Sorption of anionic amphiphilic block copolymers by a network polycation

The interaction of amphiphilic block copolymers comprising an anionic block (polyacrylate or polymethacrylate) and a hydrophobic block (polystyrene, poly(butyl acrylate) or polyisobutylene) with lightly crosslinked poly(N,N-diallyl-N,N-dimethylammonium chloride) is studied for the first time. It is shown that the cationic hydrogel can sorb anionic amphiphilic block copolymers via electrostatic interaction with the corona of block copolymer micelles. The rate of sorption of block copolymer polyelectrolytes is significantly lower than the rate of sorption of linear polyions and is controlled by the lengths of the hydrophilic and hydrophobic blocks and the flexibility of the latter blocks. The sorption of amphiphilic block copolymers is accompanied by their self-assembly in the polycomplex gel and formation of a continuous hydrophobic layer impermeable to water and the low-molecular-mass salt dissolved in it.     

Self-assembled micelles of novel graft amphiphilic copolymers for drug controlled release

In this study, with the aim of designing an ideal anticancer drug carrier, we synthesized novel amphiphilic graft copolymers, P(Glu-alt-PEG)-graft-PCLA, based on poly(ethylene glycol) (PEG) segments and glutamic acid (Glu) units as the hydrophilic main chain, and poly(?-caprolactone-co-lactide) (PCLA) as hydrophobic branches. The chemical structure of the copolymers was characterized by (1)H MNR and FT-IR. The self-assembly of the copolymers to form micelles was studied by TEM, DLS and fluorescence spectroscopy. In vitro doxorubicin controlled release studies demonstrated that these graft copolymer micelles had high drug loading capacity and good controlled released properties, demonstrating their potential as a novel anticancer drug carrier. The drug loaded graft copolymer micelles exhibited efficient inhibition of HeLa cells in in vitro studies.     

Preparation and characterization of biodegradable nanoparticles based on amphiphilic poly(3-hydroxybutyrate)-poly(ethylene glycol)-poly(3-hydroxybutyrate) triblock copolymer

Amphiphilic triblock copolymers of poly(3-hydroxybutyrate)-poly(ethylene glycol)-poly(3-hydroxybutyrate) (PHB-PEG-PHB) were directly synthesized by the ring-opening copolymerization of β-butyrolactone monomer using PEG as macroinitiator. Their structure, thermal properties and crystallization were investigated by ¹H NMR, differential scanning calorimetry (DSC) and X-ray diffraction. It was found that both PHB and PEG blocks were miscible. With the increase in the PHB block length, the triblock copolymers became amorphous because amorphous PHB block remarkably depressed the crystallization of the PEG block. Biodegradable nanoparticles with core-shell structure were prepared in aqueous solution from the amphiphilic triblock copolymers, and characterized by ¹H NMR, SEM and fluorescence. The hydrophobic PHB segments formed the central solid-like core, and stabilized by the hydrophilic PEG block. The nanoparticle size was close related to the initial concentrations of the nanoparticle dispersions and the compositions of the triblock copolymers. Moreover, the PHB-PEG-PHB nanoparticles also showed good drug loading properties, which suggested that they were very suitable as delivery vehicles for hydrophobic drugs.     

Synthesis and self‐assembly of novel amphiphilic copolymers poly(lactic acid)‐block‐poly(ascorbyl acrylate)

In this study, a novel type of amphiphilic block copolymers poly(lactic acid)‐block‐poly(ascorbyl acrylate) (PLA‐block‐PAAA) with biodegradable poly(lactic acid) as hydrophobic block and poly(ascorbyl acrylate) (PAAA) as hydrophilic block was successfully developed by a combination of ring‐opening polymerization and atom transfer radical polymerization, followed by hydrogenation under normal pressure. The chemical structures of the desired copolymers were characterized by ¹H NMR and gel permeation chromatography. The thermal physical properties and crystallinity were investigated by thermogravimetric analysis, differential scanning calorimetry, and wide angle X‐ray diffraction, respectively. Their self‐assembly behavior was monitored by fluorescence‐probe technique and turbidity change using UV–vis spectrometer, and the morphology and size of the nanocarriers via self‐assembly were detected by cryo‐transmission electron microscopy and dynamic light scattering. These polymeric micelles with PAAA shell extending into the aqueous solution have potential abilities to act as promising nanovehicles for targeting drug delivery. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

