Influences of poly[(styrene)x-stat-(chloromethylstyrene)y]s additives on dewetting behaviors of polystyrene thin films: effects of polar group ratio and film thickness

This contribution investigates the addition of poly(styrene-stat-chloromethylstyrene (ClMS))s as dewetting inhibitors of polystyrene (PS) thin films with thicknesses ranging from 12 to 38 nm. The ClMS ratios in the copolymers are 5, 25 and 45 mol%. Atomic force microscopy and optical microscopy are utilized to follow morphological changes of blended PS/copolymer films upon annealing above their glass transition temperatures. We have found that thermal stability of the PS films is greatly improved when a small amount of the copolymers is added into the system. The polar ClMS groups provide anchoring sites with the polar SiO_x/Si substrate while the styrene segments favorably interact with the PS matrix. The effectiveness of the copolymers as dewetting inhibitors is also found to increase with mole ratio of ClMS group. While the stability of PS films is systematically improved upon addition of the highly substituted copolymers, using the copolymer with relatively low ratio of ClMS group could lead to the opposite result. This class of copolymers can be utilized for improving thermal stability of ultrathin PS films. The fundamental knowledge from this study is also important for designing or selecting structure of additives used to improve the stability of polymeric thin films.     

Synthesis and physicochemical characterization of copolymers of 3-octylthiophene and thiophene functionalized with azo chromophore

Polythiophene derivatives with azo chromophore were synthesized via copolymerization of 3-octylthiophene (3OT) and 2-[N-ethyl-N-[4-[(4-nitrophenyl)azo]phenyl]amino]ethyl 3-thienylacetate (3-DRT). This copolymer has interesting optoelectronic properties and a variety of applications such as electrochromic and electronic devices. The polymerization process of 3OT and the functionalized thiophene was carried out via FeCl₃ oxidative polymerization. Thin films of poly(3OT-co-3-DRT) copolymer were prepared by spin-coating technique from toluene. FTIR and ¹H NMR spectroscopy revealed the presence of chromophore groups in the copolymer chain. Molecular weight and polydispersity of the polymers were measured by size exclusion chromatography. Changes in the surface topography of copolymers were analyzed by atomic force microscopy; the results showed that the copolymers presented some protuberances of variable size unlike the homogeneous granular morphology of P3OT. It is believed that these changes appeared by the incorporation of 3-DRT in the polymer. P3ATs are electrochromic materials that show color change upon oxidation-reduction process. We report that electrochemical characterization of poly(3OT-co-3-DRT) copolymer films synthesized chemically on indium-tin oxide (ITO) glass substrates showed an additional color to the P3OT homopolymer. Optical absorption properties of the polymer films were analyzed in the undoped and doped states and as a function of 3-DRT concentration in the copolymer. The nonlinear optical properties of the copolymers in the undoped and doped states were analyzed by Z-scan technique. The copolymers showed a change of non-linearity sign when the film was doped and results showed that the copolymers have a positive (self-focusing) and negative (self-defocusing) nonlinear optical properties which make them interesting for application as optoelectronic devices. We determined that the nonlinearity of the polymer films was a Kerr type.     

Anti-fouling properties of polylactic acid film modified by pegylated phosphorylcholine derivatives

Anti-fouling properties are important for both pharmaceutical and biomedical applications of polylactic acid (PLA). In this study, highly hydrated hydrophilic bilayers containing phosphatidylcholine (PC) and polyethylene glycol (PEG) were applied to PLA films to prevent the protein adsorption and blood platelet adhesion. The PLA films were coated with three PLA copolymers of PC and PEG, namely, a PLA-b-PEG block copolymer with a PC group on the end of a PEG chain (PC-PEG-PLA), a poly[2-methacryloyloxyethyl phosphatidylcholine (MPC)]-PLA graft copolymer (PMPC-g-PLA), and a PMPC-PLA graft copolymer with PEG serving as a spacer (PMPC-g-(PEG-b-PLA)). The influence of the copolymer structure on the anti-fouling properties of PLA film was then investigated. The results showed that the introduction of PC and PEG polar copolymers decreased the water-contact angle (WCA) and increased the equilibrated degree of hydration (H_eq) of the PLA surface significantly. The PMPC-g-(PEG-b-PLA) copolymer achieved the lowest WCA value and the highest H_eq value as it provided a higher density of PC on the outer surface. In addition, the strong hydration of the PEG and PC groups efficiently suppressed the bovine serum albumin (BSA) and fibrinogen (Fg) adsorption and subsequently inhibited platelet adhesion. The above results demonstrated that a good “anti-fouling” surface layer on the PLA substrate could be achieved by a combination of PEG and PC in copolymers.     

