Increasing Number Of Arms Research Articles

Zinc Phthalocyanine Core-First Star Polymers Through Nitroxide Mediated Polymerization and Nitroxide Exchange Reaction.

Nitroxide-mediated polymerization (NMP) and nitroxide exchange reaction (NER) are very efficient methodologies that require only suitable alkoxyamine derivatives and create different polymeric architectures in a controlled manner. Herein, the synthesis of star polymers containing TEMPO-substituted symmetric zinc phthalocyanine (ZnPc) is presented via NMP and NER. Moreover, linear polymer formation is conducted in a single arm on TEMPO-substituted asymmetric ZnPc to elucidate the properties of star polymers. All linear and star polymers are characterized by FT-IR, UV-vis, fluorescence, GPC, NMR, and EPR techniques. The results show that the proposed reactions are capable of forming controlled star-shaped polymers. The increasing arm number (from a single to four arms) results in variable dispersity values (Đ) (1.2-3) due to different arm lengths, especially in NMP. However, this difficulty has been overcome via NER, and star polymers have been successfully synthesized with relatively low molecular weight (30 K > 10 K) and low dispersity (1.2-1.9). The results clearly indicate that while styrene and 4-vinyl benzyl chloride monomers are introduced to the structure equally, star polymers with phthalocyanine can be synthesized in a controlled manner, and their quarternized derivatives have the potential to be effective as photoactive agents in photodynamic therapy.

Aszulcicrinus, a new genus of the Triassic crinoid family Dadocrinidae (Articulata; Encrinida) from Poland

The new genus and species Aszulcicrinus pentebrachiatus of the family Dadocrinidae from the early Middle Triassic Lower Gogolin Formation of Upper Silesia Upland is described. In contrast to Dadocrinus , the second primibrachial of Aszulcicrinus is not axillary for articulation with two arms but articulates with a third primibrachial and the first pinnule. This character results in five unbranched arms, which is unique in the order Encrinida. The significance of this character is discussed and paedomorphic or ecophe otypic explanations are excluded. The presence of only five unbranched arms predominates through the ontogeneny of Aszulcicrinus from early postlarval to adult stage. Within the family Dadocrinidae ( Aszulcicrinus - Dadocrinus - Carnallicrinus ), a phylogenetic trend towards size increase coincident with increasing arm number and denser pinnulation is interpreted as an improvement in filter-feeding efficiency. The sedimentological and taphonomic setting of the obrutional conservation lagerstätte of the type locality is described.

Triple Function Lubricant Additives Based on Organic-Inorganic Hybrid Star Polymers: Friction Reduction, Wear Protection, and Viscosity Modification.

Polymer-based lubricant additives for friction reduction, wear protection, or viscosity improvement have been widely studied. However, single additives achieving all three functions are rare. To address this need, we have explored the combination of polymer topology with organic-inorganic hybrid chemistry to simultaneously vary the temperature- and shear-dependent properties of polymer additives in solution and at solid surfaces. A topological library of lubricant additives, based on statistical copolymers of stearyl methacrylate and methyl methacrylate, ranging from linear to branched star architectures, was prepared using ruthenium-catalyzed controlled radical polymerization. Control over the polymerization yielded additives with low dispersity and comparable molecular weights, allowing evaluation of the influence of polymer architecture on friction reduction, wear protection, and bulk viscosity improvement in a commercial base oil (Yubase 4). Structure-performance relationships for these functions were assessed by a combination of a high-speed surface force apparatus (HS-SFA) experiments, wear track profilometry, quartz crystal microbalance analysis, and solution viscometry. The custom-built HS-SFA provides a unique experimental environment to measure the boundary lubrication performance under extreme shear rates (≈107 s-1) for prolonged times (24 h), mimicking the extreme conditions of automotive applications. These experiments revealed that the performance of the additives as boundary lubricants and wear protectants scales with the degree of branching. The branched architectures prohibit ordering of the additives in thin films under high-load conditions, leading to a thicker absorbed polymer brush boundary layer and therefore enhanced film fluidity and lubricity. Additionally, star polymers with increasing arm number lead to bulk viscosity modification, reflected by a significant increase in the viscosity index compared to the commercial base oil. Although outperformed by linear polymers for bulk viscosity improvement, the (hybrid) star polymers successfully combine the three distinct lubricant additive functions: friction reduction, wear protection, and bulk viscosity improvement-in a single polymeric structure. It should also be noted that, judging from HS-SFA experiments, hybrid stars carrying a silicate-based core outperform their fully organic analogues as boundary lubricants. The enhanced performance is most likely driven by attractive forces between the silicate cores and the employed metallic surfaces. Combining three function in one minimizes formulation complexity and thus opens a route to fundamentally understand and formulate key design parameters for the development of novel multifunction lubricant additives.

