Full-Quantum Treatment of Molecular Systems Confirms Novel Supracence Photonic Properties.

Our understanding of molecules has stagnated at a single quantum system, with atoms as Newtonian particles and electrons as quantum particles. Here, however, we reveal that both atoms and electrons in a molecule are quantum particles, and their quantum-quantum interactions create a previously unknown, newfangled molecular property-supracence. Molecular supracence is a phenomenon in which the molecule transfers its potential energy from quantum atoms to photo-excited electrons so that the emitted photon has more energy than that of the absorbed one.

Cooperatively assembled liquid crystals enable temperature-controlled Förster resonance energy transfer.

Balancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal-optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system.

Molecular Supracence Resolving Eight Colors in 300-nm Width: Unprecedented Spectral Resolution.

Monitoring multiple molecular probes simultaneously establishes their correlations and reveals the holistic mechanism. Current fluorescence imaging, however, is limited to about four colors because of typically circa 100-nm spectral width. Herein, we show that molecular supracence imparts superior spectral resolution, resolving eight colors in 300-nm width, about 37.

Discovery of a New Light-Molecule Interaction: Supracence Reveals What Is Missing in Fluorescence Imaging.

The currently understood principles about light-molecule interactions are limited, and thus scientific scope beyond current theories is rarely harvested. Herein we demonstrate supracence phenomena, in which the emitted photons have more energy than the absorbed photons. The extra energy comes from couplings of the absorbed and emitted photon to molecular phonons, whose potentials are constantly exchanging with molecular quantum energy and the environment.

Chemomechanical-force-induced folding-unfolding directly controls distinct fluorescence dual-color switching.

Folding-unfolding imparts fluorescence dual color switching, thus a novel concept to switch fluorescence between two distinct colors while avoiding traditional bond rupturing and bond forming in photoswitching. Because folding and unfolding minimize the wear and tear on molecular structures, the new systems have excellent reversibility and fatigue resistance.

Photoswitchable fluorescent nanoparticles and their emerging applications.

Although fluorescence offers ultrasensitivity, real-world applications of fluorescence techniques encounter many practical problems. As a noninvasive means to investigate biomolecular mechanisms, pathways, and regulations in living cells, the intrinsic heterogeneity and inherent complexity of biological samples always generates optical interferences such as autofluorescence. Therefore, innovative fluorescence technologies are needed to enhance measurement reliability while not compromising sensitivity.

Reversible photoswitching specifically responds to mercury(II) ions: the gated photochromism of bis(dithiazole)ethene.

Photoswitching of bis(dithiazole)ethene can be regulated by Hg(II) ions and EDTA in a "lock-and-unlock" manner. The molecular photoswitch provides an enzyme-like binding pocket that selectively binds specifically to mercury ions, thus modulating the degree of photoswitching in its presence.

Chromophoric and dendritic phosphoramidites enable construction of functional dendrimers with exceptional brightness and water solubility.

The fluorescence brightness of a molecular probe determines whether it can be effectively measured and its water solubility dictates if it can be applied in real-world biological systems. However, molecules brighter than the most efficient fluorescent dyes or particles brighter than quantum dots are hard to come by, especially when they must also be soluble in water. In this report, chromophoric phosphoramidites are used in a solid-state synthesis to construct functional dendrimers.

Quantitative photoswitching in bis(dithiazole)ethene enables modulation of light for encoding optical signals.

Using one ray of light to encode another ray of light is highly desirable because information in optical format can be directly transferred from one beam to another without converting back to the electronic format. One key medium to accomplish such an amazing task is photoswitchable molecules. Using bis(dithiazole)ethene that can be photoswitched between its ring-open and ring-closed states quantitatively with excellent fatigue resistance and high thermal stability, it is shown that quantitative photoreversibility allowed the photoswitching light to control other light travelling through the photoswitchable medium, a phenomenon of transferring information encoded in one light ray to others, thus imparting photo-optical modulation on the orthogonal light beam.

Understanding super-resolution nanoscopy and its biological applications in cell imaging.

Optical microscopy has been an ideal tool for studying phenomena in live cells because visible light at reasonable intensity does not perturb much of the normal biological functions. However, optical resolution using visible light is significantly limited by the wavelength. Overcoming this diffraction-limit barrier will reveal biological mechanisms, cellular structures, and physiological processes at a nanometer scale, orders of magnitude lower than current optical microscopy.

Photoswitching-enabled novel optical imaging: innovative solutions for real-world challenges in fluorescence detections.

