About
94
Publications
7,394
Reads
How we measure 'reads'
A 'read' is counted each time someone views a publication summary (such as the title, abstract, and list of authors), clicks on a figure, or views or downloads the full-text. Learn more
2,396
Citations
Introduction
Publications
Publications (94)
Supramolecular recognition of nucleobases and short sequences is an emerging research field focusing on possible applications to treat many diseases. Controlling the affinity and selectivity of synthetic receptors to target desired nucleotides or short sequences is a highly challenging task. Herein, we elucidate the effect of substituents in the ph...
Self-assembly of triazatriangulenium dyes (TATA) bearing C3-C8 substituents and their interaction with aromatic compounds were studied. The dyes with alkyl chains longer than C5 were strongly aggregated in solution, while those with shorter alkyl chains formed hetero-stacks with aromatic compounds in chloroform. Anthracene, pyrene, coronene, and a...
Nucleoside monophosphates perform various essential functions and serve as second messengers in living systems. Despite the success of nucleotide‐selective probes based on proteins, the creation of synthetic receptors for nucleoside monophosphates remains a challenging task. In this paper, we explore the design of synthetic receptors based on a com...
Supramolecular recognition of nucleotides would enable manipulating crucial biochemical pathways like transcription and translation directly and with high precision. Therefore, it offers great promise in medicinal applications, not least in treating cancer or viral infections. This work presents a universal supramolecular approach to target nucleos...
Recognition of anions by synthetic receptors is an integral part of supramolecular chemistry continuing to expand and find new application areas in our daily life. Many applications require visualization of anion recognition events, and the generated analytical signal is used to quantify anions in solution. Transferring a binding event to a measure...
The design of high‐affinity synthetic host‐guest complexes is of paramount importance because they are key elements in constructing unprecedented supramolecular assemblies, functional materials, molecular probes, artificial signal transduction events, and interfaces with the biological world. The present review article collects recent achievements...
Tandem bond activation: The dual Lewis acidity of alumina has been discovered and employed to activate C−F and triple C≡C bonds in a tandem manner to provide rapid access to elusive nonplanar PAHs such as π‐extended helicenes, buckybowls and fragments of geodesic nanoribbons. More information can be found in the Research Article by K. Amsharov and...
We have discovered a dual (i. e., soft and hard) Lewis acidity of alumina that enables rapid one‐pot π‐extension through the activation of terminal alkynes followed by C−F activation. The tandem reaction introduces an acenaphthene fragment – an essential moiety of geodesic polyarenes. This reaction provides quick access to elusive non‐alternant pol...
A novel strategy to design “turn-on” fluorescent receptors for G-quadruplexes of DNA is presented, which relies on the connection of phosphate binding macrocycles (PBM) with naphthalimide dyes. A new PBM-dye...
Supramolecular recognition of perrhenate is a challenging task due to therelatively large size and low charge density of this anion. In this work, we design and synthesize a family of helix-like synthetic receptors that can bind perrhenate by forming hydrogen bonds with all four oxygen atoms of the anion. Among the investigated rigid helix-forming...
Selective recognition of nucleotides with synthetic receptors is an emerging direction to solve a series of nucleic acid-related challenges in biochemistry. Towards this goal, a new aza-cyclophane with two different dyes, naphthalimide and pyrene, connected through a triamine linker has been synthesized and studied for the ability to bind and detec...
The beginning of the 21st century was marked by the intensive development of fiber‐optic sensors. New functional materials with excellent sensory properties are required to design such sensors. Fluorescent probes for neutral and charged molecules are constantly developing. However, only a small part of the reported probes was successfully converted...
Pyrene‐based cyclophanes have been synthesized with the aim to realize a bellows‐type sensing mechanism for the ratiometric detection of nucleotide concentrations in a buffered aqueous solution. The sensing mechanism involves the encapsulation of a nucleobase between two pyrene rings, which affects the monomer‐excimer equilibrium of the receptor in...
