Spiropyran 2025 March Papers List
| Authors | Author Full Names | Article Title | Source Title | Author Keywords | Keywords Plus | Abstract | Addresses | Affiliations | Reprint Addresses | Email Addresses | Journal Abbreviation | Journal ISO Abbreviation | Publication Date | Publication Year | Volume | Issue | Start Page | End Page | Article Number | DOI | DOI Link |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Zou, XQ; Xiao, XZ; Zhang, SX; Zhong, JJ; Hou, YL; Liao, LQ | Zou, Xueqing; Xiao, Xiaozhen; Zhang, Shixiong; Zhong, Jiajun; Hou, Yulin; Liao, Liqiong | A photo-switchable and thermal-enhanced fluorescent hydrogel prepared from N-isopropylacrylamide with water-soluble spiropyran derivative | JOURNAL OF BIOMATERIALS SCIENCE-POLYMER EDITION | Hydrogel; fluorescent; photo-switchable; thermal-enhanced; spiropyran | POLY(N-ISOPROPYLACRYLAMIDE) HYDROGEL; TEMPERATURE; SURFACE; NANOPARTICLES; SENSOR; PH; SPIRONAPHTHOXAZINE; ENVIRONMENT; MODULATION; DETACHMENT | Herein, a photo-switchable and thermal-enhanced fluorescent hydrogel has been fabricated from N-isopropylacrylamide (NIPAAm) with a mixture of water-soluble acryloyl-alpha-cyclodextrin/acryloyl-alpha-cyclodextrin-spiropyran (acryloyl-alpha-CD/acryloyl-alpha-CD-SP) as cross-linkers. The physical properties, photochromic properties, and fluorescent behavior of the hydrogel were characterized. The fluorescence emission of the hydrogel can be reversibly switched 'on/off' by UV/visible light irradiation, and meanwhile the fluorescence intensity can be enhanced by increasing the temperature above the volume phase transition temperature (VPTT) of the hydrogel. The hydrogel also shows spatiotemporal fluorescent behavior, excellent cytocompatibility, and fatigue resistance in photochromic and photo-switchable fluorescent behaviors. | [Zou, Xueqing; Liao, Liqiong] Wuhan Univ, Coll Chem & Mol Sci, Wuhan, Hubei, Peoples R China; [Xiao, Xiaozhen; Liao, Liqiong] Southern Med Univ, Sch Biomed Engn, Guangzhou, Guangdong, Peoples R China; [Zhang, Shixiong; Zhong, Jiajun; Hou, Yulin] Sun Yat Sen Univ, Sch Engn, Guangzhou, Guangdong, Peoples R China | Wuhan University; Southern Medical University - China; Sun Yat Sen University | Liao, LQ （連絡著者）、Wuhan Univ, Coll Chem & Mol Sci, Wuhan, Hubei, Peoples R China.;Liao, LQ （連絡著者）、Southern Med Univ, Sch Biomed Engn, Guangzhou, Guangdong, Peoples R China. | liqiongliao@hotmail.com | J BIOMAT SCI-POLYM E | J. Biomater. Sci.-Polym. Ed. | 2018 | 29 | 13 | 1579 | 1594 | 10.1080/09205063.2018.1475942 | http://dx.doi.org/10.1080/09205063.2018.1475942 | ||
