不同尺寸COM、COD对阳离子表面活性剂CTAB的吸附性质差异

doi:10.15541/jim20150293

摘要/Abstract

摘要：

为比较研究不同纳微米尺寸的一水草酸钙(COM)和二水草酸钙(COD)晶体对阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)的吸附差异, 探讨抑制剂对结石形成的抑制机理, 本研究测定了各浓度CTAB下不同尺寸COM或COD对CTAB的吸附量; 采用XRD和FT-IR表征吸附前后晶体是否发生晶相改变; 采用Zeta电位仪测定吸附后晶体表面的Zeta电位随CTAB浓度的变化。结果发现, 随着c(CTAB)浓度升高, 3 μm和10 μm的COM、COD晶体的吸附曲线由上升段和平台段组成, 而小尺寸的50 nm、100 nm、1 μm的COM、COD晶体的吸附曲线为直线型。随着晶体尺寸的增大, COM和COD晶体的吸附量依次降低。当尺寸相同时, COM对CTAB的吸附量要大于COD, 归因于CTAB更容易选择吸附在COM表面负电荷的区域。上述结果表明, 草酸钙晶体对阳离子表面活性剂的吸附量与比表面积和晶体的晶面结构有关。晶体尺寸越小, 比表面积越大, 晶面暴露的草酸根密度越大, CTAB的吸附量越大, 导致晶体表面Zeta电位绝对值增大, 静电排斥力增强, 从而抑制尿微晶的聚集, 有利于抑制草酸钙结石的形成。

关键词: 晶体尺寸, 阳离子表面活性剂, 吸附模型, 草酸钙

Abstract:

The aim of this study was to compare the adsorption difference of cetyltrimethylammonium bromide (CTAB) on nano/micron calcium oxalate monohydrate (COM) and dihydrate (COD) crystals, so as to explore the stone formation mechanism. The crystal phase transformation before and after adsorption was analyzed by XRD and FT-IR. Adsorbed amount of nano/micron COM and COD to CTAB was detected by colorimetry. Zeta potentials of crystals were measured by Zeta potential analyzer. The adsorption curves of large-sized COM and COD (3 μm and 10 μm) formed a platform with increase of c (CTAB), while the small-sized COM and COD (50 nm, 100 nm and 1 μm) showed linear-type. The adsorbed amounts of COM and COD crystals were reduced with increase of crystal size. Adsorbed amounts of CTAB on COM were more than COD with the same size, because CTAB is more likely to adsorb to the negative charges on the COM surface. In conclusion, adsorption of crystals is related to the specific surface area and crystal structure. The adsorption quantity, absolute values of zeta potential of crystals and electrostatic repulsive-force are increased with the decrease of crystal size because of the increased specific surface area and exposed oxalate ions. The adsorption could inhibit the aggregation of urine crystals thus reduce the risk of calcium oxalate stone formation.

Key words: crystal size, cationic surfactant, adsorption model, calcium oxalate

中图分类号:

TQ174

甘琼枝, 温小玲, 丁一鸣, 欧阳健明. 不同尺寸COM、COD对阳离子表面活性剂CTAB的吸附性质差异[J]. 无机材料学报, 2016, 31(2): 159-164.

GAN Qiong-Zhi, WEN Xiao-Ling, DING Yi-Ming, OUYANG Jian-Ming. Adsorption of Cetyltrimethylammonium Bromide on Different-sized Calcium Oxalate Monohydrate and Dihydrate Crystals[J]. Journal of Inorganic Materials, 2016, 31(2): 159-164.

图/表 8

图1 吸附CTAB 24 h后不同尺寸COM(A)和COD晶体(B)的XRD图谱

Fig. 1 XRD patterns of COM (A) and COD crystals (B) with different sizes after CTAB adsorption for 24 h (a1, b1): 50 nm; (a2, b2): 100 nm; (a3, b3): 1 μm; (a4, b4): 3 μm; (a5, b5): 10 μm

图2 吸附CTAB后不同尺寸COM(A)和COD晶体(B)的FT-IR图谱

Fig. 2 FT-IR spectra of COM (A) and COD crystals (B) with different sizes after CTAB adsorption (a1, b1) 50 nm; (a2, b2) 100 nm; (a3, b3) 1 μm; (a4, b4) 3 μm; (a5, b5) 10 μm

