Boosting Circularly Polarized Luminescence from Alkyl-Locked Axial Chirality Scaffold by Restriction of Molecular Motions.

Boosting the circularly polarized luminescence of small organic molecules has been a stubborn challenge because of weak structure rigidity and dynamic molecular motions. To investigate and eliminate these factors, here, we carried out the structure-property relationship studies on a newly-developed axial chiral scaffold of bidibenzo[b,d]furan. The molecular rigidity was finely tuned by gradually reducing the alkyl-chain length. The environmental factors were considered in solution, crystal, and polymer matrix at different temperatures. As a result, a significant amplification of the dissymmetry factor glum from 10-4 to 10-1 was achieved, corresponding to the situation from (R)-4C in solution to (R)-1C in polymer film at room temperature. A synergistic strategy of increasing the intramolecular rigidity and enhancing the intermolecular interaction to restrict the molecular motions was thus proposed to improve circularly polarized luminescence. The though-out demonstrated relationship will be of great importance for the development of high-performance small organic chiroptical systems in the future.

A Conceptual Framework to Understand the Self-Assembly of Chemically Active Colloids.

Colloids that generate chemicals, or "chemically active colloids", can interact with their neighbors and generate patterns via forces arising from such chemical gradients. Examples of such assemblies of chemically active colloids are abundant in the literature, but a unified theoretical framework is needed to rationalize the scattered results. Combining experiments, theory, Brownian dynamics, and finite element simulations, we present here a conceptual framework for understanding how immotile, yet chemically active, colloids assemble. This framework is based on the principle of ionic diffusiophoresis and diffusioosmosis and predicts that a chemically active colloid interacts with its neighbors through short- and long-range interactions that can be either repulsive or attractive, depending on the relative diffusivity of the released cations and anions, and the relative zeta potential of a colloidal particle and the planar surface on which it resides. As a result, 4 types of pairwise interactions arise, leading to 4 different types of colloidal assemblies with distinct patterns. Using short-range attraction and long-range attraction (SALR) systems as an example, we show quantitative agreement between the framework and experiments. The framework is then applied to rationalize a wide range of patterns assembled from chemically active colloids in the literature exhibiting other types of pairwise interactions. In addition, the framework can predict what the assembly looks like with minimal experimental information and help infer ionic diffusivity and zeta potential values in systems where these values are inaccessible. Our results represent a solid step toward building a complete theory for understanding and controlling chemically active colloids, from the molecular level to their mesoscopic superstructures and ultimately to the macroscopic properties of the assembled materials.

Synthesis and Structural Characterization of Carbazole-Tailored Luminescent Triarylmethyl Radical and its Stable Cation.

The development of novel luminescent radicals, characterized by their unique doublet emission, endows a significant challenge. In this study, we reported the synthesis of a luminescent neutral radical, BCzAnM-R, tailored by two carbazolyl groups and an anthryl group to achieve a nonalternant structure. It exhibited near-infrared emission with a peak at 1020 nm in toluene. Interestingly, its corresponding cation, BCzAnM-C, was synthesized through an unconventional SnCl2-mediated reduction-aromatization-oxidation reaction in one-pot and gram-scale. The cation demonstrated remarkable stability for up to weeks in ambient conditions and facilitated the silica-gel chromatography isolation as an organic salt with SnCl3- as the counter ion. The carbazolyl groups effectively modulate molecular structures, photophysical properties, and stabilities. Notably, BCzAnM-R represents the first luminescent triarylmethyl radical with two carbazolyl groups directly attached to the central carbon.

Efficient Visible-Light-Activated Ultra-Long Room-Temperature Phosphorescence Triggered by Multi-Esterification.

