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Xiong, Ruisheng
Publications (10 of 12) Show all publications
Xiong, R., Arkhypchuk, A. I. & Borbas, K. E. (2019). Attempted syntheses of N-confused hydroporphyrins through modified Lindsey routes. Journal of Porphyrins and Phthalocyanines, 23(4-5), 589-598
Open this publication in new window or tab >>Attempted syntheses of N-confused hydroporphyrins through modified Lindsey routes
2019 (English)In: Journal of Porphyrins and Phthalocyanines, ISSN 1088-4246, E-ISSN 1099-1409, Vol. 23, no 4-5, p. 589-598Article in journal (Refereed) Published
Abstract [en]

Unlike N-confused porphyrins which are well-known and extensively studied tetrapyrroles, N-confused hydroporphyrins are almost unknown, largely because so far they have resisted attempts at rational synthesis. Here, we report our efforts towards the total synthesis of N-confused hydroporphyrins. We have prepared N-confused building blocks analogous to the non-N-confused substrates in the Lindsey synthesis of sparsely substituted chlorins. We have systematically flipped the A, B and C pyrrole rings in the dipyrrolic precursors of the target N-confused macrocycles, preparing in total an N-confused "Western half' (tetrahydrodipyrrin) and two N-confused "Eastern halves" (brominated formyldipyrromethanes). These were subjected to a range of cyclization conditions. While we successfully isolated and identified three macrocyclic products, none of these proved to be the desired N-confused hydroporphyrin.

Place, publisher, year, edition, pages
WORLD SCI PUBL CO INC, 2019
Keywords
hydroporphyrins, N-confused tetrapyrroles, chlorins, 2+2 condensation, corrins
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-387228 (URN)10.1142/S1088424619500524 (DOI)000468181100026 ()
Funder
Swedish Research CouncilStiftelsen Olle Engkvist Byggmästare
Available from: 2019-06-20 Created: 2019-06-20 Last updated: 2019-06-20Bibliographically approved
Xiong, R., Mara, D., Liu, J., Van Deun, R. & Borbas, K. E. (2018). Excitation- and Emission-Wavelength-Based Multiplex Spectroscopy Using Red-Absorbing Near-Infrared-Emitting Lanthanide Complexes. Journal of the American Chemical Society, 140(35), 10975-10979
Open this publication in new window or tab >>Excitation- and Emission-Wavelength-Based Multiplex Spectroscopy Using Red-Absorbing Near-Infrared-Emitting Lanthanide Complexes
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2018 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 140, no 35, p. 10975-10979Article in journal (Refereed) Published
Abstract [en]

Multiplex imaging in the red and near-infrared (NIR) should be an enabling tool for the real-time investigation of biological systems. Currently available emitters have short luminescent lifetimes, broad absorption and emission bands, and small Stokes shifts, which limits multiplexing in this region to two colors. NIR-emitting luminescent lanthanide (Ln) complexes carrying hydroporphyrin (chlorin) sensitizing antennae are excitable in the red through the narrow, intense and tunable chlorin absorptions. Both emission- and excitation-based multiplexing are possible, the former by exciting the same antenna appended to different Lns, the latter by attaching different chlorins with nonoverlapping absorptions to the same Ln. The combination of excitation and emission spectroscopies allows for the straightforward differentiation of up to four different complexes.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-365657 (URN)10.1021/jacs.8b07609 (DOI)000444219100011 ()30122038 (PubMedID)
Funder
Swedish Research Council, 2013-4655
Available from: 2018-11-16 Created: 2018-11-16 Last updated: 2018-11-16Bibliographically approved
Xiong, R. & Erdelyi, M. (2018). Paramagnetic lanthanide tags for identifying ligand-protein binding site. In: : . Paper presented at 1ST NATIONAL MEETING OF THE SWEDISH CHEMICAL SOCIETY in Lund, 17-20 June 2018.
Open this publication in new window or tab >>Paramagnetic lanthanide tags for identifying ligand-protein binding site
2018 (English)Conference paper, Poster (with or without abstract) (Refereed)
Abstract [en]

