Vibrational-Mode-Selective Modulation of Electronic Excitation.

Vibrational-mode-selective modulation of electronic excitation is conducted with a synchronized femtosecond (fs) visible (vis) pulse and a picosecond (ps) infrared (IR) pulse. The mechanism of modulation of vibrational and vibronic relaxation behavior of excited state is investigated with ultrafast vis/IR, IR/IR, and vis-IR/IR transient spectroscopy, optical gating experiments and theoretical calculations. An organic molecule, 4'-(N,N-dimethylamino)-3-methoxyflavone (DMA3MHF) is chosen as the model system. Upon 1608 cm-1 excitation, the skeleton stretching vibration of DMA3MHF is energized, which can significantly increase the Franck-Condon factor for electronic transition, facilitate the radiative decay and promote emission from vibrational excited states. As results, a remarkable enhancement and a slight blueshift in fluorescence are observed. The mode-selective modulation of electronic excitation is not limited in luminescence or photophysics. It is expected to be widely applicable in tuning many photochemical processes.

Spin-Frustrated Trisradical Trication of PrismCage.

Organic trisradicals featuring threefold symmetry have attracted significant interest because of their unique magnetic properties associated with spin frustration. Herein, we describe the synthesis and characterization of a triangular prism-shaped organic cage for which we have coined the name PrismCage6+ and its trisradical trication─TR3(•+). PrismCage6+ is composed of three 4,4'-bipyridinium dications and two 1,3,5-phenylene units bridged by six methylene groups. In the solid state, PrismCage6+ adopts a highly twisted conformation with close to C3 symmetry as a result of encapsulating one PF6- anion as a guest. PrismCage6+ undergoes stepwise reduction to its mono-, di-, and trisradical cations in MeCN on account of strong electronic communication between its 4,4'-bipyridinium units. TR3(•+), which is obtained by the reduction of PrismCage6+ employing CoCp2, adopts a triangular prism-shaped conformation with close to C2v symmetry in the solid state. Temperature-dependent continuous-wave and nutation-frequency-selective electron paramagnetic resonance spectra of TR3(•+) in frozen N,N-dimethylformamide indicate its doublet ground state. The doublet-quartet energy gap of TR3(•+) is estimated to be -0.08 kcal mol-1, and the critical temperature of spin-state conversion is found to be ca. 50 K, suggesting that it displays pronounced spin frustration at the molecular level. To the best of our knowledge, this example is the first organic radical cage to exhibit spin frustration. The trisradical trication of PrismCage6+ opens up new possibilities for fundamental investigations and potential applications in the fields of both organic cages and spin chemistry.

One-Dimensional Organic Conjugated Polymers as Recyclable Heterogeneous Photocatalysts.

Organic conjugated polymers with long-range conjugation generally have strong light absorption capacity in the visible light region and impressive performance in charge transfer, which endows them great application potential in the field of opto-electronic materials. However, there are few reports on their use in photocatalytic reactions. At present, it has been reported that a variety of donor-acceptor (D-A) type organic dyes can be used in efficient organic photocatalytic transformations. We designed and synthesized one-dimensional organic conjugated polymers pPhCzBP-Th and pPhCzBP-DTh with D-A structure, and proved that they are good heterogeneous photo-redox catalysts, which can photocatalyze hydrodehalogenation reduction of α-bromoacetophenone and its derivatives. Due to the strong reducibility of the excited state, pPhCzBP-Th can also efficiently reduce α-chloroacetophenone. Furthermore, by simply wrapping the catalyst powder, high-efficient separation of products and catalysts recycling can be achieved.

Aromatic Stacking Mediated Spin-Spin Coupling in Cyclophane-Assembled Diradicals.