Improvement of ultrathin polystyrene film stability by addition of poly(styrene-stat-chloromethylstyrene) copolymer: An atomic force microscopy study

A method to improve the stability of ultrathin polystyrene (PS) films on SiO_x/Si substrate is introduced. In this method, interfacial interactions between PS film and substrate are enhanced by addition of poly(styrene-stat-chloromethylstyrene(ClMS)) copolymer containing 5 mol% of ClMS group. The resulting slight structural modification of the copolymer does not cause phase separation in the polymer blend. On the other hand, the existence of polar ClMS groups provides anchoring sites on the polar SiO_x surface via dipolar interactions. In this study, ratios of the copolymers are varied from 0 to 40 wt.% in the thin films resulting in a systematic increase of the interfacial interactions. The dewetting behaviors of all films subjected to the same annealing conditions are explored via atomic force microscopy. The analyses of root mean square roughness and dewetting area as a function of annealing time and copolymer ratio provide information about the film stability. Our results indicate that blending small quantity of the copolymer with PS significantly increases the stability of ultrathin films.     

Synthesis and characterization of novel biodegradable pentablock copolymers from L‐lactide,p‐dioxanone and poly (ethylene glycol)

ABCBA type pentablock copolymers, in which the A, B and C blocks are poly (p‐Dioxanone) (PPDO), poly (L‐Lactide) (PLLA), and polyethylene glycol (PEG), respectively, were synthesized via a two‐step ring‐opening polymerization in bulk using stannous octoate as the catalyst. PLA‐b‐PEG‐b‐PLA Triblock copolymer was synthesized at first and then p‐Dioxanone monomers as the other blocks were added to it. In the first step, poly ethylene glycol and, in the second step, triblock copolymer acts as the macro initiator. The obtained copolymers were identified by ?1&/sup;H&/I;, ?13&/sup;CNMR&/I; and IR&/I; spectroscopy. The intrinsic viscosity of copolymers was measured in chloroform/phenol (3/1 v/w) solution. The thermal properties, such as melting point, melting enthalpy and crystallinity, were studied. From the results of differential scanning calorimetry and thermal gravimetric analysis, it was observed that the PPDO blocks show similar crystallization behavior like homopolymer and also melting temperature of two PPDO end blocks raise with an increase in DON content in copolymer.     

Adsorptive features of poly(glycidyl methacrylate-<Emphasis Type="Italic">co</Emphasis>-hydroxyethyl methacrylate): effect of porogen formulation on heavy metal ion adsorption

Preparation of crosslinked copolymer beads based on glycidyl methacrylate (GMA), 2-hydroxyethyl methacrylate (HEMA), and divinyl benzene for the use of heavy metal adsorption has been investigated. In our study, a series of porous copolymer beads were synthesized by suspension polymerization in the presence of porogens, 1-dodecanol, toluene, and heptane at different dilutions. The effect of the porogens on the surface appearance and the porous structure of copolymer beads was studied by scanning electron microscopy and BET method. Diethylene triamine chelating copolymers were obtained through a reaction between amine groups of diethylene triamine and epoxide pendant groups of GMA. Adsorption isotherm and quantitative analysis for adsorption capacity involving copper, chromium, manganese, cadmium, iron, and zinc ions were investigated using atomic absorption spectrophotometer. The adsorption was a function of types of metal ions, adsorption time, and solution properties including pH and metal concentration. Adsorption equilibrium was achieved in approximately 50 min with a maximum adsorption capacity at pH 5.0. The Langmuir isotherm was found to be well fitted on the adsorption behavior. The maximum metal adsorption capacities in single ion solution in mole basis were in the order Cu(II) > Cr(VI) > Mn(II) > Zn(II) > Cd (II) > Fe(II). It was found that introducing porogen in the polymerization mixture produced the copolymer beads with better adsorption capacity. The maximum Cu(II) adsorption capacity of chelating poly(GMA-co-HEMA) beads were 1.35 mmol/g (85.79 mg/g) measured from the beads prepared in the presence of 1-heptane with 50% dilution. Consecutive adsorption–desorption experiments showed that crosslinked poly(GMA-co-HEMA) micro-beads can be reused almost without any change in the adsorption capacity.     