| Machida, S; Nakamura, Y; Itaya, A; Ikeda, N | Machida, Shinjiro; Nakamura, Yuta; Itaya, Akira; Ikeda, Noriaki | Poly(2-isopropyl-2-oxazoline) Bearing a Spiropyran Side-Chain: Synthesis and Evaluation of Photo and Temperature-Responsive Properties | MACROMOLECULAR CHEMISTRY AND PHYSICS | photoinduced phase change; poly(2-isopropyl-2-oxazoline); spiropyran; temperature responsive polymers; turbidity | AQUEOUS-SOLUTION; PHOTORESPONSIVE POLYMERS; N-ISOPROPYLACRYLAMIDE; RAFT POLYMERIZATION; ALPHA-CYCLODEXTRIN; BLOCK-COPOLYMERS; PHASE-SEPARATION; POLY(N-ISOPROPYLACRYLAMIDE); LIGHT; STIMULI | Poly(2-isopropyl-2-oxazoline)s with varied loading of the spiropyran side-chain are synthesized, and their photochemical and thermosensitive properties are characterized in aqueous solution. The absorption spectrum of the sample aqueous solution (0.1 wt%) indicates that 7.8 mol% of the pendant groups are in the zwitterionic merocyanine form. The introduction of spiropyran groups causes a marked decrease in the cloud point of the aqueous solution even when the pendant groups contain the zwitterionic merocyanine form. The cloud point of the aqueous solution of the samples in the spiropyran form is slightly (less than 1 degrees C) lower than that bearing the merocyanine group. Moreover, the photoinduced phase transition is demonstrated at an optimum temperature for the spiropyran-bearing poly(2-isopropyl-2-oxazoline). This material can be made applicable to a light-driven drug releasing system by introducing a hydrophobic group to form micelles and increasing the photoinduced change of the cloud point. | [Machida, Shinjiro; Nakamura, Yuta; Itaya, Akira; Ikeda, Noriaki] Kyoto Inst Technol, Fac Mat Sci & Engn, Sakyo Ku, Kyoto 6060962, Japan | Kyoto Institute of Technology | Machida, S （連絡著者）、Kyoto Inst Technol, Fac Mat Sci & Engn, Sakyo Ku, Kyoto 6060962, Japan. | machida@kit.ac.jp | MACROMOL CHEM PHYS | Macromol. Chem. Phys. | NOV | 2019 | 220 | 22 | 1900240 | 10.1002/macp.201900240 | http://dx.doi.org/10.1002/macp.201900240 | ||
| Wang, BB; Xiao, XZ; Zhang, YH; Liao, LQ | Wang, Beibei; Xiao, Xiaozhen; Zhang, Yuhuan; Liao, Liqiong | High strength dual-crosslinked hydrogels with photo-switchable color changing behavior | EUROPEAN POLYMER JOURNAL | Hydrogel; Dual-crosslinked; High strength; Spiropyran | RESPONSIVE HYDROGELS; SURFACE; POLYMERS; DELIVERY; SYSTEMS; ROBUST | Herein, high strength dual-crosslinked hydrogels with photo-switchable color changing behavior were designed and fabricated. In the mixture solution of alpha-cyclodextrin (alpha-CD), alpha-cydodextrin-spiropyran (alpha-CD-SP), and poly (ethylene glycol) diacrylate (PEGDA), the PEGDA chains first threaded into the cavity of alpha-CD/alpha-CD-SP and form inclusion complexes to generate the physical gel; then, the as-prepared physical gels were subjected to photo-polymerization to form a covalently crosslinked network. With the contribution of both no-covalent and covalent bond, the dual-crosslinked hydrogels possess high tensile strength, which is about fifteen times that of the pure PEG hydrogel. And due to the sacrifice