无规共聚物自组装球形胶束表面亲水性的耗散粒子动力学模拟

建立了含不同亲疏水粒子比的双亲性无规共聚物粗粒化模型. 采用耗散粒子动力学方法模拟了两亲性无规共聚物选择性溶剂自组装球形胶束表面的亲水性能. 模拟结果表明, 无规共聚物在选择性溶剂中自组装得到实心球形胶束, 球形胶束表面的亲水性与聚合物链亲水粒子含量、溶剂的选择性有关. 随着聚合物链所含亲水粒子增加, 球形胶束表面的亲水性增强. 球形胶束表面的亲水性随着疏水粒子与溶剂粒子间的排斥参数增大而增强, 模拟结果与实验结论一致. 该模拟方法给出的胶束微结构信息可以为双亲无规共聚物分子设计及自组装双亲胶束制备提供一定的理论指导.     

丙烯酰胺-苯乙烯双亲嵌段共聚物水溶液的表面活性及增溶性

在微乳液介质中制备了系列的丙烯酰胺 (AM)与苯乙烯 (St)的双亲嵌段共聚物 (PAM b PSt) ,用紫外分光光度法测定了共聚物的组成 ,用乌氏粘度计测定了共聚物的特性粘数 [η],并用其相对表征共聚物的分子量大小 .重点研究了双亲嵌段共聚物 (PAM b PSt)疏水链段在水溶液中的缔合行为、共聚物的表面活性及其对有机物的增溶性能 ,考察了共聚物分子组成 (疏水链段含量 )与分子量对其表面活性与增溶性能的影响规律 .研究结果表明 ,由于疏水链段的憎水性 ,PAM b PSt的分子链在水溶液表面会形成表面吸附 ,从而降低水溶液的表面张力 ;而在水溶液中 ,在疏水相互作用下 ,PAM b PSt分子链中的苯乙烯疏水链段会形成分子间或分子内的胶束 ,烃类有机物可增溶其中 ;疏水链段含量越大 ,分子量越小 ,PAM b PSt的表面活性与增溶性能越强     

丙烯酰胺-苯乙烯双亲嵌段共聚物的微结构及水溶液行为

通过改变丙烯酰胺(AM)与苯乙烯(St)的投料比、苯乙烯与表面活性剂的加入量之比及引发剂加入量,在微乳液中制备了分子链微结构系列变化的丙烯酰胺-苯乙烯双亲嵌段共聚物(PAM-b-PSt),用荧光探针法与表面活性测定法详细地研究了共聚物中PSt嵌段长度、含量及分子量等微结构因素对共聚物在水溶液中的疏水缔合性与表面活性的影响.结果表明,当共聚物水溶液的浓度高于临界缔合浓度时,PAM-b-PSt的疏水缔合作用以分子间的缔合为主.若共聚物中PSt嵌段含量及分子链长一定时,随着PSt疏水嵌段长度增长,PAM-b-PSt的疏水缔合性增强,而对共聚物的表面活性影响很小.若共聚物中PSt疏水嵌段长度及分子链长一定时,PAM-b-PSt的疏水缔合性随着PSt嵌段含量的变化而变化,当PSt嵌段含量一定时,使大分子链之间产生最强的疏水缔合作用;而其表面活性则随着PSt嵌段含量的增大而增强.若共聚物中PSt疏水嵌段长度及含量一定时,分子量对其表面活性有较大的影响,分子量越高,表面活性越差;同时,在较稀的溶液浓度范围内,分子量对PAM-b-PSt的疏水缔合性的影响则很小.     

