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      • Mechanochemical Degradation of Denpols: Synthesis and Ultrasound-Induced Chain Scission of Polyphenylene-Based Dendronized Polymers

        Peterson, Gregory I.,Bang, Ki-Taek,Choi, Tae-Lim American Chemical Society 2018 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.140 No.27

        <P>New polyphenylene-based dendronized polymers (denpols), exhibiting extended and rigid conformations, were prepared using ring-opening metathesis polymerization (ROMP). Their mechanochemical degradation was explored in ultrasound-induced elongational flow fields. Degradation rate constants were obtained for polyphenylene-based denpols, of varying generation, across a degree of polymerization (DP) range of ∼100-600. In general, it was found that larger side chains led to increased degradation rates and that the rate enhancement was proportional to the natural log of persistence length (Ln(<I>l</I><SUB>p</SUB>)) or the square root of monomer molecular weight (<I>M</I><SUB>mon</SUB><SUP>0.5</SUP>). These relationships led to the generation of “master curves” in which the rate constant trends for each polymer series converged, enabling accurate prediction of degradation rate constants for related polymers bearing long alkyl chains or ester-type dendrons. Furthermore, we observed evidence for, and used computational modeling to support, polymer chains undergoing multiple scissions during a single elongation event, leading to faster degradation of daughter fragments that come from parent polymers with large side chains.</P> [FIG OMISSION]</BR>

      • KCI등재

        Women's Genealogy

        Peterson, Mark 淑明女子大學校 亞細亞女性問題硏究所 1981 아시아여성연구 Vol.20 No.-

        韓國에서의 族譜에 대한 개념은 우선 男子에 속하는 것이다. 또는 女子는 族譜와는 전혀 부관하다고 할 수 있다. 그러나 女子에 대해서도 族譜를 硏究하고자 한다면 이를 위한 資料가 많이 있다. 歷史上에 나타난 歷代王朝의 왕비들, 宮女, 또는 높은 벼슬을 지낸 집안의 女人들에 대한 族譜등이 女性 系譜硏究의 좋은 資料가 될 것이다. 그 외에 호적, 文集, 王朝實錄, 토지문서, 상속文書 등도 좋은 資料가 된다. 韓國에 있어서의 女性硏究를 族譜에 초점을 맞추어 그 系譜를 硏究해 본다면 새로운 사실들이 많을 것으로 본다. 너무 심한 비유가 될지는 모르겠으나 美國의 作家 알렉스·헤일리가 쓴 $quot;Roots$quot;와 같이 社會의 意識構造 속에서 당연시되었던 흑인들의 위치가 혈통찾기가 소재가 된 과감한 이 글을 통하여 지금까지의 一般認識에 도전하는 새로운 흑인들의 正統性과 위치를 찾아냄으로써 世界 全讀者의 사고에 커다란 충격을 준 바 있듯이, 韓國女性에 대한 族譜硏究가 하나의 충격적인 女性에 대한 認識의 變化를 可能케 할 수도 있을 것이다. 現在 상태에서 女子의 족보를 찾으려면 各世代의 男子의 族譜에서 그의 부인데 대한 기록이나 父의 사위의 婦人에 대한 기록에서 찾아야 할 것이다. 즉, 女子가 族譜上에 나타나 있기는 하나 단독의 系譜가 기록되어 있지 않기 때문이다. 이렇게 본다면 또 女子는 一貫된 氏族도 갖지 못하고 있다. 결혼 전까지는 父와 같이, 後에는 남편과 같이 族譜에 올라 있기 때문에 結婚 前과 後가 다른 氏族에 속하게 되는 것이며, 결혼 後 다른 氏族 속에서도 完全한 構成員이 되는 것이 아니다. 李氏 姓을 가진 한 女子가 金氏와 結婚한 後에도 그녀는 李氏의 姓을 가지고 있는 것이다. 그러나 그녀가 死後 숭배를 받을때에는 李氏 後孫에 의한 奉祭가 아니고 金氏 後孫에 의한 奉祭를 받기 때문이다. 現在의 상태에서는 韓國女性들이 族譜에 대해 無關心하거나 族譜自體가 잘못된 制度라고 회피하려는 경향이 있다고 보며, 더구나 女性 문제에 關心이 많고, 知識수준이 높은 사람일수록 더 강하다고 본다. 그러나 그것은 잘못된 생각일 것이다. 現在와 같은 族譜기록에 대한 개념은 300∼400年前에 새로 생긴 것으로 오히려 李朝初期에는 男子後孫과 女子後孫이 同等하게 족보에 기록되었다. 오늘날과 같이 族譜가 男子中心으로 된 것은 儒敎思想의 영향인 것으로 보인다. 韓國에서 제일 오래된 族譜가 安東權氏의 족보인데 그것이 安東權氏의 족보이지만 男·女의 後孫을 모두 기록하였으며 外孫까지 그 族譜에 기록되어 있으므로 사실상 安東權氏姓을 가진 사람은 小數를 차지했을 뿐이다. 이렇게 볼 때 오늘날의 族譜가 男女平等의 개념에 위배된다는 이유 때문에 反對하는 입장에 서게 되는 문제도 李祖때의 개념으로 族譜를 기록한다면 女性이 족보를 피할 理由가 없을 것이다. 女性硏究의 方向을 歷史的인 업적이나 사실의 고찰에만 머물지 말고 人物中心의 系譜硏究에 초점을 맞춘다면 여성의 社會的 위치, 정통성과 역할을 재정립하는 좋은 계기가 될 것으로 보이며 族譜가 女性硏究의 새로운 관념을 제공해 주는 좋은 資料가 될 수 있을 것이다.