Architectural Effects of Star-Shaped "Structurally Nanoengineered Antimicrobial Peptide Polymers" (SNAPPs) on Their Biological Activity.

In this work, the effect of two key structural parameters, number of arms and arm length, of star-shaped "structurally nanoengineered antimicrobial peptide polymers" (SNAPPs) on their antimicrobial activity and biocompatibility, is investigated. A library of star-shaped SNAPPs is prepared, containing varying arm numbers and arm lengths. Antimicrobial assays are then performed to assess the capacity of the SNAPPs to disrupt the membrane, inhibit the growth, and kill pathogenic bacteria. A major finding of the study is that increasing arm number and length of SNAPPs enhanced antimicrobial activity, which can be respectively attributed to the higher local concentrations of polypeptide arms and increased α-helical content. SNAPP architecture is shown to affect the bacteria membrane state and therefore mechanism of killing. Two more potent structures with up to twice the antimicrobial activity of the previously reported SNAPP are discovered in this process. Toxicities of the SNAPPs also increase with arm number and arm length, however therapeutic index calculations identified a 16-arm SNAPP and an easier to prepare 4-arm SNAPP as the best therapeutic agents. The biocompatibility of the SNAPP with the best biological activity is also evaluated in vivo, showing no markers of systemic damage in mice.

Doxorubicin-loaded micelles based on multiarm star-shaped PLGA-PEG block copolymers: influence of arm numbers on drug delivery.

Star-shaped block copolymers based on poly(D,L-lactide-co-glycolide) (PLGA) and poly(ethylene glycol) (PEG) (st-PLGA-PEG) were synthesized with structural variation on arm numbers in order to investigate the relationship between the arm numbers of st-PLGA-PEG copolymers and their micelle properties. st-PLGA-PEG copolymers with arm numbers 3, 4 and 6 were synthesized by using different cores such as trimethylolpropane, pentaerythritol and dipentaerythritol, and were characterized by nuclear magnetic resonance and gel permeation chromatography. The critical micelle concentration decreased with increasing arm numbers in st-PLGA-PEG copolymers. The doxorubicin-loaded st-PLGA-PEG micelles were prepared by a modified nanoprecipitation method. Micellar properties such as particle size, drug loading content and in vitro drug release behavior were investigated as a function of the number of arms and compared with each other. The doxorubicin-loaded 4-arm PLGA-PEG micelles were found to have the highest cellular uptake efficiency and cytotoxicity compared with 3-arm PLGA-PEG micelles and 6-arm PLGA-PEG micelles. The results suggest that structural tailoring of arm numbers from st-PLGA-PEG copolymers could provide a new strategy for designing drug carriers of high efficiency. Structural tailoring of arm numbers from star shaped-PLGA-PEG copolymers (3-arm/4-arm/6-arm-PLGA-PEG) could provide a new strategy for designing drug carriers of high efficiency.

