0000000001301995
AUTHOR
Tiia-riikka Tero
Synthesis and structure of mono-bridged resorcinarene host: a ditopic receptor for ammonium guests.
The synthesis and structural properties of tetramethoxy resorcinarene mono-crown-5 (1) are described. The binding characteristics of 1 toward acetylcholine and tetramethylammonium salts were investigated by 1H NMR titration. It was observed that the cavity of 1 provides a better fit to acetylcholine compared to the smaller tetramethylammonium cation, as acetylcholine is able to interact with both the crown ether moiety and the free hydroxyl groups of receptor 1 simultaneously.
The Structural Diversity of Benzofuran Resorcinarene Leads to Enhanced Fluorescence
An unexpected and previously unknown resorcinarene mono-crown with a fused benzofuran moiety in its macrocyclic core was obtained as a byproduct from a bridging reaction of tetramethoxy resorcinarene with tetraethylene glycol ditosylate. The formation of the fused benzofuran moiety in the resorcinarene macrocycle resulted in a unique rigid and puckered boat conformation, as shown by XRD studies in the solid state. Modification of the macrocycle was also observed to affect the photophysical properties in solution by enhancing the fluorescence brightness compared with a conventional resorcinarene macrocycle. The fluorescent properties enabled unique detection of structural features, that is, …
Photodynamics of a Molecular Water-Soluble Nanocluster Identified as Au130(pMBA)50
Photodynamics of a highly monodisperse sample of a water-soluble gold nanocluster tentatively identified as Au130(pMBA)50 (pMBA = p-mercaptobenzoic acid) was studied by mid-IR transient absorption spectroscopy with visible excitation. The observed long-lived excited states (>1 ns) indicate a molecular behavior of the cluster. By combining the transient absorption data with DFT calculation results the observed relaxation dynamics could be fully explained by identifying several relaxation processes involving singlet and triplet manifolds. The results indicate that the cluster may have interesting transient magnetic properties due to a long-lived triplet population.
Template-Free Supracolloidal Self-Assembly of Atomically Precise Gold Nanoclusters : From 2D Colloidal Crystals to Spherical Capsids
We report supracolloidal self-assembly of atomically precise and strictly monodisperse gold nanoclusters involving p-mercaptobenzoic acid ligands (Au102-pMBA44) under aqueous conditions into hexagonally packed monolayer-thick two-dimensional facetted colloidal crystals (thickness 2.7 nm) and their bending to closed shells leading to spherical capsids (d ca. 200 nm), as controlled by solvent conditions. The 2D colloidal assembly is driven in template-free manner by the spontaneous patchiness of the pMBA ligands around the Au102-pMBA44 nanoclusters preferably towards equatorial plane, thus promoting inter-nanocluster hydrogen bonds and high packing to planar sheets. More generally, the findin…
Development of functionalized SYBR green II related cyanine dyes for viral RNA detection
Fluorescent probes for sensing nucleic acids have found widespread use in the field of cell and molecular biology. However, probes combined with potential for post-synthetic conjugation, e.g. for intra-endosomal measurements of RNA, are unavailable. Herein we developed cyanine dyes that can be conjugated to viral capsid or other targets. First, we solved the crystal structure of SYBR Green II. The structural elucidation of this commonly used RNA probe provided the basis for synthesizing similar molecules with much desired function for post-synthetic conjugation. To address this need, cyanine dyes were prepared using an alternative synthesis protocol. All studied compounds showed considerabl…
Influence of lower rim C-methyl group on crystal forms and metal complexation of resorcinarene bis-crown-5