      • Multimechanophore Graft Polymers: Mechanochemical Reactions at Backbone-Arm Junctions

        Peterson, Gregory I.,Lee, Jaeho,Choi, Tae-Lim American Chemical Society 2019 Macromolecules Vol.52 No.24

        <P>Typical multimechanophore polymers (MMPs) are comprised of numerous mechanophores (force-responsive moieties) distributed throughout the backbone of linear polymers. We have developed a new MMP design based on graft polymers with mechanophores linking each arm to the backbone. By utilizing maleimide-anthracene cycloadducts, polymeric species containing anthracene were released from the parent polymer, enabling facile quantification of mechanophore activation. With pulsed ultrasound experiments, we observed that mechanophore activation was dependent on the arm length (a faster rate with longer arms), and we observed that 85% of the polystyrene (PS) arms underwent scission (64% specifically at the mechanophore site) for a graft polymer with 23 kDa arms. Solid-state activation was also investigated with hand-grinding experiments. Fast reactions were observed, with up to 96% of PS arms undergoing scission and 70-75% of mechanophores being activated, for all arm lengths studied. Multimechanophore graft polymers provide important insight into the distribution of forces in topologically complex polymers and may enable the development of new mechanoresponsive materials.</P> [FIG OMISSION]</BR>

      • KCI등재
      • SCIESCOPUSKCI등재

        Flow Cytometric Analysis of Human Lysozyme Production in Recombinant Saccharomyces cerevisiae

        Peterson Marvin S.,Kim Myoung-Dong,Han Ki-Cheol,Kim Ji-Hyun,Seo Jin-Ho The Korean Society for Biotechnology and Bioengine 2002 Biotechnology and Bioprocess Engineering Vol.7 No.1

        Flow cytometric techniques were used to investigate cell size, protein content and cell cycle behavior of recombinant Saccharomyces cerevisiae strains producing human lysozyme (HLZ). Two different signal sequences, the native yeast $MF\alpha1$ signal sequence and the rat $\alpha-amylase$ signal sequence, were used for secretion of HLZ. The strain containing the rat $\alpha-amylase$ signal sequence showed a higher level of internal lysozyme and lower specific growth rates. Flow cytometric analysis of the total protein content and cell size showed the strain harboring the native yeast signal sequence had a higher total protein content than the strain containing the rat $\alpha-amylase$ signal sequence. Cell cycle analysis indicated that the two lysozyme producing recombinant strains had an increased number of cells in the $G_2+M$ phase of the yeast cell cycle compared with the host strain SEY2102.

