Browse
Submit Data
Databases
API
Help

Dataset Information

4 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Controlled assembly of a bicyclic porphyrinoid and its 3-dimensional boron difluoride arrays.

ABSTRACT: A fully conjugated cryptand-like bicyclic porphyrinoid ligand 4, incorporating three carbazole linkages and four dipyrrin moieties, was prepared via the acid-catalysed condensation of an extended 2,2'-bipyrrole analogue containing a central carbazole moiety and 3,4-diethyl-2,5-diformylpyrrole in 79% isolated yield. This new cryptand-like system acts as an effective ligand and allows for complexation of BF₂ (boron difluoride) subunits. Three BODIPY arrays, containing two, three, and four BF₂ subunits, namely 4·2BF₂, 4·3BF₂ and 4·4BF₂, could thus be isolated from the reaction of 4 with BF₃·Et₂O in the presence of triethylamine at 110 °C, albeit in relatively low yield. As prepared, bicycle 4 is characterized by a rigid C ₂ symmetric structure as inferred from VT NMR spectroscopic analyses. In contrast, the three BODIPY-like arrays produced as the result of BF₂ complexation are conformationally flexible and unsymmetric in nature as deduced from similar analyses. All four products, namely 4, 4·2BF₂, 4·3BF₂ and 4·4BF₂, were characterized by means of single crystal X-ray diffraction analyses. Tetramer 4·4BF₂ gives rise to a higher extinction coefficient (by 2.5 times) relative to the bis- and tris-BODIPY arrays 4·2BF₂ and 4·3BF₂. This was taken as evidence for stronger excitonic coupling in the case of 4·4BF₂. All three BODIPY-like arrays proved nearly non-fluorescent, as expected given their conformationally mobile nature. The efficiency of reactive oxygen species (ROS) generation was also determined for the new BODIPY arrays of this study.

SUBMITTER: Zhou W

PROVIDER: S-EPMC9214847 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

The development of peptide-boron difluoride formazanate conjugates as fluorescence imaging agents.

Project description:Two new fluorescence imaging probes have been synthesized by incorporating a versatile alkyne-substituted boron difluoride formazanate precursor with peptides through copper-catalyzed alkyne-azide cycloaddition. The formazanate dye was appended to a C-terminal amino acid of ghrelin for imaging the growth hormone secretagogue receptor (GHSR-1a). To demonstrate versatile bioconjugation chemistry, the formazanate dye was added to the N-terminus of bombesin for targeting the gastrin releasing peptide receptor (GRPR). These are the first examples of using this emerging class of dyes, boron difluoride formazanates, for the labelling of biomolecules.

| S-EPMC9053952 | biostudies-literature

Structure-mechanical property correlations in mechanochromic luminescent crystals of boron difluoride dibenzoylmethane derivatives.

Project description:The structure and mechanical properties of crystalline materials of three boron difluoride dibenzoylmethane (BF2dbm) derivatives were investigated to examine the correlation, if any, among mechanochromic luminescence (ML) behaviour, solid-state structure, and the mechanical behaviour of single crystals. Qualitative mechanical deformation tests show that the crystals of BF2dbm( (t) Bu)2 can be bent permanently, whereas those of BF2dbm(OMe)2 exhibit an inhomogeneous shearing mode of deformation, and finally BF2dbmOMe crystals are brittle. Quantitative mechanical analysis by nano-indentation on the major facets of the crystals shows that BF2dbm( (t) Bu)2 is soft and compliant with low values of elastic modulus, E, and hardness, H, confirming its superior suceptibility for plastic deformation, which is attributed to the presence of a multitude of slip systems in the crystal structure. In contrast, both BF2dbm(OMe)2 and BF2dbmOMe are considerably stiffer and harder with comparable E and H, which are rationalized through analysis of the structural attributes such as the intermolecular interactions, slip systems and their relative orientation with respect to the indentation direction. As expected from the qualitative mechanical behaviour, prominent ML was observed in BF2dbm( (t) Bu)2, whereas BF2dbm(OMe)2 exhibits only a moderate ML and BF2dbmOMe shows no detectable ML, all examined under identical conditions. These results confirm that the extent of ML in crystalline organic solid-state fluorophore materials can be correlated positively with the extent of plasticity (low recovery). In turn, they offer opportunities to design new and improved efficient ML materials using crystal engineering principles.

| S-EPMC4645105 | biostudies-literature

External environment sensitive circularly polarized luminescence properties of a chiral boron difluoride complex.