of no-covalent bond, hydrogels showed high energy dissipation ratio, up to 75.3% and high fatigue resistance during loading-unloading tests. While the ingenious introduction of SP moieties, enables the as-prepared gels photo-switchable spatiotemporal color changing behavior reversibly. Erasable patterns on hydrogels could be written using UV light and erased by Vis light for multiple cycles. This flexible hydrogel with good physical performance shows high potential in photochromic flexible wearable devices. | [Wang, Beibei] Wuhan Univ, Coll Chem & Mol Sci, Wuhan, Hubei, Peoples R China; [Xiao, Xiaozhen; Liao, Liqiong] Southern Med Univ, Biomat Res Ctr, Guangdong Prov Key Lab Construct & Detect Tissue, Sch Biomed Engn, Guangzhou, Guangdong, Peoples R China; [Zhang, Yuhuan] Southwest Univ, ICEAM, Chongqing, Peoples R China | Wuhan University; Southern Medical University - China; Southwest University - China | Liao, LQ （連絡著者）、Southern Med Univ, Biomat Res Ctr, Guangdong Prov Key Lab Construct & Detect Tissue, Sch Biomed Engn, Guangzhou, Guangdong, Peoples R China. | liqiongliao@hotmail.com | EUR POLYM J | Eur. Polym. J. | JUL | 2019 | 116 | 545 | 553 | 10.1016/j.eurpolymj.2019.04.035 | http://dx.doi.org/10.1016/j.eurpolymj.2019.04.035 | ||
| Zhang, H; Zhang, Y; Chen, Y; Wang, SP; Zhang, C; Liu, Y | Zhang, Hui; Zhang, Yi; Chen, Yong; Wang, Shuai-Peng; Zhang, Chang; Liu, Yu | Polyrotaxane in-situ copolymerization stretchable supramolecular hydrogels for photo-controlled cascade energy transfer | EUROPEAN POLYMER JOURNAL | Polyrotaxane; Cascade energy transfer; Hydrogel; Copolymerization; Photo-control | Amphiphilic polysorbate (Tween 80) encapsulated hydrophobic methyl acrylate (MA), spiropyran (SP), nitro-benzoxadiazole (NBDAE) and cyanine 5 (Cy5) was mixed to form micelles, which in-situ copolymerized with acrylamide (AM) and polyrotaxane (PR) containing polyethylene glycol (PEG) threaded into vinyl modified alpha-cyclodextrin (alpha-CD) with amantadine end-capping to form stretchable supramolecular hydrogel. Benefiting from the sliding cross-linking points of PR, the hydrogel exhibited excellent mechanical properties (1300 % breaking strain and 0.26 MPa breaking stress). Meanwhile, photoreactive achievement of reversible SP acted as primary energy acceptor tuned cascade energy transfer from energy donor NBDAE to secondary acceptor Cy5 (energy transfer efficiency = 80 % for primary transfer, 65 % for secondary transfer). Therefore, this stretchable supramolecular hydrogel material can achieve phototunable multi-color emission and be applied in the field of time-resolved information anti-counterfeiting. | [Zhang, Hui; Zhang, Yi; Chen, Yong; Wang, Shuai-Peng; Zhang, Chang; Liu, Yu] Nankai Univ, Coll Chem, State Key Lab Elemento Organ Chem, Tianjin 300071, Peoples R China; [Liu, Yu] Collaborat Innovat