Aggregation Behavior In Aqueous Solution Research Articles

Surface active properties of N-(2-Aminoethyl)-3-aminopropyltetrasiloxane lactobionamide and aggregation behavior in aqueous solution

The aggregation behavior of tetrasiloxane-lactobionamide (Si4N2-LA) in aqueous solution has been characterized by dynamic light scattering (DLS), negative-stained transmission electron microscopy (TEM) and X-ray Diffraction methods. Compared with the micellar sizes 7.0 nm of n-dodecyllactobionamide (C12Glu2), the Si4N2-LA molecule can self-assemble into spherical vesicle with diameters in the range from 60 to 300 nm.

Synthesis of trisiloxane-tailed surface active ionic liquids and their aggregation behavior in aqueous solution

The aggregation behavior of two trisiloxane-tailed surface active ionic liquids (ILs), 1-methyl-3- trisiloxaneimidazolium chloride ([Si(3)Mim]Cl) and trisiloxanepyridinium chloride ([Si(3)Py]Cl), in aqueous solution was investigated by the measurement of surface tension, electrical conductivity, transmission electron microscopy (TEM), dynamic light scattering (DLS), and X-ray diffraction (XRD). The surface tension measurement showed the critical aggregation concentration (cac) of [Si(3)Mim]Cl and [Si(3)Py]Cl is 15.5 and 24.8mmoll−1 respectively, and the corresponding surface tension at cac (γcac) is 23.8 and 23.0mNm−1, respectively. The phenomenon was mainly ascribed to the branched trisiloxane hydrophobic moieties and these results demonstrated that the surface activity of these trisiloxane-tailed ILs was somewhat superior to that of conventional ILs. The vesicular-like structure of the aggregates was observed by TEM while DLS provided the diameter distribution of these aggregates. In addition, a probable two-layered arrangement of molecules in aggregates for the two ILs in aqueous solution was proposed based upon the results of XRD studies. This investigation may contribute to expand understanding of trisiloxane-tailed ILs. Furthermore, high thermal stability of such compounds may improve their potential applications in the fields of colloids and interfaces science.

Salt-free catanionic surface active ionic liquids 1-alkyl-3-methylimidazolium alkylsulfate: Aggregation behavior in aqueous solution

A series of salt-free catanionic surface active ionic liquids (SAILs), 1-alkyl-3-methylimidazolim alkyl sulfates (denoted as [Cnmim][CmSO4], n=6, 8, 10; m=12 and n=4; m=10, 14) were synthesized by an ion exchange reaction and their surface properties in aqueous solution were examined systematically by surface tension, fluorescence and electrical conductivity measurements. As catanionic surfactants, these SAILs exhibit notably higher surface activity, compared to the cationic or anionic analogues. Increment in both cationic and anionic alkyl chain lengths for [Cnmim][CmSO4] can both improve the amphiphilic character remarkably. This can be ascribed to cooperative interactions as formation of catanionic pairs between alkyl-substituted imidazolium cations and alkyl sulfate anions. The negative micellization Gibbs free energy values prove that the micellization of all the 1-alkyl-3-methylimidazolim alkyl sulfates investigated is a spontaneous process. Any additional CH2 group makes the micellization process easier regardless if it is on a cation or an anion. When keeping the total carbon atom number constant, we find that the [Cnmim][CmSO4] molecules with greater asymmetric alkyl chains display superior surface activity. This work indicates that the self-assembly of these imidazolium-based salt-free catanionic SAILs can be tailored by adjusting the mismatch of alkyl chains. These SAILs are expected to have potential applications in the fields of colloidal and interface and nanomaterial synthesis.

Synthesis, adsorption and aggregation properties of new saccharide-cationic surfactants

A novel saccharide-cationic surfactants containing a quaternary ammonium as cation and saccharide-amide as nonion N,N-dimethyl-N-[3-(gluconamide/lactobionamide)]propyl-N-alkylammonium bromides (CnDGPB and CnDLPB, where n represents hydrocarbon chain lengths of 8, 10, 12, and 14) were designed and synthesized. Their surface activities, adsorption, and aggregation behavior in aqueous solution were investigated by surface tension, conductivity, dynamic light scattering (DLS) and transmission electron microscopy (TEM). Surface tension measurement was used to derive surface adsorption properties such as adsorption efficiency (pC20), the (CMC/C20) ratio, maximal surface excess concentration (Γmax), and minimum surface area per molecule (Amin) at the air–water interface. From the results of temperature dependent conductivity measurements we could obtain the degree of counterion binding (β), and the thermodynamic parameters such as standard free energy (ΔGmic0), enthalpy (ΔHmic0), and entropy (ΔSmic0) of aggregation. DLS and TEM analysis of C14DGPB aqueous solutions revealed the morphology of molecular self-assembles.