Project description:A chiral Schiff-base boron difluoride complex bearing a diethylamino group was synthesized. Its photophysical properties were investigated and compared with those of its non-substituted analogue. The complex was found to exhibit solvatofluorochromism with bluish-white emission in moderately polar solvents and intense blue emission in nonpolar solvent. Circularly polarized luminescence (CPL) properties were also examined and it was found that the absolute value of the luminescence dissymmetry factor (g lum) increases significantly in the KBr-dispersed pellet state compared to the solution state. Notably, CPL intensity of the complex enhanced approximately three times upon addition of CH3SO3H in CH2Cl2. Density functional theory (DFT) calculations were conducted to further understand the photophysical properties.

| S-EPMC9724127 | biostudies-literature

Interplay between π-Conjugation and Exchange Magnetism in One-Dimensional Porphyrinoid Polymers.

Project description:The synthesis of novel polymeric materials with porphyrinoid compounds as key components of the repeating units attracts widespread interest from several scientific fields in view of their extraordinary variety of functional properties with potential applications in a wide range of highly significant technologies. The vast majority of such polymers present a closed-shell ground state, and, only recently, as the result of improved synthetic strategies, the engineering of open-shell porphyrinoid polymers with spin delocalization along the conjugation length has been achieved. Here, we present a combined strategy toward the fabrication of one-dimensional porphyrinoid-based polymers homocoupled via surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituents on Au(111). Scanning tunneling microscopy and noncontact atomic force microscopy describe the thermal-activated intra- and intermolecular oxidative ring closure reactions as well as the controlled tip-induced hydrogen dissociation from the porphyrinoid units. In addition, scanning tunneling spectroscopy measurements, complemented by computational investigations, reveal the open-shell character, that is, the antiferromagnetic singlet ground state (S = 0) of the formed polymers, characterized by singlet-triplet inelastic excitations observed between spins of adjacent porphyrinoid units. Our approach sheds light on the crucial relevance of the π-conjugation in the correlations between spins, while expanding the on-surface synthesis toolbox and opening avenues toward the synthesis of innovative functional nanomaterials with prospects in carbon-based spintronics.

| S-EPMC9305978 | biostudies-literature

One-dimensional gold nanoparticle arrays by electrostatically directed organization using polypeptide self-assembly.

Project description: Not available

| S-EPMC2796555 | biostudies-literature

Metal-directed, chemically tunable assembly of one-, two- and three-dimensional crystalline protein arrays.

Project description:Proteins represent the most sophisticated building blocks available to an organism and to the laboratory chemist. Yet, in contrast to nearly all other types of molecular building blocks, the designed self-assembly of proteins has largely been inaccessible because of the chemical and structural heterogeneity of protein surfaces. To circumvent the challenge of programming extensive non-covalent interactions to control protein self-assembly, we have previously exploited the directionality and strength of metal coordination interactions to guide the formation of closed, homoligomeric protein assemblies. Here, we extend this strategy to the generation of periodic protein arrays. We show that a monomeric protein with properly oriented coordination motifs on its surface can arrange, on metal binding, into one-dimensional nanotubes and two- or three-dimensional crystalline arrays with dimensions that collectively span nearly the entire nano- and micrometre scale. The assembly of these arrays is tuned predictably by external stimuli, such as metal concentration and pH.

| S-EPMC3335442 | biostudies-literature

Spontaneous assembly of chemically encoded two-dimensional coacervate droplet arrays by acoustic wave patterning.

Project description:The spontaneous assembly of chemically encoded, molecularly crowded, water-rich micro-droplets into periodic defect-free two-dimensional arrays is achieved in aqueous media by a combination of an acoustic standing wave pressure field and in situ complex coacervation. Acoustically mediated coalescence of primary droplets generates single-droplet per node micro-arrays that exhibit variable surface-attachment properties, spontaneously uptake dyes, enzymes and particles, and display spatial and time-dependent fluorescence outputs when exposed to a reactant diffusion gradient. In addition, coacervate droplet arrays exhibiting dynamical behaviour and exchange of matter are prepared by inhibiting coalescence to produce acoustically trapped lattices of droplet clusters that display fast and reversible changes in shape and spatial configuration in direct response to modulations in the acoustic frequencies and fields. Our results offer a novel route to the design and construction of 'water-in-water' micro-droplet arrays with controllable spatial organization, programmable signalling pathways and higher order collective behaviour.

| S-EPMC5059748 | biostudies-literature

Field-controlled ultrafast magnetization dynamics in two-dimensional nanoscale ferromagnetic antidot arrays.

