TY  - JOUR
A1  - Tumir, Lidija-Marija
A1  - Pavlović Saftić, Dijana
A1  - Crnolatac, Ivo
A1  - Ban, Željka
A1  - Maslać, Matea
A1  - Griesbeck, Stefanie
A1  - Marder, Todd B.
A1  - Piantanida, Ivo
T1  - The nature of the (oligo/hetero)arene linker connecting two triarylborane cations controls fluorimetric and circular dichroism sensing of various ds-DNAs and ds-RNAs
JF  - Molecules
N2  - A series of tetracationic bis-triarylborane dyes, differing in the aromatic linker connecting two dicationic triarylborane moieties, showed very high submicromolar affinities toward ds-DNA and ds-RNA. The linker strongly influenced the emissive properties of triarylborane cations and controlled the fluorimetric response of dyes. The fluorene-analog shows the most selective fluorescence response between AT-DNA, GC-DNA, and AU-RNA, the pyrene-analog’s emission is non-selectively enhanced by all DNA/RNA, and the dithienyl-diketopyrrolopyrrole analog’s emission is strongly quenched upon DNA/RNA binding. The emission properties of the biphenyl-analog were not applicable, but the compound showed specific induced circular dichroism (ICD) signals only for AT-sequence-containing ds-DNAs, whereas the pyrene-analog ICD signals were specific for AT-DNA with respect to GC-DNA, and also recognized AU-RNA by giving a different ICD pattern from that observed upon interaction with AT-DNA. The fluorene- and dithienyl-diketopyrrolopyrrole analogs were ICD-signal silent. Thus, fine-tuning of the aromatic linker properties connecting two triarylborane dications can be used for the dual sensing (fluorimetric and CD) of various ds-DNA/RNA secondary structures, depending on the steric properties of the DNA/RNA grooves.
KW  - triarylborane
KW  - fluorescent probe
KW  - circular dichroism
KW  - DNA recognition
KW  - RNA recognition
Y1  - 2023
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-319322
SN  - 1420-3049
VL  - 28
IS  - 11
ER  - 
TY  - JOUR
A1  - Košćak, Marta
A1  - Pehar, Isabela
A1  - Božinović, Ksenija
A1  - Kole, Goutam Kumar
A1  - Sobočanec, Sandra
A1  - Podgorski, Iva I.
A1  - Pinterić, Marija
A1  - Müller-Buschbaum, Klaus
A1  - Majhen, Dragomira
A1  - Piantanida, Ivo
A1  - Marder, Todd B.
T1  - Para-N-methylpyridinium pyrenes: impact of positive charge on ds-DNA/RNA and protein recognition, photo-induced bioactivity, and intracellular localisation
JF  - Pharmaceutics
N2  - The 2- and 2,7- substituted para-N-methylpyridinium pyrene cations show high-affinity intercalation into ds-DNAs, whereas their non-methylated analogues interacted with ds-DNA/RNA only in the protonated form (at pH 5), but not at physiological conditions (pH 7). The fluorescence from non-methylated analogues was strongly dependent on the protonation of the pyridines; consequently, they act as fluorescence ratiometric probes for simultaneous detection of both ds-DNA and BSA at pH 5, relying on the ratio between intensities at 420 nm (BSA specific) and 520 nm (DNA specific), whereby exclusively ds-DNA sensing could be switched-off by adjustment to pH 7. Only methylated, permanently charged pyrenes show photoinduced cleavage of circular DNA, attributed to pyrene-mediated irradiation-induced production of singlet oxygen. Consequently, the moderate toxicity of these cations against human cell lines is strongly increased upon irradiation. Detailed studies revealed increased total ROS production in cells treated by the compounds studied, accompanied by cell swelling and augmentation of cellular complexity. The most photo-active 2-para-N-methylpyridinium pyrene showed significant localization at mitochondria, its photo-bioactivity likely due to mitochondrial DNA damage. Other derivatives were mostly non-selectively distributed between various cytoplasmic organelles, thus being less photoactive.
KW  - N-methylpyridinium pyrene
KW  - DNA sensing
KW  - protein sensing
KW  - singlet oxygen
KW  - photodynamic therapy
KW  - fluorescence
KW  - theranostics
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-297247
SN  - 1999-4923
VL  - 14
IS  - 11
ER  - 
TY  - JOUR
A1  - Zhang, Xiaolei
A1  - Friedrich, Alexandra
A1  - Marder, Todd B.
