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Precipitation-Mediated PEGylation of Plant-Derived Nanovesicles

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COVER PAPER

Investigating the Characteristics and Responses of Diacetylene Based Materials as Spray-On Colorimetric Sensors

Priyanka Shiveshwarkar, Savier Vega Siurano, Mahri Kadyrova, Natalie Tran, and Justyn Jaworski*

Vol. 30, No. 1, pp 1-5 (2022)│JAN 25, 2022│DOI 10.1007/s13233-022-0006-z

COMMUNICATION Investigating the Characteristics and Responses of Diacetylene Based Materials as Spray-On Colorimetric Sensors

Priyanka Shiveshwarkar, Savier Vega Siurano, Mahri Kadyrova, Natalie Tran, and Justyn Jaworski*

Diacetylene-containing amphiphiles were formulated and deposited by spray-coating to demonstrate a polymerizable spray-on sensing material. The ability to spray on a stimuli responsive material was demonstrated to provide detection of heat, chemical, or UV exposure on a variety of surfaces depending on the different diacetylene derivatives used.

Spray-on sensors were demonstrated that can enable visual monitoring of environmental physio-chemical exposures. This scalable approach to coating of surfaces with custom, stimuli-responsive polymers has important implications for widely-deployable sensing applications.

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ARTICLES

Dynamic Protein Adsorption- Desorption Analysis of Contact Lenses in a Three-Dimensional- Printed Eye Model

Wan-Hsin Chang, Pei-Yi Liu, Dai-En Lin, Yuan-Ting Jiang, Chien-Ju Lu*,

and Yuan-Hao Howard Hsu*

Macromol. Res., 30, 6 (2022)

3D printed eye model simulates the actual human eyeball. Protein solution can flow into the eye model that installed contact lens, and eye model outlet connects a UV detector to monitor the dynamic protein adsorption-desorption in real time.

Controlled Cationic Polymerization of Sulfide-Containing Vinyl Ethers Takeshi Namikoshi*,

Yuhei Watanabe, Ayaka Kaneda, Kazuma Ishikawa, Shinji Watanabe, and Miki Murata

Macromol. Res., 30, 16 (2022)

The living cationic polymerizations of sulfide-containing vinyl ethers, namely, the alkyl-sulfide-containing 2-(ethylthio)ethyl vinyl ether (ESEVE) and aryl- sulfide-containing 2-(phenylthio)ethyl and 2-[4-(methylthio)phenoxy]ethyl vinyl ethers (PSEVE and MSPEVE, respectively), were examined using HCl/ZnCl2, 1-(isobutoxy)ethyl acetate (IBEA)/Et1.5AlCl1.5, and IBEA /Et1.5AlCl1.5/SnCl4 as initiators. The polymerization of ESEVE terminated at a 35% conversion, and a high-molecular-weight polymer was not obtained; instead, the nucleophilicity of the sulfur moiety in ESEVE led to cyclization, forming five-membered ring sulfonium species. In contrast, the side reactions were suppressed when PSEVE was used, which has a less-nucleophilic sulfur moiety on its benzene ring, and polymerization proceeded to an 88% conversion, affording a high-molecular- weight polymer with a narrow molecular weight distribution (Mw= 12,500,Mw/Mn

= 1.18). Furthermore, cyclic sulfonium was not produced during the polymerization of MSPEVE, in which the sulfur atom is farther from the generated carbocation;

the polymerization proceeded quantitatively producing a high-molecular-weight polymer with a narrow molecular weight distribution, despite the short lifetime of the growing species. In particular, a high-molecular-weight polymer with the narrowest distribution (Mw= 13,500,Mw/Mn= 1.08) was obtained when SnCl4

was used as the Lewis acid.