Synthesis of antibacterial amphiphilic elastomer based on polystyrene-block-polyisoprene-block-polystyrene via thiol-ene addition

A new type of amphiphilic antibacterial elastomer has been described. Thermoplastic elastomer, polystyrene–block-polyisoprene–block-polystyrene (PS–b-PI–b-PS) triblock copolymer was functionalized in toluene solution by free radical mercaptan addition in order to obtain an amphiphilic antibacterial elastomer. Thiol terminated PEG was grafted through the double bonds of PS–b-PI–b-PS via free radical thiol-ene coupling reaction. The antibacterial properties of the amphiphilic graft copolymers were observed. The original and the modified polymers were used to create microfibers in an electro-spinning process. Topology of the electrospun micro/nanofibers were studied by using scanning electron microscopy (SEM). The chemical structures of the amphiphilic comb type graft copolymers were elucidated by the combination of elemental analysis, ¹H NMR, ¹³C NMR, GPC and FTIR.     

Modification of nylon-6 with poly (m-phenylene isophthalamide) via MDI as a chain extender

Reinforcement of flexible nylon-6 by using poly (m-phenylene isophthalamide) PmIA (Nomex) using (MDI) 4,4-diphenylene methane diisocyanate as a chain extender was studied. Observation by scanning electron microscopy showed that the multiblock copolymer had a homogeneous texture. From the differential scanning calorimetry measurements, the multiblock copolymers were shown to have only one melting point, T _m, which is higher than that of nylon-6. The wide-angle X-ray diffraction pattern shows that nylon-6 has two diffraction peaks at 2=20° and 23.8°. However, the multiblock copolymer has only one peak at 2=20°, indicating a different crystal structure of multiblock copolymers. The copolymers appear to have a significant reinforcing effect on the mechanical properties.     

Thin films of block copolymer blends for enhanced performance of acoustic wave-based chemical sensors

The performance of quartz crystal oscillator-based volatile organic compound (VOC) sensors has been enhanced by using coatings made from poly(styrene-block-ethylene-co-butylene-block-styrene) block copolymers blended with resins and homopolymers. Enhanced performance is characterized by a wider operational temperature range (-10 to +50 degrees C) over which the sensors displayed, concurrently, an analyte sensitivity of >0.2 Hz/ppm toluene, minimal energy loss (resistance <120 ohms), and response times of <20 min (time required to reach 90% of full response). Atomic force microscopy images are consistent with a process in which the additive associates with the polystyrene portions of the microphase-separated block copolymer. This association reinforces the rigidity of the polystyrene network while allowing the rapid uptake of VOCs by the softer polyethylene/butylene phase.     

Biodegradable amphiphilic block-graft copolymers based on methoxy poly(ethylene glycol)-b-(polycarbonates-g-polycarbonates) for controlled release of doxorubicin

In this paper, novel biodegradable amphiphilic block-graft copolymers based on methoxy poly(ethylene glycol)-b-(polycarbonates-g-polycarbonates) (mPEG-b-(PATMC-g-PATMC)) were synthesized successfully for controlled release of doxorubicin (DOX). Backbone block copolymer, methoxy poly(ethylene glycol)-b-poly(5-allyloxy-1,3-dioxan-2-one) (mPEG-b-PATMC) was synthesized in bulk catalyzed by immobilized porcine pancreas lipase (IPPL). Then, mPEG-b-PATMC-O, the allyl epoxidation product of mPEG-b-PATMC, was further grafted by PATMC itself also using IPPL as the catalyst. The copolymers were characterized by ¹N HMR and gel permeation chromatography results showed narrow molecular weight distributions. Stable micelle solutions could be prepared by dialysis method, while a monomodal and narrow size distribution could be obtained. Transmission electron microscopy (TEM) observation showed the micelles dispersed in spherical shape with nano-size before and after DOX loading. Compared with the block copolymers, the grafted structure could enhance the interaction of polymer chains with drug molecules and improve the drug-loading capacity and entrapment efficiency. Furthermore, the amphiphilic block-graft copolymers mPEG-b-(PATMC-g-PATMC) had low cytotoxicity and more sustained drug release behavior.     

