Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Modulation of supramolecular chirality by stepwise axial coordination in a nano-size trizinc(ii)porphyrin trimer.

ABSTRACT: Herein, we report a chiral guest's triggered spring-like contraction and extension motions coupled with unidirectional twisting in a novel flexible and 'nano-size' achiral trizinc(ii)porphyrin trimer host upon step-wise formation of 1 : 1, 1 : 2, and 1 : 4 host-guest supramolecular complexes based on the stoichiometry of the diamine guests for the first time. During these processes, porphyrin CD responses have been induced, inverted, and amplified, and reduced, respectively, in a single molecular framework due to the change in the interporphyrin interactions and helicity. Also, the sign of the CD couplets is just the opposite between R and S substrates which suggests that the chirality is dictated solely by the stereographic projection of the chiral center. Interestingly, the long-range electronic communications between the three porphyrin rings generate trisignate CD signals that provide further information about molecular structures.

SUBMITTER: Dhamija A

PROVIDER: S-EPMC10246700 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Modulation of supramolecular chirality by stepwise axial coordination in a nano-size trizinc(ii)porphyrin trimer.

Dhamija Avinash A Chandel Dolly D Rath Sankar Prasad SP

Chemical science 20230510 22

Herein, we report a chiral guest's triggered spring-like contraction and extension motions coupled with unidirectional twisting in a novel flexible and 'nano-size' achiral trizinc(ii)porphyrin trimer host upon step-wise formation of 1 : 1, 1 : 2, and 1 : 4 host-guest supramolecular complexes based on the stoichiometry of the diamine guests for the first time. During these processes, porphyrin CD responses have been induced, inverted, and amplified, and reduced, respectively, in a single molecula ...[more]

PMID: 37293642

Similar Datasets

Synthesis of cyclobutane-fused chromanones via gold-mediated photocatalysis†‡ † Dedicated to Prof. Carl D. Hoff on the occasion o his 75th birthday.‡ Electronic supplementary information (ESI) available. CCDC 2283605. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc06675d

Project description: Not available

| S-EPMC10952090 | biostudies-literature

Novel practical stereoselective synthesis of a bicyclic hydantoino-thiolactone as the key intermediate for production of (+)-biotin†‡ † Dedicated to esteemed Professor Li-Xin Dai on the occasion of his 100th birthday.‡ Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3ra04721k

Project description:Bicyclic hydantoinothiolactone (1), as the key intermediate for production of (+)-biotin, has been efficiently and high-stereoselectively synthesized from the cheap starting material l-cystine via nine steps in 44% overall yield. In this new practical synthesis, there are two characteristic steps worthy of note. One step is TMSOTf-catalyzed efficient cyanation of (3S,7aR)-6-benzyl-5-oxo-3-phenyltetrahydro-1H,3H-imidazo[1,5-c]thiazol-7-yl acetate, the other step is DBU-catalyzed rapid isomerization of trans-isomer to cis-isomer of the bicyclic hydantoinothiolactone. Bicyclic hydantoinothiolactone, as the key intermediate for production of (+)-biotin, has been efficiently and high-stereoselectively synthesized from the cheap starting material l-cystine via nine steps in 44% overall yield.

| S-EPMC10475979 | biostudies-literature

Open shell (4n + 2)π and closed shell 4nπ planar core-modified decaphyrins†‡ † Dedicated to Prof. Vadapalli Chandrasekhar on the occasion of his 65th birthday‡ Electronic supplementary information (ESI) available. CCDC 2293502, 2294107, 2294108 and 2294163. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc05251f

Project description: Not available

| S-EPMC11041311 | biostudies-literature

Trypsin-Instructed Self-Assembly on Endoplasmic Reticulum for Selectively Inhibiting Cancer Cells: Dedicated to Professor George M. Whitesides on the occasion of his 80th birthday.

