Si Wu

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Organization: Max Planck Institute for Polymer Research , Germany
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Title: (PhD)

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Co-reporter:Si Wu;Hans-Jürgen Butt
Physical Chemistry Chemical Physics 2017 vol. 19(Issue 35) pp:23585-23596
Publication Date(Web):2017/09/13
DOI:10.1039/C7CP01838J
Near-infrared (NIR) light is better suited than ultraviolet (UV) light for biomedical applications because it penetrates deeper into tissue and causes less photodamage to biological systems. The use of NIR light to control biointerfaces has attracted increasing interest. Here, we review NIR photoreactions at interfaces based on upconverting nanoparticles (UCNPs). UCNPs can convert NIR light to UV or visible light, which can then induce photoreactions of photosensitive compounds. This process is referred to as UCNP-assisted photochemistry. Recently, we and others demonstrated UCNP-assisted photochemistry at interfaces to control interfacial properties of nano-carriers, implants, emulsions, and cells. We introduce the fundamentals of UCNP-assisted photochemistry at interfaces, highlight its potential applications, and discuss remaining challenges.
Co-reporter:Dongsheng Wang;Dr. Manfred Wagner;Andrew K. Saydjari;Julius Mueller;Dr. Svenja Winzen; Dr. Hans-Jürgen Butt;Dr. Si Wu
Chemistry - A European Journal 2017 Volume 23(Issue 11) pp:2628-2634
Publication Date(Web):2017/02/21
DOI:10.1002/chem.201604634
AbstractWe synthesized a novel green-light-responsive tetra-ortho-isopropoxy-substituted azobenzene (ipAzo). Cis-ipAzo forms a strong host–guest complex with γ-cyclo dextrin (γ-CD) whereas trans-ipAzo binds weakly. This new photoresponsive host–guest interaction is reverse to the well-known azobenzene (Azo)/α-cyclodextrin (α-CD) complex, which is strong only between trans-Azo and α-CD. By combining the UV-light-responsive Azo/α-CD and green-light-responsive ipAzo/γ-CD host–guest complexes, a photoresponsive orthogonal supramolecular system is developed.
Co-reporter:Si Wu;Hans-Jürgen Butt
Advanced Materials 2016 Volume 28( Issue 6) pp:1208-1226
Publication Date(Web):
DOI:10.1002/adma.201502843

The near-infrared (NIR) region of the spectrum is called the “therapeutic window” because NIR light can penetrate deeply into tissue. Therefore, NIR-sensitive materials are attractive for biomedical applications. Recently, upconverting nanoparticles (UCNPs) were used to construct NIR-sensitive materials. UCNPs convert NIR light to UV or visible light, which can trigger photoreactions of photosensitive materials. Here, how to use UCNPs to construct NIR-sensitive materials is introduced, applications of NIR-sensitive materials with a focus on biomedical applications are highlighted, and the associated challenges are discussed.

Co-reporter:Wen Sun;Maria Parowatkin;Werner Steffen;Hans-Jürgen Butt;Volker Mailänder
Advanced Healthcare Materials 2016 Volume 5( Issue 4) pp:467-473
Publication Date(Web):
DOI:10.1002/adhm.201500827

The use of self-assembled nanostructures consisting of red-light-responsive Ru(II)-containing block copolymers (BCPs) for anticancer phototherapy is demonstrated. Three Ru-containing BCPs with different molecular weights are synthesized. Each BCP contains a hydrophilic poly(ethylene glycol) block and an Ru-containing block. In the Ru-containing block, more than half of the side chains are coordinated with [Ru(2,2′:6′,2′′-terpyridine)(2,2′-biquinoline)]2+, resulting in more than 40 wt% Ru complex in the BCPs. The Ru complex acts as both a red-light-cleavable moiety and a photoactivated prodrug. Depending on their molecular weights, the BCPs assemble into micelles, vesicles, and large compound micelles. All of the BCP assemblies are taken up by cancer cells. Red-light irradiation releases the Ru complex and generates singlet oxygen (1O2) in cancer cells. The released Ru complex and 1O2 inhibit the growth of cancer cells. Among the three BCP assemblies, the BCP micelle exhibits the most efficient cellular uptake and best anticancer performance.