To investigate the capability of π-π stacking motifs to enable spin-spin coupling, we designed and synthesized three pairs of regio-isomers featuring two radical moieties joined by a [2.2]paracyclophane (CP) unit. By fusing indeno units to CP, two partially stacked fluorene radicals are covalently linked, exhibiting evident antiferromagnetic (AFM) coupling regardless of the orientation of two spins. Remarkably, while possessing high diradical indices of 0.8 and 0.9, the two molecules demonstrate good air stability by virtue of their singlet ground state. Single crystals help unravel the structural basis of their AFM coupling behaviors. When two radical centers are arranged at the pseudometa-positions around CP, the face-to-face stacked phenylene rings intrinsically confer orbital interactions that promote AFM coupling. On the other hand, if two radicals are directed in the pseudopara-orientation, significant orbital overlapping is observed between the radical centers (i.e., C9 of fluorene) and the aromatic carbons laid on the side, rendering AFM coupling between the two spins. In contrast, when two fluorene radicals are tethered to CP via C9 through a single C-C bond, ferromagnetic (FM) coupling is manifested by both diradical isomers featuring pseudometa- and pseudopara-connectivity. With minimal spin distributed on CP and thus limited contribution from π-π stacking, their spin-spin coupling properties are more similar to a pair of nitroxide diradical analogues, in which the two spins are dominantly coupled via through-space interactions. From these results, important conclusions are elucidated such as that although through-space interactions may confer FM coupling, with weakened strength shown by PAH radicals due to their lower polarity, face-to-face stacked π-frameworks tend to induce AFM coupling, because favorable orbital interactions are readily achieved by PAH systems hosting delocalized spins that are capable of adopting varied stacking motifs.

Photocontrolled RAFT Polymerization Catalyzed by Conjugated Polymers under Aerobic Aqueous Conditions.

Photocontrolled polymerization offers a convenient way to direct the reaction progress and tailor the polymer structures. Nevertheless, conjugated polymers are yet to be utilized as the photocatalyst in associated reactions. Herein, we employed poly(boron dipyrromethene-alt-fluorene) (PBF), a conjugated polymer with better photostability than eosin Y, as the photocatalyst for photo-RAFT polymerizations of acrylic monomers, and the polymers were obtained with moderately narrow molecular weight distributions. The reaction progress was effectively controlled by switching irradiation conditions, and the block copolymers were prepared from chain extension of a macroinitiator. As electron spin resonance (ESR) and optical spectra results suggested, the reductive quenching of PBF* by ascorbate was the key step leading to the reduction of a chain transfer agent (CTA), whereas the hydroxyl radical derived from superoxide was considered as a byproduct of deoxygenation.

Cyclometalated iridium(iii) complex nanoparticles for mitochondria-targeted photodynamic therapy.

Cyclometalated Ir(iii) complexes, with a long triplet state lifetime and good photophysical properties, are good candidates for simultaneous imaging and photodynamic therapy (PDT). Herein, we synthesize a cyclometalated Ir(iii) complex, Ir(tiq)2ppy, whose triplet excited state lifetime is 2.9 µs and singlet oxygen generation quantum yield is approximately 100% (compared to tetraphenylporphyrin). Ir(tiq)2ppy nanoparticles (Ir(tiq)2ppy NPs) are prepared to achieve water solubility and mitochondria-targeting ability by co-precipitating with polystyrene grafted with carboxyl-terminated poly(ethylene glycol) (PS-PEG). Ir(tiq)2ppy NPs have higher PDT efficiency than Ir(tiq)2ppy at concentrations as low as 1.6 µg mL-1 for MCF-7 breast cancer cells under white light irradiation at quite low light intensity (5 mW cm-2). Besides, it is worth noting that the emission quenching of Ir(tiq)2ppy in aqueous solution has been conquered by using Ir(tiq)2ppy NPs, thus the distribution of the therapeutic agents in mitochondria can be tracked by confocal laser scanning microscopy (CLSM). The mechanism of killing cancer cells under irradiation is investigated, and the results indicate that cell death is caused by mitochondria-mediated apoptosis, which is induced by the ROS generated under light irradiation.

Toward Möbius and Tubular Cyclopolyarene Nanorings via Arylbutadiyne Macrocycles.

By harnessing a highly efficient metal-catalyzed tandem cycloaddition reaction as the key benzannulation step, a series of cyclopolyarene nanorings of varied sizes are obtained from poly(arylene-butadiynylene) macrocyclic precursors, which can be synthesized relatively conveniently. Interestingly, due to the nonparallel bond connectivity of the repeat unit, unique Möbius topology is manifested by the cyclopolyarene nanorings composed of an odd number of repeat units, whereas cylindrical tubular structures with radial conjugation are formed with those consisting of an even number of repeat units.