图3 不同尺寸COM (A)和COD (B)草酸钙晶体的吸附量随CTAB浓度的变化

Fig. 3 Absorption amount changes of different sizes of COM (A) and COD (B) crystals in different concentrations of CTAB solution (a, f) 50 nm; (b, g) 100 nm; (c, h) 1 μm; (d, i) 3 μm; (e, j) 10 μm

表1 不同尺寸COM和COD的比表面积、孔径、孔容以及对CTAB的最大吸附量和吸附密度

Table 1 The maximum adsorption amount and adsorption density of CTAB on different sizes of COM and COD crystals at different surface areas, pore volumes and pore diameters

Crystal type	Crystal size (SEM characterization)	Specific surface area (S_BET) / (m²·g^-1)	Pore volume /(mm³·g^-1)	Pore diameter /nm	Maximum adsorption amount (Q_max) /(mg·g^-1)	Adsorption density (Γ^#) / (N·nm^-2)
COM-50 nm	47.70± 6.20 nm	26.30	49.20	7.49	53.90	3.39
COM-100 nm	92.10±10.40 nm	14.70	37.30	10.10	42.70	4.78
COM-1 μm	0.91±0.22 μm	13.60	37.70	11.10	35.60	4.31
COM-3 μm	2.65±0.43 μm	1.51	3.30	6.71	12.60	13.80
COM-10 μm	9.67±1.76 μm	0.83	1.30	6.37	11.10	22.10
COD-50 nm	44.10±8.70 nm	40.80	95.70	9.37	40.30	1.63
COD-100 nm	98.30±8.10 nm	21.40	40.90	7.63	35.80	2.76
COD-1 μm	0.92±0.31 μm	9.12	31.50	13.80	23.70	4.29
COD-3 μm	3.41±0.57 μm	1.36	1.20	4.61	8.97	10.90
COD-10 μm	9.58±0.97 μm	0.80	1.10	5.71	5.13	10.60

图4 CTAB分子吸附在草酸钙晶体表面的示意图

Fig. 4 Diagrams of CTAB molecules adsorbed on the surface of calcium oxalate crystals Phase 1: CTAB molecules formed monolayer absorption on the surface of calcium oxalate crystals Phase 2: CTAB molecules completely covered on crystal surface with bilayer or micelle

图5 不同尺寸COM和COD晶体表面Zeta电位随c(CTAB)的变化

Fig. 5 Zeta potential change of different sizes of COM and COD crystals in different c (CTAB) (a) COM-50 nm; (b) COD-50 nm; (c) COM-3 μm; (d) COD-3 μm

图6 CTAB分子在草酸钙晶体上的吸附

Fig. 6 Diagram of CTAB adsorption on calcium oxalate crystals

图7 不同尺寸COM、COD晶体的CTAB最大吸附量

Fig. 7 The maximum adsorption amount of CTAB to different sizes of COM and COD crystals