Ctr Chem Sci & Engn Tianjin, Tianjin, Peoples R China | Nankai University; Collaborative Innovation Center of Chemical Science & Engineering Tianjin | Liu, Y （連絡著者）、Nankai Univ, Coll Chem, State Key Lab Elemento Organ Chem, Tianjin 300071, Peoples R China. | yuliu@nankai.edu.cn | EUR POLYM J | Eur. Polym. J. | JUN 23 | 2023 | 192 | 112070 | 10.1016/j.eurpolymj.2023.112070 | http://dx.doi.org/10.1016/j.eurpolymj.2023.112070 |
シクロデキストリン × スピロピランで拓く「光で操る」ハイドロゲル材料
（研究トピック要約／HP掲載用）
概要
シクロデキストリン（CD）の包接能やポリロタキサンの“すべり架橋”を土台に、スピロピラン（SP）の可逆的な光異性化（UVで開環→着色・発光、可視光で元に戻る）を組み合わせることで、光と温度で応答し、力学的に強靭で、書いて消せる発色・発光やエネルギー移動制御まで可能なソフトマテリアルが相次いで報告されています。センサー、ウェアラブル、情報記録、ドラッグデリバリーなどへの応用が期待されます。
ここがポイント（共通の知見）
- 二重応答性：UV/可視光で色・蛍光をON/OFF、VPTT（体積相転移温度）付近では温度で発光強度や相状態も制御。
- 高強度・高耐久：CDの包接による“物理架橋”と、ポリマーの“共有結合架橋”を重ねたデュアル架橋で、強度・エネルギー散逸・疲労耐性が大幅に向上。
- 相転移・雲点の設計：SP導入により水溶液の雲点（クラウドポイント）を調整でき、光誘起の相転移が狙える。
- エネルギー移動の光制御：SPを一次受容体として組み込むと、ドナー→SP→別色素へのカスケード型エネルギー移動を光で微調整可能。
- 実装イメージ：温度・pH・光センサー、消去可能パターン、タイムスタンプ型偽造防止、多色発光タグ、光駆動薬物放出など。
論文別ハイライト
1) NIPAAm系「光スイッチ／温度増強」蛍光ハイドロゲル
- 設計：N-isopropylacrylamide（NIPAAm）にアクリロイル化α-CDとα-CD-SPを架橋剤として導入。
- 機能：UV/可視光で蛍光を可逆スイッチ、VPTT（相転移温度）以上で蛍光増強。
- 特長：細胞適合性とフォトクロミズムの疲労耐性を確認。
- 用途像：温度域を鍵にした生体センシングやオンデマンド発光タグ。
2) SP側鎖をもつ Poly(2-isopropyl-2-oxazoline)（PIPOx-SP）
- 設計：主鎖にPIPOx、側鎖にSPを可変量導入して水溶液特性を解析。
- 知見：溶液の一部がメロシアニン（MC）形をとる条件でも、SP導入で雲点が低下。温度条件を最適化すると光で相転移が引き起こせる。
- 展望：疎水基を付与してミセル化すれば、光駆動ドラッグリリースへの展開が可能。
3) α-CD/α-CD-SP × PEGDA の高強度デュアル架橋ハイドロゲル
- 設計：PEGDA鎖がα-CD/α-CD-SPに包接してまず“物理ゲル”化→その後に光重合で共有結合ネットワーク化。
- 性能：通常のPEGゲル比で約15倍の引張強度、エネルギー散逸率 ~75%、繰返し荷重に強い。
- 機能：SP導入により、“UVで書く／可視で消す”発色パターンを空間・時間的に制御。
- 用途像：フレキシブル・ウェアラブルの表示素子や可逆情報メディア。
4) ポリロタキサンを用いた伸長型ハイドロゲルと光制御カスケードエネルギー移動
- 設計：Tween 80ミセルにMA・SP・NBDAE・Cy5を内包し、アクリルアミドと、ビニル修飾α-CDにPEGが貫通しアマンタジンで端止めしたポリロタキサンとin situ共重合。
- 力学：破断ひずみ ~1300%, 破断応力 ~0.26 MPaの高伸長・高靭性（すべり架橋点が寄与）。
- 発光制御：NBDAE→SP（一次受容体：効率~80%）→Cy5（二次受容体：~65%）のカスケード移動を光でチューニングし多色発光。
- 用途像：時分解型の偽造防止、動的マーカ、インタラクティブ表示。
用語ミニ解説
- スピロピラン（SP）：UVで開環して発色・蛍光性のメロシアニン（MC）に変化、可視光で閉環し元に戻る可逆フォトクロミック分子。
- シクロデキストリン（CD）：環状オリゴ糖。疎水性空洞にゲスト分子を取り込み、包接複合体やポリロタキサン（“輪”に鎖が通った構造）を形成。
- デュアル架橋：包接などの物理架橋＋共有結合架橋の二重ネットワーク。強度・耐久・エネルギー散逸を両立。
- VPTT：ハイドロゲルが体積相転移を起こす温度。ここをまたぐと発光・透過・力学が大きく変化。
想定アプリケーション
- スマートセンサー：温度・光・pHの多重応答を統合したウェアラブル／医療センシング。
- 情報記録・表示：書いて消せる発色・蛍光パターン、多色発光タグ、時限表示。
- セキュリティ：カスケードエネルギー移動を利用したタイムスタンプ型偽造防止。
- ドラッグデリバリー：光で相転移・ミセル崩壊を誘導し、放出制御。
関連キーワード（HPタグ）
#Cyclodextrin #αCD #Polyrotaxane #Spiropyran #Photochromism #Hydrogel #ThermoResponsive #DualCrosslink #EnergyTransfer #WearableSensor #AntiCounterfeiting #DrugDelivery
参考文献
- Zou, X.; Xiao, X.; Zhang, S.; Zhong, J.; Hou, Y.; Liao, L. A photo-switchable and thermal-enhanced fluorescent hydrogel prepared from N-isopropylacrylamide with water-soluble spiropyran derivative. Journal of Biomaterials Science, Polymer Edition 2018, 29(13), 1579–1594. DOI: 10.1080/09205063.2018.1475942.