The cover feature illustrates the mechanism of ATP detection by a new fluorescent receptor in aqueous solution. The receptor works like bellows: it exists in solution in a stacked form but opens only for binding of ATP. Moreover, the receptor represent an example of a ratiometric probe, which changes its color from yellow to blue upon ATP recogniti...
Control of a receptor isomerization bearing multiple light-switchable subunits in a confined space is critical for the design of synthetic molecular machines. Towards this goal, a new azacryptand containing three azobenzene subunits has been developed and its photoisomerization in aqueous solution has been studied depending on anion coordination an...
Phosphonates have found a broad commercial applications as scale inhibitors in reverse osmosis facilities, boilers, heat exchangers, evaporation plants, and oilfield. Irrespective of a long term use, there is a cogent need to detect phosphonates in aqueous solution “on line” to control their actual concentration in industrial water treatment. Towar...
Novel naphthalimide-functionalized bisphosphonates with different spacer length have been designed and synthesized. The spectroscopic properties, dissociation constants and complexation behavior with calcium(II) have been studied in aqueous solution. It has been shown that the length of the spacer has a dramatic effect on the fluorescence, Ca²⁺ bin...
Invited for this month's cover picture is the group of Evgeny A. Kataev at the Technical University Chemnitz. The cover picture shows the authors’ association of fluorescence anion sensing with pearl hunting – the activity of recovering pearls from wild molluscs. In the presented work, the group of Kataev has developed a new water‐soluble amido‐ami...
The Front Cover shows the authors’ association of fluorescence anion sensing with pearl hunting – the activity of recovering pearls from wild molluscs. In the presented work, the group of Kataev has developed a new water‐soluble amido‐amine azacryptand bearing a fluorescence anthracene dicarboxamide fragment. With the help of the fluorescent recept...
A new amido−amine cage receptor, which combines 1,8‐anthracene diacarboxamide subunit and a polyammonium azamacrocycle, is reported. Bearing both the hydrogen bond donor and the acceptor binding sites, the receptor is able to bind phosphate selectively under neutral (pH 7.2) aqueous conditions. The recognition events for phosphate and dicarboxylate...
Herein we describe the design, synthesis, and anion binding properties of bicyclic receptors with two or three anthracenes, which show a turn-on fluorescence response in the presence of nitrate and chaotropic anions in a buffered aqueous solution. The receptor with two anthracenes binds nitrate with 103 M-1 affinity and stabilizes it in the inner c...
Amido-amine macrocycles with two and four naphthalimide dyes were designed to bind nucleoside monophosphates and oligonucleotides in aqueous buffered solution. Anion-templated synthesis was used to direct the macrocyclization reaction to the 2+2 product, while high dilution conditions favored the formation of the 4+4 macrocycle with an unprecedente...
Three anthracene‐based cyclophanes were synthesized and their binding properties towards nucleoside triphosphates were studied. A new polycyclic amine derived from dearomatized anthracene was identified as a major side product in the cyclization reaction between 9,10‐anthracenedicarboxaldehyde and diethylenetriamine. Its structure was determined by...
Cyclophanes with two anthracene rings can bind nucleoside triphosphates in aqueous solution. We have found that the five natural nucleotides produce not only different fluorescence responses upon binding to receptors, but also show different binding modes. For instance, TTP is bound though phosphate, while UTP forms stacking interactions with the a...
Nucleotides are constituents of nucleic acids and they have a variety of functions in cellular metabolism. Synthetic receptors and sensors are required to reveal the role of nucleotides in living organisms and mechanisms of signal transduction events. In recent years, a large number of nucleotide‐selective synthetic receptors have been devised, whi...
1. Fundamental Physics and Chemistry of Tc and Re.
Chairs : K.E. German and Masaki Ozawa
Roald Hoffmann. MESSAGE TO INTERNATIONAL SYMPOSIUM ON TECHNETIUM
AND RHENIUM SCIENCE AND UTILIZATION, 2018
Aleksey Buryak. WELCOME ADDRESS FROM IPCE - RUSSIAN ACADEMY OF
SCIENCES
Andrey Romanov. WELCOME ADDRESS FROM THE MINISTRY OF SCIENCE AND
HIGHER EDUCATION...