Ligand-protein interactions are pivotal in living organisms. Knowing the binding sites of small-molecule ligands, especially low affinity ones, is an important step for modern drug discovery as it enables the development of high affinity lead compounds. Due to the lack of robust characterization approaches, the determination of weak binding is still cumbersome. We have reported a paramagnetic ligand tagging method by taking advantage of pseudo-contact shifts of protein NMR, which requires the ligand to be linked to a paramagnetic lanthanide complex.1 In this project we have improved the structure of our original paramagnetic tag to increase the accuracy of the NMR-based  structure determination as compared to our previously presented approach. 

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-355921 (URN)
Conference
1ST NATIONAL MEETING OF THE SWEDISH CHEMICAL SOCIETY in Lund, 17-20 June 2018
Funder
Swedish Research Council
Available from: 2018-07-09 Created: 2018-07-09 Last updated: 2018-07-09
Xiong, R. (2018). Paramagnetic ligand tagging to identify ligand-protein binding sites. In: : . Paper presented at EMBO Course: Multidimensional NMR in Structural Biology 2018.
Open this publication in new window or tab >>Paramagnetic ligand tagging to identify ligand-protein binding sites
2018 (English)Conference paper, Poster (with or without abstract) (Refereed)
Abstract [en]

Ligand-protein interactions are pivotal in living organisms. Knowing the binding sites of small-molecule ligands, especially low affinity ones, is an important step for modern drug discovery as it enables the development of high affinity lead compounds. Due to the lack of robust characterization approaches, the determination of weak binding is still cumbersome. We have reported a paramagnetic ligand tagging method by taking advantage of pseudo-contact shifts of protein NMR, which requires the ligand to be linked to a paramagnetic lanthanide complex.1 In this project we have improved the structure of our original paramagnetic tag to increase the accuracy of the NMR-based  structure determination as compared to our previously presented approach.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-357805 (URN)
Conference
EMBO Course: Multidimensional NMR in Structural Biology 2018
Funder
Swedish Research Council
Available from: 2018-08-21 Created: 2018-08-21 Last updated: 2018-08-21
Xiong, R. (2017). Development of Novel Hydroporphyrins for Light Harvesting and Sensitising NIR Lanthanide Luminescence. (Doctoral dissertation). Uppsala: Acta Universitatis Upsaliensis
Open this publication in new window or tab >>Development of Novel Hydroporphyrins for Light Harvesting and Sensitising NIR Lanthanide Luminescence
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Chlorins, as the core structures of chlorophylls, have been extensively studied for harvesting solar energy, fluorescent imaging and photodynamic therapy against cancer. This thesis is concerned with design and synthesis of novel chlorins as antennae for harvesting light and sensitising near infrared lanthanide luminescence.

In the first part, a series of chlorin monomers, dimers and polymers were synthesised and their photophysical properties were characterised. The chlorin monomers were substituted with five-membered heterocycles, such as thiophenes and furans. These heterocycles function as auxochromes analogous to the natural ones in chlorophylls, and extend chlorin absorption and emission strongly to the red (up to λem = 680 nm). A borylation method was developed to prepare borylated chlorins, which gave access to directly linked chlorin dimers through Suzuki coupling reaction. Different regioisomers of chlorin dimer were prepared, including β-meso homodimers, meso-meso homodimers and heterodimers. The dimerisation resulted in red-shifted absorption and emission. Chlorin polymerisations were performed both electrochemically and chemically. Bis-thienylchlorins yielded chlorin films and an organic solvent soluble copolymer with hexylthiophene, respectively. These polymers from both polymerisations have red absorptions beyond 700 nm, and might be used as light-harvesting antennae.