- Machida, S.; Nakamura, Y.; Itaya, A.; Ikeda, N. Poly(2-isopropyl-2-oxazoline) Bearing a Spiropyran Side-Chain: Synthesis and Evaluation of Photo and Temperature-Responsive Properties. Macromolecular Chemistry and Physics 2019, 220(22), 1900240. DOI: 10.1002/macp.201900240.
- Wang, B.; Xiao, X.; Zhang, Y.; Liao, L. High strength dual-crosslinked hydrogels with photo-switchable color changing behavior. European Polymer Journal 2019, 116, 545–553. DOI: 10.1016/j.eurpolymj.2019.04.035.
- Zhang, H.; Zhang, Y.; Chen, Y.; Wang, S.-P.; Zhang, C.; Liu, Y. Polyrotaxane in-situ copolymerization stretchable supramolecular hydrogels for photo-controlled cascade energy transfer. European Polymer Journal 2023, 192, 112070. DOI: 10.1016/j.eurpolymj.2023.112070.
Light-Programmable Hydrogels Built from Cyclodextrin and Spiropyran
(Website summary — English version)
Overview
By combining the host–guest inclusion power of cyclodextrins (CDs) with the reversible photoisomerization of spiropyrans (SPs) (UV light opens to the colored/fluorescent merocyanine; visible light closes back), recent studies have created soft materials that respond to light and temperature, exhibit high mechanical toughness, and even write/erase color or fluorescence on demand. These features point to applications in wearable/biomedical sensors, rewritable displays, anti-counterfeiting tags, and light-triggered drug delivery.
Why it matters
- Dual responsiveness: Color/fluorescence switchable by UV/Vis; intensity and phase behavior tunable around the gel’s volume phase transition temperature (VPTT).
- Robust mechanics: Dual-crosslinked networks (physical inclusion + covalent crosslinks) deliver high tensile strength, energy dissipation, and fatigue resistance.
- Programmable phase behavior: SP incorporation lowers cloud point and enables photo-induced phase transitions in water.
- Optically gated energy flow: SP can act as a primary energy acceptor, enabling cascade Förster energy transfer and multicolor emission under light control.
- Biocompatibility (selected systems): Cytocompatible and photo-fatigue-resistant operation has been demonstrated.
Highlights by study
1) NIPAAm-based “photo-switchable / thermo-enhanced” fluorescent hydrogel
- Design: N-isopropylacrylamide network crosslinked with acryloyl-α-CD and acryloyl-α-CD–SP.
- Function: Reversible fluorescence ON/OFF by UV/Vis; stronger emission above VPTT.
- Notes: Shows excellent cytocompatibility and photo-fatigue resistance — promising for bio-sensing and tagging.
2) Spiropyran-grafted poly(2-isopropyl-2-oxazoline) (PIPOx–SP)
- Design: PIPOx main chain with tunable SP side-chain loading; behavior evaluated in water.