The development of ultra-long room-temperature phosphorescence (UL-RTP) in processable amorphous organic materials is highly desirable for applications in flexible displays, anti-counterfeiting, and bio-imaging. However, achieving efficient UL-RTP from amorphous materials remains a challenging task, especially with activation by visible light and a bright afterglow. Here we report a general and rational molecular-design strategy to enable efficient visible-light-excited UL-RTP by multi-esterification of a rigid large-plane phosphorescence core. Notably, multi-esterification minimizes the aggregation-induced quenching and accomplishes a 'four birds with one stone' possibility in the generation and radiation process of UL-RTP: i) shifting the excitation from ultraviolet light to blue-light through enhancing the transition dipole moment of low-lying singlet-states, ii) facilitating the intersystem crossing process through the incorporation of lone-pair electrons, iii) boosting the decay process of long-lived triplet excitons resulting from a significantly increased transition dipole moment, and iv) reducing the intrinsic triplet nonradiative decay by substitution of high-frequency vibrating hydrogen atoms. All these factors synergistically contribute to the most efficient and stable visible-light-stimulated UL-RTP (lifetime up to 2.01 s and efficiency up to 35.4 % upon excitation at 450 nm) in flexible films using multi-esterified coronene, which allows high-tech applications in single-component time-delayed white light-emitting diodes and information technology based on flashlight-activated afterglow encryption.

Strong Circularly-Polarized Room-Temperature Phosphorescence from a Feasibly Separable Scaffold of Bidibenzo[b,d]furan with Locked Axial Chirality.

Novel accessible scaffold featuring circularly-polarized room-temperature phosphorescence (RTP) is attractive but challenging. Herein, we report a new feasibly separable bidibenzo[b,d]furan compound with strong circularly-polarized RTP when doping into the rigid polymer matrix. The simple silica-gel column can separate the absolute chiral R-isomer with excellent chiroptical properties. The experimental data reveal that the treated films exhibit an RTP efficiency of 14.8 %, a largest dissymmetric factor of 0.12, and a longest lifetime of 0.56 s under ambient conditions. It is found that reducing the nonradiative decays boosts the intrinsic circularly-polarized RTP emission. The impressive results indicate that the locked axial chirality skeleton endows the potential of achieving superior circularly-polarized emission for the small organic optoelectronic molecules.

Spiro-Functionalized Diphenylethenes: Suppression of a Reversible Photocyclization Contributes to the Aggregation-Induced Emission Effect.

Many aggregation-induced emission (AIE) materials are featured by the diphenylethene (DPE) moiety which exhibits rich photophysical and photochemical activities. The understanding of these activities behind AIE is essential to guide the design of fluorescent materials with improved performance. Herein by fusing a flexible DPE with a rigid spiro scaffold, we report a class of novel deep-blue material with solid-state fluorescent quantum yield (ΦF) up to 99.8%. Along with the AIE phenomenon, we identified a reversible photocyclization (PC) on DPE with visible chromism, which is, on the contrary, popularized in solutions but blocked by aggregation. We studied the steric and electronic effects of structural perturbation and concluded that the PC is a key process behind the RIMs (restriction of intramolecular motions) mechanism for these materials. Mitigation of the PC leads to enhanced fluorescence in solutions and loss of the AIE characteristics.

How does hard-to-reach status affect antiretroviral therapy adherence in the HIV-infected population? Results from a meta-analysis of observational studies.

