Kamil Lang

Kamil Lang
Institute of Inorganic Chemistry of the Czech Academy of Sciences, Řež, Czech Republic · Department of Material Chemistry

Research Professor

About

186
Publications
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Publications

Publications (186)
Preprint
The unprecedented co-thermolysis of nido-decaborane (B10H14) and toluene results in a novel porous material (that we have named “Activated Borane”) containing micropores of 1.0 and 1.5 nm in diameter and a specific surface area of 774 m2 g-1 (Ar, 87 K) that is thermally stable up to 1000 oC. Solid-state 1H, 11B and 13C MAS NMR, UV-vis and IR spectr...
Article
X-Ray-induced photodynamic therapy represents a suitable modality for the treatment of various malignancies. It is based on the production of reactive oxygen species by radiosensitizing nanoparticles activated by X-rays. Hence, it allows overcoming the depth-penetration limitations of conventional photodynamic therapy and, at the same time, reducin...
Article
Photosensitizers, which produce singlet oxygen O2(¹Δg) under light irradiation, have attracted much attention due to their application potential in medicine and material science. In this respect, we recently reported on cationic metallocene complexes with pendant N-donor moieties, which exhibited enhanced luminescence in the solid-state originating...
Article
Despite the wide variety of strategies developed to combat pathogenic microorganisms, the infectious diseases they cause remain a worldwide health issue. Hence, the search for new disinfectants, which prevent infection spread, constitutes an extremely urgent task. One of the most promising methods is the use of photoactive compounds - photosensitiz...
Article
Diaryl and dialkyl phosphinic acids are diverse groups of ligands capable of bonding to a wide variety of metal ions. This review provides a brief overview of their synthesis methods, and summarizes various functions and binding motifs phosphinic acids can have in the area of materials chemistry. The combination of these characteristics allows for...
Article
X-ray-induced photodynamic therapy (X-PDT) has recently evolved into a suitable modality to fight cancer. This technique, which exploits radiosensitizers producing reactive oxygen species, allows for a reduction of the radiation dose needed to eradicate cancer in the frame of the radiotherapy treatment of deep tumors. The use of transition metal co...
Article
Full-text available
UiO-66 is a zirconium-based metal-organic framework (MOF) that has numerous applications. Our group recently determined that UiO-66 is not as inert in aqueous dispersions as previously reported in the literature. The present work therefore assessed the behaviour of UiO-66 in buffers: 2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS), 4-(2-hydroxyeth...
Article
We present the first examples of alkylated derivatives of the macropolyhedral boron hydride, anti-B18H22, which is the gain medium in the first borane laser. This new series of ten highly stable and colorless organic-inorganic hybrid clusters are capable of the conversion of UVA irradiation to blue light with fluorescence quantum yields of unity. T...
Article
Full-text available
The fight against infective microorganisms is becoming a worldwide priority due to serious concerns about the rising numbers of drug-resistant pathogenic bacteria. In this context, the inactivation of pathogens by singlet oxygen, O2(1Δg), produced by photosensitizers upon light irradiation has become an attractive strategy to combat drug-resistant...
Preprint
div> UiO-66 is a zirconium-based metal-organic framework (MOF) that has numerous applications. Our group recently determined that UiO-66 is not as inert in aqueous dispersions as previously reported in the literature. The present work therefore assessed the behaviour of UiO-66 in buffers: 2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS), 4-(2-hydro...
Article
Two new octahedral molybdenum cluster complexes act as an efficient singlet oxygen supplier in the context of the photodynamic therapy of cancer cells under blue-light irradiation. These complexes integrate the {Mo6I8}4+ core with 4'-carboxybenzo-15-crown-5 or cholate apical ligands and were characterized by 1H NMR, HR ESI-MS, and CHN elemental ana...
Article
Porous metal-organic frameworks (MOFs) have excellent characteristics for the adsorptive removal of environmental pollutants. Herein, we introduce a new series of highly stable MOFs constructed using Fe3+ and Al3+ metal ions and bisphosphinate linkers. The isoreticular design leads to ICR-2, ICR-6, and ICR-7 MOFs with a honeycomb arrangement of lin...
Article
Methylation of anti-B18H22 (1) affords the first example of alkyl substitution of terminal hydrogen atoms on the fluorescent octadecaborane-22 molecule to give highly methylated 2,2'-Cl2-1,1',3,3',4,4',7,7',8,8',10,10'-Me12-anti-B18H8 (2). This extensive chemical substitution leads to a swelling in the polyhedral volume of the 18-vertex boron atomi...