Effect of architecture on the micellar properties of poly (ɛ-caprolactone) containing sulfobetaines

Linear and star-shape poly(ɛ-caprolactone)-b-poly(N-(3-sulfopropyl)-N-methacryloxyethyl-N,N-diethylammoniumbetaine) (L/sPCL-b-PDEAS) with 4 and 6 arms were synthesized with the combination of Ring Opening Polymerization (ROP) and Atom Transfer Radical Polymerization (ATRP). These copolymers self-assembled into micelles via solvent evaporation method. The critical micelle concentration (CMC), determined by fluorescence spectroscopy using pyrene as a probe, was lower than 10−3mg/mL and decreased with increasing arm numbers. Atom force microscopy (AFM) images showed that the micelles were spherical in shape with narrow size distribution. The hydrophobic drug model carotene was efficiently loaded in the polymeric micelles. The sizes and drug loading content (DLC) of the carotene-loaded micelles increased with increasing drug content in feed. In vitro drug release experiment demonstrated that the release rate of carotene from the micelles was closely related to the arm numbers and drug loading content. Linear copolymer micelles showed the fastest release rate, 4-arm star shape copolymer micelles exhibited the lowest release rate. The micelles with higher drug loading content showed lower release rate. The release kinetics of carotene from micelles fitted the Ritger–Peppas equation.

Synthesis, micellization and gelation of temperature‐responsive star‐shaped block copolymers

A series of amphiphilic temperature‐responsive star‐shaped poly(D,L‐lactic‐co‐glycolic acid)‐b‐methoxy poly(ethylene glycol) (PLGA‐mPEG) block copolymers with different arm numbers were synthesized via the arm‐first method. Gel permeation chromatography data confirmed that star‐shaped PLGA‐mPEG copolymers had narrow polydispersity index, indicating the successful formation of star‐shaped block copolymers. Indirectly, the 1H NMR spectra in two kinds of solvents and dye solubilization method had confirmed the formation of core‐shell micelles. Further, core‐shell micelles with sizes of about 30–50 nm were directly observed by transmission electron microscopy. Subsequently, the micellar sizes and distributions as a function of concentrations and temperature were measured. At various copolymer concentrations, individual micelles with size of 20–40 nm and grouped micelles with size of 600–700 nm were found. Micellar mechanism of star‐shaped block copolymers in aqueous solution was simultaneously discussed. In addition, sol–gel transition of star‐shaped block copolymers in water was also investigated via the inverting test method. The critical gel temperature (CGT) and critical gel concentration (CGC) values of two‐arm, three‐arm and four‐arm copolymer solutions were markedly higher than ones of one‐arm copolymer. Moreover, the same CGC values of copolymer solution with different molecular weight and the same arm composition were ~15 wt %, and CGT values increased from ~38 to ~47°C with increasing arm numbers. Finally, the temperature‐dependent micellar packing gelation mechanism of star‐shaped block copolymer was schematically illustrated. Copyright © 2013 John Wiley & Sons, Ltd.

Star‐shape poly(acrylic acid)‐composed glass‐ionomer cements: Effects of MW and arm number on mechanical properties

AbstractThis study reports the synthesis and characterization of the star‐shape poly(acrylic acid)s with different arm numbers and molecular weight (MW)s. The effects of arm number and initiator concentration on the atom‐transfer radical polymerization reaction kinetics and solution viscosity were studied. The effects of MW and arm number on mechanical properties were evaluated. The results showed that both arm number and MW had significant impacts on the polymerization kinetics, solution viscosity, mechanical strengths, and wear‐resistance. Decreasing arm number and increasing initiator concentration increased the reaction rate. Increasing arm number and initiator concentration decreased the solution viscosity. Decreasing arm number and increasing MW increased mechanical strengths and wear‐resistance. Within the limitations of this study, the experimental cement was 28% in compressive strength, 48% in compressive modulus, 39% in diametral tensile strength, 60% in flexural strength, and 62% in Knoop hardness higher but 19% in fracture toughness lower than commercial Fuji II LC cement. The abrasion and attrition of the experimental cement were only 1.3% and 9.5% of Fuji II LC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Thermal degradation of star-shaped poly(ɛ-caprolactone)