Co-reporter:Dongsheng Wang and Si Wu
Langmuir 2016 Volume 32(Issue 2) pp:632-636
Publication Date(Web):December 23, 2015
DOI:10.1021/acs.langmuir.5b04399
Red-light-responsive supramolecular valves constructed by tetra-ortho-methoxy-substituted azobenzene (mAzo) and β-cyclodextrin (β-CD) were used to control drug release from mesoporous silica nanoparticles (MSNs). Doxorubicin (DOX) was used as a model drug and loaded into nanopores of mAzo modified MSNs. β-CD formed supramolecular valves with mAzo by host–guest interaction and closed the nanopores. Red light was able to open the supramolecular valves and induce DOX release even in deep tissue.
Co-reporter:Philipp Weis, Dongsheng Wang, and Si Wu
Macromolecules 2016 Volume 49(Issue 17) pp:6368-6373
Publication Date(Web):August 26, 2016
DOI:10.1021/acs.macromol.6b01367
Photoswitchable polymers are promising candidates for information storage. However, two general problems for photoswitchable polymers used in rewritable optical storage are photobleaching and inefficient switching processes in solid state. To overcome both of these obstacles, we demonstrate the synthesis of a new visible-light-switchable azobenzene-containing polymer (azopolymer) with nonstackable azo chromophores for reversible and stable information storage. The new azopolymer (PmAzo) contains ortho-methoxy-substituted azobenzene (mAzo) groups on the polymer side chains and shows reversible trans-to-cis or cis-to-trans isomerization by using distinct wavelengths of visible light. PmAzo is better suited for reversible optical storage than conventional UV-responsive azopolymers because visible light avoids the photodamage caused by UV light. Additionally, mAzo groups do not π–π stack in solid state, making photopatterning of PmAzo fully reversible. Moreover, photoinduced patterns on PmAzo can be stored for more than half a year. These properties distinguish PmAzo as a promising candidate for rewritable and stable information storage.
Co-reporter:Zhijun Chen;Shuqing He;Hans-Jürgen Butt
Advanced Materials 2015 Volume 27( Issue 13) pp:2203-2206
Publication Date(Web):
DOI:10.1002/adma.201405933
Co-reporter:Ying Zhou, Dongsheng Wang, Shilin Huang, Günter Auernhammer, Yujian He, Hans-Jürgen Butt and Si Wu  
Chemical Communications 2015 vol. 51(Issue 13) pp:2725-2727
Publication Date(Web):06 Jan 2015
DOI:10.1039/C4CC09672J
Reversible assembly of Janus particles was manipulated by host–guest interaction of β-cyclodextrin (β-CD) and azobenzene. One side of every Janus particle was modified with β-CD. Superstructures of Janus particles were formed by adding azobenzene-containing polymers to the dispersion of Janus particles. The superstructures were reversibly disassembled by adding α-CD or light irradiation.
Co-reporter:Shuqing He, Kristina Krippes, Sandra Ritz, Zhijun Chen, Andreas Best, Hans-Jürgen Butt, Volker Mailänder and Si Wu  
Chemical Communications 2015 vol. 51(Issue 2) pp:431-434
Publication Date(Web):11 Nov 2014
DOI:10.1039/C4CC07489K
Mesoporous silica coated upconverting nanoparticles are loaded with the anticancer drug doxorubicin and grafted with ruthenium complexes as photoactive molecular valves. Drug release was triggered by 974 nm light with 0.35 W cm−2. Such low light intensity minimized overheating problems and prevented photodamage to biological samples.
Co-reporter:Dongsheng Wang, Manfred Wagner, Hans-Jürgen Butt and Si Wu  
Soft Matter 2015 vol. 11(Issue 38) pp:7656-7662
Publication Date(Web):17 Aug 2015
DOI:10.1039/C5SM01888A
We report a novel red-light-responsive supramolecule. The tetra-ortho-methoxy-substituted azobenzene (mAzo) and β-cyclodextrin (β-CD) spontaneously formed a supramolecular complex. The substituted methoxy groups shifted the responsive wavelength of the azo group to the red light region, which is in the therapeutic window and desirable for biomedical applications. Red light induced the isomerization of mAzo and the disassembly of the mAzo/β-CD supramolecular complex. We synthesized a mAzo-functionalized polymer and a β-CD-functionalized polymer. Mixing the two polymers in an aqueous solution generated a supramolecular hydrogel. Red light irradiation induced a gel-to-sol transition as a result of the disassembly of the mAzo/β-CD complexes. Proteins were loaded in the hydrogel. Red light could control protein release from the hydrogel in tissue due to its deep penetration depth in tissue. We envision the use of red-light-responsive supramolecules for deep-tissue biomedical applications.
Co-reporter:Zhijun Chen;Wen Sun;Dr. Hans-Jürgen Butt ;Dr. Si Wu
Chemistry - A European Journal 2015 Volume 21( Issue 25) pp:9165-9170
Publication Date(Web):
DOI:10.1002/chem.201500108