Thermoresponsive hydrogels from symmetrical triblock copolymers poly(styrene-block-(methoxy diethylene glycol acrylate)-block-styrene)

A series of symmetrical, thermo-responsive triblock copolymers was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization, and studied in aqueous solution with respect to their ability to form hydrogels. Triblock copolymers were composed of two identical, permanently hydrophobic outer blocks, made of low molar mass polystyrene, and of a hydrophilic inner block of variable length, consisting of poly(methoxy diethylene glycol acrylate) PMDEGA. The polymers exhibited a LCST-type phase transition in the range of 20-40 °C, which markedly depended on molar mass and concentration. Accordingly, the triblock copolymers behaved as amphiphiles at low temperatures, but became water-insoluble at high temperatures. The temperature dependent self-assembly of the amphiphilic block copolymers in aqueous solution was studied by turbidimetry and rheology at concentrations up to 30 wt %, to elucidate the impact of the inner thermoresponsive block on the gel properties. Additionally, small-angle X-ray scattering (SAXS) was performed to access the structural changes in the gel with temperature. For all polymers a gel phase was obtained at low temperatures, which underwent a gel-sol transition at intermediate temperatures, well below the cloud point where phase separation occurred. With increasing length of the PMDEGA inner block, the gel-sol transition shifts to markedly lower concentrations, as well as to higher transition temperatures. For the longest PMDEGA block studied (DP(n) about 450), gels had already formed at 3.5 wt % at low temperatures. The gel-sol transition of the hydrogels and the LCST-type phase transition of the hydrophilic inner block were found to be independent of each other.     

Self-assembly of amphiphilic liquid crystal polymers obtained from a cyclopropane-1,1-dicarboxylate bearing a cholesteryl mesogen

We study the self-assembly of a new family of amphiphilic liquid crystal (LC) copolymers synthesized by the anionic ring-opening polymerization of a new cholesterol-based LC monomer, 4-(cholesteryl)butyl ethyl cyclopropane-1,1-dicarboxylate. Using the t-BuP(4) phosphazene base and thiophenol or a poly(ethylene glycol) (PEG) functionalized with thiol group to generate in situ the initiator during the polymerization, LC homopolymer and amphiphilic copolymers with narrow molecular weight distributions were obtained. The self-assemblies of the LC monomer, homopolymer, and block copolymers in bulk and in solution were studied by small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and transmission electron microscopy (TEM). All polymers exhibit in bulk an interdigitated smectic A (SmA(d)) phase with a lamellar period of 4.6 nm. The amphiphilic copolymers self-organize in solution into vesicles with wavy membrane and nanoribbons with twisted and folded structures, depending on concentration and size of LC hydrophobic block. These new morphologies will help the comprehension of the fascinating organization of thermotropic mesophase in lyotropic structures.     

Self-assembly of charged amphiphilic diblock copolymers with insoluble blocks of decreasing hydrophobicity: from kinetically frozen colloids to macrosurfactants

We have investigated the self-assembly properties in aqueous solution of amphiphilic diblock copolymers with insoluble blocks of different hydrophobicity and demonstrated that the condition to obtain dynamic micelles is to design samples with insoluble blocks of low enough hydrophobicity. We focus here on results with new water-soluble amphiphilic diblock copolymers poly(diethyleneglycol ethylether acrylate)-b-poly(acrylic acid), or PDEGA-b-PAA. The physical characteristics of PDEGA-b-PAA micelles at high ionization have been determined by small angle neutron scattering (SANS). We show that PDEGA-b-PAA samples form micelles at thermodynamic equilibrium. The critical micelle concentrations (CMCs) decrease strongly with ionic strength and temperature due to a solvent quality decrease for, respectively, the corona and the core. This behavior of reversible aggregation is remarkable as compared to the behavior of kinetically frozen aggregation that has been widely observed with samples of similar architecture and different hydrophobic blocks, for example, poly(styrene)-b-poly(acrylic acid), PS-b-PAA, and poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA. We have measured the interfacial tension between water and the homopolymers PDEGA and PBA at, respectively, 3 and 20 mN/m at room temperature, which permits one to estimate the energy cost to extract a unimer from a micelle. The results are consistent with a micelle association that is fast for PDEGA-b-PAA and kinetically frozen PBA-b-PAA. Hence, PDEGA-b-PAA samples form a new system of synthetic charged macrosurfactant with unique properties of fast dynamic association, tunable charge, and water solubility even at temperatures and NaCl concentrations as high as 65 °C and 1 M.     

Formation of polymer vesicles by amphiphilic fluorosiloxane graft copolymers in solution

Amphiphilic fluorosiloxane graft copolymers with a poly(dimethylsiloxane)(PDMS) backbone,a hydrophobic fluorosiloxane side-chain and three hydrophilic poiyether side-chains were synthesized by hydrosilation reaction in this work.The micellization of amphiphilic graft copolymers in the water/ethanol solvent system was investigated,and vesicles with different size were formed after the self-assembly system was aged for different time.     

