Circularly Polarized Luminescence Bioimaging Using Chiral BODIPYs: A Model Scaffold for Advancing Unprecedented CPL Microscopy Using Small Full-Organic Probes.

Unprecedented circularly polarized luminescence bioimaging (CPL-bioimaging) of live cells using small full-organic probes is first reported. These highly biocompatible and adaptable probes are pivotal to advance emerging CPL Laser-Scanning Confocal Microscopy (CPL-LSCM) as an undeniable tool to distinguish, monitor, and understand the role of chirality in the biological processes. The development of these probes was challenging due to the poor dichroic character associated with the involved CPL emissions.

DNA-Modulated and Mechanoresponsive Excitonic Couplings Reveal Chiroptical Correlation of Conformation, Tension, and Dynamics of DNA Self-Assembly.

Study of the conformational and mechanical behaviors of biomolecular assemblies is vital to the rational design and realization of artificial molecular architectures with biologically relevant functionality. Here, we revealed DNA-modulated and mechanoresponsive excitonic couplings between organic chromophores and verified strong correlations between the excitonic chiroptical responses and the conformational and mechanical states of DNA self-assemblies irrespective of fluorescence background interference. Besides, the excitonic chiroptical effect allowed sensitive monitoring of DNA self-assembled nanostructures due to small molecule bindings or DNA strand displacement reactions.

Is ultrasonography accurate for the diagnosis of gallbladder polyps? A review of cholecystectomy specimens from patients diagnosed with gallbladder polyps over a 14-years period.

Introduction: Incidence of gallbladder polyps is 0,3-12%. It is important to differentiate pseudopolyps (cholesterol polyps, adenomyomatosis, inflammatory polyps), which do not have the capacity to become malignant, from true polyps (adenomas and adenocarcinomas). The main risk factors for malignancy are >6-10 mm, growth, sessile morphology, Indian ethnicity and primary sclerosing cholangitis.

Polar ammoniostyryls easily converting a clickable lipophilic BODIPY in an advanced plasma membrane probe.

A very simple, small and symmetric, but highly bright, photostable and functionalizable molecular probe for plasma membrane (PM) has been developed from an accessible, lipophilic and clickable organic dye based on BODIPY. To this aim, two lateral polar ammoniostyryl groups were easily linked to increase the amphiphilicity of the probe and thus its lipid membrane partitioning. Compared to the BODIPY precursor, the transversal diffusion across lipid bilayers of the ammoniostyryled BODIPY probe was highly reduced, as evidenced by fluorescence confocal microscopy on model membranes built up as giant unilamellar vesicles (GUVs).

Triplet-triplet sensitizing within pyrene-based COO-BODIPY: a breaking molecular platform for annihilating photon upconversion.

We envisioned a new approach for achieving triplet-triplet annihilation-assisted photon upconversion based on the rational design of a heavy-atom-free, all-organic and photoactivatable triplet-triplet synergistic multichromophoric molecular assembly. This single molecular architecture is easily built by covalently anchoring triplet-annihilator units (pyrenes) to a triplet-photosensitizer moiety (BODIPY), to improve the effectiveness and probability of the required triplet-triplet energy transfer and the ulterior triplet-triplet annihilation. This unprecedented design takes advantage of the high synthetic accessibility and chemical versatility of the -BODIPY scaffold.

BINOL blocks as accessible triplet state modulators in BODIPY dyes.

BINOL moieties of different electronic demand are useful blocks for enabling the photo-production and modulation of triplet excited states in readily-accesible BINOL-based -BODIPY dyes from standard -BODIPY precursors. The rapid and rational development of smarter triplet-enabling BODIPY dyes on the basis of this strategy (, TADF biomarker 4a or room temperature phosphor 4g) paves the way for advancing photonic applications based on organic triplet photosensitizers.

Insight into the Influence of the Chiral Molecular Symmetry on the Chiroptics of Fluorescent BINOL-Based Boron Chelates.

The prominent influence of the molecular symmetry, as defined by the symmetry point group, on the chiroptical behavior (electronic circular dichroism and, especially, circularly polarized luminescence) of simple fluorescent boron chelates (BODIPY and related BOPHY analogues) is studied and discussed. It is shown that increasing the dye symmetry by means of the chiral symmetry group is a workable design option to enhance the level of differential emission of right- and left-circularly polarized light in BODIPY dyes and related emitters, and that the influence of the level of symmetry is stronger than the influence of the higher number of chiral moieties perturbing the acting achiral chromophore.

BINOLated aminostyryl BODIPYs: a workable organic molecular platform for NIR circularly polarized luminescence.