Self-Assembly of Trisiloxane-Tailed Sugar Surfactant in Aqueous Solution

A lactobionamide-based trisiloxane surfactant (Si3N2–LA) was prepared via a two-step method. Structure characterization of Si3N2–LA was performed by Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (1H NMR). Surface activity and aggregation behavior in aqueous solution of Si3N2–LA were investigated by surface tension measurements, dynamic light scattering (DLS) and negative-stained transmission electron microscopy (TEM). The results show that the surfactants can self-assemble into spherical vesicles with diameters in the range from 50 to 150 nm due to the introduction of trisiloxane tail.

Effect of hydrophilic ionic liquid on aggregation behavior of aqueous solutions of sodium dodecylsulfate (SDS)

This paper delineates the change in aggregation behavior of aqueous sodium dodecylsulfate (SDS), an anionic surfactant upon addition of “hydrophilic” ionic liquid (IL) 3-methy-1-pentylimidazolium tetrafluoroborate in an increase in critical micelle concentration (cmc). The results demonstrate the presence of electrostatic and hydrophobic interactions between the ions of IL and the head group of the surfactant. From the cmc values and their temperature dependence, the thermodynamic parameters, viz. free energy of micellization (ΔGm0) and entropy of micellization (ΔSm0) were evaluated to permit speculation of the interactions existing in the studied aqueous surfactant-IL systems. Further, 1H NMR chemical shift measurements in micelle solutions containing IL have also been carried out. The results obtained are compared with the conclusions drawn from the conductance and fluorescence measurements.

Aggregation Behavior of Aqueous Solutions of 1-Dodecyl-3-methylimidazolium Salts with Different Halide Anions

The interfacial and bulk properties of the aqueous solutions of imidazolium-based ionic liquids with different halide anions ([C12mim]Cl, [C12mim]Br, [C12mim]I) were investigated by surface tension and electrical conductivity measurements. The lowest surface tension (γcmc) and maximum surface excess concentration (Γmax) values from the surface tension measurements showed that [C12mim]I had the highest surface activity. The thermodynamic pontentials of micellization (ΔG0m, ΔH0m, ΔS0m) indicated that the micellization of [C12mim]Cl and [C12mim]Br was entropy-driven, while that of [C12mim]I was enthalpy-driven at 15 °C but entropy-driven above 20 °C. This distinct behavior for [C12mim]I was thought to be due to the higher binding affinity of I– to the micellar interface.

Synthesis and Characterization of a Lipidic Alpha Amino Acid: Solubility and Interaction with Serum Albumin and Lipid Bilayers

The lipidic α-amino acid with 11 carbons in the alkyl lateral chain (α-aminotridecanoic acid) was synthesized via multicomponent hydroformylation/Strecker reaction, which is a greener synthetic approach to promote this transformation relative to previously described methods. Its solubility and aggregation behavior in aqueous solutions was characterized, as well as the interaction with lipid bilayers. Lipidic amino acids are very promising molecules in the development of prodrugs with increased bioavailability due to the presence of the two polar functional groups and nonpolar alkyl chain. They are also biocompatible surfactants that may be used in the food and pharmaceutical industry. In this work we have conjugated the lipidic amino acid with a fluorescent polar group (7-nitrobenz-2-oxa-1,3-diazol-4-yl), to mimic drug conjugates, and its association with serum proteins and lipid bilayers was characterized. The results obtained indicate that conjugates of polar molecules with lipidic α-amino acid, via covalent attachment to the amine group, have a relatively high solubility in aqueous solutions due to their negative global charge. They bind to serum albumin with intermediate affinity and show a very high partition coefficient into lipid bilayers in the liquid-disordered state. The attachment of the polar group to the lipidic amino acid increased strongly the aqueous solubility of the amphiphile, although the partition coefficient into lipid membranes was not significantly reduced. Conjugation of polar drugs with lipidic amino acids is therefore an efficient approach to increase their affinity for biomembranes.