Long-lived 99Tc has the spin of the nucleus 9/2, so it is an NMR active isotope. Thus, 99Tc- NMR can be applied to investigations in chemistry and nuclear medicine. Some recent advances are summarized in an excellent review by Farnan and Berthon [1]. Here we present new results on Tc speciation and analyses. Tc speciation was investigated the in H2...
Receptors bearing hydrogen and halogen bond donors for recognition of perrhenate and pertechnetate were designed and studied. Acyclic hosts with N-H and C-H binding sites showed the best selectivity for...
Synthesis and anion binding properties of hybrid macrocycles containing ammonium and hydrogen bond donor groups are reported. Receptor properties were studied in a 10 mM MES buffer solution at pH 6.2, at which the receptors carry two positive charges at the secondary amine groups. Receptor 1 was found to bind fluoride with the highest affinity (105...
Much like catching a star in the night sky, selective recognition of sulfate anions in an aqueous solution remains a challenge in chemistry. Herein, the design and synthesis of a bright fluorescent sensor for sulfate is reported. Non-covalent interactions that contribute to the formation of receptor–sulfate complex were also studied to understand t...
A straightforward design of receptors for binding and sensing of sulfate in aqueous medium was developed. The design involves the connection of two naphthalimide-based pH-probes through a hydrogen-bonding motif. The structure of the receptor-sulfate complex, predicted by DFT calculations, was unambiguously confirmed by NMR measurements. There are t...
Bicyclic receptors bearing anthracene as a strap were designed for selective oxalate binding in a buffered aqueous solution. The receptors were found to possess two mechanisms of fluorescence response depending...
New naphthalimide-based receptors for anions have been synthesized. Efficient synthetic routes have been found to functionalize the naphthalimide core with branched polyamines. Binding and sensing properties of the receptors have been studied by potentiometric, NMR and fluorescence titrations. The receptors bind selectively the pyrophosphate anion...
Design of PET probes for anions working in an aqueous buffered solution is described. The design has been used to develop selective fluorescent probes for sulfate and pyrophosphate. The relationship between receptors selectivity towards anions, their conformation, fluorescnece response and the pH of the solution have been studied in detail.
Poly(cyclic) oxamates represent novel and potentially multidentate ligands for coordination chemistry. To obtain them, the treatment of 2-nitroaniline with two equivalents of oxalyl chloride afforded N,N′-bis(2-nitrophenyl)oxalamide (1), and by reduction of 1 with [NH4][CO2H] and Pd/C, N,N′-bis(2-aminophenyl)oxalamide (2, bapoxH6) was synthesized....
A receptor containing amidopyrrole binding subunits and free amino groups, conjugated to a naphthalimide dye, has been designed and synthesized. The intrinsic selectivity of the binding motif for phosphate present in DMSO completely disappears in 10 % DMSO aqueous buffer at pH 3.6, at which the receptor is protonated. The electrostatic interactions...
Stacking interactions between aromatic compounds and nucleobases are crucial in recognition of nucleotides and nucleic acids, but a comprehensive understanding of the strength and selectivity of these interactions in aqueous solution has been elusive. To this end, model complexes have been designed and analyzed by experiment and theory. For the fir...
The synthesis of macrocycles, which proceeds with the help of inter- or intramolecular non-covalent interactions, is discussed. Three groups of interactions are considered: precursor–anionic template, precursor–cationic template, and intramolecular hydrogen bonds formed during the reaction. These interactions have been suggested or found to have a...
Sensing of chloride in aqueous solution with high selectivity is a challenging task and has a great potential for cellular imaging and analytical applications in food chemistry. Supramolecular binding motif calix[4]pyrrole has been conjugated with a known fluorescent probe for chloride – a quinolinium dye - through conformationally flexible and rig...