Project description:Ferromagnetic antidot arrays have emerged as a system of tremendous interest due to their interesting spin configuration and dynamics as well as their potential applications in magnetic storage, memory, logic, communications and sensing devices. Here, we report experimental and numerical investigation of ultrafast magnetization dynamics in a new type of antidot lattice in the form of triangular-shaped Ni80Fe20 antidots arranged in a hexagonal array. Time-resolved magneto-optical Kerr effect and micromagnetic simulations have been exploited to study the magnetization precession and spin-wave modes of the antidot lattice with varying lattice constant and in-plane orientation of the bias-magnetic field. A remarkable variation in the spin-wave modes with the orientation of in-plane bias magnetic field is found to be associated with the conversion of extended spin-wave modes to quantized ones and vice versa. The lattice constant also influences this variation in spin-wave spectra and spin-wave mode profiles. These observations are important for potential applications of the antidot lattices with triangular holes in future magnonic and spintronic devices.

| S-EPMC5905244 | biostudies-literature

Tuning the Properties of Donor-Acceptor and Acceptor-Donor-Acceptor Boron Difluoride Hydrazones <i>via</i> Extended π-Conjugation.

Project description:Molecular materials with π-conjugated donor-acceptor (D-A) and acceptor-donor-acceptor (A-D-A) electronic structures have received significant attention due to their usage in organic photovoltaic materials, in organic light-emitting diodes, and as biological imaging agents. Boron-containing molecular materials have been explored as electron-accepting units in compounds with D-A and A-D-A properties as they often exhibit unique and tunable optoelectronic and redox properties. Here, we utilize Stille cross-coupling chemistry to prepare a series of compounds with boron difluoride hydrazones (BODIHYs) as acceptors and benzene, thiophene, or 9,9-dihexylfluorene as donors. BODIHYs with D-A and A-D-A properties exhibited multiple reversible redox waves, solid-state emission with photoluminescence quantum yields up to 10%, and aggregation-induced emission (AIE). Optical band gaps (or highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps) determined for these compounds (2.02-2.25 eV) agree well with those determined from cyclic voltammetry experiments (2.05-2.42 eV). The optoelectronic properties described herein are rationalized with density functional theory calculations that support the interpretation of the experimental findings. This work provides a foundation of understanding that will allow for the consideration of D-A and A-D-A BODIHYs to be incorporated into applications (e.g., organic electronics) where fine-tuning of band gaps is required.

| S-EPMC9476501 | biostudies-literature

Controlled and Stable Patterning of Diverse Inorganic Nanocrystals on Crystalline Two-Dimensional Protein Arrays.

Project description:Controlled patterning of nanoparticles on bioassemblies enables synthesis of complex materials for applications in optics, nanoelectronics, and sensing. Biomolecular self-assembly offers molecular control for engineering patterned nanomaterials, but current approaches have been limited in their ability to combine high nanoparticle coverage with generality that enables incorporation of multiple nanoparticle types. Here, we synthesize photonic materials on crystalline two-dimensional (2D) protein sheets using orthogonal bioconjugation reactions, organizing quantum dots (QDs), gold nanoparticles (AuNPs), and upconverting nanoparticles along the surface-layer (S-layer) protein SbsB from the extremophile Geobacillus stearothermophilus. We use electron and optical microscopy to show that isopeptide bond-forming SpyCatcher and SnoopCatcher systems enable the simultaneous and controlled conjugation of multiple types of nanoparticles (NPs) at high densities along the SbsB sheets. These NP conjugation reactions are orthogonal to each other and to Au-thiol bond formation, allowing tailorable nanoparticle combinations at sufficient labeling efficiencies to permit optical interactions between nanoparticles. Fluorescence lifetime imaging of SbsB sheets conjugated to QDs and AuNPs at distinct attachment sites shows spatially heterogeneous QD emission, with shorter radiative decays and brighter fluorescence arising from plasmonic enhancement at short interparticle distances. This specific, stable, and efficient conjugation of NPs to 2D protein sheets enables the exploration of interactions between pairs of nanoparticles at defined distances for the engineering of protein-based photonic nanomaterials.

| S-EPMC8162747 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data