Effect of hydrophobic chains on the aggregation behavior of cationic silicone surfactants in aqueous solution

Three cationic silicone surfactants, (2-hydroxyethyl)-N,N-dimethyl-3-[tri-(trimethylsiloxy)]silylpropylammonium chloride (Si4ACl), (2-hydroxyethyl)-N,N-dimethyl-3-[bis(trimethylsiloxy)methyl]silylpropylammonium chloride (Si3ACl), and (2-hydroxyethyl)-N,N-dimethyl-3-[bis(trimethylsilylmethyl)methyl]silylpropyl-ammonium chloride (Si3C2ACl), with the same headgroups and different hydrophobic groups were synthesized. Their aggregation behavior in aqueous solution was investigated by surface tension and electrical conductivity. The results show that all the three cationic silicone surfactants perform admirable surface activity. Because of the effect of the hydrophobic groups, the critical micelle concentration values increase following the order Si3C2ACl < Si4ACl < Si3ACl, and Si3C2ACl packs more compactly at the air/water interface compared with Si4ACl and Si3ACl. Electrical conductivity studies show that all the three cationic silicone surfactants have low degree of counterion binding. Thermodynamic parameters ( $$ \varDelta\;H_m^0 $$ , $$ \varDelta S_m^0 $$ , and $$ \varDelta G_m^0 $$ ) of micellization derived from electrical conductivities indicate that the micellization for both Si3C2AC and Si3ACl in aqueous solution is enthalpy-driven, and that for the Si4ACl is entropy-driven. For the heat capacities, $$ \varDelta\;c_{m,p}^0 $$ , values are positive for Si4ACl, indicating that there is an attractive interaction between the nitrogen atom of one surfactant molecule and the oxygen atom of another surfactant molecule for Si4ACl.

Effect of headgroups on the aggregation behavior of cationic silicone surfactants in aqueous solution

Three cationic silicone surfactants, 1-methyl-3-[tri-(trimethylsiloxy)]silylpropyl-imidazolium chloride (Si4mimCl), (2-hydroxyethyl)-N,N-dimethyl-3-[tri-(trimethylsiloxy)]silylpropylammonium chloride (Si4mam-OHCl), 1-methyl-1-[tri-(trimethylsiloxy)]silylpropylpyrrolidinium chloride (Si4pyCl), with the same hydrophobic group and different headgroups were synthesized. Their aggregation behavior in aqueous solution was systematically investigated by surface tension, electrical conductivity, and steady-state fluorescence. Surface tension of water can be reduced almost to 20mNm−1 with the addition of the cationic silicone surfactants. This result indicates that all the three surfactants exhibit remarkable surface activity. Because of the effect of the headgroups, the critical micelle concentrations (CMC) values increase following the order Si4pyCl<Si4mimCl<Si4mam-OHCl, and Si4pyCl packs more tightly at the air/water interface compared with Si4mimCl and Si4mam-OHCl. Electrical conductivity measurements show that all the three cationic silicone surfactants have low degree of counterion binding (β) and the β values for Si4pyCl and Si4mam-OHCl increase with increasing the temperature in the investigated temperature range. Thermodynamic parameters (ΔHm0, ΔSm0, and ΔGm0) of micellization indicate that the micellization for Si4mimCl in aqueous is enthalpy-driven, and that for both the Si4pyCl and Si4mam-OHCl entropy-driven.

Synthesis and Properties of Gluconamide-Based Trisiloxane Surfactant

A gluconamide-based trisiloxane surfactant (Si3N2-GA) was prepared via a two-step method. Structure characterization of the Si3N2-GA was performed by fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (1H NMR). Surface activity and aggregation behavior in aqueous solution of the Si3N2-GA were investigated by surface tension measurements, dynamic light scattering (DLS), and negative-stained transmission electron microscopy (TEM). The results show that the critical micelle concentration (CAC) and surface tension (γCAC) at the cmc in aqueous solution of the Si3N2-GA are 3.77 × 10−4 M and 20.5 mN · m−1, respectively, and the surfactants can self-assemble into spherical vesicle with diameters in the range from 50 to 150 nm.