BACKGROUND: Socially disadvantaged groups, such as drug users, sex workers and homeless individuals, are labelled as "hard-to-reach" (HTR) in public health and medical research. HIV disproportionately impacts these populations, but data on how the HTR status could affect antiretroviral therapy (ART) adherence among HIV-positive people are limited and have not been previously synthesized in a systematic manner. We performed a meta-analysis to explore the association between HTR status and optimal antiretroviral therapy adherence in the HIV-infected population to provide evidence and recommendations regarding ART adherence improvement and HIV infection control and prevention among HTR people. METHODS: The PubMed, EMBASE, and Cochrance Library databases and the bibliographies of relevant studies were systematically searched up to December 2018. Full-text studies published in English were included, and no geographic or race restrictions were applied. Studies that quantitatively assessed the association between HTR status and optimal ART adherence among HIV-infected populations with a status of homelessness, sex work, or drug use were eligible for inclusion. We estimated the pooled odds ratios (ORs) of HTR characteristics related to ART adherence from each eligible study using a random effects model. The sensitivity, heterogeneity and publication bias were assessed. RESULTS: Our search identified 593 articles, of which 29 studies were eligible and included in this meta-analysis. The studies were carried out between 1993 and 2017 and reported between 1999 and 2018. The results showed that HTR status resulted in a 45% reduction in the odds of achieving optimal ART adherence compared to odds in the general population (OR = 0.55, 95% confidential intervals (CIs) 0.49-0.62), and this significant inverse association was consistently found regardless of study design, exposure measurement, adherence cut-off points, etc. Subgroup analyses revealed that the HTRs tend to be suboptimal adhering during a longer observational period. CONCLUSIONS: HIV treatment adherence is extremely negatively affected by HTR status. It is crucial to develop appropriate interventions to improve ART adherence and health outcomes among HTR people who are HIV-infected.

Synthesis of poly(1,5-diaminonaphthalene) microparticles with abundant amino and imino groups as strong adsorbers for heavy metal ions.

Poly(1,5-diaminonaphthalene) microparticles with abundant reactive amino and imino groups on their surface were synthesized by one-step oxidative polymerization of 1,5-diaminonaphthalene using ammonium persulfate as the oxidant. The molecular, supramolecular, and morphological structures of the microparticles were systematically characterized by IR and UV-vis spectroscopies, elementary analysis, wide-angle X-ray diffractometry, and transmission electron microscopy. The microparticles demonstrate electrical semiconductivity and high resistance to strong acid and alkali, and strong adsorption capability for lead(II), mercury(II), and silver(I) ions. The experimental conditions for adsorption of Pb(II) were optimized by varying the persulfate/monomer ratio, adsorption time, sorbent concentration, and pH value of the Pb(II) solution. The maximum adsorption capacity is 241 mg·g-1 for particles after a 24 h-exposure to a solution at an initial Pb(II) concentration of 29 mM. The adsorption data fit a Langmuir isotherm and follow a pseudo-second-order reaction kinetics. This indicates a chemical adsorption that is typical for a chelation interaction between Pb(II) and amino/imino groups on the sorbent. Graphical abstract Poly(1,5-diaminonaphthalene) microparticles with abundant functional amino and imino groups have been synthesized by one-step direct polymerization of non-volatile 1,5-diaminonaphthalene in aqueous medium for sustainable preparation of high-performance adsorbents to strongly adsorb lead(II), mercury(II), and silver(I) ions.

Multiple Anti-Counterfeiting Guarantees from a Simple Tetraphenylethylene Derivative - High-Contrasted and Multi-State Mechanochromism and Photochromism.

Herein the novel tetraphenylethylene (TPE) derivative 1 was designed with an integration of aggregation-induced emission (AIE), multi-state mechanochromism and self-recovery photochromism. The molecule was susceptible to grinding, heating and vapor fuming and showed corresponding transition of its emission colors. The heated powder or single crystal of 1 exhibited reversible photochromism. After a short period of UV irradiation, it showed a bright red color, but recovered to its original white appearance within 1 min. The photochromism is due to the formation of photocyclization intermediates upon UV irradiation, while the eversible mechanochromism is attributed to the weak molecular interactions derived from head-to-tail stacking of the molecules. This reversible multi-state, high-contrasted and rapid responsive mechanochromic and photochromic property cooperatively provide double enhancement of a multimode guarantee in advanced anti-counterfeiting.

Designing Efficient and Ultralong Pure Organic Room-Temperature Phosphorescent Materials by Structural Isomerism.