- Findings: SP lowers the cloud point; with optimized temperature, light can trigger phase transitions even when some groups are in the merocyanine form.
- Outlook: Adding hydrophobes to form micelles could realize light-driven drug release.
3) α-CD/α-CD–SP × PEGDA dual-crosslinked high-strength hydrogel
- Design: PEGDA threads into α-CD/α-CD–SP to form a physical gel, then photopolymerization creates a covalent network.
- Performance: ~15× the tensile strength of a pure PEG gel; high energy dissipation (~75%) and fatigue resistance.
- Feature: Rewritable patterns — write with UV, erase with visible light — with spatiotemporal control.
4) Polyrotaxane-based stretchable hydrogel with photo-controlled cascade energy transfer
- Design: Tween-80 micelles co-encapsulating MA, SP, NBDAE, Cy5; in-situ copolymerized with acrylamide and a polyrotaxane (PEG threaded through vinyl-modified α-CD; amantadine end-capped).
- Mechanics: ~1300% elongation and ~0.26 MPa breaking stress (sliding crosslinks help).
- Optical control: Light-tuned cascade transfer NBDAE → SP (~80%) → Cy5 (~65%), enabling multicolor, time-resolved emission for security labeling.
Mini-glossary
- Spiropyran (SP): Photochromic molecule switching between closed SP and open merocyanine (MC) with distinct color/fluorescence.
- Cyclodextrin (CD): Cyclic oligosaccharide with a hydrophobic cavity for host–guest inclusion; basis of polyrotaxane architectures.
- Dual-crosslinking: Combination of physical inclusion (CD–guest) and covalent crosslinks for toughness and durability.
- VPTT: Temperature at which a hydrogel undergoes a volume phase transition affecting optics and mechanics.
Potential applications
- Wearable/medical sensors: Multi-stimuli (light/temperature/pH) detection and readout.
- Rewritable displays & tags: UV-written / Vis-erased color or fluorescence.
- Security & anti-counterfeiting: Cascade energy-transfer signatures and time-stamped labels.
- Drug delivery: Light-triggered phase change or micelle disassembly for controlled release.
Suggested tags
#Cyclodextrin #αCD #Polyrotaxane #Spiropyran #Photochromism #Hydrogel #ThermoResponsive #DualCrosslink #EnergyTransfer #WearableSensor #AntiCounterfeiting #DrugDelivery
References
- Zou, X.; Xiao, X.; Zhang, S.; Zhong, J.; Hou, Y.; Liao, L. A photo-switchable and thermal-enhanced fluorescent hydrogel prepared from N-isopropylacrylamide with water-soluble spiropyran derivative. Journal of Biomaterials Science, Polymer Edition 2018, 29(13), 1579–1594. DOI: 10.1080/09205063.2018.1475942.
- Machida, S.; Nakamura, Y.; Itaya, A.; Ikeda, N. Poly(2-isopropyl-2-oxazoline) Bearing a Spiropyran Side-Chain: Synthesis and Evaluation of Photo- and Temperature-Responsive Properties. Macromolecular Chemistry and Physics 2019, 220(22), 1900240. DOI: 10.1002/macp.201900240.
- Wang, B.; Xiao, X.; Zhang, Y.; Liao, L. High strength dual-crosslinked hydrogels with photo-switchable color-changing behavior. European Polymer Journal 2019, 116, 545–553. DOI: 10.1016/j.eurpolymj.2019.04.035.
- Zhang, H.; Zhang, Y.; Chen, Y.; Wang, S.-P.; Zhang, C.; Liu, Y. Polyrotaxane in-situ copolymerization stretchable supramolecular hydrogels for photo-controlled cascade energy transfer. European Polymer Journal 2023, 192, 112070. DOI: 10.1016/j.eurpolymj.2023.112070.
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