Thermal degradation of a serials of star-shaped poly(ɛ-caprolactone) (PCL) with well-defined arm numbers and arm length was investigated. The weight loss of star-shaped PCL during heating process showed a two-stage character, and its dependence on molecular weight and multi-armed structure was well discussed. It was found that the thermal stability could be improved not only by increasing molecular weight but also by increasing arm numbers when the molecular weight is in a certain range. Based on the analyses of pyrolytic products by 1H NMR and TGA–FTIR, two mechanisms of thermal degradation for the random cleavage of ester bonds of PCL chains were proposed. Ester bonds were pyrolyzed into alkene and carboxyl functional groups in mechanism I while they were pyrolyzed into ketene and hydroxyl functional groups in mechanism II. The effects of multi-armed structure of star-shaped PCL on the cleavage of ester bonds of PCL chains were discussed in terms of the limitation of central “core” on mobility of each PCL arm. Combined the results of viscosity analysis with thermal analysis, it could be concluded that both thermal stability and processability of PCL materials can be improved by controlling the multi-armed structures.

Synthesis and characterization of novel β-cyclodextrin cored poly(α-caprolactone)s by anionic ring opening polymerization

Abstract By anionic ring opening polymerization initiated by cyclodextrin oxyanions generated from NaH and β-cyclodextrin(β-CD), novel biodegradable β- CD cored star-shaped poly(ε-caprolactone)s (s-PCLs) were synthesized and then characterized by means of FTIR, GPC, 1H-NMR. The effects of different feed molar ratios of NaH and β-CD on arm number and on the molecular weight of s-PCLs, and the relationship between the polymerization time and monomer conversion were investigated. Moreover, the physical properties of linear PCL (l-PCL) and s- PCLs with similar molecular weights but different arm number were studied and compared by DSC, SEM and intrinsic viscosity measurement, respectively. It was found that the feed molar ratio of NaH and β-CD is an important factor which influences both the molecular weight and arm number. The melting points and intrinsic viscosities of s-PCLs with similar molecular weights were lower than that of l-PCL, and were found to decrease with increasing arm number. Both SEM and AFM showed that the surface morphology of s-PCL films was different from that of l-PCL. These results indicated that s-PCL with different arms and physical properties could be synthesized using just a β-CD core by adjusting the feed molar ratio of NaH and β-CD

Comparison of micelles formed by amphiphilic poly(ethylene glycol)‐b‐poly(trimethylene carbonate) star block copolymers

AbstractIn this article, we describe the synthesis and solution properties of PEG‐b‐PTMC star block copolymers via ring‐opening polymerization (ROP) of trimethylene carbonate (TMC) monomer initiated at the hydroxyl end group of the core PEG using HCl Et2O as a monomer activator. The ROP of TMC was performed to synthesize PEG‐b‐PTMC star block copolymers with one, two, four, and eight arms. The PEG‐b‐PTMC star block copolymers with same ratio of between hydrophobic PTMC and hydrophilic PEG segments were obtained in quantitative yield and exhibited monomodal GPC curves. The amphiphilic PEG‐b‐PTMC star block copolymers formed spherical micelles with a core–shell structure in an aqueous phase. The mean hydrodynamic diameters of the micelles increased from 17 to 194 nm with increasing arm number. As arm number increased, the critical micelle concentration (CMC) of the PEG‐b‐PTMC star block copolymers increased from 3.1 × 10−3 to 21.1 × 10−3 mg/mL but the partition equilibrium constant, which is an indicator of the hydrophobicity of the micelles of the PEG‐b‐PTMC star block copolymers in aqueous media, decreased from 4.44 × 104 to 1.34 × 104. In conclusion, we confirmed that the PEG‐b‐PTMC star block copolymers form micelles and, hence, may be potential hydrophobic drug delivery vehicles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Poly(L‐lactide)‐b‐poly(ethylene oxide) copolymers with different arms: Hydrophilicity, biodegradable nanoparticles, in vitro degradation, and drug‐release behavior