Project description:Selectively targeting the endoplasmic reticulum (ER) of cancer cells, though promising a new strategy for cancer therapy, remains underdeveloped. Enzyme-instructed self-assembly (EISA) is emerging as a promising approach for selectively targeting ER of cancer cells. This work reports an easily accessible branched peptide that consists of a D-tetrapeptide backbone and a branch with the sequence of KYDKKKKDG (K: lysine; Y: tyrosine; D: aspratic acid; G: glycine), being an EISA substrate of typsin-1 (PRSS1), selectively inhibits cancer cells. Depending on the type of cells, the level of PRSS1 expression dictates the cytotoxicity of the branched peptide. Moreover, immunostaining and fluorescent imaging reveal that PRSS1 overexpresses on the ER of a high-grade serous ovarian cancer cell line (OVSAHO). The overexpression of PRSS1 renders the branched peptide to exhibit high selectivity against OVSAHO by the in situ formation of the peptide assemblies on the ER of OVSAHO cells, which causes ER stress and eventual cell death. This work, illustrating trypsin-guided EISA for inhibiting cancer cells by enzymatic reaction on ER for the first time, offers a new way to target the subcellular organelles of cancer cells for potential cancer therapy.

| S-EPMC7725443 | biostudies-literature

Construction of an Au12Cd2 nanocluster with circularly polarized luminescence by a metal- and ligand-exchange strategy† † Electronic supplementary information (ESI) available: Experimental and characterization details and additional figures and tables (Scheme S1, Fig. S1–S38 and Tables S1–S8) offer more details on the nanoclusters. CCDC 2266860 and 2266865. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc06810b

Project description: Not available

| S-EPMC10967255 | biostudies-literature

Efficient light harvesting in self-assembled organic luminescent nanotubes†‡ † Dedicated to Prof. Uday Maitra on the occasion of his 65th birthday.‡ Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3sc00375b

Project description:Luminescent organic nanotubes derived from the co-assembly of cyanostilbene (CS) based cationic supramolecular polymers and bio-polyanion heparin, a known anticoagulant, have been utilized as highly efficient FRET (fluorescence resonance energy transfer) donors in aqueous media resulting in amplified acceptor emission in the orange-red and near-infrared (NIR). Energy transfer efficiencies higher than 80% and an ultra-high antenna effect of 150 were achieved even at high donor/acceptor ratios (500 : 1–100 : 1) translating to emission quenching of several hundred donors by one acceptor. Utilizing the temperature responsiveness of the FRET process, these systems were employed as ratiometric emission thermometers in the temperature range 20–90 °C. Moreover, the energy transfer was very effective in solid and polymer films. This allowed us to generate multi-color emissions ranging from blue to red including white light in solution as well as in solid and polymer films. Luminescent supramolecular nanotubes derived from the co-assembly of cyanostilbene amphiphiles and bio-polyanion heparin have demonstrated efficient energy transfer to various acceptor dyes in aqueous media as well as in solid and polymer films.

| S-EPMC10132123 | biostudies-literature

The smallest superatom Au4(PPh3)4I2 with two free electrons: synthesis, structure analysis, and electrocatalytic conversion of CO2 to CO† † Electronic supplementary information (ESI) available: Supporting figures and tables. Details and crystal data of Au4(PPh3)I2 (cif). CCDC 2251680. See DOI: https://doi.org/10.1039/d3na00191a

Project description:Atomically precise metal nanoclusters (NCs) have emerged as a new class of ultrasmall nanoparticles with both free valence electrons and precise structures (from the metal core to the organic ligand shell) and provide great opportunities to understand the relationship between their structures and properties, such as electrocatalytic CO2 reduction reaction (eCO2RR) performance, at the atomic level. Herein, we report the synthesis and the overall structure of the phosphine and iodine co-protected Au4(PPh3)4I2 (Au4) NC, which is the smallest multinuclear Au superatom with two free e− reported so far. Single-crystal X-ray diffraction reveals a tetrahedral Au4 core stabilized by four phosphines and two iodides. Interestingly, the Au4 NC exhibits much higher catalytic selectivity for CO (FECO: > 60%) at more positive potentials (from −0.6 to −0.7 V vs. RHE) than Au11(PPh3)7I3 (FECO: < 60%), a larger 8 e− superatom, and Au(i)PPh3Cl complex; whereas the hydrogen evolution reaction (HER) dominates the electrocatalysis when the potential becomes more negative (FEH2 of Au4 = 85.8% at −1.2 V vs. RHE). Structural and electronic analyses reveal that the Au4 tetrahedron becomes unstable at more negative reduction potentials, resulting in decomposition and aggregation, and consequently the decay in catalytic performance of Au based catalysts towards the eCO2RR. Au4(PPh3)4I2, having a Au4 tetrahedral structure is the smallest multinuclear Au superatom with two free e− reported so far. Au4 exhibits higher selectivity for CO (>60%); while the HER dominates when the potential becomes more negative.