Pure organic materials with ultralong room-temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, they generally show inefficient intersystem crossing (ISC) owing to weak spin-orbit coupling (SOC). A design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔEST ) and pure ππ* configuration of the lowest triplet state (T1 ) via structural isomerism was used to obtain efficient and ultralong RTP materials. The meta isomer of carbazole-substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1 %. Study of the structure-property relationship shows that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔEST and pure ππ* configuration of T1 .

Why Do Simple Molecules with "Isolated" Phenyl Rings Emit Visible Light?

π-Bonds connected with aromatic rings were generally believed as the standard structures for constructing highly efficient fluorophores. Materials without these typical structures, however, exhibited only low fluorescence quantum yields and emitted in the ultraviolet spectral region. In this work, three molecules, namely bis(2,4,5-trimethylphenyl)methane, 1,1,2,2-tetrakis(2,4,5-trimethylphenyl)ethane, and 1,1,2,2-tetraphenylethane, with nonconjugated structures and isolated phenyl rings were synthesized and their photophysical properties were systematically investigated. Interestingly, the emission spectra of these three molecules could be well extended to 600 nm with high solid-state quantum yields of up to 70%. Experimental and theoretical analyses proved that intramolecular through-space conjugation between the "isolated" phenyl rings played an important role for this abnormal phenomenon.

A Luminescent Nitrogen-Containing Polycyclic Aromatic Hydrocarbon Synthesized by Photocyclodehydrogenation with Unprecedented Regioselectivity.

We present a nitrogen-containing polycyclic aromatic hydrocarbon (N-PAH), namely 12-methoxy-9-(4-methoxyphenyl)-5,8-diphenyl-4-(pyridin-4-yl)pyreno[1,10,9-h,i,j]isoquinoline (c-TPE-ON), which exhibits high quantum-yield emission both in solution (blue) and in the solid state (yellow). This molecule was unexpectedly obtained by a three-fold, highly regioselective photocyclodehydrogenation of a tetraphenylethylene-derived AIEgen. Based on manifold approaches involving UV/Vis, photoluminescence, and NMR spectroscopy as well as HRMS, we propose a reasonable mechanism for the formation of the disk-like N-PAH that is supported by density functional theory calculations. In contrast to most PAHs that are commonly used, our system does not suffer from entire fluorescence quenching in the solid state due to the peripheral aromatic rings preventing π-π stacking interactions, as evidenced by single-crystal X-ray analysis. Moreover, its rod-like microcrystals exhibit excellent optical waveguide properties. Hence, c-TPE-ON comprises a N-PAH with unprecedented luminescent properties and as such is a promising candidate for fabricating organic optoelectronic devices. Our design and synthetic strategy might lead to a more general approach to the preparation of solution- and solid-state luminescent PAHs.

Aggregation-Induced-Emission-Active Macrocycle Exhibiting Analogous Triply and Singly Twisted Möbius Topologies.

Molecules with Möbius topology have drawn increasing attention from scientists in a variety of fields, such as organic chemistry, inorganic chemistry, and material science. However, synthetic difficulties and the lack of functionality impede their fundamental understanding and practical applications. Here, we report the facile synthesis of an aggregation-induced-emission (AIE)-active macrocycle (TPE-ET) and investigate its analogous triply and singly twisted Möbius topologies. Because of the twisted and flexible nature of the tetraphenylethene units, the macrocycle adjusts its conformations so as to accommodate different guest molecules in its crystals. Moreover, theoretical studies including topological and electronic calculations reveal the energetically favorable interconversion process between triply and singly twisted topologies.

Temperature-Modulated Evolution of Surface Structures Induces Significant Enhancement of Two-Photon Fluorescent Emission from a Dye Molecule.