T1  - Copper-Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds
JF  - Chemistry—A European Journal
N2  - Herein, the copper-catalyzed borylation of readily available acyl chlorides with bis(pinacolato)diboron, (B\(_{2}\)pin\(_{2}\)) or bis(neopentane glycolato)diboron (B\(_{2}\)neop\(_{2}\)) is reported, which provides stable potassium acyltrifluoroborates (KATs) in good yields from the acylboronate esters. A variety of functional groups are tolerated under the mild reaction conditions (room temperature) and substrates containing different carbon-skeletons, such as aryl, heteroaryl and primary, secondary, tertiary alkyl are applicable. Acyl N-methyliminodiacetic acid (MIDA) boronates can also been accessed by modification of the workup procedures. This process is scalable and also amenable to the late-stage conversion of carboxylic acid-containing drugs into their acylboron analogues, which have been challenging to prepare previously. A catalytic mechanism is proposed based on in situ monitoring of the reaction between p-toluoyl chloride and an NHC-copper(I) boryl complex as well as the isolation of an unusual lithium acylBpinOBpin compound as a key intermediate.
KW  - boronate
KW  - catalysis
KW  - borylation
KW  - carbonyl
KW  - copper
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-318318
VL  - 28
IS  - 42
ER  - 
TY  - JOUR
A1  - Wu, Zhu
A1  - Dinkelbach, Fabian
A1  - Kerner, Florian
A1  - Friedrich, Alexandra
A1  - Ji, Lei
A1  - Stepanenko, Vladimir
A1  - Würthner, Frank
A1  - Marian, Christel M.
A1  - Marder, Todd B.
T1  - Aggregation-Induced Dual Phosphorescence from (o-Bromophenyl)-Bis(2,6-Dimethylphenyl)Borane at Room Temperature
JF  - Chemistry—A European Journal
N2  - Designing highly efficient purely organic phosphors at room temperature remains a challenge because of fast non-radiative processes and slow intersystem crossing (ISC) rates. The majority of them emit only single component phosphorescence. Herein, we have prepared 3 isomers (o, m, p-bromophenyl)-bis(2,6-dimethylphenyl)boranes. Among the 3 isomers (o-, m- and p-BrTAB) synthesized, the ortho-one is the only one which shows dual phosphorescence, with a short lifetime of 0.8 ms and a long lifetime of 234 ms in the crystalline state at room temperature. Based on theoretical calculations and crystal structure analysis of o-BrTAB, the short lifetime component is ascribed to the T\(^M_1\) state of the monomer which emits the higher energy phosphorescence. The long-lived, lower energy phosphorescence emission is attributed to the T\(^A_1\) state of an aggregate, with multiple intermolecular interactions existing in crystalline o-BrTAB inhibiting nonradiative decay and stabilizing the triplet states efficiently.
KW  - AIE
KW  - luminescence
KW  - phosphorescence
KW  - triarylborane
KW  - triplet
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-318297
VL  - 28
IS  - 30
ER  - 
TY  - JOUR
A1  - Wu, Zhu
A1  - Roldao, Juan Carlos
A1  - Rauch, Florian
A1  - Friedrich, Alexandra
A1  - Ferger, Matthias
A1  - Würthner, Frank
A1  - Gierschner, Johannes
A1  - Marder, Todd B.
T1  - Pure Boric Acid Does Not Show Room-Temperature Phosphorescence (RTP)
JF  - Angewandte Chemie
N2  - Boric acid (BA) has been used as a transparent glass matrix for optical materials for over 100 years. However, recently, apparent room-temperature phosphorescence (RTP) from BA (crystalline and powder states) was reported (Zheng et al., Angew. Chem. Int. Ed. 2021, 60, 9500) when irradiated at 280 nm under ambient conditions. We suspected that RTP from their BA sample was induced by an unidentified impurity. Our experimental results show that pure BA synthesized from B(OMe)\(_{3}\) does not luminesce in the solid state when irradiated at 250–400 nm, while commercial BA indeed (faintly) luminesces. Our theoretical calculations show that neither individual BA molecules nor aggregates would absorb light at >175 nm, and we observe no absorption of solid pure BA experimentally at >200 nm. Therefore, it is not possible for pure BA to be excited at >250 nm even in the solid state. Thus, pure BA does not display RTP, whereas trace impurities can induce RTP.
KW  - boric acid
KW  - room-temperature phosphorescence (RTP)
KW  - optical materials
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-318308
VL  - 61
IS  - 15
ER  - 
TY  - JOUR
A1  - Huang, Mingming
A1  - Hu, Jiefeng
A1  - Shi, Shasha
A1  - Friedrich, Alexandra
A1  - Krebs, Johannes
A1  - Westcott, Stephen A.