C-methyl resorcinarene bis-crown-5 (1) with pendant methyl groups at the lower rim was prepared and crystallized in various solvent mixtures with and without selected metal salts. The crystal structures of two polymorphic forms of unsolvated 1 (1-I and 1-II), three solvates (acetonitrile, chloroform and dichloromethane-methanol), and three metal complexes with silver and cesium salts were obtained. The lower rim methyl groups and the block shape of the host promote crystal packing in brick-wall type assemblies, in which the binding cavities are efficiently filled by the crown bridges. Thus, solvents are found in the interstitial space or coordinated to the crown bridges on top of the cavity…
Resorsinareenien metallikompleksit
Tämän pro gradu -tutkielman kirjallisuusosa käsittelee resorsinareenien metallikomplekseja. Tarkastelussa on keskitytty erityisesti resorsinareenien metallikompleksien rakenteeseen ja koordinaatiogeometriaan. Tutkielma on jaoteltu siirtymä- ja alkalimetalleihin sitoutuviin resorsinareeneihin, ja nämä on jaoteltu vielä tarkemmin resorsinareenien mukaan. Kokeellisen osan tarkoituksena oli syntetisoida terpyridiinifunktionalisoitu resorsinareeni, joka pystyy muodostamaan metallikomplekseja. Aromaattiset amiinit ovat typpiatomiensa takia mielenkiintoisia substituenttiryhmiä. Yhdisteen terpyridiinisillat ovat hyviä koordinoitumaan useisiin eri metalleihin, kuten sinkkiin ja kupariin, juuri typpi…
A perspective to resorcinarene crowns
In this report, we have summarized different synthesis methods of the resorcinarene crowns, discussed their structural and complexation properties together with the possible application aspects. peerReviewed
The Missing Member of the Partially O-Alkylated Resorcinarene Family: Synthesis and Conformation of Methyl Tetramethoxy Resorcinarene
An improved Lewis acid catalyzed synthesis method for methyl tetramethoxy resorcinarene is described, which produced the missing lower rim methyl derivative of this partially O-alkylated resorcinarene family. Structural characterization by means of variable temperature NMR experiments and single crystal X-ray diffraction studies furthermore revealed that the resorcinarene core adopts different conformations in the solid state and in solution. peerReviewed
Covalently linked multimers of gold nanoclusters Au102(p-MBA)44 and Au∼250(p-MBA)n
We present the synthesis, separation, and characterization of covalently-bound multimers of para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au102(p-MBA)44 nanocluster with biphenyl-4,4′-dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BP…
Solid state halogen bonded networks vs. dynamic assemblies in solution: explaining N⋯X interactions of multivalent building blocks
Tetrapyridine functionalized resorcinarene macrocycles were used as multivalent building blocks for the construction of halogen bonded networks with aryl halide linkers. In the solid state, resorcinarene macrocycles and aryl halide linker molecules assembled into interpenetrated, multidimensional halogen bonded networks with porous structure caused by the 3D block scaffold of the resorcinarenes. 19F NMR spectroscopy proved halogen bond formation also in solution, as either upfield or downfield shifts were observed depending on the bivalent or monovalent halogen bond binding mode. The binding mode in solution was explained by density functional theory computations. peerReviewed
Covalently linked multimers of gold nanoclusters Au102(p-MBA)44and Au∼250(p-MBA)n
We present the synthesis, separation, and characterization of covalently-bound multimers of para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au102(p-MBA)44 nanocluster with biphenyl-4,4′-dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BP…
Development of functionalized SYBR green II related cyanine dyes for viral RNA detection