An efficient and green method has been developed for the synthesis of kojic acid derivatives by employing 20 mol% β-cyclodextrin in aqueous media. The high functional group tolerance and shorter reaction times make this method suitable for the synthesis of kojic acid derivatives with a wide substitution pattern.
Complexation of 4-amino-1,8-naphthalimide derivative containing an aza-15-crown-5 ether receptor unit in the N-aryl substituent at the imide nitrogen atom of the naphthalimide core with alkaline earth metal cations was studied using optical and NMR spectroscopy. The binding of the cations with crown ether receptors was accompanied by signifacant fl...
Cyclo[8]pyrrole, an octapyrrolic expanded porphyrin with no meso-linking atoms, was found to interact with a series of anions in the solid state and in a chloroform solution. The anion selectivities have been determined relative to a structurally characterised salt, H2cyclo[8]pyrrole2+·I− ·I3 − , via counter anion exchange. Although cyclo[8]pyrrole...
Phosphates are ubiquitous in biology and nearly half of all proteins interact with their partners by means of recognition of phosphate residues. Therefore, a better understanding of the phosphate ion binding by peptidic structures is highly desirable. Two new receptors have been designed and synthesized and their anion binding properties in an acet...
Receptors based on guanidinium- and pyrrole-containing binding sites were designed and synthesized for selective recognition of orthophosphate in aqueous solution. Various analytical techniques were used to understand solution behavior and anion binding properties of the receptors in methanol and methanol/water mixtures. Binding studies revealed th...
Inorganic anions were used as templates in the reaction between a diamine and an activated diacid to form macrocyclic amides. The reaction conditions were found to perform the macrocyclization sufficiently slow to observe a template effect. A number of analytical methods were used to clarify the reaction mechanisms and to show that the structure of...
Fluorescent ligands have been designed to form ternary complexes with a Cu(II) cation and phosphates in a buffer solution at physiological pH 7.4. It has been shown that a combination of two different ligands and CuCl(2) allows one to achieve high adenosine triphosphate/adenosine diphosphate, adenosine 5'-monophosphate selectivity, and ratiometric...
Phosphate esters are essential to any living organism and their specific hydrolysis plays an important role in many metabolic processes. As phosphodiester bonds can be extraordinary stable, as in DNA, great effort has been put into mimicking the active sites of hydrolytic enzymes which can easily cleave these linkages and were often found to contai...
The design and synthesis of a neutral macrocyclic host that is capable of perrhenate and pertechnetate recognition is described. The anion affinities and underlying coordination modes were estimated by several experimental and theoretical methods including a new technique--reverse (99)Tc NMR titration.
A series of water-soluble bis- and tetrakis-ZnII–cyclen complexes with rigid structures was prepared to enhance the carboxylate and phosphate ion binding response in contrast to analogues with less-confined molecular structures. Boc-protected 6-chloro-1,3,5-triazine–bis-cyclen was coupled to different aryl and alkyl moieties in moderate to high yie...
The complexation of a tweezers ligand with zinc perchlorate in the absence and presence of amines in methanol solution was explored. L(2)Zn(2)(ClO(4))(4) was a thermodynamic product of the reaction in the absence of an amine. The complex was shown to interact with aliphatic amines resulting in the formation of a Zn-N(amine) bond. If metal-ligand co...
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
In the title solvate, C30H24N4O2S·CH3CN, the substituted thiophene possesses approximate Cs(m) intrinsic symmetry, with the mirror plane passing through the S atom and the mid-point of the (Ph)C—C(Ph) bond. Despite the main backbone of the molecule being a long chain of conjugated bonds, it adopts a non-planar conformation due to the presence of va...
In the title solvate, C30H24N4O2S·CH3CN, the substituted thiophene possesses approximate Cs(m) intrinsic symmetry, with the mirror plane passing through the S atom and the mid-point of the (Ph)C—C(Ph) bond. Despite the main backbone of the molecule being a long chain of conjugated bonds, it adopts a non-planar conformation due to the presence of v...
