinion in Colloid&Interface Science,2011,16(4):326-334.
[3]袁会珠,杨代斌,闫晓静,张琳娜.农药有效利用率与喷雾技术优化.植物保护,2011,37(5):14-20.YUAN H Z,YANG D B,YAN X J,ZHANG L N.Pesticide efficiency and the way to optimize the spray application.Plant Protection,2011,37(5):14-20.(in Chinese)
[4]MüLLER C,RIEDERER M.Plant surface properties in chemical ecology.Journal of Chemical Ecology,2005,31(11):2621-2651.
[5]SCHREIBER L.Transport barriers made of cutin,suberin and associated waxes.Trends in Plant Science,2010,15(10):546-553.
[6]GASKIN R E,STEELE K D,FORSTER W A.Characterising plant surfaces for spray adhesion and retention.New Zealand Plant Protection,2005,58:179-183.
[7]NAIRN J J,FORSTER W A.Methods for evaluating leaf surface free energy and polarity having accounted for surface roughness.Pest Management Science,2017,73(9):1854-1865.
[8]范仁俊,张晓曦,周璐,曹冲,杜凤沛.利用OWRK法预测桃叶表面润湿性能的研究.农药学学报,2011,13(1):79-83.FAN R J,ZHANG X X,ZHOU L,CAO C,DU F P.Research on the wettability of peach leaf surfaces by OWRK method.Chinese Journal of Pesticide Science,2011,13(1):79-83.(in Chinese)
[9]WU S.Calculation of interfacial tension in polymer systems.Journal of Polymer Science Polymer Symposia,1971,34(1):19-30.
[10]OWENS D K,WENDT R C.Estimation of the surface free energy of polymers.Journal of Applied Polymer Science,1969,13(8):1741-1747.
[11]VAN OSS C J,CHAUDHURY M K,GOOD R J.Interfacial Lifshitz-van der Waals and polar interactions in macroscopic systems.Chemical Reviews,1988,88(6):927-941.
[12]朱定一,戴品强,罗晓斌,张远超.润湿性表征体系及液固界面张力计算的新方法(Ⅰ).科学技术与工程,2007,7(13):3057-3062.ZHU D Y,DAI P Q,LUO X B,ZHANG Y C.Novel characterization of wetting properties and the calculation of liquid-solid interface tension(Ⅰ).Science Technology and Engineering,2007,7(13):3057-3062.(in Chinese)
[13]FERNáNDEZ V,KHAYET M.Evaluation of the surface free energy of plant surfaces:toward standardizing the procedure.Frontiers in Plant Science,2015,6:510.
[14]SHALEL-LEVANON S,MARMUR A.Validity and accuracy in evaluating surface tension of solids by additive approaches.Journal of Colloid and Interface Science,2003,262(2):489-499.
[15]张晨辉,赵欣,雷津美,马悦,杜凤沛.非离子表面活性剂Triton X-100溶液在不同生长期小麦叶片表面的润湿行为.物理化学学报,2017,33(9):1846-1854.ZHANG C H,ZHAO X,LEI J M,MA Y,DU F P.Wettability of Triton X-100 on wheat(Triticum aestivum)leaf surfaces with respect to developmental changes.Acta Physico-Chimica Sinica,2017,33(9):1846-1854.(in Chinese)
[16]关明杰,薛明慧.化学处理对竹笋壳润湿性的影响.农业工程学报,2016,32(11):309-314.GUAN M J,XUE M H.Wettability of bamboo shoot shell under chemical treatment.Transactions of the Chinese Society of Agricultural Engineering,2016,32(11):309-314.(in Chinese)
[17]REVILLA P,FERNáNDEZ V,ALVAREZ-IGLESIAS L,MEDINA E T,CAVERO J.Leaf physico-chemical and physiological properties of maize(Zea mays L.)populations from different origins.Plant Physiology and Biochemistry,2016,107:319-325.