The accessible at-boron-BINOLated 3,5-bis(4-aminostyryl)ated BODIPY scaffold is highlighted as a workable platform for developing enantiopure small organic molecules exhibiting CPL in the NIR region, even in water solution, the latter being key for CPL-based bioapplications. Synthetic simplicity, noticeable chiroptical efficiency in the NIR and the possibility to access water-soluble emitters pave the way for advancing CPL tools based on organic emitters and NIR radiation.

BCl-Activated Synthesis of COO-BODIPY Laser Dyes: General Scope and High Yields under Mild Conditions.

A general and straightforward method for the synthesis of COO-BODIPYs from F-BODIPYs and carboxylic acids is established. The method is based on the use of boron trichloride to activate the involved substitution of fluorine, which leads to high yields through rapid reactions under soft conditions. This mild method opens the way to unprecedented laser dyes with outstanding efficiencies and photostabilities, which are difficult to obtain by the current methods.

Manipulating Charge-Transfer States in BODIPYs: A Model Strategy to Rapidly Develop Photodynamic Theragnostic Agents.

On the basis of a family of BINOL (1,1'-bi-2-naphthol)-based O-BODIPY (dioxyboron dipyrromethene) dyes, it is demonstrated that chemical manipulation of the chromophoric push-pull character, by playing with the electron-donating capability of the BINOL moiety (BINOL versus 3,3'-dibromoBINOL) and with the electron-acceptor ability of the BODIPY core (alkyl substitution degree), is a workable strategy to finely balance fluorescence (singlet-state emitting action) versus the capability to photogenerate cytotoxic reactive oxygen species (triplet-state photosensitizing action). It is also shown that the promotion of a suitable charge-transfer character in the involved chromophore upon excitation enhances the probability of an intersystem crossing phenomenon, which is required to populate the triple state enabling singlet oxygen production. The reported strategy opens up new perspectives for rapid development of smarter agents for photodynamic theragnosis, including heavy-atom-free agents, from a selected organic fluorophore precursor.

-BODIPYs: Exploring a New Strategy to Transfer Chirality towards BODIPY Chiroptics.

-BODIPYs, that is, boron dipyrromethenes (BODIPYs) which have chiral carbons attached directly to the boron center, are introduced for the first time. These novel chiral BODIPYs mean a new strategy for the chiral perturbation of the inherently achiral BODIPY chromophore that is directed to enable chiroptical properties. Their preparation is very simple and only implies the complexation of a dipyrrin with an enantiopure dialkylborane having boron bonded to chiral carbons.

Chiral Microneedles from an Achiral Bis(boron dipyrromethene): Spontaneous Mirror Symmetry Breaking Leading to a Promising Photoluminescent Organic Material.

Supramolecular self-assembly of a highly flexible and achiral meso bis(boron dipyrromethene) [bis(BODIPY)] dye straightforwardly yields fluorescent microfibers, exhibiting an intriguing anisotropic photonic behavior. This performance includes the generation of chiroptical activity owing to spontaneous mirror symmetry breaking (SMSB). Repetition of several self-assembly experiments demonstrates that the involved SMSB is not stochastic but quasi deterministic in the direction of the induced chiral asymmetry.

Modulating ICT emission: a new strategy to manipulate the CPL sign in chiral emitters.

A new strategy to manipulate the circularly polarized luminescence (CPL) handedness in chiral emitters, based on modulating the population of an emissive ICT state, is proposed. Such a strategy is particularly interesting for conformationally rigid and non-aggregating chiral organic emitters, opening up new perspectives for the development of CPL applications based on organic molecules.

Differential phosphorylation and n-terminal configuration of capsid subunits in parvovirus assembly and viral trafficking.

The T1 parvovirus Minute Virus of Mice (MVM) was used to study the roles that phosphorylation and N-terminal domains (Nt) configuration of capsid subunits may play in icosahedral nuclear viruses assembly. In synchronous MVM infection, capsid subunits newly assembled as two types of cytoplasmic trimeric intermediates (3VP2, and 1VP1:2VP2) harbored a VP1 phosphorylation level fivefold higher than that of VP2, and hidden Nt. Upon nuclear translocation at S phase, VP1-Nt became exposed in the heterotrimer and subsequent subviral assembly intermediates.

Chiral Organic Dyes Endowed with Circularly Polarized Laser Emission.

The direct generation of efficient, tunable, and switchable circularly polarized laser emission (CPLE) would have far-reaching implications in photonics and material sciences. In this paper, we describe the first chiral simple organic molecules (SOMs) capable of simultaneously sustaining significant chemical robustness, high fluorescence quantum yields, and circularly polarized luminescence (CPL) ellipticity levels (||) comparable to those of similar CPL-SOMs. All these parameters altogether enable efficient laser emission and CPLE with ellipticity levels 2 orders of magnitude stronger than the intrinsic CPL ones.

Modulation of ICT probability in bi(polyarene)-based O-BODIPYs: towards the development of low-cost bright arene-BODIPY dyads.