Fluorescence is an essential property of molecules and materials that plays a pivotal role across various areas such as lighting, sensing, imaging, and other applications. For instance, temperature-sensitive fluorescence emission is widely utilized for chemo-/biosensing but usually decreases the intensity upon the increase in temperature. In this study, we observed a temperature-induced enhancement of up to ∼150 times in two-photon fluorescence (TPF) emission from a dye molecule, 4-(4-diethylaminostyry)-1-methylpyridinium iodide (D289), as it interacted with binary complex vesicles composed of two commonly applied surfactants: sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB). By employing second harmonic generation (SHG) and TPF techniques, we clearly revealed the temperature-dependent kinetic behavior of D289 on the surface of the vesicles and utilized it to interpret the origin of the significant TPF enhancement. Additionally, we also demonstrated a similar heating-induced enhancement of the TPF emission from D289 on the membrane of phospholipid vesicles, indicating the potential application of TPF in temperature sensing in the biology systems. The embedding of D289 in the tightly packed alkane chains was identified as the key factor in enhancing the TPF emission from D289. This finding may provide valuable information for synthesizing fluorescence materials with a high optical yield.

Utilizing weakly donor-acceptor ternary π-conjugated architecture to achieve single-component white luminescence and stimulus-responsive room-temperature phosphorescence.

Purely organic room-temperature phosphorescence (RTP) has garnered substantial attention for its delayed emission, environmental sensitivity, and potential diverse applications. However, the quest for high-performance RTP materials has always been a challenge. In this study, we introduce novel weakly donor-acceptor (D-A) ternary π-conjugated architecture to construct an efficient RTP system. The strategy utilizes synergistic effects of the analogous El-Sayed rule, halogen-free heavy-atom effect, reduction of the singlet-triplet energy gap, and manipulation of flexible molecular conformation. A remarkable enhancement in the phosphorescence-to-fluorescence ratio was achieved, elevating from 0.4 in carbazole to 35.2 in DBTDBTCZ. Furthermore, the RTP system demonstrates single-component white luminescence, yielding warm and cool white colors. Intriguingly, we unveil the novel position-dependent heavy-atom effects, discerningly promoting intersystem crossing or phosphorescence decay. Benefiting from efficient RTP, multifunctional applications of real-time humidity monitoring, oxygen sensing, anti-counterfeiting labeling, and white lighting are demonstrated.

Can medication management review reduce anticholinergic burden (ACB) in the elderly? Encouraging results from a theoretical model.

BACKGROUND: Review of recent journal articles and various relevant current textbooks provides strong evidence to show that anticholinergic burden is a material issue in frail and at-risk patients. This study assesses the anticholinergic burden in a group of patients in residential care facilities and then applies a theoretical intervention model. It is based on a scoring system known as the Anticholinergic Cognitive Burden (ACB) scale, and attempts to reduce the anticholinergic burden while maintaining therapeutic benefits. METHODS: A database of 691 patients was analyzed for each individual's ACB based on the scale of scoring produced by groups of experts in the area. A theoretical intervention was then conducted using relevant, evidence-based practice guidelines for clinical therapeutics in Australia. The intervention had the aim of reducing the total ACB without affecting the apparent intended effectiveness of the prescribed therapy. RESULTS: Of the 35% (n = 242) patients who score at least 1 point on the ACB, a reduction is achievable in 59% of the cases. In particular, the reduction from a clinically significant score of 3 or above to 2 or below for 49 of those patients is possible in 85% of the cases. Overall, this represents a reduction from 7.10% to 1.01% for the entire population. It is also found that of the 246,960 counts of items dispensed (both prescription and non-prescription) for these patients, 47,334 (or 19.2%) of these were of agents on the ACB scale. CONCLUSIONS: The study found that it appears to be possible that the total ACB of a group of 691 patients can be significantly reduced.

Manipulating D-A interaction to achieve stable photoinduced organic radicals in triphenylphosphine crystals.