[18]顾中言.植物的亲水疏水特性与农药药液行为的分析.江苏农业学报,2009,25(2):276-281.GU Z Y.Analysis of the relationship between hydrophilic or hydrophobic property of plant and action of pesticides solution on plants leaves.Jiangsu Journal of Agricultural Sciences,2009,25(2):276-281.(in Chinese)
[19]KHAYET M,FERNáNDEZ V.Estimation of the solubility parameters of model plant surfaces and agrochemicals:a valuable tool for understanding plant surface interactions.Theoretical Biology and Medical Modelling,2012,9:45.
[20]JA?CZUK B,BIALOPIOTROWICZ T,ZDZIENNICKA A.Some remarks on the components of the liquid surface free energy.Journal of Colloid and Interface Science,1999,211(1):96-103.
[21]KOLYVA F,STRATAKIS E,RHIZOPOULOU S,CHIMONA C,FOTAKIS C.Leaf surface characteristics and wetting in Ceratonia siliqua L.Flora,2012,207(8):551-556.
[22]ZHENG Q S,LU C J.Size effects of surface roughness to superhydrophobicity.Procedia IUTAM,2014,10:462-475.
[23]ZHU L,GE J R,QI Y Y,CHEN Q,HUA R M,LUO F,CHEN P R.Droplet impingement behavior analysis on the leaf surface of Shu-Cha Zao under different pesticide formulations.Computers and Electronics in Agriculture,2018,144:16-25.
[24]SIKORSKA D,PAPIEROWSKA E,SZATY?OWICZJ,SIKORSKI P,SUPRUN K,HOPKINS R J.Variation in leaf surface hydrophobicity of wetland plants:the role of plant traits in water retention.Wetlands,2017,37(5):997-1002.
[25]DOMI?CZUK J,KRAWCZUKA.Comparison of surface free energy calculation methods.Applied Mechanics and Materials,2015,791:259-265.
[26]陈晓磊.固体聚合物表面接触角的测量及表面能研究[D].长沙:中南大学,2012.CHEN X L.Surface free energy and contact angle measurement of solid polymer[D].Changsha:Central South University,2012.(in Chinese)
[27]FERNáNDEZ V,SANCHO-KNAPIK D,GUZMAN P,PEGUEROPINA J J,GIL L,KARABOURNIOTIS G,KHAYET M,FASSEAS C,HEREDIA-GUERRERO J A,HEREDIA A,GIL-PELEGRIN E.Wettability,polarity,and water absorption of holm oak leaves:effect of leaf side and age.Plant Physiology,2014,166(1):168-180.
[28]BAUER S,SCHULTE E,THIER H P.Composition of the surface waxes from bell pepper and eggplant.European Food Research and Technology,2005,220(1):5-10.
[29]徐广春,顾中言,徐德进,许小龙.稻叶表面特性及雾滴在倾角稻叶上的沉积行为.中国农业科学,2014,47(21):4280-4290.XU G C,GU Z Y,XU D J,XU X L.Characteristics of rice leaf surface and droplets deposition behavior on rice leaf surface with different inclination angles.Scientia Agricultura Sinica,2014,47(21):4280-4290.(in Chinese)
[30]GASKIN R E,PATHAN A K.Characterising plant surfaces and adjuvant interactions to improve pesticide spray retention and coverage on avocados.New Zealand Avocado Growers’Association Annual Research Report,2006,6:63-70.
[31]顾中言,徐德进,徐广春.田间药液用量影响农药单位剂量防治效果的原因分析.中国农业科学,2018,51(13):2513-2523.GU Z Y,XU D J,XU G C.The cause of influence of spray volume on control effect of pesticide unit dose in rice fields.Scientia Agricultura Sinica,2018,51(13):2513-2523.(in Chinese)
[32]徐广春,顾中言,徐德进,许小龙,董玉轩.常用农药在水稻叶片上的润湿能力分析.中国农业科学,2012,45(9):1731-1740.XU G C,GU Z Y,XU D J,XU X L,DONG Y X.Wettablity analysis of pesticides on rice leaf.Scientia Agricultura Sinica,2012,45(9):1731-1740.(in Chinese)
[2]TAYLOR P.The wetting of leaf surface.Current Opinion in Colloid&Interface Science,2011,16(4):326-334.