Improvements of fill factor in solar cells based on blends of polyfluorene copolymers as electron donors

The photovoltaic characteristics of solar cells based on alternating polyfluorene copolymers, poly(2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)) (APFO-3), and poly(2,7-(9,9-didodecyl-fluorene)-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)) (APFO-4), blended with an electron acceptor fullerene molecule [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM), have been investigated and compared. The two copolymers have the same aromatic backbone structure but differ by the length of their alkyl side chain. The overall photovoltaic performance of the solar cells is comparable irrespective of the copolymer used in the active layer. However, the fill factor (FF) values of the devices are strongly affected by the copolymer type. Higher FF values were realized in solar cells with APFO-4 (with longer alkyl side chain)/PCBM bulk heterojunction active layer. On the other hand, devices with blends of APFO-3/APFO-4/PCBM were found to render fill factor values that are intermediate between the values obtained in solar cells with APFO-3/PCBM and APFO-4/PCBM active film. Upon using APFO-3/APFO-4 blends as electron donors, the cell efficiency can be enhanced by about 16% as compared to cells with either APFO-3 or APFO-4. The transport of holes in each polymer obeys the model of hopping transport in disordered media. However, the degree of energetic barrier against hopping was found to be larger in APFO-3. The tuning of the photovoltaic parameters will be discussed based on studies of hole transport in the pure polymer films, and morphology of blend layers. The effect of bipolar transport in PCBM will also be discussed.     

Physicochemical and morphological properties of poly(aniline-co-pyrrole)

Copolymers of aniline and pyrrole have been prepared by chemical oxidative-polymerization of aniline and pyrrole using ammonium per sulphate and ferric chloride as oxidants. The structural and morphological properties were studied by X-ray diffraction and scanning electron microscopy. Both copolymers showed an amorphous behaviour compared to their homopolymers. SEM micrographs of poly(aniline–pyrrole) copolymer showed agglomerated spherical structures where as poly(2,5-dimethoxyaniline-pyrrole) showed disordered structures of spherical agglomerates. The copolymers showed improved UV–Vis absorption with the broad peak from 450 to 850 nm. The copolymers exhibited a lower conductivity compared to the homopolymers due to the unsuccessful complex between PANI and PPy, induced by the use of APS as the oxidant.     

聚乙二醇单甲醚/聚己内酯嵌段共聚物的微波合成及胶束制备

微波辅助下聚乙二醇单甲醚(MPEG)引发ε-己内酯(ε-CL)开环聚合合成了聚乙二醇单甲醚/聚己内酯(MPEG-b-PCL)嵌段共聚物,利用核磁共振(1H-NMR)和凝胶渗透色谱(GPC)方法对共聚物结构进行了表征。以芘作荧光探针,研究了共聚物胶束的形成及其临界胶束浓度(CMC)),利用动态光散射(DLS)和透射电镜(TEM)分别研究了胶束的粒径分布和形态。结果表明,在微波辅助下MPEG能够在较短时间内引发ε-CL开环聚合得到嵌段共聚物,当反应时间为5min,微波功率为700 W时能够得到理想的目标共聚物;嵌段共聚物在一定条件下能够形成球形的单分散纳米级胶束,CMC的数量级为10-3mg/mL。     

Antimicrobial activity of novel biocompatible wound dressings based on triblock copolymer hydrogels