The macrocycle of the title compound, C36H24N4O3S·2CHCl3, contains a rigid framework with the nitrogen and oxygen heteroatoms pointing in towards the center of the macrocyclic cavity. The macrocycle is essentially planar (r.m.s. deviation = 0.027 Å) except for the thiophene ring. The dihedral angle between the thiophene ring plane and the mean p...
The synthesis and anion binding properties of a neutral macrocyclic receptor bearing H-bond donor coordination sites are described.
The anion binding studies by use of UV-vis and 99Tc NMR methods revealed that the receptor can coordinate perrhenate and pertechnetate in dimethylsulfoxide and chloroform
solutions with the relatively high binding cons...
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
A new rational strategy for assembling highly selective neutral macrocyclic anionic receptors proposed by the authors is considered.
The strategy includes preliminary theoretical modeling of supramolecular complexes, analysis of synthetic paths for receptor
preparation, selection and synthesis of building blocks followed by their cyclocondensation...
This tutorial review covers the chemistry of artificial receptors designed to recognize the pertechnetate and perrhenate anions. It focuses on the molecular features that give rise to effective and selective complexation. Specific receptor classes are discussed in the context of available solution-phase and solid-state data with differences between...
Novel palladium(II) complexes with α,α'-bis(phenylimino)- and α,α'-bis(picolyl)-substituted meso-H-dipyrromethanes have been prepared. The complexes are able to react with dioxygen upon activation with potassium tert-butoxide. Reactions with dioxygen afford C-N or C-C self-bond cleavage producing α-pyrrole-carboxylate or α-hydroxypyrrole residues,...
The anion-templated syntheses and binding properties of novel macrocyclic oligopyrrole receptors in which pyrrole rings are linked through amide or imine bonds are described. The efficient synthesis was accomplished by anion-templated [1+1] Schiff-base condensation and acylation macrocyclization reactions. Free receptors and their host-guest comple...
The synthesis, characterisation and anion-binding properties of new pyrrole–pyridine-based macrocyclic polyamides 7a and 7b are presented. Chloride anion templation in the macrocyclisation reaction has been shown to control [1 + 1] acylation. The anion-binding properties of the receptors have been determined by UV–vis titrations in a DMSO solution...
The macrocyclic receptors 4-6 were synthesized via the anion-templated condensation of appropriately chosen dialdehyde and diamine building blocks. Whereas all three products could be obtained directly via the appropriate choice of reaction conditions, the larger [3+3] product, 6, which incorporates three of each precursor subunit, could also be ob...
The interaction of a Pd(II) salt with macrocyclic ligand 1 containing thiophene-2,5-carboxamide and bipyrrole fragments is studied. It is demonstrated that only mono-palladium complex
2 is formed in the reaction of PdCl2(CH3CN)2 with ligand 1. Complex 2 was isolated as crystalline compound 2b additionally involving also triethylammonium acetate and...
Diiminodipyrromethane complexes of Ni, Pd, and Pt are able to activate O2, resulting in a metal-dependent autoxidation of the ligand.
Three new amido-imine-type hybrid macrocycles based on substituted pyrrole units have been synthesized and shown to act as effective receptors for oxoanions in the solid state and in acetonitrile solution. One of the macrocycles in question, compound 15, was characterized by X-ray diffraction analysis as the free macrocycle and as a complex with su...
The reaction of diamidopyridine-dipyrromethane or dipyrromethene hybrid macrocycles with palladium(II) affords mono-metalated complexes, wherein the metal centre is coordinated to the macrocycle exclusively through pyrrolic nitrogen donor atoms.
This chapter discusses supramolecular chemistry of environmentally relevant anions. The ultimate goal of the studies on the basic chemical aspects of anion receptor design of functional pH-independent systems is to target selective binding of anions of environmental significance. In applications-oriented aspects of the research on the design of sep...
This review covers the field of anion recognition from the perspective of tetrahedral oxyanion recognition. The bulk of the attention is devoted to metal-free systems that are able to effect the recognition, binding or transport of phosphate and sulfate. Particular emphasis is devoted to design criteria that allow for discrimination and selectivity...