Preprint
Herein, we introduce a new series of highly stable MOFs, constructed using Fe<sup>3+</sup> and Al<sup>3+</sup> metal ions and bisphosphinate linkers. The isoreticular design leads to ICR-2, ICR-4, ICR-6, and ICR-7 MOFs with a honeycomb arrangement of linear pores, surface areas up to 1360 m<sup>2</sup> g<sup>-1</sup>, and high solvothermal stabilit...
Article
Full-text available
Recent studies have unraveled the potential of octahedral molybdenum cluster complexes (Mo6) as relevant red phosphors and photosensitizers of singlet oxygen, O2(1Δg), for photobiological applications. However, these complexes tend to hydrolyze in an aqueous environment, which deteriorates their properties and limits their applications. To address...
Article
Photoswitchable molecules have attracted wide interest for many applications in chemistry, physics, and materials science. In this work, we revisit the reversible photochemical and thermal rearrangements of the two B20H18²⁻ isomers reported by Hawthorne and Pilling in 1966, whose mechanism had not been understood so far. We investigate the rearrang...
Article
Treatment of the laser borane anti-B18H22 (compound 1) with iodine in ethanol gives the monoiodinated derivative 7-I-anti-B18H21 (compound 2) in 67% yield, or, by reaction with iodine or ICl in the presence of AlCl3 in dichloromethane, the diiodinated derivative 4,4'-I2-anti-B18H20 (compound 3) in 85% yield. On excitation with 360 nm light, both co...
Article
Full-text available
The first Ce(III)-based coordination polymer ICR-9 (ICR stands for Inorganic Chemistry Řež), with the formula Ce2(C8H10P2O4)3, containing ditopic phenylene-1,4-bis(methylphosphinic acid) linker, was synthetized under solvothermal conditions. The crystal structure, solved using electron diffraction tomography (EDT), revealed 2D layers of octahedrall...
Article
The spatiotemporal sensing of specific cationic and anionic species is crucial for understanding the processes occurring in living systems. Herein, we developed new fluorescence sensors derived from tetrapyrazinoporphyrazines (TPyzPzs) with a recognition moiety that consists of an aza-crown and supporting substituents. Their sensitivity and selecti...
Article
The development of water-soluble hexanuclear cluster complexes of low toxicity is a promising task due to their potential in biomedical applications such as bioimaging and photodynamic therapy. Herein, we present the syntheses of two new water-soluble hexarhenium cluster complexes with terminal amphiphilic phosphine ligands, and delineate their pho...
Article
Full-text available
Octahedral molybdenum cluster complexes have recently come forth as pertinent singlet oxygen photosensitizers towards biological applications. Still, their phototoxic efficiency in the absence of nanocarrier remains limited in reason of poor cellular uptake. Here, two cationic octahedral molybdenum cluster complexes, bearing carboxylate ligands wit...
Article
Despite the apparent diversity of the protocols developed for the synthesis of helicenes, they essentially follow the same strategy: the closure of one, or several, internal rings in a key step. Herein, we report the synthesis of a new family of the heterohelicenes consisting of fused silacyclopentadiene rings formed via a facile and novel process....
Article
Despite the apparent diversity of the protocols developed for the synthesis of helicenes, they essentially follow the same strategy: the closure of one, or several, internal rings in a key step. Herein, we report the synthesis of a new family of the heterohelicenes consisting of fused silacyclopentadiene rings formed via a facile and novel process....
Article
Full-text available
Nanosized porphyrin-containing metal-organic frameworks (MOFs) attract considerable attention as solid-state photosensitizers for biological applications. In this study, we have for the first time synthesised and characterised phosphinate-based MOF nanoparticles, nanoICR-2 (Inorganic Chemistry Rez). We demonstrate that nanoICR-2 can be decorated wi...
Article
Zirconium-based metal−organic frameworks were recently investigated as catalysts for degradation of organophosphate toxic compounds, such as pesticides or chemical warfare agents. The most utilized UiO-66 is considered as a stable material for these applications in an aqueous environment. However, the presented results indicate that the properties...
Article
The development of effective photosensitizers is particularly attractive for photodynamic therapy of cancer. Three novel porphyrin photosensitizers functionalized with phosphinic groups were synthesized and their physicochemical, photophysical, and photobiological properties were collected. Phosphinic acid groups (R1R2POOH) attached to the porphyri...
Article
Full-text available
Invited for the cover of this issue is Anton A. Ivanov, Mohamed Haouas, Stéphane Cordier, Pavel Abramov, Emmanuel Cadot, and co‐workers involved within the CLUSPOM‐CNRS International Laboratory, including the Nikolaev Institute of Inorganic Chemistry (Novosibirsk, Russia) University of Versailles Saint Quentin and University of Rennes 1 (France). T...