Biodegradable and amphiphilic poly(L-lactide)-b-poly(ethylene oxide) copolymers with different arms (PLLA-b-PEO having one, two, four, and six arms) were successfully synthesized via a two-step synthetic strategy. The hydrophilicity-hydrophobicity balance of these copolymers was mainly controlled by both the arm number of copolymers (i.e., macromolecular architecture) and the poly(ethylene oxide) (PEO) composition. Biodegradable nanoparticles could be generated by direct injection of these PLLA-b-PEO copolymers solutions into distilled water, and their critical micelles concentrations decreased with the increasing arm number of copolymers. Moreover, both the hydrophilic PEO composition and the arm number of copolymers controlled the average size of PLLA-b-PEO nanoparticles, and the nanoparticles with adjustable sizes (20-85 nm) completely meet the size prerequisite (less than 100 nm) for targeted drug delivery. In vitro degradation of PLLA-b-PEO nanoparticles showed that the PLLA composition gradually increased over the degradation time, and the degree of crystallinity of PLLA block within copolymers increased simultaneously. Furthermore, the nimodipine drug loading efficiency of the PLLA-b-PEO copolymers was apparently higher than that of PLLA homopolymers. The drug-release experiments demonstrated that these biodegradable nanoparticles might be used for a short-time controlled release system. Consequently, this will provide a facile method not only to design new PLLA-based biomaterials from both the macromolecular architecture and the hydrophilicity-hydrophobicity balance, but also to fabricate biodegradable nanoparticles with adjustable sizes for drug delivery.

Comparison of micelles formed by amphiphilic star block copolymers prepared in the presence of a nonmetallic monomer activator

AbstractIn this article, we describe the synthesis of PEG‐b‐polyester star block copolymers via ring‐opening polymerization (ROP) of ester monomers initiated at the hydroxyl end group of the core poly(ethylene glycol) (PEG) using HCl Et2O as a monomer activator. The ROP of ε‐caprolactone (CL), trimethylene carbonate (TMC), or 1,4‐dioxan‐2‐one (DO) was performed to synthesize PEG‐b‐polyester star block copolymers with one, two, four, and eight arms. The PEG‐b‐polyester star block copolymers were obtained in quantitative yield, had molecular weights close to the theoretical values calculated from the molar ratio of ester monomers to PEG, and exhibited monomodal GPC curves. The crystallinity of the PEG‐b‐polyester star block copolymers was determined by differential scanning calorimetry and X‐ray diffraction. Copolymers with a higher arm number had a higher tendency toward crystallization. The crystallinity of the PEG‐b‐polyester star block copolymers also depended on the nature of the polyester block. The CMCs of the PEG‐b‐PCL star block copolymers, determined from fluorescence measurements, increased with increasing arm number. The CMCs of the four‐arm star block copolymers with different polyester segments increased in the order 4a‐PEG‐b‐PCL < 4a‐PEG‐b‐PDO < 4a‐PEG‐b‐PLGA < 4a‐PEG‐b‐PTMC, suggesting a relationship between CMC and star block copolymer crystallinity. The partition equilibrium constant, Kv, which is an indicator of the hydrophobicity of the micelles of the PEG‐polyester star block copolymers in aqueous media, increased with decreasing arm number and increasing crystallinity. A key aspect of the present work is that we successfully prepared PEG‐b‐polyester star block copolymers by a metal‐free method. Thus, unlike copolymers synthesized by ROP using a metal as the monomer activator, our copolymers do not contain traces of metals and hence are more suitable for biomedical applications. Moreover, we confirmed that the PEG‐b‐polyester star block copolymers form micelles and hence may be potential hydrophobic drug delivery vehicles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2084–2096, 2008

Integral equation theory study on the phase separation in star polymer nanocomposite melts

The polymer reference interaction site model theory is used to investigate phase separation in star polymer nanocomposite melts. Two kinds of spinodal curves were obtained: classic fluid phase boundary for relatively low nanoparticle-monomer attraction strength and network phase boundary for relatively high nanoparticle-monomer attraction strength. The network phase boundaries are much more sensitive with nanoparticle-monomer attraction strength than the fluid phase boundaries. The interference among the arm number, arm length, and nanoparticle-monomer attraction strength was systematically investigated. When the arm lengths are short, the network phase boundary shows a marked shift toward less miscibility with increasing arm number. When the arm lengths are long enough, the network phase boundaries show opposite trends. There exists a crossover arm number value for star polymer nanocomposite melts, below which the network phase separation is consistent with that of chain polymer nanocomposite melts. However, the network phase separation shows qualitatively different behaviors when the arm number is larger than this value.