A1  - Radius, Udo
A1  - Marder, Todd B.
T1  - Selective, Transition Metal-free 1,2-Diboration of Alkyl Halides, Tosylates, and Alcohols
JF  - Chemistry-A European Journal
N2  - Defunctionalization of readily available feedstocks to provide alkenes for the synthesis of multifunctional molecules represents an extremely useful process in organic synthesis. Herein, we describe a transition metal-free, simple and efficient strategy to access alkyl 1,2-bis(boronate esters) via regio- and diastereoselective diboration of secondary and tertiary alkyl halides (Br, Cl, I), tosylates, and alcohols. Control experiments demonstrated that the key to this high reactivity and selectivity is the addition of a combination of potassium iodide and N,N-dimethylacetamide (DMA). The practicality and industrial potential of this transformation are demonstrated by its operational simplicity, wide functional group tolerance, and the late-stage modification of complex molecules. From a drug discovery perspective, this synthetic method offers control of the position of diversification and diastereoselectivity in complex ring scaffolds, which would be especially useful in a lead optimization program.
KW  - organic synthesis
KW  - boronate esters
KW  - alkyl halides
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-318262
VL  - 28
IS  - 24
ER  - 
TY  - JOUR
A1  - Barak, Arvind
A1  - Dhiman, Nishant
A1  - Sturm, Floriane
A1  - Rauch, Florian
A1  - Lakshmanna, Yapamanu Adithya
A1  - Findlay, Karen S.
A1  - Beeby, Andrew
A1  - Marder, Todd B.
A1  - Umapathy, Siva
T1  - Excited‐State Intramolecular Charge‐Transfer Dynamics in 4‐Dimethylamino‐4′‐cyanodiphenylacetylene: An Ultrafast Raman Loss Spectroscopic Perspective
JF  - ChemPhotoChem
N2  - Photo‐initiated intramolecular charge transfer (ICT) processes play a pivotal role in the excited state reaction dynamics in donor‐bridge‐acceptor systems. The efficacy of such a process can be improved by modifying the extent of π‐conjugation, relative orientation/twists of the donor/acceptor entities and polarity of the environment. Herein, 4‐dimethylamino‐4′‐cyanodiphenylacetylene (DACN‐DPA), a typical donor‐π‐bridge‐acceptor system, was chosen to unravel the role of various internal coordinates that govern the extent of photo‐initiated ICT dynamics. Transient absorption (TA) spectra of DACN‐DPA in n‐hexane exhibit a lifetime of >2 ns indicating the formation of a triplet state while, in acetonitrile, a short time‐constant of ∼2 ps indicates the formation of charge transferred species. Ultrafast Raman loss spectroscopy (URLS) measurements show distinct temporal and spectral dynamics of Raman bands associated with C≡C and C=C stretching vibrations. The appearance of a new band at ∼1492 cm\(^{−1}\) in acetonitrile clearly indicates structural modification during the ultrafast ICT process. Furthermore, these observations are supported by TD‐DFT computations.
KW  - charge transfer
KW  - ultrafast Raman loss spectroscopy
KW  - 4-dimethylamino-4′-cyanodiphenylacetylene
KW  - transient absorption
KW  - TD-DFT
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-312280
VL  - 6
IS  - 12
ER  - 
TY  - JOUR
A1  - Jos, Swetha
A1  - Szwetkowski, Connor
A1  - Slebodnick, Carla
A1  - Ricker, Robert
A1  - Chan, Ka Lok
A1  - Chan, Wing Chun
A1  - Radius, Udo
A1  - Lin, Zhenyang
A1  - Marder, Todd B.
A1  - Santos, Webster L.
T1  - Transition Metal‐Free Regio‐ and Stereo‐Selective trans Hydroboration of 1,3‐Diynes: A Phosphine‐Catalyzed Access to (E)‐1‐Boryl‐1,3‐Enynes
JF  - Chemistry – A European Journal
N2  - We report a transition metal‐free, regio‐ and stereo‐selective, phosphine‐catalyzed method for the trans hydroboration of 1,3‐diynes with pinacolborane that affords (E)‐1‐boryl‐1,3‐enynes. The reaction proceeds with excellent selectivity for boron addition to the external carbon of the 1,3‐diyne framework as unambiguously established by NMR and X‐ray crystallographic studies. The reaction displays a broad substrate scope including unsymmetrical diynes to generate products in high yield (up to 95 %). Experimental and theoretical studies suggest that phosphine attack on the alkyne is a key process in the catalytic cycle.