[3]袁会珠,杨代斌,闫晓静,张琳娜.农药有效利用率与喷雾技术优化.植物保护,2011,37(5):14-20.YUAN H Z,YANG D B,YAN X J,ZHANG L N.Pesticide efficiency and the way to optimize the spray application.Plant Protection,2011,37(5):14-20.(in Chinese)
[4]MüLLER C,RIEDERER M.Plant surface properties in chemical ecology.Journal of Chemical Ecology,2005,31(11):2621-2651.
[5]SCHREIBER L.Transport barriers made of cutin,suberin and associated waxes.Trends in Plant Science,2010,15(10):546-553.
[6]GASKIN R E,STEELE K D,FORSTER W A.Characterising plant surfaces for spray adhesion and retention.New Zealand Plant Protection,2005,58:179-183.
[7]NAIRN J J,FORSTER W A.Methods for evaluating leaf surface free energy and polarity having accounted for surface roughness.Pest Management Science,2017,73(9):1854-1865.
[8]范仁俊,张晓曦,周璐,曹冲,杜凤沛.利用OWRK法预测桃叶表面润湿性能的研究.农药学学报,2011,13(1):79-83.FAN R J,ZHANG X X,ZHOU L,CAO C,DU F P.Research on the wettability of peach leaf surfaces by OWRK method.Chinese Journal of Pesticide Science,2011,13(1):79-83.(in Chinese)
[9]WU S.Calculation of interfacial tension in polymer systems.Journal of Polymer Science Polymer Symposia,1971,34(1):19-30.
[10]OWENS D K,WENDT R C.Estimation of the surface free energy of polymers.Journal of Applied Polymer Science,1969,13(8):1741-1747.
[11]VAN OSS C J,CHAUDHURY M K,GOOD R J.Interfacial Lifshitz-van der Waals and polar interactions in macroscopic systems.Chemical Reviews,1988,88(6):927-941.
[12]朱定一,戴品强,罗晓斌,张远超.润湿性表征体系及液固界面张力计算的新方法(Ⅰ).科学技术与工程,2007,7(13):3057-3062.ZHU D Y,DAI P Q,LUO X B,ZHANG Y C.Novel characterization of wetting properties and the calculation of liquid-solid interface tension(Ⅰ).Science Technology and Engineering,2007,7(13):3057-3062.(in Chinese)
[13]FERNáNDEZ V,KHAYET M.Evaluation of the surface free energy of plant surfaces:toward standardizing the procedure.Frontiers in Plant Science,2015,6:510.
[14]SHALEL-LEVANON S,MARMUR A.Validity and accuracy in evaluating surface tension of solids by additive approaches.Journal of Colloid and Interface Science,2003,262(2):489-499.
[15]张晨辉,赵欣,雷津美,马悦,杜凤沛.非离子表面活性剂Triton X-100溶液在不同生长期小麦叶片表面的润湿行为.物理化学学报,2017,33(9):1846-1854.ZHANG C H,ZHAO X,LEI J M,MA Y,DU F P.Wettability of Triton X-100 on wheat(Triticum aestivum)leaf surfaces with respect to developmental changes.Acta Physico-Chimica Sinica,2017,33(9):1846-1854.(in Chinese)
[16]关明杰,薛明慧.化学处理对竹笋壳润湿性的影响.农业工程学报,2016,32(11):309-314.GUAN M J,XUE M H.Wettability of bamboo shoot shell under chemical treatment.Transactions of the Chinese Society of Agricultural Engineering,2016,32(11):309-314.(in Chinese)
[17]REVILLA P,FERNáNDEZ V,ALVAREZ-IGLESIAS L,MEDINA E T,CAVERO J.Leaf physico-chemical and physiological properties of maize(Zea mays L.)populations from different origins.Plant Physiology and Biochemistry,2016,107:319-325.