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Hybrid Adsorbent Based on Zeolite NaX Modified with Hyperbranched Polyester

Poly(N-benzoylthiocarbamate) Aleksei Maksimov*, Alina Vagapova, Marianna Kutyreva,

and Gennadiy Kutyrev Macromol. Res., 30, 26 (2022)

A new hybrid adsorbent has been synthesized by covalent linking of activated zeolite with hyperbranched polyester containing 8 terminalN-benzoylthiocarbamate groups. The structure of the polymer ligand was defined by IR,1H and13C NMR spectroscopy. The complexing properties of the adsorbent have been studied using the example of complexes with Cu(II) and Co(II) ions. It was proved by IR spectroscopy that N-benzoylthiocarbamate and toluylenecarbamate groups participate in complexation with metal ions. According to electron microscopy and porometry data, the average particle diameter of the adsorbent is 34.56 ¥ m and the mesopore diameter is 4.19 nm. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) have shown that the hybrid adsorbent is thermally stable up to 150 ℃. The sorption capacities of the adsorbent for Cu(II) and Co(II) ions are 31.92 and 17.7 g/kg. It was shown that the desorption process of metal ions from the complexes occurs in an acidic medium at pH 4 with the regeneration of the original adsorbent.

Drug-Loaded Chondroitin Sulfate Microspheres Generated from Microfluidic Electrospray for Wound Healing

Hongzhen Zhang, Ronghua Xu, Zuowen Yin, Jun Yu, Ning Liang*, and Qian Geng*

Macromol. Res., 30, 36 (2022)

A kind of novel drug-loaded methacryloyl chondroitin sulfate (CSMA) microspheres for promoting the wound healing process was presented in this work. The CSMA droplets were generated from microfluidic electrospray and polymerized with ultraviolet light. With further freeze-drying and drug uploading, the drug-loaded CSMA microspheres were achieved. The prepared microspheres exhibited excellent biocompatibility, and the following animal experiments indicated they could promote wound healing significantly. This study opens the door to drug-loaded CSMA microspheres for wound healing applications.

Synthesis of Crosslinkable Polyetherimide and Application as an Additive in 3D Printing of Photopolymers

Crosslinkable glycidyl methacrylate-grafted polyetherimide (PEI-GMA) is synthesized in a three-step reaction procedure and dissolved in a photocurable resin, from which several components with high resolution and a polyetherimide-like finish are built on a 3D resin printer. Their properties markedly improve after adding 20 wt% PEI-GMA to the resin mixture.

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Novel Potentially Biobased Copolyesters Comprising 1,3-Butanediol,

1,4-Cyclohexanedimethanol and Dimethyl Terephthalate; Effect of Different Catalysts on

Polymerization Behavior Ji-Hyun Kim, Moo Song Kim, Hyung Jun Kim, Jong-Ryang Kim*, and Cheol-Hee Ahn*

Macromol. Res., 30, 51 (2022)

New potentially bio-based poly(1,3-butylene 1,4-cyclohexylenedimethylene terephthalate) (P13BCT) series were successfully synthesized. Dibutyltin oxide (DBTO) and titanium(IV) butoxide (TBT) were employed as a catalyst and the resulting copolymers were analyzed to evaluate the performance of each catalyst. The structures of copolymers and by-product were analyzed using correlation spectroscopy (COSY), heteronuclear single-quantum correlation spectroscopy (HSQC),1H and13C NMR.

Thermal and mechanical properties of copolymers were characterized depending on the molecular weights.

Synthesis of Multifunctional Organic Nanoparticles Combining Photodynamic Therapy and Chemotherapeutic Drug Release Fazli Sozmen*, Merve Kucukoflaz, Mustafa Ergul,

Zeynep Deniz Sahin Inan,

Yasemin Bozkurt, and Dilsad Taydas Macromol. Res., 30, 61 (2022)

Chitosan and BODIPY based nanoparticles that were capable of carrying out drug delivery and producing singlet oxygen (1O2) have been synthesized successfully.

These drug-free and drug-loaded organic nanoparticles showed very good PDT properties and they were found to be effective on MCF7 cancer cells and less toxic to L929 cells.

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COVER PAPER

Precipitation-Mediated PEGylation of Plant-Derived Nanovesicles

Van Quy Nguyen, Wooram Um, Jae Yoon An, Hyeyeon Joo, Young Chan Choi, Jae Min Jung, Ji Suk Choi, Dong Gil You, Yong Woo Cho*, and Jae Hyung Park*

Vol. 30, No. 2, pp 85-89 (2022)│FEB 25, 2022│DOI 10.1007/s13233-022-0016-x

REVIEW

Diketopyrrolopyrrole (DPP)-Based Polymers and Their Organic Field-Effect Transistor Applications: A Review Hyung Jin Cheon, Tae Kyu An*, and Yun-Hi Kim*

The pathways used to synthesize diketopyrrolopyrrole (DPP)-based polymers, the effects of engineering the main chains and side chains of these polymers on the p-type/n-type/ambipolar semiconducting performances of organic field-effect transistors (OFETs) made using these polymers, and applications of these OFETs as chemical sensors were regarded in this review.