Wound infection is a common complication often resulting in delayed healing with adverse clinical and financial consequences. Current antimicrobial treatments are far from ideal, side effects can include both bacterial resistance and toxicity. As a result, a great deal of effort over the last 20 years has been spent on investigating new forms of antimicrobial dressings. Here, we report the unexpected antimicrobial activity of a relatively new biocompatible thermo-responsive PHPMA–PMPC–PHPMA triblock copolymer gelator [where PHPMA denotes poly(2-hydroxypropyl methacrylate) and PMPC denotes poly(2-(methacryloyloxy)ethyl phosphorylcholine)]. In a radial diffusion assay, a 20% w/v copolymer gel produced an inhibitory zone up to six times greater than the corresponding control against Staphylococcus aureus. Similarly, in a broth inhibition assay the same copolymer reduced bacterial growth by 45% compared with control experiments conducted in the absence of any copolymer. Moreover, addition of the copolymer to a 3D-infected skin model reduced bacterial recovery by 38% compared to that of controls over 24–48 h. This is particularly relevant since these antimicrobial triblock copolymers were recently shown to be non-toxic when exposed to a tissue-engineered skin model. This antimicrobial activity was also successfully immobilised by grafting PMPC–PHPMA diblock copolymer brushes onto silicon wafers. Our results indicate that both PMPC–PHPMA diblock and PHPMA homopolymer brushes exhibit antimicrobial activity. Our hypothesis for the mode of action is that the moderately hydrophobic PHPMA chains penetrate the bacterial membrane, causing leakage of the cell contents. In summary, these gels and surfaces offer a promising new approach to antimicrobial dressings.     

9,9-二(丙酸二甲氨基乙酯)芴共聚物的合成及荧光性能

采用迈克尔加成反应制备了单体2,7-二溴-9,9-二(丙酸二甲氨基乙酯)芴(FDMAEA);采用Suzuki偶合反应制备了不同FDMAEA结构单元含量的醇溶性9,9-二(丙酸二甲氨基乙酯)芴-9,9-二辛基芴共聚物(PFDMAEA)。通过核磁共振、凝胶渗透色谱、溶解性测试、紫外-可见光光谱、荧光发射光谱等对其进行了分析研究。结果表明,成功合成了2,7-二溴-9,9-二(丙酸二甲氨基乙酯)芴及9,9-二(丙酸二甲氨基乙酯)芴-9,9-二辛基芴共聚物。该共聚物在极性溶剂,如甲醇中具有良好的溶解性。由于含有DMAEA支链的PFDMAEA主链容易扭曲,共轭长度变短,共聚物的紫外吸收光谱和荧光光谱随着FDMAEA含量的增加而发生蓝移。荧光发光光谱研究表明,溶剂的极性、溶液的浓度、温度和pH值对共聚物的发光性能有很大的影响。随着溶剂极性增大,共聚物的荧光发射强度不断增加。荧光发射强度随溶液浓度的增加先增加后降低,随着溶液温度的上升而降低。当溶液pH值由1增大到14时,荧光强度不断降低,直至淬灭。     

Synthesis of densely grafted copolymers with tert-butyl methacrylate/2-(dimethylamino ethyl) methacrylate side chains as precursors for brush polyelectrolytes and polyampholytes

Methacrylate-based densely grafted copolymers were synthesized by atom transfer radical polymerization (ATRP) and activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) techniques. The linear poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) PBIEM prepared by ATRP served as a macroinitiator backbone. The “grafting from” strategy was used to initiate polymerization of tert-butyl methacrylate (tBuMA) from PBIEM under ATRP and/or AGET ATRP conditions yielding densely grafted copolymers PBIEM-graft-P(tBuMA). The low polydispersity indices (PDI) of the synthesized brushes evidenced by SEC analysis were consistent with a controlled/living radical polymerization (CLRP) mechanism. The chlorine-terminated PBIEM-graft-P(tBuMA)-Cl macroinitiators were subsequently employed for chain extension with 2-(dimethylamino ethyl) methacrylate (DMAEMA) yielding densely grafted copolymers with diblock copolymer side chains PBIEM-graft-P(tBuMA)-block-PDMAEMA. Further, PBIEM macroinitiator was used to initiate the copolymerization of a binary mixture of tBuMA and DMAEMA through both ATRP and AGET ATRP initiating systems, yielding densely grafted copolymers with statistical distribution of the side chains. The reactivity ratios for random graft copolymerization of tBuMA and DMAEMA from PBIEM backbone established by three different methods (Finemann-Ross, Kelen-Tüdös and Error-in-Variable) did not substantially differ from literature values for conventional free-radical copolymerization of the same monomers. Polyampholyte brushes with PMAA-stat-PDMAEMA side chains were eventually synthesized by hydrolysis of the shielding tert-butyl groups.     