Article
Full-text available
Rhenium‐containing octahedral clusters [Re6Q8(CN)6]4− with Q=S, Se or Te exhibit high propensity to interact with γ‐cyclodextrin in aqueous solutions, leading to host–guest supramolecular assemblies, driven by the chaotropic nature of these ions. Encapsulation processes give rise to significant alterations of the intrinsic physical–chemical propert...
Article
Water‐soluble salts of anionic [Re6Q8(CN)6]4‐ (Q = S, Se, Te) chalcogenide octahedral rhenium clusters react with γ‐cyclodextrin (γ‐CD) producing a new type of inclusion compounds. Crystal structures determined through single‐crystal X‐ray diffraction analysis revealed supramolecular host‐guest assemblies resulting from close encapsulations of the...
Article
Full-text available
The use of radiosensitizers recently emerged as a promising approach to circumvent the depth penetration limitations of photodynamic therapy of cancer and to enhance radiotherapeutical effects. A widely explored current strategy is based on complex nanoarchitectures that facilitate the transfer of energy harvested from X-ray radiation by scintillat...
Article
Microbial colonization of biomedical devices is a recognized complication contributing to healthcare-associated infections. One of the possible approaches to prevent surfaces from the biofilm formation is antimicrobial photodynamic inactivation, based on the cytotoxic effect of singlet oxygen, O2(¹Δg), a short-lived, highly oxidative species, produ...
Article
Reaction of anti -B 18 H 221 with pyridine in neutral solvents gives sparingly soluble B 16 H 18 -3′,8′-Py 23a as the major product (ca. 53 %) and B 18 H 20 -6′,9′-Py 22 (ca. 15 %) as the minor...
Article
The singlet oxygen photogeneration, cellular uptake kinetics, subcellular localization and in vitro photoinduced oxidative stress, and the dark and photodynamic cytotoxicity of octahedral rhenium cluster complexes [{Re6Q8}(CN)6]⁴⁻, where Q = S, Se, Te, were investigated. The results have demonstrated that the complexes penetrate through cell membra...
Article
We report the synthesis and characterization of sulfonated polystyrene nanoparticles (average diameter 30 ± 14 nm) with encapsulated 5,10,15,20-tetraphenylporphyrin or ionically entangled tetracationic 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin, their photooxidation properties and the application of singlet oxygen-sensitized delayed fluo...
Article
We report intensive visible light radioluminescence upon X-ray irradiation of archetypal tetranuclear copper(I) iodide complexes containing triphenylphosphine or pyridine ligands in the solid state. These properties, attractive for the design of X-ray responsive materials, can be attributed to the heavy {Cu4I4} cubane-like core, the absence of oxyg...
Article
The photocytotoxic activity of porphyrin-containing materials including metal-organic frameworks (MOFs) has attracted ever increasing interest. We have developed a simple synthesis of hexagonal PCN-222/MOF-545 nanoparticles, which are powerful in inducing reactive oxygen species-mediated apoptosis of cancer cells upon visible light irradiation. The...
Article
Highly luminescent anisotropic materials are promising for light harvesting systems, sensors, solid lasers and optical devices. To achieve this, polyethylene glycol (PEG) was derivatized with a reactive rhodamine B (RhB) fluorophore to produce a luminescent, water-soluble and positively-charged polymer (RhPEG) that can be intercalated between layer...
Article
This paper reports the synthesis, characterization, and electrochemical performance of nickel-cobalt hydroxide nanosheets. The hydroxide nanosheets of approximately 0.7 nm thickness were prepared by delamination of layered nickel-cobalt hydroxide lactate in water and formed transparent colloids that were stable for months. The nanosheets were depos...
Article
B18H20(NC5H5)2 is a rare example of two conjoined boron hydride subclusters of nido and arachno geometrical character. At room temperature, solutions of B18H20(NC5H5)2 emit a 690 nm fluorescence. In the solid state, this emission is shifted to 620 nm and intensifies due to restriction of the rotation of the pyridine ligands. In addition, there is a...
Article
The design and preparation of highly active heterogeneous palladium catalysts is attracting ever-increasing attention. In this paper, we report on the self-assembly of palladium centers and an octahedral molybdenum cluster complex bearing phosphine terminal ligands. This leads to a coordination polymer exhibiting high catalytic activity in the Suzu...
Article
Novel non-toxic materials with antimicrobial surfaces are needed for medicinal applications. Potential alternatives for bacterial inactivation include materials that produce singlet oxygen, O2(1Δg), a short-lived, highly oxidative, and cytotoxic species. We synthesized a promising group of materials, porphyrin-based conjugated microporous polymers...
Article
A series of zinc azaphthalocyanines with two azacrowns in a rigid tweezer arrangement were prepared and the fluorescence sensing properties were investigated. The size-driven recognition of alkali and alkaline earth metal cations was significantly enhanced by the close cooperation of the two azacrown units, in which both donor nitrogen atoms need t...