Precipitation in the presence of poly(ethylene glycol) is reported as a facile and economic methodology to improve the stability of plant-derived nanovesicles. The surface of plant-derived nanovesicles were covered to poly(ethylene glycol) hydrophobic exclusion with a high yield (approximately 80%) in the presence of 10 wt% poly(ethylene glycol). Moreover, the protein concentration in the particles and the antioxidant activity test demonstrated that the quantity and quality of internal contents were not affected by the precipitation.

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COMMUNICATION

Precipitation-Mediated PEGylation of Plant-Derived Nanovesicles Van Quy Nguyen, Wooram Um, Jae Yoon An, Hyeyeon Joo, Young Chan Choi, Jae Min Jung, Ji Suk Choi, Dong Gil You,

Yong Woo Cho*, and Jae Hyung Park*

Macromol. Res., 30, 85 (2022) Cover Paper

Plant-derived nanovesicles have attracted interest in the field of regenerative medicine because of their abundant immune-regulatory RNAs and phytochemicals with cell proliferation activity. However, the poor stability and rapid clearance of vesicles remain major challenges in their clinical applications. Herein, we report a facile method for surface modification of plant-derived nanovesicles by precipitation in the presence of poly(ethylene glycol) (PEG). Our precipitation-based method is a useful technique for PEGylation of plant-derived nanovesicles without loss of bioactivity.

ARTICLES

Molecular Weight Determination of Chitosan with Antibacterial Activity Using Matrix-Assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry Analysis

Yong Hyun Lee, So Yeon Park, You Jin Hwang*,

and Jae Kweon Park*

Macromol. Res., 30, 90 (2022)

The antibacterial effect of chitosan with different molecular weights was investigated to define their potent biological activity. Both chitosan hydrolysates designated to CTSN-P30 and CTSN-B8 derived from the hydrolysis of high molecular weight chitosan showed significant synergistic antibacterial effects toward Staphylococcus aureus in the presence of 1,3-butylene glycol. The concentration-dependent antimicrobial effect is very important in determining the minimum inhibitory concentration (MIC) of both CTSN-P30 and CTSN-B8.

Each MIC50 of CTSN-P30 and CTSN-B8 was determined to be about 25 and 50 g/mL, respectively. Among chitosan hydrolysates, CTSN-P30 can effectively protect the membrane from the penetrating of fine dust which may contain unspecified microorganisms. Also, CTSN-P30, which showed very significant antimicrobial activity, was confirmed to be a hydrolysate containing (GlcNAc)3, and other hydrolysates consisting of (GlcN)5to (GlcN)15using matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry analysis. These results demonstrated the feasibility of CTSN-P30 and 1,3-butylene glycol to use as a potent antibacterial and find a dustproof agent for the preparation of various industrial products.

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Ionic Cross-Linkable Alendronate-Conjugated

Biodegradable Polyurethane Films for Potential Guided Bone Regeneration

Young-Hyun Ryu, Kangho Choi, Do-Hyun Oh, and Sung-Wook Choi*

Macromol. Res., 30, 99 (2022)

Waterborne polyurethane (PU) with carboxyl groups has hydrophilicity and a wide range of tunable mechanical properties. Alendronate (Alen), a well-known antiresorptive drug for osteoporosis, was conjugated to the PUvia an amide bond.

The ionic cross-linking of the Alen-conjugated PU (Alen-PU) resulted in the enhancement of mechanical properties. The ionic cross-linked Alen-PU can be a promising material for guided bone regeneration.