Pressure-Induced Emission Enhancement and Multicolor Emission for 1,2,3,4-Tetraphenyl-1,3-cyclopentadiene: Controlled Structure Evolution.

Mechanoresponsive luminescent (MRL) materials have attracted considerable attention because of their potential applications in mechanical sensors, memory chips, and security inks; MRL materials possessing high efficiency and multicolor emission qualities are especially interesting. In this Letter, we found 1,2,3,4-tetraphenyl-1,3-cyclopentadiene (TPC) crystal exhibited both pressure-induced emission enhancement (PIEE) and multicolor behavior. In addition, infrared spectroscopy analysis indicated that the ring-opening reaction of the phenyl ring occurred when pressure was beyond 24.7 GPa. The reaction was promoted from 24.7 to 35.9 GPa, which resulted in the redder irreversible color change for the sample released from 35.9 GPa than from 24.7 GPa. The results regarding the mechanoresponsive behavior of TPC offered a deep insight into PIEE and multicolor properties from the structural point of view and inspired the idea of capturing different colors by hydrostatic pressure, which will facilitate the design of and search for high-performance MRL materials.

Visible responses under high pressure in crystals: phenolphthalein and its analogues with adjustable ring-opening threshold pressures.

The ring-opening reaction of phenolphthalein (PP) crystals under hydrostatic pressure provided by using a diamond anvil cell (DAC) is described in this paper for the first time. The color of the crystals changed into red from colorless visibly. The ring-opening threshold pressures could be adjusted by changing the substituent groups. Mechanochromic responses under hydrostatic pressure could also be achieved in polymer blends, which contributes to their practical applications.

Building a Cocrystal by Using Supramolecular Synthons for Pressure-Accelerated Heteromolecular Azide-Alkyne Cycloaddition.

Facilitated by the supramolecular synthons of carboxylic acids and amides through cooperative hydrogen-bonding and arene-perfluoroarene interactions, the azide-alkyne cycloaddition reaction between two different molecules in a cocrystal was achieved. This reaction could be accelerated by pressure using a common hydraulic press equipment with excellent regioselectivity to yield 1,4-triazole products. The absence of decarboxylation side reactions in the products in the solid state demonstrated that this strategy can provide a green synthetic route for products not directly accessible by traditional syntheses in solution.

Reactive Amphiphilic Conjugated Polymers for Inhibiting Amyloid ß Assembly.

Protein misfolding and aberrant aggregations are associated with multiple prevalent and intractable diseases. Inhibition of amyloid assembly is a promising strategy for the treatment of amyloidosis. Reported here is the design and synthesis of a reactive conjugated polymer, a poly(p-phenylene vinylene) derivative, functionalized with p-nitrophenyl esters (PPV-NP) and it inhibits the assembly of amyloid proteins, degrades preformed fibrils, and reduces the cytotoxicity of amyloid aggregations in living cells. PPV-NP is attached to the proteins through hydrophobic interactions and irreversible covalent linkage. PPV-NP also exhibited the capacity to eliminate Aß plaques in brain slices in ex vivo assays. This work represents an innovative attempt to inhibit protein pathogenic aggregates, and may offer insights into the development of therapeutic strategies for amyloidosis.

Enhanced Triplet Sensitizing Ability of an Iridium Complex by Intramolecular Energy-Transfer Mechanism.