Abstract Fluorescent probes for sensing nucleic acids have found widespread use in the field of cell and molecular biology. However, probes combined with potential for post-synthetic conjugation, e.g. for intra-endosomal measurements of RNA, are unavailable. Herein we developed cyanine dyes that can be conjugated to viral capsid or other targets. First, we solved the crystal structure of SYBR Green II. The structural elucidation of this commonly used RNA probe provided the basis for synthesizing similar molecules with much desired function for post-synthetic conjugation. To address this need, cyanine dyes were prepared using an alternative synthesis protocol. All studied compounds showed co…
Dynamic Stabilization of the Ligand-Metal Interface in Atomically Precise Gold Nanoclusters Au68 and Au144 Protected by meta-Mercaptobenzoic Acid
Ligand-stabilized, atomically precise gold nanoclusters with a metal core of a uniform size of just 1–3 nm constitute an interesting class of nanomaterials with versatile possibilities for applications due to their size-dependent properties and modifiable ligand layers. The key to extending the usability of the clusters in applications is to understand the chemical bonding in the ligand layer as a function of cluster size and ligand structure. Previously, it has been shown that monodispersed gold nanoclusters, stabilized by meta-mercaptobenzoic acid (m-MBA or 3-MBA) ligands and with sizes of 68–144 gold atoms, show ambient stability. Here we show that a combination of nuclear magnetic reson…
The Effect of Halogen Bonding on the Packing of Bromine Substituted Pyridine and Benzyl Functionalized Resorcinarene Tetrapodands in the Solid State
The synthesis and characterization of new bromine-substituted pyridine and benzyl functionalized tetramethoxy resorcinarene tetrapodands are described and their solid-state structural properties and interactions were studied by single crystal X-ray crystallography. Three different crystal structures were obtained for the pyridine derivative and one for the benzyl derivative, which revealed that the interactions of the bromine substituent have an explicit effect on the crystal packing of the resorcinarene molecules. One of the structures obtained had very interesting halogen–halogen interactions with the same geometry as is generally found for compounds used in nonlinear optical studies. pee…
The Effect of Halogen Bonding on the Packing of Bromine Substituted Pyridine and Benzyl Functionalized Resorcinarene Tetrapodands in the Solid State
The synthesis and characterization of new bromine-substituted pyridine and benzyl functionalized tetramethoxy resorcinarene tetrapodands are described and their solid-state structural properties and interactions were studied by single crystal X-ray crystallography. Three different crystal structures were obtained for the pyridine derivative and one for the benzyl derivative, which revealed that the interactions of the bromine substituent have an explicit effect on the crystal packing of the resorcinarene molecules. One of the structures obtained had very interesting halogen–halogen interactions with the same geometry as is generally found for compounds used in nonlinear optical studies.
ChemInform Abstract: A Perspective to Resorcinarene Crowns
Dynamic Stabilization of the Ligand-Metal Interface in Atomically Precise Gold Nanoclusters Au68 and Au144 Protected by meta-Mercaptobenzoic Acid
Ligand-stabilized, atomically precise gold nanoclusters with a metal core of a uniform size of just 1-3 nm constitute an interesting class of nanomaterials with versatile possibilities for applications due to their size-dependent properties and modifiable ligand layers. The key to extending the usability of the clusters in applications is to understand the chemical bonding in the ligand layer as a function of cluster size and ligand structure. Previously, it has been shown that monodispersed gold nanoclusters, stabilized by meta-mercaptobenzoic acid (m-MBA or 3-MBA) ligands and with sizes of 68-144 gold atoms, show ambient stability. Here we show that a combination of nuclear magnetic reson…
4,4-Di-fluoro-2,3;5,6-bis-(tetra-methylene)-4-bora-3a,4a-di-aza-s-indacene (LD540).