聚环氧乙烷-g-聚己内酯两亲性接枝共聚物的合成及药物释放行为

通过环氧丙醇(GL)与环氧乙烷(EO)的阴离子顺序开环聚合制备了水溶性嵌段共聚物PEO-b-PGL, 以PGL嵌段每个重复单元的侧羟基为引发点进一步引发ε-己内酯(CL)的开环聚合, 合成了结构规整的以聚环氧乙烷(PEO)为主链的两亲性接枝共聚物(PEO-b-PGL-g-PCL). 研究了PEO-b-PGL-g-PCL在水相中的自组装行为, 采用稳态荧光探针法测定了胶束的临界胶束浓度(cmc). 以疏水性药物阿霉素(DOX)为模型药物, 研究了两亲性接枝共聚物的化学组成对药物的扩散释放以及降解释放行为的影响.     

聚醚树枝体－聚丙烯酸嵌段共聚物的水溶液自组装行为

应用UV－Vis、荧光、光物理探针、动态激光光散射和透射电镜(TEM)方法研究了聚醚树枝体与聚丙烯酸两亲嵌段共聚物(Dendr,PE-PAA)在水溶液中分子自组装行为。实验结果表明通过聚醚树枝体嵌段的疏水作用,易缔合形成聚集体,具有很低(10^-6～10^-7mol·L^-1)的临界缔合浓度(cac)。透过电镜观察到聚集体具有双层膜结构的球状、单室囊泡。临界缔合浓度(cac)以及聚集体的大小对枝状体的代数(Gi)及线性体的聚合度(n)具有明显的依赖关系。     

Lyotropic liquid-crystalline phases formed by Pluronic P123 in ethylammonium nitrate

Aggregation of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymer, Pluronic P123, is promoted in a room temperature ionic liquid, ethylammonium nitrate (EAN). A series of lyotropic mesophases including normal micellar cubic (I1), normal hexagonal (H1), lamellar (Lalpha), and reverse bicontinuous cubic (V2) are identified at 25 degrees C by using polarized optical microscopy and small-angle X-ray scattering techniques. Such self-assembly behavior of P123 in EAN is similar to those observed in H2O or 1-n-butyl-3-methylimidazolium hexafluorophosphate ([BMim(+)][PF6(-)]) systems except for the presence of the V2 phase in EAN and the absence of the I 1 phase in [BMim(+)][PF6(-)]. This suggests that the ionic solvent of EAN plays similar roles as H2O and [BMim(+)][PF6(-)] during the aggregation process and solvates the PEO blocks through hydrogen-bond interaction. Furthermore, the hydrogen bonds are considered to form between the ethylammonium cations and oxygen atoms of the PEO blocks as confirmed by Fourier transform infrared spectra of P123-EAN assemblies. This deduction is also consistent with the results from differential scanning calorimetry and thermogravimetric analysis. The additional V2 phase appearing in the P123-EAN system is attributed to the higher affinity for the relatively hydrophobic PPO blocks to EAN than to water, which might reduce the effective area of the solvophilic headgroup and increase the volume of the solvophobic part. The obtained results may help us to better understand the self-assembly process for amphiphilic block copolymers in protic solvents.     

酶促缩聚和原子转移自由基聚合法合成AB型两亲性嵌段共聚物

Novozyme-435催化10-羟基癸酸进行自缩聚反应得到线性聚酯, 端基分别是羟基(—OH)和羧基(—COOH), 在三乙胺催化下, 分别用α-溴代丙酰溴和三甲基氯硅烷(TMSCL)进行端基官能化生成一个单官能度的大分子引发剂, 在CuCl/2,2'-联吡啶(bpy)催化体系中, 引发甲基丙烯酸环氧丙酯(GMA)的原子转移自由基反应(ATRP), 得到聚(10-羟基癸酸酯)/聚甲基丙烯酸环氧丙酯(PHDA-b-PGMA) AB 型两亲性嵌段共聚物, 其结构及分子量(分布)通过核磁共振和凝胶渗透色谱(GPC)确证. 此AB型两亲性嵌段共聚物在水溶液中能自组装形成纳米粒子, 用原子力显微镜(AFM)观察粒子的形状和大小.     