The photodynamic properties involving both intra- and intermolecular triplet energy transfers (ET) of a bichromophoric photosensitizer having a tris-cyclometalated Ir(III) tethered with a pyrene derivative are studied. Due to the triplet energy gap of the two chromophores, a reversible intramolecular triplet ET equilibrium is quickly established upon photoexcitation, with the triplet exciton mainly residing on the acceptor side in the photostationary state. By virtue of the very small decay rate of triplet pyrene, a considerably extended triplet lifetime (2 ms) is observed. Next, the intermolecular triplet-triplet ET properties are investigated. Using steady-state and time-resolved spectroscopy, the ET rate constants from the Ir complex and pyrene unit in the sensitizer to an external triplet acceptor (unattached, free pyrene derivative) in solution are found to be around 109 s-1 and 108 M -1 s-1, respectively. In spite of a lower ET rate constant, the tethered pyrene serves as the main intermolecular ET channel because of the large, favorable intramolecular ET equilibrium ( K ∼ 103). Importantly, this cascade ET process, from Ir complex to linked pyrene, and then to free pyrene, offers an overall improved ET efficiency than a direct ET from Ir complex to free pyrene, by virtue of the much smaller spontaneous decay rate compared to that of the metal complex. Finally, the more efficient ET ability is demonstrated experimentally by applying the molecule as sensitizer in a triplet-triplet annihilation upconversion. The bichromophoric sensitizer achieved upconverted emission intensity 5 times higher than a monochromophoric Ir-complex analogue.

Energy Transfer Dynamics in Triplet-Triplet Annihilation Upconversion Using a Bichromophoric Heavy-Atom-Free Sensitizer.

A heavy-atom-free triplet sensitizer suitable for triplet-triplet annihilation-based photon upconversion was developed from the thermally activated delayed fluorescence (TADF) molecule 4CzPN by covalently tethering a pyrene derivative (DBP) as a triplet acceptor. The triplet exciton produced by 4CzPN is captured by the intramolecular pyrenyl acceptor and subsequently transferred via intermolecular triplet-triplet energy transfer (TTET) to freely diffusing pyrenyl acceptors in toluene. Transient absorption and time-resolved photoluminescence spectroscopy were employed to examine the dynamics of both the intra- and intermolecular TTET processes, and the results indicate that the intramolecular energy transfer from 4CzPN to DBP is swift, quantitative, and nearly irreversible. The reverse intersystem crossing is suppressed while intersystem crossing remains efficient, achieving high triplet yield and long triplet lifetime simultaneously. The ultralong excited state lifetime characteristic of the DBP triplet was shown to be crucial for enhancing the intermolecular TTET efficiency and the subsequent triplet-triplet annihilation photochemistry. It was also demonstrated that with the long triplet lifetime of the tethered DBP, TTET was enabled under low free acceptor concentrations and/or with sluggish molecular diffusion in polymer matrixes.

GZD824 suppresses the growth of human B cell precursor acute lymphoblastic leukemia cells by inhibiting the SRC kinase and PI3K/AKT pathways.

Available therapeutic options for advanced B cell precursor acute lymphoblastic leukemia (pre-B ALL) are limited. Many lead to neutropenia, leaving patients at risk of life-threatening infections and result in bad outcomes. New treatment options are needed to improve overall survival. We previously showed that GZD824, a novel BCR-ABL tyrosine kinase inhibitor, has anti-tumor activity in Philadelphia chromosome-positive (Ph+) chronic myeloid leukemia cells and tumor models. Here, we show that GZD824 decreases cell viability, induces cell-cycle arrest, and causes apoptosis in pre-B ALL cells. Furthermore, Ph- pre-B ALL cells were more sensitive to GZD824 than Ph+ pre-B ALL cells. GZD824 consistently reduced tumor loads in Ph- pre-B ALL xenografts but failed to suppress Ph+ pre-B ALL xenografts. GZD824 decreased phosphorylation of SRC kinase, STAT3, RB and C-myc. It also downregulated the expression of BCL-XL, CCND1 and CDK4 and upregulated expression of CCKN1A. Expression of IRS1 was decreased in GZD824-treated pre-B ALL cells, blocking the PI3K/AKT pathway. These data demonstrate that GZD824 suppresses pre-B ALL cells through inhibition of the SRC kinase and PI3K/AKT pathways and may be a potential therapeutic agent for the management of pre-B ALL.

Bright long-lived luminescence of silicon nanocrystals sensitized by two-photon absorbing antenna.

Silicon nanocrystals of the average diameter of 5 nm, functionalized with 4,7-di(2-thienyl)-2,1,3-benzothiadiazole chromophores (TBT) and dodecyl chains, exhibit near-infrared emission upon one-photon (1P) excitation at 515 nm and two-photon (2P) excitation at 960 nm. By using TBT chromophores as an antenna we were able to enhance both 1P and 2P absorption cross-sections of the silicon nanocrystals to more efficiently excite their long-lived luminescence. These results chart a path to two-photon-excitable imaging probes with long-lived oxygen-independent luminescence - a rare combination of properties that should allow for a substantial increase in imaging contrast.