In the second part, chlorins were used as chromophores to sensitise near infrared lanthanide luminescence. Two types of chlorin-lanthanide dyads were prepared through lanthanide coordination with cyclen derivatives and dipicolinic acids (DPA). The cyclen-based dyads were poorly soluble in water, thus their near infrared emissions were not observed. The other type of complexes was fully soluble in H2O and THF. Both Nd and Yb emission were recorded even upon excitation into the Q bands of chlorins. In the dyads with free base chlorins, the singlet state of chlorins might be involved in the sensitisation of lanthanide luminescence. These DPA-based dyads presented two-color emission based on one chlorin and two-color excitation based on one lanthanide ion. These dyads would enable in theory 4-color imaging.

In the last part, a microwave-assisted two-step synthesis was described to prepare dipyrromethanes, which are the key intermediates in the chlorin synthesis. This mild method took advantage of the nucleophilicity of pyrrole and the electrophilicity of N,N-dimethylaminomethyl pyrroles. The usually used acid catalysis is detrimental to many functionalities, thus our methods enable the synthesis of dipyrromethanes with acid sensitive groups or a formyl group.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. p. 78
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1509
Keywords
chlorin, hydroporphyrin, chlorophyll analogues, light harvesting, lanthanide luminescence
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-319909 (URN)978-91-554-9898-6 (ISBN)
Public defence
2017-06-02, 2001, Ångstroöm laboratory, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2017-05-12 Created: 2017-04-10 Last updated: 2017-05-29
Xiong, R. & Borbas, K. E. (2017). Excitation- and emission-based multiplexing with near infrared-emitting luminescent lanthanide complexes using red-light excitation. Paper presented at 253rd National Meeting of the American-Chemical-Society (ACS) on Advanced Materials, Technologies, Systems, and Processes, APR 02-06, 2017, San Francisco, CA. Abstract of Papers of the American Chemical Society, 253
Open this publication in new window or tab >>Excitation- and emission-based multiplexing with near infrared-emitting luminescent lanthanide complexes using red-light excitation
2017 (English)In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 253Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2017
National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-377535 (URN)000430569104150 ()
Conference
253rd National Meeting of the American-Chemical-Society (ACS) on Advanced Materials, Technologies, Systems, and Processes, APR 02-06, 2017, San Francisco, CA
Available from: 2019-02-25 Created: 2019-02-25 Last updated: 2019-02-25Bibliographically approved
Xiong, R., Bornhof, A.-B., Arkhypchuk, A., Orthaber, A. & Borbas, E. (2017). Furan- and Thiophene-Based Auxochromes Red-shift Chlorin Absorptions and Enable Oxidative Chlorin Polymerizations. Chemistry - A European Journal, 23(17), 4089-4095
Open this publication in new window or tab >>Furan- and Thiophene-Based Auxochromes Red-shift Chlorin Absorptions and Enable Oxidative Chlorin Polymerizations
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2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 17, p. 4089-4095Article in journal (Refereed) Published
Abstract [en]

The de novo syntheses of chemically stable chlorins with five-membered heterocyclic (furane, thiophene, formylfurane and formylthiophene) substituents in selected meso- and beta-positions are reported. Heterocycle incorporation in the 3- and 13-positions shifted the chlorin absorption and emission to the red (up to lambdaem =680 nm), thus these readily incorporated substituents function analogously to auxochromes present in chlorophylls, for example, formyl and vinyl groups. Photophysical, theoretical and X-ray crystallographic experiments revealed small but significant differences between the behavior of the furan- and the thiophene-based auxochromes. Four regioisomeric bis-thienylchlorins (3,10; 3,13, 3,15 and 10,15) were oxidatively electropolymerized; the chlorin monomer geometry had a profound impact on the polymerization efficiency and the electrochemical properties of the resulting material. Chemical co-polymerization of 3,13-bis-thienylchlorin with 3-hexylthiophene yielded an organic-soluble red-emitting polymer.