Drug release and biocompatibility of self‐assembled micelles prepared from poly (ɛ‐caprolactone/glycolide)‐poly (ethylene glycol) block copolymers

A series of poly(?‐caprolactone/glycolide)‐poly(ethylene glycol) (P(CL/GA)‐PEG) diblock copolymers were prepared by ring opening polymerization of a mixture of ?‐caprolactone and glycolide using mPEG as macro‐initiator and stannous octoate as catalyst. Self‐assembled micelles were prepared from the copolymers using nanoprecipitation method. The micelles were spherical in shape. The micelle size was larger for copolymers with longer PEG blocks. In contrast, the critical micelle concentration of copolymers increased with decreasing the overall hydrophobic block length. Drug loading and drug release studies were performed under in vitro conditions, using paclitaxel as a hydrophobic model drug. Higher drug loading was obtained for micelles with longer poly(ε‐caprolactone) blocks. Faster drug release was obtained for micelles of mPEG2000 initiated copolymers than those of mPEG5000 initiated ones. Higher GA content in the copolymers led to faster drug release. Moreover, drug release rate was enhanced in the presence of lipase from Pseudomonas sp., indicating that drug release is facilitated by copolymer degradation. The biocompatibility of copolymers was evaluated from hemolysis, dynamic clotting time, and plasma recalcification time tests, as well as MTT assay and agar diffusion test. Data showed that copolymer micelles present outstanding hemocompatibility and cytocompatibility, thus suggesting that P(CL/GA)‐PEG micelles are promising for prolonged release of hydrophobic drugs.     

A novel approach to biodegradable block copolymers of epsilon-caprolactone and delta-valerolactone catalyzed by new aluminum metal complexes

The chemical preparation of structurally well-defined biodegradable amphiphilic block copolymers is now of great interest for biomedical applications and the fundamental mimetic study of biomacromolecule self-assembly. For this purpose, in this study, (R,R)-N,N'-bis(3-tert-butylsalicylidene)-1,2-cyclohexanediamine 2 as a ligand was first synthesized from 1,2-cyclohexanediamine (DACH) and was allowed to further react with AlMe3, leading to a precursor compound 3. Then, the novel five-coordinated aluminum metal complexes 4-6 and 7-8 were prepared with good yields of 80-90%, bearing various molar mass monofunctional methoxy-poly(ethylene glycol) MPEG and difunctional poly(ethylene glycol) PEG as the alkoxy moieties, respectively. By means of nuclear magnetic resonance spectrometry (NMR), mass spectrometry (MALDI-FTMS) and Fourier Transform infrared spectrometry (FT-IR), new metal aluminum complexes 4-8 were characterized as having distinct chemical structures. Utilizing the synthesized metal complexes 4-8 as novel coordination polymerization catalytic templates, biodegradable amphiphilic MPEG-b-PCL, MPEG-b-PVL, PCL-b-PEG-b-PCL and PVL-b-PEG-b-PVL were synthesized with good control of the molecular weight distribution via the ring opening polymerization of epsilon-caprolactone and delta-valerolactone monomers at 100 degrees C in toluene. In addition, the chemical and crystalline structures and the thermal properties of these block biodegradable copolymers were analyzed by means of NMR, gel permeation chromatography (GPC), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). It was found that the melting points and crystallinities of the block copolymers synthesized strongly depended on the molecular structures of the polyether and polyester building blocks. Only one glass transition stage was detected, indicating good chain/segmental miscibility between the hydrophilic MPEG/PEG and hydrophobic PCL/PVL blocks in the non-crystalline regions. Moreover, TGA analysis exhibited typical two-step decomposition profiles with the weight-loss percentages in good agreement with block compositions from NMR calculations.     

pH-responsive amphiphilic hybrid random-type copolymers of poly(acrylic acid) and poly(acrylate-POSS): synthesis by ATRP and self-assembly in aqueous solution