Pressure-Induced Emission Enhancement of Carbazole: The Restriction of Intramolecular Vibration.

Pressure-induced emission enhancement (PIEE), a novel phenomenon in the enhancement of the solid-state emission efficiency of fluorophores, has been arousing wide attention in recent years. However, research on PIEE is still in the early stage. To further pursue more enhanced efficiency, discovering and designing more PIEE systems would be urgently desirable and of great importance. In this Letter, we found that carbazole presented a conspicuous emission enhancement under high pressure up to 1.0 GPa. In situ high-pressure infrared spectroscopy and angle-dispersive X-ray diffraction analysis combined with Hirshfeld surface theory calculation indicated that the PIEE of carbazole was attributed to the decrease of the nonradiation vibration process. This phenomenon mainly resulted from restriction of the N-H stretching vibration by increased N-H···π interactions under high pressure. Our study puts forward a mechanism of PIEE related to the restriction of intramolecular vibration, which provided deep insight into the essential role of intermolecular interaction in fluorescence emission properties.

Heterogeneity of CD34 and CD38 expression in acute B lymphoblastic leukemia cells is reversible and not hierarchically organized.

The existence and identification of leukemia-initiating cells in adult acute B lymphoblastic leukemia (B-ALL) remain controversial. We examined whether adult B-ALL is hierarchically organized into phenotypically distinct subpopulations of leukemogenic and non-leukemogenic cells or whether most B-ALL cells retain leukemogenic capacity, irrespective of their immunophenotype profiles. Our results suggest that adult B-ALL follows the stochastic stem cell model and that the expression of CD34 and CD38 in B-ALL is reversibly and not hierarchically organized.

An intracellular anchor regulates the distribution of bioactive molecules.

Based on bioorthogonal tetrazine ligation, a pre-targeted anchor strategy was developed to regulate the intracellular distribution of bioactive molecules. This strategy could solve the issue regarding the permeability and targeting ability of bioactive molecules in the specific organelles of living cells.

Triplet-Triplet Annihilation Photon Upconversion in Polymer Thin Film: Sensitizer Design.

Efficient visible-to-UV photon upconversion via triplet-triplet annihilation (TTA) is accomplished in polyurethane (PU) films by developing new, powerful photosensitizers fully functional in the solid-state matrix. These rationally designed triplet sensitizers feature a bichromophoric scaffold comprising a tris-cyclometalated iridium(III) complex covalently tethered to a suitable organic small molecule. The very rapid intramolecular triplet energy transfer from the former to the latter is pivotal for achieving the potent sensitizing ability, because this process out-competes the radiative and nonradiative decays inherent to the metal complex and produces long-lived triplet excitons localized with the acceptor moiety readily available for intermolecular transfer and TTA. Nonetheless, compared to the solution state, the molecular diffusion is greatly limited in solid matrices, which even creates difficulty for the Dexter-type intramolecular energy transfer. This is proven by the experimental results showing that the sensitizing performance of the bichromophoric molecules strongly depends on the spatial distance separating the donor (D) and acceptor (A) units and that incorporating a longer linker between the D and A evidently curbs the TTA upconversion efficiency in PU films. Using a rationally optimized sensitizer structure in combination with 2,7-di-tert-butylpyrene as the annihilator/emitter, the doped polyurethane (PU) films demonstrate effective visible-to-UV upconverted emission signal under noncoherent-light irradiation, attaining an upconversion quantum yield of 2.6%. Such quantum efficiency is the highest value so far reported for the visible-to-UV TTA systems in solid matrices.

A Mechanochromic Single Crystal: Turning Two Color Changes into a Tricolored Switch.

The single crystal of M-4-B was obtained by attaching the boron of BH3 to the amine linker between a tetraphenylethylene (TPE) unit and rhodamine B. M-4-B showed a novel sequential tricolor switching from dark blue to bluish-green and to a reddish color upon grinding. The boron atom played a key role in developing the single crystal.