Article
Newly synthesized octahedral molybdenum cluster compound (n-Bu4N)2[Mo6I8(OOC-1-adamantane)6] revealed uncharted features applicable for the development of X-ray inducible luminescent materials and sensitizers of singlet oxygen, O2((1)Δg). The compound exhibits a red-NIR luminescence in the solid state and in solution (e.g., quantum yield of 0.76 in...
Article
Full-text available
This review aims to summarize the current status of photoactivatable nanostructured film and polymeric nanofiber surfaces used in biomedical applications with emphasis on their photoantimicrobial activity, oxygen-sensing in biological media, light-triggered release of drugs, and physical or structural transformations. Many light-responsive function...
Article
This work describes the multistep Förster resonance energy transfer (FRET) among laser dyes adsorbed onto the nanoparticles of a layered silicate, saponite (Sap). Six cationic laser dyes with appropriate spectral properties to fit the resonance conditions were selected. Fluorescence spectroscopy proved cascade FRET in the experiments based on hybri...
Article
The main strategies to modify layered silicates with dyes have been based on ion exchange reactions. In this work, the modification was performed via the chemisorption of reactive rhodamine on the surface of kaolinite (Kaol) particles. The reactive dye (RhAptes) was synthesized via the reaction of rhodamine B (RhB) with 3-aminopropyl-triethoxy sila...
Article
A series of luminescent octahedral molybdenum cluster complexes were obtained by treating Na2[Mo6I8(OMe)6] with icosahedral closo-dicarbaborane C-carboxylic acids in refluxing tetrahydrofuran. The study of the photophysical properties of Na2[Mo6I8(1-OOC-1,2-closo-C2B10H11)6] (1), Na2[Mo6I8(1-OOC-1,7-closo-C2B10H11)6] (2), and Na2[Mo6I8(1-OOC-1,12-c...
Article
This Article presents the systematic experimental and theoretical investigation of the structural arrangements of dodecyl sulfate (DS) anions in the interlayer space of layered zinc hydroxide salts (LZH-DS) and of the structure of zinc hydroxide layers, with a detailed description of the zinc ions’ coordination environment. As-prepared, well-crysta...
Article
Phosphorescent hexamolybdenum cluster complexes with pyrene and anthracene carboxylates exhibit energy transfer from the grafted ligands to the {Mo 6I8} core. The complex with the pyrene ligands exhibits the highest brightness of emission ever reported for a Mo6 cluster complex excited in the near-UV region (355 = 2.3 105 M-1cm-1, L = 0.60). These...
Article
Full-text available
We report the preparation of monometallic Co(2+)/Co(3+) layered double hydroxide, intercalated with lactate anions (LCoH-Lactate), and its spontaneous delamination in water to form cobalt hydroxide nanosheets. These hydroxide nanosheets formed stable aqueous dispersions. The thickness of a nanosheet was estimated to be approximately 1 nm by atomic...
Article
Full-text available
Nanometric thin films were prepared by dip-coating and inkjet printing ZnO nanosheets on glass plates. The side-by-side alignment of the ZnO nanosheets on the substrate resulted in thin, transparent, oriented ZnO surfaces with the high-energy {001} facets exposed. The method of nanosheet deposition affected the film morphology; the dip-coated films...
Article
The bimetalladodecaborane cluster compound [(PMe2Ph)4Pt2B10H10] 1, quantitatively reacts with EtNC at room temperature to afford [{(EtNC)(PMe2Ph)3}(μ-EtNC)Pt2B10H10] 3 in which one molecule of EtNC replaces a terminal PMe2Ph ligand, and a second molecule of EtNC bridges the Pt–Pt vector. The metal-bridging EtNC molecule can be ejected from 3, eithe...
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Layered nickel hydroxides (LNHs), intercalated with lactate and nitrate anions, were synthesised using controlled precipitation and anion exchange methods. The present study reports a novel approach for the delamination of LNHs in water into nickel hydroxide nanosheets. The thickness of a single nanosheet varied between 0.7 and 1.0 nm with a latera...
Article
Full-text available
Samples representing two modifications of halloysites, dehydrated (7 Å) and hydrated (10 Å) forms, respectively, were examined with the aim to select suitable candidates for to be used as carriers of porphyrine photoactive molecules. The samples were analysed by powder X-ray diffraction (pXRD), infrared spectroscopy (FT-IR), and high resolution tra...
Article
The tuning of the photophysical properties of the highly fluorescent boron hydride cluster anti-B18H22 (1), by straightforward chemical substitution to produce 4,4'-(HS)2-anti-B18H20 (2), facilitates intersystem crossing from excited singlet states to a triplet manifold. This subsequently enhances O2((1)Δg) singlet oxygen production from a quantum...