参考文献 24

[1]	FARMANESH S, RAMAMOORTHY S, CHUNG J, et al.Specificity of growth inhibitors and their cooperative effects in calcium oxalate monohydrate crystallization.J. Am. Chem. Soc., 2014, 136(1): 367-376.
[2]	THURGOOD L A, GROVER P K, RYALL R L.High calcium concentration and calcium oxalate crystals cause significant inaccuracies in the measurement of urinary ostepontin by enzyme linked immunosorbent assay.Urol. Res., 2008, 36: 103-110.
[3]	GROHE B, O’YOUNG J, IONESCU D A, et al. Control of calcium oxalate crystal growth by face-specific adsorption of an osteopontin phosphopeptide.J. Am. Chem. Soc., 2007, 129: 14946-14951.
[4]	FISCHER V, LANDFESTER K, MUNOZ-ESPÍ R.Stabilization of calcium oxalate metastable phases by oligo(L-glutamic acid): effect of peptide chain length.Cryst. Growth Des., 2011, 11: 1880-1890.
[5]	GRASES F, MARCH J G.The crystallization of calcium oxalate in the presence of amino acids.J. Cryst. Growth, 1988, 87: 299-304.
[6]	SHENG X X, JUNG T, WESSON J A, et al.Adhesion at calcium oxalate crystal surfaces and the effect of urinary constituents.Proc. Nat. Acad. Sci., USA, 2005, 102(2): 267-272.
[7]	POON N W, GOHEL M D I. Urinary glycosaminoglycans and glycoproteins in a calcium oxalate crystallization system. Carbihyd. Res., 2012, 347: 64-68.
[8]	WALTON R C, KAVANAGH J P, HEYWOOD B R, et al.The association of different urinary proteins with calcium oxalate hydromorphs. Evidence for non-speciﬁc interactions.Biochim. Biophys. Acta, 2005, 1723(1/2/3): 175-183.
[9]	SUN X Y, OUYANG J M, ZHU W Y, et al.Size-dependent toxicity and interactions of calcium oxalate dihydrate crystal on Vero renal epithelial cells.J. Mater. Chem. B, 2015, 3: 1864-1878.
[10]	SASO L, GRIPPA E, GATTO M T, et al.Inhibition of calcium oxalate precipitation by bile salts. Int. J. Urol., 2001, 8(3): 124-127.
[11]	TUNIK L, FUREDI-MILHOFER H, GARTI N.Adsorption of sodium diisooctyl sulfosuccinate onto calcium oxalate crystals.Langmuir, 1998, 14: 3351-3355.
[12]	SUN X Y, OUYANG J M, LIU A J, et al.Preparation, characterization, and in vitro cytotoxicity of COM and COD crystals with various sizes.Mater. Sci. Eng. C, 2015, 57: 147-156.
[13]	CHEBOTAREV A N, PALADENKO T V, SHCHERBAKOVA T M.Adsorption-photometric determination of cationic surfactant traces.J. Anal. Chem., 2004, 59(4): 309-313.
[14]	KING M, MCCLURE W F, ANDREWS L C.Powder diffraction file alphabetic index, inorganic phases-organic phases. International Center for Diffraction Data: Newtown Square, PA, 1992.
[15]	SELVARAJU R, THIRUPPATHI G, RAJA A.FT-IR spectral studies on certain human urinary stones in the patients of rural area.Spectrochim. Acta A, 2012, 93: 260-265.
[16]	OUYANG J M, DUAN L, TIEKE B.Effects of carboxyl acids on the crystal growth of calcium oxalate nanoparticles in lecithin- water liposome systems. Langmuir, 2003, 19(21): 8980-8985.
[17]	STOCKER I N, MILLER K L, WELBOURN R J, et al.Adsorption of aerosol-OT at the calcite/water interface-comparison of the sodium and calcium salts. J. Colloid Interf. Sci., 2014, 418: 140-146.
[18]	WALSH R B, WU B, HOWARD S C, et al.Surface forces between titanium dioxide surfaces in the presence of cationic surfactant as a function of surfactant concentration, electrolyte concentration, and pH.Langmuir, 2014, 30(10): 2789-2798.
[19]	WEN Q, LI C, CAI Z, et al.Study on activated carbon derived from sewage sludge for adsorption of gaseous formaldehyde.Bioresour. Technol., 2011, 102(2): 942-947.
[20]	WANG X, JIANG Z Y, XIE Z X, et al.High-energy-surface engineered metal oxide micro- and nanocrystallites and their applications.Acounts Chem. Res., 2014, 42(7): 308-318.
[21]	RNSARI R, SHAHABODINI A, FAGHIH SHOJAEI M, et al.On the bending and buckling behaviors of mindlin nanoplates considering surface energies.Physica E, 2014, 57: 126-137.
[22]	CHUNG T H, WU S H, YAO M, et al.The effect of surface charge on the uptake and biological function of mesoporous silica nanoparticles in 3T3-L1 cells and human mesenchymal stem cells. Biomaterials, 2007, 28: 2959-2966.
[23]	SIKIRIC M, FILIPOVIC-VINCEKOVIC N, BABIC-IVANCIC V, et al.Interactions in calcium oxalate hydrate/surfactant systems.J. Colloid Interf. Sci., 1999, 212: 384-389.
[24]	WEI X X, YANG J, LI Z Y, et al.Comparison investigation of the effects of ionic surfactants on the crystallization behavior of calcium oxalate: From cationic to anionic surfactant.Colloids Surf. A, 2012, 401: 107-115.