      • KCI등재
      • SCISCIESCOPUS

        Synthesis of Functional Polyacetylenes via Cyclopolymerization of Diyne Monomers with Grubbs-type Catalysts

        Peterson, Gregory I.,Yang, Sanghee,Choi, Tae-Lim American Chemical Society 2019 Accounts of chemical research Vol.52 No.4

        <P><B>Conspectus</B></P><P>Metathesis cyclopolymerization (CP) of α,ω-diynes is a powerful method to prepare functional polyacetylenes (PAs). PAs have long been studied due to their interesting electrical, optical, photonic, and magnetic properties which make them candidates for use in various advanced applications. Grubbs catalysts are widely used throughout synthetic chemistry, largely due to their accessibility, high reactivity, and tolerance to air, moisture, and many functional groups. Prior to our entrance into this field, only a few examples of CP using modified Grubbs catalysts existed. Inspired by these works, we saw an opportunity to expand the accessibility and utility of Grubbs-catalyzed CPs. We began by exploring CP with popular and commercially available Grubbs catalysts. We found Grubbs third-generation catalyst (G3) to be an excellent catalyst when we used strategies to stabilize the propagating Ru carbene, such as decreasing the polymerization temperature or using weakly coordinating solvent or ligands. Controlled living polymerizations were demonstrated using various 1,6-heptadiyne monomers and yielded polymers with exclusively 5-membered rings (via α-addition) in the polymer backbone. The strategy of stabilizing the Ru carbene was also critical to successful CP with Hoveyda-Grubbs second-generation (HG2) and Grubbs first-generation (G1) catalysts. We found that decomposed Ru species were catalyzing side reactions which could be completely shut down by decreasing the reaction temperature or using weakly coordinating ligands. While HG2 generally led to uncontrolled polymerizations, we found it to be an effective catalyst for monomers with very large side chains. G1 displayed broader functional group tolerance and thus broader monomer scope than G3. We next looked at our ability to change the regioselectivity of the polymerization by using <I>Z</I>-selective catalysts which favor β-addition and the formation of 6-membered rings in the polymer backbone. While modest β-selectivity could be obtained using Grubbs Z-selective catalyst at low temperatures, we found that by using one of Hoveyda and co-workers’ catalysts with decreased carbene electrophilicity, we could achieve exclusive formation of 6-membered rings. We also pursued alternative routes to achieve 6+-membered rings in the polymer backbone by using diyne monomers with increased distance between alkynes. We found that optimizing the monomer structure for CP was an effective strategy to achieve controlled polymerizations. By using bulky substituents (maximizing the Thorpe-Ingold effect) and/or using heteroatoms (shorter bonds) to bring the alkynes closer together, controlled living CP could be achieved with various 1,7-octadiyne and 1,8-nonadiyne monomers. Finally, we took advantage of several inherent properties of controlled CP techniques to prepare polymers with advanced architectures and nanostructures. For instance, the living nature of the polymerization enabled production of block copolymers, the tolerance of very large substituents enabled production of dendronized and brush polymers, and the insolubility or crystallinity of some monomers was utilized for the spontaneous self-assembly of polymers into various one- and two-dimensional nanostructures. Overall, the strategies of stabilizing the propagating Ru carbene, modulating the selectivity and reactivity of the Ru carbene, and enhancing the inherent reactivity of monomers were key to improving the utility and performance of CP with Grubbs-type catalysts. The insight provided by these studies will be important for future developments of CP and other metathesis polymerizations utilizing ring-closing steps.</P> [FIG OMISSION]</BR>

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