[18]顾中言.植物的亲水疏水特性与农药药液行为的分析.江苏农业学报,2009,25(2):276-281.GU Z Y.Analysis of the relationship between hydrophilic or hydrophobic property of plant and action of pesticides solution on plants leaves.Jiangsu Journal of Agricultural Sciences,2009,25(2):276-281.(in Chinese)
[19]KHAYET M,FERNáNDEZ V.Estimation of the solubility parameters of model plant surfaces and agrochemicals:a valuable tool for understanding plant surface interactions.Theoretical Biology and Medical Modelling,2012,9:45.
[20]JA?CZUK B,BIALOPIOTROWICZ T,ZDZIENNICKA A.Some remarks on the components of the liquid surface free energy.Journal of Colloid and Interface Science,1999,211(1):96-103.
[21]KOLYVA F,STRATAKIS E,RHIZOPOULOU S,CHIMONA C,FOTAKIS C.Leaf surface characteristics and wetting in Ceratonia siliqua L.Flora,2012,207(8):551-556.
[22]ZHENG Q S,LU C J.Size effects of surface roughness to superhydrophobicity.Procedia IUTAM,2014,10:462-475.
[23]ZHU L,GE J R,QI Y Y,CHEN Q,HUA R M,LUO F,CHEN P R.Droplet impingement behavior analysis on the leaf surface of Shu-Cha Zao under different pesticide formulations.Computers and Electronics in Agriculture,2018,144:16-25.
[24]SIKORSKA D,PAPIEROWSKA E,SZATY?OWICZJ,SIKORSKI P,SUPRUN K,HOPKINS R J.Variation in leaf surface hydrophobicity of wetland plants:the role of plant traits in water retention.Wetlands,2017,37(5):997-1002.
[25]DOMI?CZUK J,KRAWCZUKA.Comparison of surface free energy calculation methods.Applied Mechanics and Materials,2015,791:259-265.
[26]陈晓磊.固体聚合物表面接触角的测量及表面能研究[D].长沙:中南大学,2012.CHEN X L.Surface free energy and contact angle measurement of solid polymer[D].Changsha:Central South University,2012.(in Chinese)
[27]FERNáNDEZ V,SANCHO-KNAPIK D,GUZMAN P,PEGUEROPINA J J,GIL L,KARABOURNIOTIS G,KHAYET M,FASSEAS C,HEREDIA-GUERRERO J A,HEREDIA A,GIL-PELEGRIN E.Wettability,polarity,and water absorption of holm oak leaves:effect of leaf side and age.Plant Physiology,2014,166(1):168-180.
[28]BAUER S,SCHULTE E,THIER H P.Composition of the surface waxes from bell pepper and eggplant.European Food Research and Technology,2005,220(1):5-10.
[29]徐广春,顾中言,徐德进,许小龙.稻叶表面特性及雾滴在倾角稻叶上的沉积行为.中国农业科学,2014,47(21):4280-4290.XU G C,GU Z Y,XU D J,XU X L.Characteristics of rice leaf surface and droplets deposition behavior on rice leaf surface with different inclination angles.Scientia Agricultura Sinica,2014,47(21):4280-4290.(in Chinese)
[30]GASKIN R E,PATHAN A K.Characterising plant surfaces and adjuvant interactions to improve pesticide spray retention and coverage on avocados.New Zealand Avocado Growers’Association Annual Research Report,2006,6:63-70.
[31]顾中言,徐德进,徐广春.田间药液用量影响农药单位剂量防治效果的原因分析.中国农业科学,2018,51(13):2513-2523.GU Z Y,XU D J,XU G C.The cause of influence of spray volume on control effect of pesticide unit dose in rice fields.Scientia Agricultura Sinica,2018,51(13):2513-2523.(in Chinese)
[32]徐广春,顾中言,徐德进,许小龙,董玉轩.常用农药在水稻叶片上的润湿能力分析.中国农业科学,2012,45(9):1731-1740.XU G C,GU Z Y,XU D J,XU X L,DONG Y X.Wettablity analysis of pesticides on rice leaf.Scientia Agricultura Sinica,2012,45(9):1731-1740.(in Chinese)