The synthesis and subsequent self-assembly of novel, random-type amphiphilic pH-responsive hybrid copolymers, having acrylic acid as pH-responsive hydrophilic and acrylate-polyhedral oligomeric silsesquioxane (POSS) as hydrophobic constituents are reported. The synthesis was carried out in two steps: first, t-butylacrylate and acrylate-POSS are copolymerized by ATRP, followed by the acid hydrolysis of t-butyl acrylate constituents of the synthesized poly(t-butylacrylate)-co-poly(acrylate-POSS) copolymers to achieve poly(acrylic acid)-co-poly(acrylate-POSS). It was found that POSS is a powerful hydrophobic unit. With very low POSS concentration in the copolymers, i.e., one POSS unit per 40 to 110 acrylic acid repeat units, the obtained amphiphilic hybrid copolymers could self-assemble in aqueous solution to form nanoaggregates, as revealed by the laser light scattering and fluorescence studies on the aqueous solutions of the obtained copolymers. The formation of hydrophobic core in the self-assembled aggregates is verified by the solubilization of pyrene (used as probe in fluorescence measurements) in aqueous solution of the copolymers. In addition to pH-dependent self-assembly behavior, it is also demonstrated that the particle size and aggregation number of the aggregates can be tuned simply by varying the composition of the copolymer, i.e., by changing the molar ratio of poly(acrylic acid) to poly(acrylate-POSS) in the copolymer. Finally, preliminary results on the influence of salt (NaCl) on the self-assembly of poly(acrylic acid)-co-poly(acrylate-POSS) in aqueous solution are also presented.     

Noncovalent triblock copolymers based on a coiled-coil peptide motif

The formation of a noncovalent triblock copolymer based on a coiled-coil peptide motif is demonstrated in solution. A specific peptide pair (E and K) able to assemble into heterocoiled coils was chosen as the middle block of the polymer and conjugated to poly(ethylene glycol) (PEG) and polystyrene (PS) as the outer blocks. Mixing equimolar amounts of the polymer-peptide block copolymers PS-E and K-PEG resulted in the formation of coiled-coil complexes between the peptides and subsequently in the formation of the amphiphilic triblock copolymer PS-E/K-PEG. Aqueous self-assembly of the separate peptides (E and K), the block copolymers (PS-E and K-PEG), and equimolar mixtures thereof was studied by circular dichroism, dynamic light scattering, and cryogenic transmission electron microscopy. It was found that the noncovalent PS-E/K-PEG copolymer assembled into rodlike micelles, while in all other cases, spherical micelles were observed. Temperature-dependent studies revealed the reversible nature of the coiled-coil complex and the influence of this on the morphology of the aggregate. A possible mechanism for these transitions based on the interfacial free energy and the free energy of the hydrophobic blocks is discussed. The self-assembly of the polymer-peptide conjugates is compared to that of polystyrene-b-poly(ethylene glycol), emphasizing the importance of the coiled-coil peptide block in determining micellar structure and dynamic behavior.     

Self-assembly of amphiphilic ABC star triblock copolymers and their blends with AB diblock copolymers in solution: self-consistent field theory simulations

The self-assembled morphologies of amphiphilic ABC star triblock copolymers consisting of hydrophilic A blocks and hydrophobic B and C blocks and the blends with their counterpart linear AB diblock copolymers in solution are investigated by 2D real-space implementation of self-consistent field theory (SCFT) simulation. The star triblock copolymers self-assemble in solution to form various micellar structures from hamburger, to segmented wormlike, to toroidal segmented micelles, and finally to vesicles with simultaneously increasing hydrophobic lengths of blocks B and C. When the length of hydrophobic blocks B and C is asymmetric, specific bead-on-string worm micelles are found. Particularly, when the star ABC triblock copolymer is in a strong segregation regime and both B and C blocks are strongly hydrophobic, quite long segmented wormlike micelles are obtained, which had not been found in previously investigated diblock and linear ABC triblock copolymers solution. Additionally, raspberry micelles with beads dispersed on the core also occur in the strong segregation regime of bulk star ABC triblock copolymers. Furthermore, the aggregate morphology of ABC star triblock copolymers is strongly influenced by the addition of linear AB diblock copolymers. The most significant feature is that the long segmented worms will become shorter, to form hamburger micelles with the addition of AB diblock copolymers. These simulations are in good agreement with the experimental findings by Lodge's group.