Synthesis and Characterization of Star-Shaped Poly(N,N-dimethylaminoethyl methacrylate) and Its Quaternized Ammonium Salts

We report on the synthesis and characterization of star-shaped strong polyelectrolytes and their precursor stars with up to 24 arms. To achieve this we polymerized 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) by atom transfer radical polymerization employing a core-first attempt. Sugar-based scaffolds as well as silsesquioxane nanoparticles were used as oligofunctional initiators. Subsequent quaternization of the obtained poly(DMAEMA) stars yielded star-shaped poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI). The initiation site efficiency was determined both by molecular weight measurements of the cleaved arms and by a statistical method after partial destruction of the inorganic core. The rather low efficiency of the initiation sites (30−75%) leads to a moderate arm number distribution of the prepared polyelectrolyte stars. As expected, the hydrodynamic radii of these polyelectrolyte stars decrease with increasing ionic strength. However, if the ionic strength was adjusted with NaI instead of NaCl, pronounced ion-specific effects were observed; the star polyelectrolyte first strongly shrinks with increasing salt concentration and becomes insoluble at about 0.5 M NaI (“salting out”). Still higher concentrations of NaI lead to a redissolution and a reswelling of the star polyelectrolyte (“salting in”). The measured osmotic coefficients are low and decrease with increasing arm number from φ ∼ 0.12 for a 3-arm star down to φ ∼ 0.04 for an 18-arm star, confirming the expected strong counterion confinement within these objects with high charge density.

Synthesis, characterization, effect of architecture on crystallization of biodegradable poly(ε‐caprolactone)‐b‐poly(ethylene oxide) copolymers with different arms and nanoparticles thereof

Well-defined biodegradable poly(epsilon-caprolactone)-b-poly(ethylene oxide) (PCL-b-PEO) copolymers with different arms were synthesized via controlled ring-opening polymerization of epsilon-caprolactone, followed by coupling reaction with carboxyl-terminated PEO, where these copolymers included both star-shaped copolymers having four and six arms and linear analogues having one and two arms. When the weight percent of both PCL and PEO blocks within copolymer was similar to each other, the maximal melting temperature, the crystallization temperature, degree of crystallinity, and the spherulitic growth rate of these copolymers decreased with the increasing arm number of polymer. Moreover, the diameter of nanoparticles fabricated from these copolymers had a decreased tendency over the arm number of polymer, while it slightly increased with increasing weight percent of PCL within copolymer. These results indicate that both the arm number of polymer (macromolecular architecture) and the arm length ratio of PCL to PEO not only controlled the crystallization behavior and spherulitic growth, but also adjusted the size of nanoparticles. Significantly, this will provide a starting point not only to improve the physical properties and drug release profiles of PCL-based biomaterials, but also to design new PCL/PEO-based biomaterials from both the arm number of polymer and the balance between hydrophobic PCL and hydrophilic PEO.

Orientational anisotropy of bead‐spring star chains during creep process

AbstractThe bead‐spring model for star chains (Rouse–Ham model) is a fundamental model for the polymer dynamics. Despite the importance of this model, its dynamics under the stress‐controlled condition was not analyzed so far. For completeness of the model, the equation of motion of the Rouse–Ham chain was solved to derive an analytical expression of the orientation function S(n,t) for the stress‐controlled creep process. This expression indicated that the segments near the free end of the star arm exhibit overshoot of their orientational anisotropy to compensate for the slow growth of the anisotropy near the branching point and that the distribution of the anisotropy along the arm contour becomes more heterogeneous with increasing arm number f. This correlation/interplay of the segments at different locations along the arm, not seen under the strain‐controlled condition, is a natural consequence of the constant‐stress requirement during the creep process. The corresponding interplay was noted also for respective Rouse–Ham eigenmodes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3501–3517, 2006

Fluctuation effects and monomer-counterion correlations in starlike polyelectrolyte systems