Keywords
chlorins, electrochemistry, photophysics, polymerization, porphyrinoids
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-317978 (URN)10.1002/chem.201604655 (DOI)000399312700011 ()27859811 (PubMedID)
Funder
Stiftelsen Olle Engkvist ByggmästareSwedish Research Council, 2013-4655Swedish Research Council, 2013-4763
Available from: 2017-03-22 Created: 2017-03-22 Last updated: 2017-12-28Bibliographically approved
Bornhof, A.-B., Xiong, R. & Borbas, K. E. (2017). Rational Synthesis of 2-Bromoporphyrins and 2,12-Dibromoporphyrins. Journal of Organic Chemistry, 82(23), 12908-12913
Open this publication in new window or tab >>Rational Synthesis of 2-Bromoporphyrins and 2,12-Dibromoporphyrins
2017 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 82, no 23, p. 12908-12913Article in journal (Refereed) Published
Abstract [en]

Bromoporphyrins were prepared by the metal-mediated self-condensation of brominated 1-formyldipyrromethanes. Depending on the conditions, Mg(II)-2,12-dibromoporphyrin and Mg(II)-2-bromoporphyrin could be obtained in up to 11% and 17% isolated yield, respectively. Zn(II) was also a viable templating metal. The positions of the bromine substituents were confirmed by 2D-NMR spectroscopic analysis and the X-ray crystal structure of a derivative. Suzuki and Sonogashira reactions of the bromoporphyrins yielded 2-substituted or 2,12-disubstituted porphyrins with red-shifted absorption and emission spectra. This method provides access to the minimalist core of beta-mono- and beta,beta'-disubstituted porphyrins from readily available starting materials.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-343907 (URN)10.1021/acs.joc.7b02404 (DOI)000417342300100 ()
Funder
Swedish Research Council, 2013-4655
Available from: 2018-03-02 Created: 2018-03-02 Last updated: 2018-03-08Bibliographically approved
Xiong, R., Arkhypchuk, A. I., Kovacs, D., Orthaber, A. & Borbas, K. E. (2016). Directly linked hydroporphyrin dimers. Chemical Communications, 52(58), 9056-9058
Open this publication in new window or tab >>Directly linked hydroporphyrin dimers
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2016 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 52, no 58, p. 9056-9058Article in journal (Refereed) Published
Abstract [en]

Directly linked hydroporphyrin (chlorin) dimers were accessed regioselectively from bromochlorins. Versatile 15-borylated chlorins were prepared in excellent yield via Miyaura borylation. Suzuki coupling yielded meso-beta-linked homo- and heterodimers, and meso-blinked dimers. The photophysical and electrochemical properties of the dimers are reported.

National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:uu:diva-300581 (URN)10.1039/c6cc00516k (DOI)000379431000018 ()26859412 (PubMedID)
Funder
Swedish Research Council, 2013-4655Stiftelsen Olle Engkvist Byggmästare
Available from: 2016-08-09 Created: 2016-08-09 Last updated: 2017-11-28Bibliographically approved
Xiong, R. & Borbas, K. E. (2015). Mild Microwave-Assisted Synthesis of Dipyrromethanes and Their Analogues. Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, 26(4), 484-488
Open this publication in new window or tab >>Mild Microwave-Assisted Synthesis of Dipyrromethanes and Their Analogues
2015 (English)In: Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, ISSN 0936-5214, E-ISSN 1437-2096, Vol. 26, no 4, p. 484-488Article in journal (Refereed) Published
Abstract [en]

The Mannich reaction between pyrroles or indoles and Eschenmoser's salt (dimethylmethylideneammonium iodide) forms N,N-dimethylamino-methylated derivatives in good to excellent yields. The reaction is highly regioselective, and for pyrroles both 2- and 3-substituted derivatives could be obtained. The N,N-dimethylaminomethylpyrroles and indoles underwent substitution with pyrrole under microwave irradiation, affording the appropriate dipyrromethanes, N-confused, and indolo-dipyrromethanes in moderate to excellent overall yield.

Keywords
pyrroles, indoles, heterocycles, microwave synthesis, dipyrromethanes
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:uu:diva-248448 (URN)10.1055/s-0034-1378925 (DOI)000350059200010 ()
Available from: 2015-04-02 Created: 2015-03-30 Last updated: 2017-12-04Bibliographically approved
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