The title compound, C18H21BF2N2, is a lipophilic dye based on a BODIPY fluorophore backbone, which was developed for microscopic imaging of lipid droplets; the molecule has a planar BODIPY core [dihedral angle between the pyrrole rings = 2.3 (3)°] and two tetramethylene substituents at the 2,3- and 5,6-positions in a half-chair conformation. One of the tetramethylene substituents is disordered over two two sets of sites with site occupancies of 0.5. In the crystal, pairs of C—H...F interactions link the molecules into inversion dimers. Neighbouring dimers are linked by further C—H...F interactions, forming an infinite array. C—H...π and π–π [centroid–centroid distance = 4.360 (3) Å] interac…
CCDC 919270: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Aku Suhonen, Kirsi Salorinne, Hélène Campos-Barbosa, Maija Nissinen|2013|Org.Lett.|15|1096|doi:10.1021/ol400118t
CCDC 1044958: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Sami Malola, Hannu Häkkinen, Maija Nissinen|2015|CrystEngComm|17|8231|doi:10.1039/C5CE01144B
CCDC 1042084: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C
CCDC 1482405: Experimental Crystal Structure Determination
Related Article: Ville K. Saarnio, Kirsi Salorinne, Visa P. Ruokolainen, Jesper R. Nilsson, Tiia-Riikka Tero, Sami Oikarinen, L. Marcus Wilhelmsson, Tanja M. Lahtinen, Varpu S. Marjomäki|2020|Dyes Pigm.|177|108282|doi:10.1016/j.dyepig.2020.108282
CCDC 943017: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Heli Lehtivuori, Janne A. Ihalainen, Maija Nissinen|2014|Chem.Asian J.|9|1860|doi:10.1002/asia.201402016
CCDC 1042079: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C
CCDC 943016: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Heli Lehtivuori, Janne A. Ihalainen, Maija Nissinen|2014|Chem.Asian J.|9|1860|doi:10.1002/asia.201402016
CCDC 943015: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Heli Lehtivuori, Janne A. Ihalainen, Maija Nissinen|2014|Chem.Asian J.|9|1860|doi:10.1002/asia.201402016
CCDC 1042086: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C
CCDC 919269: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Aku Suhonen, Kirsi Salorinne, Hélène Campos-Barbosa, Maija Nissinen|2013|Org.Lett.|15|1096|doi:10.1021/ol400118t
CCDC 919268: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Aku Suhonen, Kirsi Salorinne, Hélène Campos-Barbosa, Maija Nissinen|2013|Org.Lett.|15|1096|doi:10.1021/ol400118t
CCDC 1044955: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Sami Malola, Hannu Häkkinen, Maija Nissinen|2015|CrystEngComm|17|8231|doi:10.1039/C5CE01144B
CCDC 1042087: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C
CCDC 1042083: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C
CCDC 1482404: Experimental Crystal Structure Determination
Related Article: Ville K. Saarnio, Kirsi Salorinne, Visa P. Ruokolainen, Jesper R. Nilsson, Tiia-Riikka Tero, Sami Oikarinen, L. Marcus Wilhelmsson, Tanja M. Lahtinen, Varpu S. Marjomäki|2020|Dyes Pigm.|177|108282|doi:10.1016/j.dyepig.2020.108282
CCDC 1042088: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C
CCDC 1042082: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C
CCDC 919271: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Aku Suhonen, Kirsi Salorinne, Hélène Campos-Barbosa, Maija Nissinen|2013|Org.Lett.|15|1096|doi:10.1021/ol400118t
CCDC 1044957: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Sami Malola, Hannu Häkkinen, Maija Nissinen|2015|CrystEngComm|17|8231|doi:10.1039/C5CE01144B
CCDC 1042081: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C
CCDC 1044956: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Sami Malola, Hannu Häkkinen, Maija Nissinen|2015|CrystEngComm|17|8231|doi:10.1039/C5CE01144B
CCDC 1044959: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Sami Malola, Hannu Häkkinen, Maija Nissinen|2015|CrystEngComm|17|8231|doi:10.1039/C5CE01144B
CCDC 1044954: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Sami Malola, Hannu Häkkinen, Maija Nissinen|2015|CrystEngComm|17|8231|doi:10.1039/C5CE01144B
CCDC 943014: Experimental Crystal Structure Determination
Related Article: Tiia-Riikka Tero, Kirsi Salorinne, Heli Lehtivuori, Janne A. Ihalainen, Maija Nissinen|2014|Chem.Asian J.|9|1860|doi:10.1002/asia.201402016
CCDC 1042080: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C
CCDC 1042085: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Tiia-Riikka Tero, Maija Nissinen|2015|CrystEngComm|17|3667|doi:10.1039/C5CE00311C