Templated synthesis of Ag-Au bimetallic nanoparticles by amphiphilic PVC-g-PSSA graft copolymer film

Amphiphilic comb-like copolymer consisting of a poly(vinyl chloride) (PVC) backbone and poly(styrene sulfonic acid) (PSSA) side chains, i.e. PVC-g-PSSA at 68:32 wt.% was synthesized via atom transfer radical polymerization (ATRP). This self-assembled graft copolymer film was used to template the growth of Ag-Au bimetallic nanoparticles in the solid state by introducing NaBH₄ as a reducing agent. The in situ formation of Ag-Au bimetallic nanoparticles in the graft copolymer film was confirmed by UV-visible spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). High resolution TEM picture showed the formation of spherical Ag-Au core-shell nanoparticles. To the best of our knowledge, this is the first report on the solid-state synthesis of Ag-Au bimetallic core-shell nanoparticles using amphiphilic comb-like copolymer film.     

Synthesis of heteropoly oxometalate/amphiphilic block copolymer composite thin films with self-ordered mesostructures

A simple, reproducible, and versatile procedure for synthesizing mesostructured 12-phosphotungstic acid thin films with large spaced mesostructures (< 17 nm) using amphiphilic block copolymers as structure-directing agents is reported. The morphology of the mesostructure can be controlled by adjusting the m/n ratio of poly (ethylene oxide)_1/2/poly (propylene oxide) (EO_1/2/PO) in the tri-block copolymer (EO)_m(PO)_n(EO)_m. This synthetic approach was adapted to prepare mesoscopically ordered heteropoly oxometalates (HPOMs) films, including 12-phosphomolybdic acid and 12-tungsto (IV) silicic acid. The electrochemical properties of the calcined HPOMs films as electrodes in Li-ion batteries were also investigated.     

Study on synthesis of glycopeptide-based triblock copolymers and their aggregation behavior in water

This paper describes a preliminary study on the synthesis of glycopeptide-based triblock copolymers and their aggregate behavior in water. Initially, a polypeptide-based triblock copolymer, poly(L-lysine)-b-poly(tetrahydrofuran)-b-poly(L-lysine) (PLL₃₀-b-PTHF-b-PLL₃₀), was synthesized by the ring-opening polymerization of ɛ-benzyloxycarbonyl-L-lysine N-carboxyanhydride using amine-terminated poly(tetrahydrofuran) as a macroinitiator in the fixed feed ratio, followed by the removal of the protecting group. The resulting copolymer then reacted with a varying amount of D-gluconolactone in the presence of dipropylethylamine to give the corresponding glycopeptide-based copolymers with high yields. This kind of amphiphilic sugar-containing triblock copolymer can self-assemble into nano-sized aggregates in water. The critical aggregation concentration (CAC) was determined in the range of around 10⁻⁶ M by fluorescence measurement. The spherical morphologies in 100–150 nm scale were also evidenced by transmission electron microscopy (TEM) measurements. They show potential as carriers for drug controlled delivery and templates for biomimetic mineralization.     

Temperature-sensitive star-shaped block copolymers hydrogels for an injection application: phase transition behavior and biocompatibility

A series of star-shaped poly(d,l-lactic-co-glycolic acid)-b–methoxy poly(ethylene glycol) (PLGA–mPEG) block copolymers with varying PLGA/mPEG block weight ratios, mPEG block length, and arm numbers were synthesized and phase transition behaviors were investigated. Phase transition characteristics, such as critical gel concentration (CGC) and critical gel temperature (CGT), were closely related to the molecular structure of the star-shaped block copolymers. The CGC was mainly determined by the balance of hydrophobic PLGA and hydrophilic mPEG block (PLGA/mPEG block ratio). The CGTs showed a stronger dependence on mPEG block length and arm number. Also, the CGTs can be adjusted by adding mPEG homopolymer additives. The weight fraction of mPEG had a stronger influence on the CGT values than molecular weight of mPEG. In addition, the MTT assay and histological observations confirmed the acceptable biocompatibility of the star-shaped block copolymer. Hence, the star-shaped PLGA-mPEG block copolymer was a promising candidate as a novel injectable gel.