Fifth Generation Communication Performance of Poly(ether ketone ketone)/Modified Montmorillonite Substrate

Guang Kui Zhou, Xiao Dong Zhi, Deng Ming Pan, Tim Hsu, and Jen-taut Yeh*

Macromol. Res., 30, 107 (2022)

All poly(ether ketone ketone) (PEKKa) and PEKKax quaternary ammonium salt modified montmorillonite (QASMMTy) films displayed smaller values, as the frequency increased. The values acquired for each PEKKaxASMMTyfilm series reduced to a lowest value as QASMMT loadings approached 3 wt%. Satisfactory (2.59, 2.71, and 2.80 at 1 MHz) for 5G communication were acquired for PEKKa97QASMMT3 films filled with only 3 wt% optimum loading of QASMMT nano-platelets.

Performance Improvement of Hydrophobized Bacterial Cellulose Films as Wound Dressing

Small molecules derived from succinic acid containing long chains and aromatic ring were prepared and conjugated to bacterial cellulose films. These films became more hydrophobic and showed antimicrobial activity, in addition to maintaining their water retention capacity and biocompatibility.

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Effect of the Morphological Characteristic and Composition of Electrospun Polyvinylidene Fluoride/

Graphene Oxide Membrane on Its Pb2+Adsorption Capacity Thuy Thi Thu Nguyen*, Huu The Nguyen, Hai Thi Trinh, Trang Thi Thu Bui, Anh-Tuan Le, and Tran Quang Huy

Macromol. Res., 30, 124 (2022)

The effect of the morphological characteristic and composition of electrospun polyvinylidene fluoride/graphene oxide (PVDF/GO) membrane on its Pb2+

adsorption capacity was investigated. The modification of electrospun PVDF/GO membranes by adding PEG increased the distribution of GO on the surface of fibres, resulting in a notable increase in Pb2+ adsorption. The electrospun PVDF/GO/PEG membrane maintained a Pb2+removal rate of over 80% after six adsorption-desorption cycles.

Isolation, Characterization, and Biological Activities of Fucoidan Derived fromCeratophyllum Submersum L.

Ngoc Nhon Hoang, Tri Khoi Nguyen, Tuyet Hoa Vo, Ngoc Hoi Nguyen, Dai Hai Nguyen, and Dieu Linh Tran*

Macromol. Res., 30, 136 (2022)

Fucoidan, a natural sulfated polysaccharide extracted from seaweed, has been widely used in pharmaceutical field due to its excellent biological activities including antiviral, anticancer, antioxidant, anticoagulant, etc. Therefore, investigating the new natural sources of fucoidan has been received growing attention recently.

This study reported for the first time the isolation, purification, characterization, and biological activities of fucoidan fromCeratophyllum submersum (FCS). The molecular weight of obtained FCS was 9.7 kDa, composed of fucose (42.11%) and sulfate (16.38%). The FCS contained (1→3)-α-L-Fucopyranose and b-D-galactose bond in the structure. In addition, FCS showed strong antioxidant properties against 2,2-diphenyl-1-picrylhydrazyl, 2,2-azinobis (3-ethyl-benzothiazoline- 6-sulfonic acid), and reactive oxygen species radicals with inhibitory concentration 50 values were 765.48 ppm, 845.31 ppm, and 1760.00 ppm, respectively. The FCS also performed good antibacterial, antifungal, anticoagulant and anti-inflammatory activities. Especially, it expressed a better inhibition activity on breast cancer cell line (MCF-7) than that on liver cancer cells (HepG2), lung cancer cells (NCI-H460), and cervical cancer cells (HeLa). FCS demonstrated potential utility in functional food, cosmeceutical, and pharmaceutical industries. In the trend of discovering new sources for fucoidan with outstanding bioactivities, this report would contribute a basic platform and valuable information for further studies on fucoidan fromC. Submersum.

Effect of the Side Chain Functionality of the Conjugated Polyelectrolytes as a Cathode Interlayer Material on the Photovoltaic Performances Sabrina Aufar Salma

The cathode interlayer material (CIM) that contains neutral polymer (PFN), polymer salt (PFN salt), and polymer-OH salt (PFN-OH salt) was applied as an interlayer in inverted polymer solar cells (ITO/ZnO/CIM/PTB7-Th:PC71BM/MoO3/Ag). We discovered that the efficiency of the device based on CIM depends on the side chain functionality. The synergy impact from the backbone and side-chain functionality is the major significant contribution to enhancing the efficiency.

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