We report the synthesis, and spectroscopic and electrochemical properties of a selected library of novel spiranic O-BODIPYs bearing a phenol-based bi(polyarene) unit tethered to the boron center through oxygen atoms. These dyes constitute an interesting family of arene-BODIPY dyads useful for the development of photonic applications due to their synthetic accessibility and tunable photonic properties. It is demonstrated that the electron-donor capability of the involved arene moiety switches on a non-emissive intramolecular charge transfer (ICT) state, which restricts the fluorescence efficiency of the dyad.

N-BODIPYs Come into Play: Smart Dyes for Photonic Materials.

N-BODIPYs (diaminoboron dipyrromethenes) are unveiled as a new family of BODIPY dyes with huge technological potential. Synthetic access to these systems has been gained through a judicious design focused on stabilizing the involved diaminoboron chelate. Once stabilized, the obtained N-BODIPYs retain the effective photophysical behavior exhibited by other boron-substituted BODIPYs, such as O-BODIPYs.

Push-pull flexibly-bridged bis(haloBODIPYs): solvent and spacer switchable red emission.

A series of uncommon bis(BODIPYs), involving a flexible bridge linking the BODIPY α-positions and key functionalities to efficiently give an electronic push-pull effect, has been synthesized, as well as photophysically and structurally studied. It is demonstrated that the designed push-pull effect efficiently enables intramolecular charge transfer (ICT) processes upon photoexcitation, with the generated low-lying ICT state being the main deactivation channel from the locally excited state and, hence, ruling the fluorescence response. Noticeably, this response is modulated by the solvent polarity, and also by the bridge structure.

Bis(haloBODIPYs) with Labile Helicity: Valuable Simple Organic Molecules That Enable Circularly Polarized Luminescence.

Simple organic molecules (SOM) based on bis(haloBODIPY) are shown to enable circularly polarized luminescence (CPL), giving rise to a new structural design for technologically valuable CPL-SOMs. The established design comprises together synthetic accessibility, labile helicity, possibility of reversing the handedness of the circularly polarized emission, and reactive functional groups, making it unique and attractive as advantageous platform for the development of smart CPL-SOMs.

Circularly Polarized Luminescence from Simple Organic Molecules.

This article aims to show the identity of "circularly polarized luminescent active simple organic molecules" as a new concept in organic chemistry due to the potential interest of these molecules, as availed by the exponentially growing number of research articles related to them. In particular, it describes and highlights the interest and difficulty in developing chiral simple (small and non-aggregated) organic molecules able to emit left- or right-circularly polarized light efficiently, the efforts realized up to now to reach this challenging objective, and the most significant milestones achieved to date. General guidelines for the preparation of these interesting molecules are also presented.

Spiranic BODIPYs: a ground-breaking design to improve the energy transfer in molecular cassettes.

Boosted excitation energy transfer in spiranic O-BODIPY/polyarene cassettes, when compared with the parent non-spiranic (flexible) system, is highlighted as a proof for the ability of a new structural design to improve the energy transfer in molecular cassettes.

Circularly polarized luminescence by visible-light absorption in a chiral O-BODIPY dye: unprecedented design of CPL organic molecules from achiral chromophores.

Circularly polarized luminescence (CPL) in simple (small, nonaggregated, nonpolymeric) O-BODIPYs (R)-1 and (S)-1 by irradiation with visible light is first detected as proof of the ability of a new structural design to achieve CPL from inherently achiral monochromophore systems in simple organic molecules. The measured level of CPL (|g(lum)|) in solution falls into the usual range of that obtained from other simple organic molecules (10(-5)-10(-2) range), but the latter having more complex architectures since axially chiral chromophores or multichromophore systems are usually required. The new design is based on chirally perturbing the acting achiral chromophore by orthogonally tethering a single axially chiral 1,1'-binaphtyl moiety to it.

Unprecedented induced axial chirality in a molecular BODIPY dye: strongly bisignated electronic circular dichroism in the visible region.

Enantiomeric bis(BODIPYs) 1a and 1b exhibit strong bisignated ECD due to the formation of a stable helical conformation with induced axial chirality, which allows efficient exciton coupling of the BODIPY chromophores in the Vis region.

Cheap and long-life reusable polymer for asymmetric organozinc catalysis based on camphor-derived hydroxyamides.

Polystyrene grafted with a chiral zinc-complexing camphor-derived N,N-disubstituted hydroxyamide is proposed as a new type of functional polymer of high reusability for the development of sustainable organozinc-catalyzed asymmetric reactions. The main goal of this new functional polymer is the ease of the hydroxyamide-moiety preparation (cheap chiral ligand obtained straightforwardly from an enantiopure starting material coming from the chiral pool), as well as its chemical robustness when compared with other related zinc-complexing functional groups. The latter allows the polymer to be active after multiple applications, without significant loss of its catalytic activity.