Because of its ultrasensitivity, fluorescence offers a noninvasive means to investigate biomolecular mechanisms, pathways, and regulations in living cells, tissues, and animals. However, real-world applications of fluorescence technologies encounter many practical challenges. For example, the intrinsic heterogeneity of biological samples always generates optical interferences.

Photoswitching-induced frequency-locked donor-acceptor fluorescence double modulations identify the target analyte in complex environments.

Precisely identifying biological targets and accurately extracting their relatively weak signals from complicated physiological environments represent daunting challenges in biological detection and biomedical diagnosis. Fluorescence techniques have become the method of choice and offer minimally invasive and ultrasensitive detections, thus, providing a wealth of information regarding the biological mechanisms in living systems. Despite fluorescence analysis has advanced remarkably, conventional detections still encounter considerable limitations.

Self-assembled hollow nanospheres strongly enhance photoluminescence.

We report that two molecular building blocks differ only by two protons, yet they form totally different nanostructures. The protonated one self-organized into hollow nanospheres (~200 nm), whereas the one without the protons self-assembled into rectangular plates. Consequently, the geometrically defined nanoassemblies exhibit radically different properties.

Sequence-controlled oligomers fold into nanosolenoids and impart unusual optical properties.

Controlled syntheses give unique block oligomers with alternating flexible ethylene glycol and rigid perylenetetracarboxylic diimide (PDI) units. The number of rigid units vary from n=1 to 10. PDI units were stitched together by using efficient phosphoramidite chemistry.

Photoswitchable nanoprobes offer unlimited brightness in frequency-domain imaging.

A single probe has limited brightness in time-domain imaging and such limitation frequently renders individual molecules undetectable in the presence of interference or complex cellular structures. However, a single photoswitchable probe produces a signal, which can be separated from interference or noise using photoswitching-enabled Fourier transformation (PFT). As a result, the light-modulated probes can be made super bright in the frequency domain simply by acquiring more cycles in the time domain.

Reversible two-photon photoswitching and two-photon imaging of immunofunctionalized nanoparticles targeted to cancer cells.

Both photoswitchable fluorescent nanoparticles and photoactivatable fluorescent proteins have been used for super-resolution far-field imaging on the nanometer scale, but the photoactivating wavelength for such photochemical events generally falls in the near-UV (NUV) region (<420 nm), which is not preferred in cellular imaging. However, using two near-IR (NIR) photons that are lower in energy, we can circumvent such problems and replace NUV single-photon excitations (e.g.

Super-resolution fluorescence nanoscopy applied to imaging core-shell photoswitching nanoparticles and their self-assemblies.

Using photo-actuated unimolecular logical switching attained reconstruction (PULSAR) nanoscopy, the structures of photoswitchable polymeric nanoparticles self-assembled on the surfaces of CaCl(2) crystals at the nanoscale were revealed; the photoswitching events and the locations of the photoswitchable fluorescent dyes inside the hydrophobic cores of the core-shell type polymeric nanoparticles were determined.

The nuclear architectural protein HMGA1a triggers receptor-mediated endocytosis.

High mobility group proteins A (HMGA), nuclear architectural factors, locate in the cell nuclei and mostly execute gene-regulation function. However, our results reveal that a HMGA member (HMGA1a) has a unique plasma membrane receptor; this receptor specifically binds to HMGA-decorated species, effectively mediates endocytosis, and internalizes extracellular HMGA-functionalized cargoes. Indeed, dyes or nanoparticles labeled with HMGA1a protein readily enter Hela cells.

Cylindrical superparticles from semiconductor nanorods.

In this communication, we report a synthesis of anisotropic colloidal superparticles (SPs) from CdSe/CdS semiconductor nanorods. These anisotropic SPs are cylindrical disks or stacked-disk arrays. We attribute the major driving forces controlling the SP shape to interparticle interactions between nanorods and solvophobic interactions between a superparticle and its surrounding solvent.

Single-chromophore-based photoswitchable nanoparticles enable dual-alternating-color fluorescence for unambiguous live cell imaging.

We have developed a class of spiropyran dyes and their fluorescence colors can be reversibly photoswitched from red to green, blue, or nearly dark, thus alternating between two colors. Such individual dyes emit either one color or the other but not both simultaneously. Nanoparticles enabled with these photoswitchable dyes, however, emit either one pure color or a combination of both colors because the nanoparticle fluorescence originates from multiple dyes therein.