| S-EPMC10262971 | biostudies-literature

Precisely synthesized segmented polyurethanes toward block sequence-controlled drug delivery† † Electronic supplementary information (ESI) available: Additional materials and characterization, experimental protocols, synthetic procedures with NMR spectra (Fig. S1–S18), figures (Fig. S19–S35) and tables (Tables S1–S6). See https://doi.org/10.1039/d1sc06457f

Project description:The construction of polyurethanes (PUs) with sequence-controlled block structures remains a serious challenge. Here, we report the precise synthesis of PUs with desirable molecular weight, narrow molecular weight distribution, and controlled block sequences from commercially available monomers. The synthetic procedure is derived from a liquid-phase synthetic methodology, which involves diisocyanate-based iterative protocols in combination with a convergent strategy. Furthermore, a pair of multifunctional PUs with different sequence orders of cationic and anion segments were prepared. We show that the sequence order of functional segments presents an impact on the self-assembly behavior and results in unexpected surface charges of assembled micelles, thereby affecting the protein absorption, cell internalization, biodistribution and antitumor effect of the nanocarriers in vitro and in vivo. This work provides a versatile platform for the development of precise multiblock PUs with structural complexity and functional diversity, and will greatly facilitate the clinical translation of PUs in biomedicine. Polyurethanes (PUs) with different segment sequence orders are prepared using a precise synthetic platform, and the sequence order of functional segments plays a crucial role in regulating the surface charges and performance of nano-drug carriers.

| S-EPMC9093123 | biostudies-literature

1-Azahomocubane† † Electronic supplementary information (ESI) available. CCDC 2177501. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc00001j

Project description:Highly strained cage hydrocarbons have long stood as fundamental molecules to explore the limits of chemical stability and reactivity, probe physical properties, and more recently as bioactive molecules and in materials discovery. Interestingly, the nitrogenous congeners have attracted much less attention. Previously absent from the literature, azahomocubanes, offer an opportunity to investigate the effects of a nitrogen atom when incorporated into a highly constrained polycyclic environment. Herein disclosed is the synthesis of 1-azahomocubane, accompanied by comprehensive structural characterization, physical property analysis and chemical reactivity. These data support the conclusion that nitrogen is remarkably well tolerated in a highly strained environment. 1-Azahomocubane has been prepared 56 years after the parent hydrocarbon. Introduction of a nitrogen atom into this constrained polycyclic environment resulted in minimal changes to the framework geometry, with s-character of the nitrogen lone pair increasing due to strain.

| S-EPMC10016339 | biostudies-literature

Activating charge-transfer state formation in strongly-coupled dimers using DNA scaffolds† † Electronic supplementary information (ESI) available: Sample characterization, spectroscopic and theoretical methods, and supplementary tables and figures. See DOI: https://doi.org/10.1039/d2sc02759c

Project description:Strongly-coupled multichromophoric assemblies orchestrate the absorption, transport, and conversion of photonic energy in natural and synthetic systems. Programming these functionalities involves the production of materials in which chromophore placement is precisely controlled. DNA nanomaterials have emerged as a programmable scaffold that introduces the control necessary to select desired excitonic properties. While the ability to control photophysical processes, such as energy transport, has been established, similar control over photochemical processes, such as interchromophore charge transfer, has not been demonstrated in DNA. In particular, charge transfer requires the presence of close-range interchromophoric interactions, which have a particularly steep distance dependence, but are required for eventual energy conversion. Here, we report a DNA-chromophore platform in which long-range excitonic couplings and short-range charge-transfer couplings can be tailored. Using combinatorial screening, we discovered chromophore geometries that enhance or suppress photochemistry. We combined spectroscopic and computational results to establish the presence of symmetry-breaking charge transfer in DNA-scaffolded squaraines, which had not been previously achieved in these chromophores. Our results demonstrate that the geometric control introduced through the DNA can access otherwise inaccessible processes and program the evolution of excitonic states of molecular chromophores, opening up opportunities for designer photoactive materials for light harvesting and computation. DNA scaffolds enable the activation and suppression of photochemistry between strongly-coupled synthetic chromophores.

| S-EPMC9667922 | 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