Abstract

Upconverting nanoparticles (UCNPs) convert near-infrared (NIR) light into UV or visible light that can trigger photoreactions of photosensitive compounds. In this paper, we demonstrate how to reduce the intensity of NIR light for UCNP-assisted photochemistry. We synthesized two types of UCNPs with different emission bands and five photosensitive compounds with different absorption bands. A λ=974 nm laser was used to induce photoreactions in all of the investigated photosensitive compounds in the presence of the UCNPs. The excitation thresholds of the photoreactions induced by λ=974 nm light were measured. The lowest threshold was 0.5 W cm−2, which is lower than the maximum permissible exposure of skin (0.726 W cm−2). We demonstrate that low-intensity NIR light can induce photoreactions after passing through a piece of tissue without damaging the tissue. Our results indicate that the threshold for UCNP- assisted photochemistry can be reduced by using highly photosensitive compounds that absorb upconverted visible light. Low excitation intensity in UCNP-assisted photochemistry is important for biomedical applications because it minimizes the overheating problems of NIR light and causes less photodamage to biomaterials.

Co-reporter:Xiaowen Wang, Rüdiger Berger, Jagoba Iturri Ramos, Tao Wang, Kaloian Koynov, Guangming Liu, Hans-Jürgen Butt and Si Wu  
RSC Advances 2014 vol. 4(Issue 85) pp:45059-45064
Publication Date(Web):05 Sep 2014
DOI:10.1039/C4RA07623K
We present fabrication of patterned poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes with sub-100 nm features over large areas. The patterned polymer brushes are fabricated by a combination of block copolymer micelle lithography and surface-initiated atom transfer radical polymerization. The PDMAEMA brushes are neutralized and collapsed at pH 9, and positively charged and swollen at pH 4. The protein adsorption and desorption on the patterned PDMAEMA brushes are studied by laser scanning confocal microscopy, atomic force microscopy (AFM), and quartz crystal microbalance with dissipation (QCM-D). In 1 mM NaCl solution at pH 5.8, the patterned brushes take up bovine serum albumin (BSA, isoelectric point ∼4.8) via electrostatic interactions. BSA adsorbs both inside the brushes and at the outer edge of the brushes. BSA at the outer edge of the brushes is released by rinsing the brushes with 1 M NaCl solutions at pH 4 and 9. Part of the absorbed BSA remains trapped inside the brushes, resulting in an increase of their volume. The regular sub-100 nm features of the patterned PDMAEMA brushes allowed us to directly visualize protein adsorption/desorption by AFM on a nanoscale. The large area of the patterned brushes allowed us to collect statistical results of the nanostructures by QCM-D.
Co-reporter:Si Wu and Christoph Bubeck
Macromolecules 2013 Volume 46(Issue 9) pp:3512-3518
Publication Date(Web):April 24, 2013
DOI:10.1021/ma400104d
We fabricated block copolymer (BCP) supramolecules by hydrogen bonding various carboxyl- and phenol-containing azo compounds to the poly(4-vinylpyridine) blocks of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP). Thin films of the BCP supramolecules were prepared by spin-coating. Optical microscopy showed that all films of BCP supramolecules are macroscopically homogeneous immediately after spin-casting. To induce phase separation, all films were exposed to 1,4-dioxane vapor at room temperature. This solvent annealing caused always microphase separation between PS and P4VP-azo phases and sometimes also macrophase separation, i.e., azo compounds crystallized out of BCP matrices. The problem of macrophase separation in the BCP supramolecules is observed already at low concentrations of carboxyl-containing azo compounds. But phenol-containing azo compounds do not macrophase separate up to a molar ratio of azo compounds to repeat units of P4VP as large as 0.5. We conclude that self-associated hydrogen bonds of carboxylic groups and π–π stacking of azo chromophores are driving forces for macrophase separation.
Co-reporter:Si Wu, Jintang Huang, Stefan Beckemper, Arnold Gillner, Keyi Wang and Christoph Bubeck  
Journal of Materials Chemistry A 2012 vol. 22(Issue 11) pp:4989-4995
Publication Date(Web):01 Feb 2012
DOI:10.1039/C2JM16442F