Surface adsorption and micelle formation of imidazolium-based zwitterionic surface active ionic liquids in aqueous solution

A novel class of zwitterionic surface active ionic liquids (SAILs), N-alkyl-N′-carboxymethyl imidazolium inner salts ([NCn, N′CO2Im], n=10, 12, 14), was synthesized. Their aggregation behavior in aqueous solution was investigated by surface tension, isothermal titration calorimetry, and steady-state fluorescence. Compared with the reported imidazolium-based cationic SAILs, 1-alkyl-3-methylimidazolium bromide ([Cnmim]Br) and zwitterionic betaine surfactants, (CnH2n+1N(CH3)2CH2COO−), [NCn, N′CO2Im] exhibits significantly lower critical micelle concentration (cmc) and surface tension at cmc (γcmc) values. It is attributed to the incorporation of a deprotonated carboxylic group into the head group, which weakens the electrostatic repulsion between head groups and favors micellization. The micellar aggregation number of [NCn, N′CO2Im] is larger than that of [Cnmim]Br, while less than that of CnH2n+1N(CH3)2CH2COO−. Similar to the traditional zwitterionic surfactants, the surface activity and adsorption properties of [NC12, N′CO2Im] at air/water interface have a slight variation with temperature, pH, and ionic strength. This indicates that the present zwitterionic SAILs display the aggregation behavior much similar to zwitterionic surfactants, distinctly different from imidazolium-based cationic SAILs. Sets in low sensitivity to the environmental conditions, superior surface activity and unique physicochemical properties of ionic liquids, [NCn, N′CO2Im] can be exploited for utilizing as a potential substitute for conventional surfactants in certain fields.

Aggregation of Modified Celluloses in Aqueous Solution: Transition from Methylcellulose to Hydroxypropylmethylcellulose Solution Properties Induced by a Low-Molecular-Weight Oxyethylene Additive

Temperature effects on the viscosity and aggregation behavior of aqueous solutions of three different cellulose ethers--methylcellulose (MC), hydroxypropylmethylcellulose (HPMC), and ethyl(hydroxyethyl)cellulose (EHEC)--were investigated using viscosity and dynamic light scattering measurements as well as cryo-TEM. In all cases, increasing temperature reduces the solvent quality of water, which induces aggregation. It was found that the aggregation rate followed the order EHEC > HPMC > MC, suggesting that cellulose ethers containing some bulky and partially hydrophilic substituents assemble into large aggregates more readly than methylcellulose. This finding is discussed in terms of the organization of the structures formed by the different cellulose ethers. The temperature-dependent association behavior of cellulose ethers was also investigated in a novel way by adding diethyleneglycolmonobutylether (BDG) to methylcellulose aqueous solutions. When the concentration of BDG was at and above 5 wt %, methylcellulose adopted HPMC-like solution behavior. In particular, a transition temperature where the viscosity was decreasing, prior to increasing at higher temperatures, appeared, and the aggregation rate increased. This observation is rationalized by the ability of amphiphilic BDG to accumulate at nonpolar interfaces and thus also to associate with hydrophobic regions of methylcellulose. In effect, BDG is suggested to act as a physisorbed hydrophilic and bulky substituent inducing constraints on aggregation similar to those of the chemically attached hydroxypropyl groups in HPMC and oligo(ethyleneoxide) chains in EHEC.

Aggregation behavior of COOH-functionalized imidazolium-based surface active ionic liquids in aqueous solution

A series of novel COOH-functionalized imidazolium-based surface active ionic liquids (SAILs), N-alkyl-N′-carboxymethyl imidazolium bromide ([N-Cn, N′-CO2H-Im]Br, n=10, 12, 14), was synthesized. Their aggregation behavior in aqueous solution was investigated by surface tension and steady-state fluorescence measurements. From surface tension data, a group of micellization parameters was obtained. Compared with 1-alkyl-3-methylimidazolium bromide ([Cnmim]Br) bearing the same hydrocarbon chain, [N-Cn, N′-CO2H-Im]Br exhibits considerably lower critical micelle concentration (cmc) and surface tension at cmc (γcmc), higher adsorption efficiency (pC20) and effectiveness of surface tension reduction (πcmc), indicating the incorporation of carboxyl group favors micelle formation. The average aggregation number (Nagg) values of [N-Cn, N′-CO2H-Im]Br, determined by fluorescence quenching method, are slightly different from those of [Cnmim]Br. The effect of temperature on the aggregation behavior of [N-C12, N′-CO2H-Im]Br was also studied. It is found that there exists a minimum cmc at nearly 38°C, which is higher than that of [C12mim]Br.