We performed molecular-dynamics simulation to investigate fluctuation effects of monomers and counterions in starlike polyelectrolyte systems. We further study correlations between monomers and counterions. These quantities are systematically studied by variation of two parameters: the functionality f and the degree of dissociation alpha. Fluctuations of monomers and counterions are quantified by comparing the corresponding form factors of the monomers and counterions with a mean-field approximation. Fluctuations being correlated at length scales of the order of the star radius turn out to be negligible with increasing arm number f of the stars. At small arm numbers where fluctuation effects play a significant role, the use of theoretical mean-field models is questionable for a proper description of the monomer- and counterion-form factors. Correlations between monomers and counterions are quantified by a cross-correlation function. At small degree of dissociation alpha this function vanishes and indicates weak correlations. Furthermore, we compare our results with theoretical mean-field models. We give an appropriate analysis of the theoretical form factors and test commonly used counterion density distributions with our form factor analysis.

Synthesis and characterization of a series of star-branched poly(ε-caprolactone)s with the variation in arm numbers and lengths

A series of star-branched poly(ε-caprolactone)s (SPCLs) was synthesized with structural variation of the arm numbers and lengths through ring-opening polymerization under bulk condition. Arm numbers were varied to be 3, 4, and 6 by using multifunctional initiating cores such as trimethylol propane, pentaerythritol, and dipentaerythritol, respectively. The lengths of the poly(ε-caprolactone) arms were varied by controlling the molar ratio of monomer-to-initiating hydroxyl group molar ratio ([CL] 0/[–OH] 0=5, 10, 15). Molecular weights were determined by both 1H NMR end-group analysis and MALDI-TOF mass spectrometry, which gave reasonably consistent values. On the contrary, the GPC method failed to give accurate values of molecular weight of SPCLs due to the discrepancy with the linear standard. The branching architecture of SPCLs was evaluated by the branching ratio, g, which is the ratio of the mean-square radius of SPCL to that of liner counterpart, linear poly(ε-caprolactone) (LPCL), which is of the same chemistry and having the same molecular weight. The radii of gyration of SPCLs and LPCLs were determined using small-angle X-ray scattering (SAXS) from the initial slopes of Zimm plots, represented as 1/ I( q) vs q 2 with I( q) and q being the scattered intensity and scattering vector, respectively. The g values were observed to decrease with increasing arm numbers, indicating more compact molecular structure for SPCLs with higher arm numbers, while no such effect was observed for arm length variation. Thermal properties as well as the degree of crystallinity of SPCLs were found to be also dependent on structural variations. The melting points and the degradation temperatures were observed to increase with increasing arm lengths but with constant arm number. On the other hand, arm number variation with constant arm length gave no such changes to the thermal transitions of SPCLs. However, for the SPCLs with equivalent molecular weights, the degree of crystallinity was found to decrease with increasing arm numbers.

Synthesis, Characterization and Behavior in Aqueous Solution of Star‐Shaped Poly(acrylic acid)

AbstractSummary: We report the synthesis of star‐shaped poly(acrylic acid) (PAA), with 5, 8, and 21 arms, by atom transfer radical polymerization of tert‐butyl acrylate. We employ the core‐first approach using glucose‐, saccharose‐ and cyclodextrin‐based initiators. Subsequent acidic treatment of poly(tert‐butyl acrylate) (PtBA) leads to star‐shaped poly(acrylic acid) (PAA). Alkaline cleavage of the arms enabled us to determine the initiation site efficiency. The PAA stars and arms were esterified to poly(methyl acrylate) (PMA). Molecular weight determination by means of GPC/viscosity, MALDI‐TOF MS and NMR end‐group determination showed that the initiation site efficiency is close to unity. Results from potentiometric titration of PAA arms and stars show that the apparent pKa values increase with increasing arm number, which is a direct result of increasing segment density. Osmometry measurements of aqueous solutions of the PAA stars result in osmotic coefficients between 0.05 and 0.38, indicating that most of the counterions are confined within the star. The confinement increases with arm number.Potentiometric titration curves for stars (PAA100)21, (PAA100)8, (PAA100)5, and linear PAA100.imagePotentiometric titration curves for stars (PAA100)21, (PAA100)8, (PAA100)5, and linear PAA100.