New strategies for the design and synthesis of stable organic radicals without additives are highly desirable. Herein, we design a series of donor-acceptor structured triarylphosphines and disclose the fast color change triggered by UV-irradiation in the crystalline state. Photoinduced organic radicals are undoubtedly verified and proved to be the reason for the color change by time-dependent and quantitative electron paramagnetic resonance analysis, X-ray crystallographic analysis, and theoretical calculations. It is revealed that the intrinsic symmetry breaking of peripheral architecture helps to form continuous molecular chains by donor-acceptor counterpart pairing. Intermolecular electron-transfer occurs among molecular chains and results in radical ion pairs upon photoirradiation.

Activating Molecular Room-Temperature Phosphorescence by Manipulating Excited-State Energy Levels in Poly(vinyl alcohol) Matrix.

Poly(vinyl alcohol) (PVA) has been found as a wonderful matrix for chromophores to boost their room-temperature phosphorescence (RTP) character by forming abundant hydrogen bonding. Despite the well-utilized protective effect, the constructive role in accelerating the intersystem crossing is less investigated. Here, we focus on its role in manipulating the excited-state energy level to facilitate multiple intersystem crossing channels. Six benzoyl carbazole derivatives do not emit RTP in their solutions, powders, or crystals but exhibit significantly persistent RTP signals when embedded into the PVA matrix. Charge-transfer excited states were trapped by cofacial stacking in crystal, which blocks the intersystem crossing channels. In the PVA matrix, the allowed broad distribution of charge-transfer states covers the locally excited states, offering multiple intersystem crossing pathways via spin-vibronic orbit coupling. Consequently, efficient and persistent heavy-atom-free phosphors have been developed with the highest quantum yields of 7.7% and the longest lifetime of 2.3 s.

Anti-Kasha triplet energy transfer and excitation wavelength dependent persistent luminescence from host-guest doping systems.

Anti-Kasha's process in organic luminogens has attracted many attentions since its discovery. However, only limited examples of anti-Kasha's rule have been reported and anti-Kasha triplet energy transfer (ET) is even less-touched. Benefiting from anti-Kasha's rule, this work provided an efficient strategy to realize excitation wavelength dependent (Ex-De) afterglow in a host-guest system. The host has almost imperceptible RTP upon 365 nm excitation and guest is totally RTP inactive, while the doping host-guest system exhibits Ex-De afterglow with improved quantum yields. Anti-Kasha triplet ET process is realized from the higher excited triplet state T2 of host to the lowest excited singlet state S1 of the aggregated/unimolecular guest. ET efficiency in the doping system could be tuned by simply changing its processing methods to guide host and guest to adopt denser or looser intermolecular packing. The strategy of anti-Kasha triplet ET endows the host-guest doping system with multiple stimuli-responsive properties, including Ex-De afterglow, mechano-, and thermal-triggered afterglow behaviors. The corresponding applications of these properties are also realized in multiple information anti-counterfeiting and display.

A dual organelle-targeting mechanosensitive probe.

Cells are responsive to the mechanical environment, but the methods to detect simultaneously how different organelles react in mechanobiological processes remain largely unexplored. We herein report a dual organelle-targeting fluorescent probe, (E)-1-[3-(diethoxyphosphoryl)propyl]-4-[4-(diethylamino)styryl]pyridin-1-ium bromide (ASP-PE), for mechanical mapping in live cells. ASP-PE is aggregation-induced emission active and is sensitive to the local mechanical environment. It targets the plasma membrane (PM) and intracellular mitochondria in cells by its phosphonate moiety and pyridinium. In this work, through ASP-PE staining, changes of membrane tension in the PM and mitochondria in response to varied osmotic pressure and substrate stiffness are visualized using fluorescence lifetime imaging microscopy. The mechanobiological importance of actin filaments and microtubules in the PM and mitochondria is also investigated using this probe. Computational simulations are applied to study the sensing mechanism of the probe. This study introduces a unique tool for mapping the membrane tension in the PM and mitochondria together, providing us great opportunities to study organelle's interactions in mechanobiology.