Synthesis and Solution Properties of Novel Sugar‐Based Polysiloxane Surfactants

AbstractTwo sugar‐based polysiloxane surfactants with well‐defined structures, 3‐(2‐aminoethylamino)propyl functional polysiloxane glucosamide grafted (AEAPFPS‐GA) and 3‐(2‐aminoethylamino)propyl functional polysiloxane lactobionamide grafted (AEAPFPS‐LA), were successfully synthesized and characterized by FT‐IR and 1H NMR. Their surface activities and aggregation behavior in aqueous solution were investigated by surface tension measurements, dynamic light scattering (DLS) and negative‐stain transmission electron microscopy (TEM). The surface tension measurements provided the critical micelle concentration (CMC) and the surface tension at the CMC (γCMC), which revealed that these two surfactants have a much higher surface activity than those of conventional hydrocarbon surfactants. DLS and TEM analysis of the two polysiloxane surfactants aqueous solutions revealed that the AEAPFPS‐GA can self‐assemble into collapsed spherical micelles, and the AEAPFPS‐LA can self‐assemble into spherical micelles.

Well‐Defined Amphiphilic Poly(2‐oxazoline) ABA‐Triblock Copolymers and Their Aggregation Behavior in Aqueous Solution

Self-organization of block copolymers in solution is a way to obtain advanced functional superstructures. The synthesis of well-defined polymethyloxazoline-block-polyphenyloxazoline-block-polymethyloxazoline triblock copolymers is described and proven by (1) H NMR spectroscopy, SEC, and ESI-MS. The surprisingly water- soluble block copolymers do self-organize in aqueous solutions uniquely forming three coexisting well-defined structures: unimolecular micelles, micellar aggregates, and very form-stable polymersomes. This is the first example of a polymersome forming ABA-triblock copolymer with a glassy middle block. The spherical vesicles are analysed by scanning electron microscopy and transmission electron microscopy. It could be shown that these vesicles are indeed hollow spheres.

The effect of the spacer rigidity on the aggregation behavior of two ester-containing Gemini surfactants

Two Gemini surfactants with very similar structure but different spacer rigidity, namely 1-dodecanaminium,N,N′-[[(2E)-1,4-dioxo-2-butene-1,4-diyl]bis(oxy-2,1-ethanediyl)]bis[N,N-dimethyl-,bromide] (12-fo-12) and 1-dodecanaminium, N,N′-[(1,4-dioxo-1,4-butanediyl)bis(oxy-2,1-ethanediyl)] bis[N,N-dimethyl-, bromide] (12-su-12), and their monomeric counterpart 1-dodecanaminium, N-[2-(acetyloxy)ethyl]-N,N-dimethyl-, bromide (DTAAB) were synthesized and their aggregation behavior in aqueous solutions was studied by measurements of surface tension, conductivity, isothermal titration calorimetry, dynamic light scattering, and transmission electron microscopy. It was found that the Krafft point of 12-fo-12 was 18.6°C, significantly higher than that of 12-su-12 (7.6°C) and DTAAB (<0°C). The minimum surface areas per surfactant Amin at the water–air interface of DTAAB, 12-su-12, and 12-fo-12 were determined. It was found that the value of Amin of DTAAB was larger than half that of 12-su-12 but smaller than half that of 12-fo-12. The values of the degree of association β of the three surfactants were found to be in a sequence of DTAAB>12-su-12>12-fo-12, which was in accord with the sequence of the entropy of micellization. The enthalpies of micellization of the two Gemini surfactants were found to be more negative than double that of DTAAB, and 12-fo-12 had the most negative standard enthalpy of micellization. It was also found that 12-su-12 and DTAAB formed micelles in aqueous solutions, while 12-fo-12 could form micelles and vesicles dependent on the concentration.