We report the fabrication of hierarchical structures by combining bottom-up self-assembly of block copolymer supramolecular assemblies with top-down three-beam interference laser ablation methods. To fabricate the shorter length scale in the hierarchical structures, we use supramolecular assemblies (SMAs) of azobenzene compounds hydrogen bonded with poly(vinyl pyridine) blocks of polystyrene-block-poly(vinyl pyridine) block copolymers. The SMAs form phase separation nanostructures by solvent vapor annealing. The longer length scale of the hierarchical structures is fabricated by three-beam interference laser ablation on the phase separated nanostructures of the SMAs. The ablation process is induced by single laser shots with 35 ns pulse duration. Tuning of both length scales is feasible by changing the interference conditions and chemical composition of the SMAs, which enables efficient and straightforward fabrication of hierarchical photonic structures.
Co-reporter:Si Wu and Jintang Huang  
RSC Advances 2012 vol. 2(Issue 32) pp:12084-12087
Publication Date(Web):29 Oct 2012
DOI:10.1039/C2RA21932H
Hierarchically ordered structures are fabricated by laser irradiation on azobenzene-containing polymers through PDMS phase masks. The longer and shorter length scale structures of the hierarchical structures are interference patterns and self-organized nanostructures, respectively. The hierarchical structures are tunable by using different masks or changing the polarization of the laser.
Co-reporter:Yubing Xiong, Zhijun Chen, Hong Wang, Lisa-Maria Ackermann, Markus Klapper, Hans-Jürgen Butt and Si Wu
Chemical Communications 2016 - vol. 52(Issue 98) pp:NaN14160-14160
Publication Date(Web):2016/11/15
DOI:10.1039/C6CC08513J
A new method is described for fabricating autonomic, self-healing, deformable organogels. We combined imidazolium-based poly(ionic liquid) (PIL) and azobenzene-grafted poly(carboxylic acid) (PAA-Azo) in N,N-dimethyl formamide. Further, complexing PIL with unirradiated (trans) or irradiated (cis) PAA-Azo tuned the elastic modulus of the organogel.
Co-reporter:Zhijun Chen, Yubing Xiong, Roberto Etchenique and Si Wu
Chemical Communications 2016 - vol. 52(Issue 97) pp:NaN13962-13962
Publication Date(Web):2016/10/10
DOI:10.1039/C6CC05287H
Near-infrared light can be used to manipulate the pH of aqueous solutions by using upconverting nanoparticle-assisted photocleavage of a ruthenium complex photobase. Upconverting nanoparticles and the photobase were also introduced into a pH-responsive hydrogel, in which near-infrared irradiation induced swelling of the hydrogel.
Co-reporter:Shuqing He, Kristina Krippes, Sandra Ritz, Zhijun Chen, Andreas Best, Hans-Jürgen Butt, Volker Mailänder and Si Wu
Chemical Communications 2015 - vol. 51(Issue 2) pp:NaN434-434
Publication Date(Web):2014/11/11
DOI:10.1039/C4CC07489K
Mesoporous silica coated upconverting nanoparticles are loaded with the anticancer drug doxorubicin and grafted with ruthenium complexes as photoactive molecular valves. Drug release was triggered by 974 nm light with 0.35 W cm−2. Such low light intensity minimized overheating problems and prevented photodamage to biological samples.
Co-reporter:Ying Zhou, Dongsheng Wang, Shilin Huang, Günter Auernhammer, Yujian He, Hans-Jürgen Butt and Si Wu
Chemical Communications 2015 - vol. 51(Issue 13) pp:NaN2727-2727
Publication Date(Web):2015/01/06
DOI:10.1039/C4CC09672J
Reversible assembly of Janus particles was manipulated by host–guest interaction of β-cyclodextrin (β-CD) and azobenzene. One side of every Janus particle was modified with β-CD. Superstructures of Janus particles were formed by adding azobenzene-containing polymers to the dispersion of Janus particles. The superstructures were reversibly disassembled by adding α-CD or light irradiation.
Co-reporter:Si Wu, Jintang Huang, Stefan Beckemper, Arnold Gillner, Keyi Wang and Christoph Bubeck
Journal of Materials Chemistry A 2012 - vol. 22(Issue 11) pp:NaN4995-4995
Publication Date(Web):2012/02/01
DOI:10.1039/C2JM16442F
We report the fabrication of hierarchical structures by combining bottom-up self-assembly of block copolymer supramolecular assemblies with top-down three-beam interference laser ablation methods. To fabricate the shorter length scale in the hierarchical structures, we use supramolecular assemblies (SMAs) of azobenzene compounds hydrogen bonded with poly(vinyl pyridine) blocks of polystyrene-block-poly(vinyl pyridine) block copolymers. The SMAs form phase separation nanostructures by solvent vapor annealing. The longer length scale of the hierarchical structures is fabricated by three-beam interference laser ablation on the phase separated nanostructures of the SMAs. The ablation process is induced by single laser shots with 35 ns pulse duration. Tuning of both length scales is feasible by changing the interference conditions and chemical composition of the SMAs, which enables efficient and straightforward fabrication of hierarchical photonic structures.
1-(Cyanomethyl)-3-vinylimidazolium bromide
1-Hexanol, 6-[4-[(4-methylphenyl)azo]phenoxy]-
Benzeneethanol, 4-(phenylazo)-
1-Hexanol, 6-[4-[(1E)-(4-nitrophenyl)azo]phenoxy]-
(E)-4-((4-hydroxyphenyl)diazenyl)benzoic acid