KW  - enediyne
KW  - enyne
KW  - hydroboration
KW  - organocatalytic
KW  - stereoselective
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-293784
VL  - 28
IS  - 63
ER  - 
TY  - JOUR
A1  - Kole, Goutam Kumar
A1  - Košćak, Marta
A1  - Amar, Anissa
A1  - Majhen, Dragomira
A1  - Božinović, Ksenija
A1  - Brkljaca, Zlatko
A1  - Ferger, Matthias
A1  - Michail, Evripidis
A1  - Lorenzen, Sabine
A1  - Friedrich, Alexandra
A1  - Krummenacher, Ivo
A1  - Moos, Michael
A1  - Braunschweig, Holger
A1  - Boucekkine, Abdou
A1  - Lambert, Christoph
A1  - Halet, Jean‐François
A1  - Piantanida, Ivo
A1  - Müller‐Buschbaum, Klaus
A1  - Marder, Todd B.
T1  - Methyl Viologens of Bis‐(4’‐Pyridylethynyl)Arenes – Structures, Photophysical and Electrochemical Studies, and their Potential Application in Biology
JF  - Chemistry – A European Journal
N2  - A series of bis‐(4’‐pyridylethynyl)arenes (arene=benzene, tetrafluorobenzene, and anthracene) were synthesized and their bis‐N‐methylpyridinium compounds were investigated as a class of π‐extended methyl viologens. Their structures were determined by single crystal X‐ray diffraction, and their photophysical and electrochemical properties (cyclic voltammetry), as well as their interactions with DNA/RNA were investigated. The dications showed bathochromic shifts in emission compared to the neutral compounds. The neutral compounds showed very small Stokes shifts, which are a little larger for the dications. All of the compounds showed very short fluorescence lifetimes (<4 ns). The neutral compound with an anthracene core has a quantum yield of almost unity. With stronger acceptors, the analogous bis‐N‐methylpyridinium compound showed a larger two‐photon absorption cross‐section than its neutral precursor. All of the dicationic compounds interact with DNA/RNA; while the compounds with benzene and tetrafluorobenzene cores bind in the grooves, the one with an anthracene core intercalates as a consequence of its large, condensed aromatic linker moiety, and it aggregates within the polynucleotide when in excess over DNA/RNA. Moreover, all cationic compounds showed highly specific CD spectra upon binding to ds‐DNA/RNA, attributed to the rare case of forcing the planar, achiral molecule into a chiral rotamer, and negligible toxicity toward human cell lines at ≤10 μM concentrations. The anthracene‐analogue exhibited intracellular accumulation within lysosomes, preventing its interaction with cellular DNA/RNA. However, cytotoxicity was evident at 1 μM concentration upon exposure to light, due to singlet oxygen generation within cells. These multi‐faceted features, in combination with its two‐photon absorption properties, suggest it to be a promising lead compound for development of novel light‐activated theranostic agents.
KW  - cell imaging
KW  - DNA/RNA binding
KW  - methyl viologen
KW  - singlet oxygen
KW  - two-photon absorption
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-287126
VL  - 28
IS  - 40
ER  - 
TY  - JOUR
A1  - Ban, Željka
A1  - Karačić, Zrinka
A1  - Tomić, Sanja
A1  - Amini, Hashem
A1  - Marder, Todd B.
A1  - Piantanida, Ivo
T1  - Triarylborane dyes as a novel non-covalent and non-inhibitive fluorimetric markers for DPP III enzyme
JF  - Molecules
N2  - Novel dyes were prepared by simple “click CuAAC” attachment of a triarylborane–alkyne to the azide side chain of an amino acid yielding triarylborane dye 1 which was conjugated with pyrene (dye 2) forming a triarylborane–pyrene FRET pair. In contrast to previous cationic triarylboranes, the novel neutral dyes interact only with proteins, while their affinity to DNA/RNA is completely abolished. Both the reference triarylborane amino acid and triarylborane–pyrene conjugate bind to BSA and the hDPP III enzyme with high affinities, exhibiting a strong (up to 100-fold) fluorescence increase, whereby the triarylborane–pyrene conjugate additionally retained FRET upon binding to the protein. Furthermore, the triarylborane dyes, upon binding to the hDPP III enzyme, did not impair its enzymatic activity under a wide range of experimental conditions, thus being the first non-covalent fluorimetric markers for hDPP III, also applicable during enzymatic reactions with hDPP III substrates.
KW  - triarylborane
KW  - pyrene
KW  - click CuAAC synthesis
KW  - DPP III enzyme
KW  - BSA
KW  - fluorescence
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-245046
SN  - 1420-3049
VL  - 26
IS  - 16
ER  -