Aggregation behavior of gemini pyrrolidine-based ionic liquids 1,1′-(butane-1,4-diyl)bis(1-alkylpyrrolidinium) bromide ([Cnpy-4-Cnpy][Br2]) in aqueous solution

Three gemini pyrrolidine-based ionic liquids, 1,1′-(butane-1,4-diyl)bis(1-alkylpyrrolidinium) bromide ([Cnpy-4-Cnpy][Br2], n=10, 12, 14), were synthesized. Their aggregation behavior in aqueous solution was systematically investigated by surface tension, electrical conductivity, and steady-state fluorescence. Compared with their corresponding monomers, N-alkyl-N-methylpyrrolidinium bromide (CnMPB), [Cnpy-4-Cnpy][Br2], have higher surface activity. The special structure of [Cnpy-4-Cnpy][Br2] that has a spacer in their hydrophilic head groups results in a lower surface excess concentration (Γmax) and a larger molecular cross-sectional area (Amin). Electrical conductivity studies show a lower degree of counter-ion binding to the aggregates. A smaller aggregation number (Nagg) is observed by the pyrene fluorescence quenching method. A series of thermodynamic parameters (ΔGagg0,ΔHagg0,-TΔSagg0) of aggregation derived from electrical conductivity indicate that the aggregation of [Cnpy-4-Cnpy][Br2] is enthalpy-driven, while aggregation of CnMPB is entropy-driven at low temperatures but enthalpy-driven at high temperatures.

Aggregation Behaviors of Dodecyl Sulfate-Based Anionic Surface Active Ionic Liquids in Water

Halogen-free, low-cost alkyl sulfate-based surface active ionic liquids (SAILs), 1-butyl-3-methylimidazolium dodecyl sulfate ([C(4)mim][C(12)SO(4)]), and N-butyl-N-methylpyrrolidinium dodecyl sulfate ([C(4)MP][C(12)SO(4)]) were easily synthesized through ion exchange reaction. The aggregation behaviors of [C(4)mim][C(12)SO(4)] and [C(4)MP][C(12)SO(4)] in aqueous solution were investigated by surface tension, electric conductivity, and static fluorescence quenching. Both [C(4)mim][C(12)SO(4)] and [C(4)MP][C(12)SO(4)] have rather lower cmc, γ(cmc) values and higher pC(20), π(cmc) values than those reported for the traditional ionic surfactant, sodium dodecyl sulfate (SDS), and imidazolium-based SAIL, 1-dodecyl-3-methylimidazolium bromide ([C(12)mim]Br), with the same hydrocarbon chain length. The thermodynamic parameters evaluated from electric conductivity measurements show that the micelle formation of [C(4)mim][C(12)SO(4)] and [C(4)MP][C(12)SO(4)] is entropy-driven in the temperature range investigated. Lower average aggregation number indicates that the micelles of two SAILs present much looser structure. It is found that both the nature and the ring type of counterions can affect the aggregation behavior in aqueous solution. (1)H NMR results of [C(4)mim][C(12)SO(4)] were used to further verify the mechanism of micelle formation. Hydration ability and steric hindrance of the imidazolium or pyrrolidinium counterion as well as the cooperative hydrophobic interaction of longer alkyl chain of [C(12)SO(4)] anion and comparatively shorter alkyl chain of [C(4)mim] or [C(4)MP] cation are proposed to play critical roles in the aggregation of [C(4)mim][C(12)SO(4)] and [C(4)MP][C(12)SO(4)].

卟啉有机纳米聚集体的研究 Research the Property of Organic Nano Gathered Based on Porphyrin

本文设计合成了两个以卟啉为核心尾端分别连有亲水基团和疏水基团的枝状化合物，并对其在水中的聚集行为进行研究及表征。通过紫外可见(UV-vis)吸收光谱和扫描电子显微镜(SEM)的分析，发现在连有疏水基团的卟啉化合物1是H型聚集的棒状结构，而连有亲水基团的卟啉化合物2则是J型聚集的空心球结构(直径大约340 nm)，与纳米粒度分析仪计算的结果基本一致。所以我们得出，通过改变卟啉外部的取代基可以调控其纳米聚集体的形貌。 We designed and synthesized dendritic porphyrin which brings hydrophilic groups and hydrophobic groups. Their different aggregation behaviors in aqueous solution were studied by using UV absorption spectroscopy, scanning electron microscopy (SEM) and Nanoparticle technology. Results indicated that porphyrin 1 bearing hydrophobic group can form rod-like structures introduced by H-aggregation. Porphyrin 2 containing hydrophilic moiety can form hollow spherical structures (diameter is about 340 nm) caused by J-aggregation. So we have come, by changing the the por- phyrins external substituents can be modulated by the morphology of nano-aggregates.