Tri-signal CdS@SiO2 nanoprobes for accurate and sensitive detection of human immunoglobulin G with enhanced flexibility and internal validation.

Accurate and sensitive determination of human immunoglobulin G (HIgG) level is critical for diagnosis and treatment of various diseases, including rheumatoid arthritis, humoral immunodeficiencies, and infectious disease. In this study, versatile tri-signal probes were developed by preparing CdS@SiO2 nanorods that integrate photoluminescence (PL), multi-phonon resonant Raman scattering (MRRS) and infrared absorption (IRA) properties. Through the coating of multiple CdS nanoparticles as cores within SiO2 shells, the PL and MRRS properties of CdS were improved, resulting in a significantly lowered limit of detection (LOD), with the lowest LOD of 12.37 ag mL-1. Integration with the distinctive IRA property of SiO2 shells widened the detection range towards higher concentrations, establishing a final linear range of 50 ag mL-1 to 10 µg mL-1. The remarkable consistency among the three signals highlighted the robust internal verification capability for accurate detection. This approach enhances flexibility in selecting detection methodologies to suit diverse scenarios, facilitating HIgG detection. The tri-signal nanoprobes also exhibited excellent detection selectivity, specificity and repeatability. This study presents a fresh idea for developing high-performance detection strategies.

Molecular Engineering Regulation Achieving Out-of-Plane Polarization in Rare-Earth Hybrid Double Perovskites for Ferroelectrics and Circularly Polarized Luminescence.

Out-of-plane polarization is a highly desired property of two-dimensional (2D) ferroelectrics for application in vertical sandwich-type photoferroelectric devices, especially in ultrathin ferroelectronic devices. Nevertheless, despite great advances that have been made in recent years, out-of-plane polarization remains unrealized in the 2D hybrid double perovskite ferroelectric family. Here, from our previous work 2D hybrid double perovskite HQERN ((S3HQ)4EuRb(NO3)8, S3HQ = S-3-hydroxylquinuclidinium), we designed a molecular strategy of F-substitution on organic component to successfully obtain FQERN ((S3FQ)4EuRb(NO3)8, S3FQ = S-3-fluoroquinuclidinium) showing circularly polarized luminescence (CPL) response. Remarkably, compared to the monopolar axis ferroelectric HQERN, FQERN not only shows multiferroicity with the coexistence of multipolar axis ferroelectricity and ferroelasticity but also realizes out-of-plane ferroelectric polarization and a dramatic enhancement of Curie temperature of 94 K. This is mainly due to the introduction of F-substituted organic cations, which leads to a change in orientation and a reduction in crystal lattice void occupancy. Our study demonstrates that F-substitution is an efficient strategy to realize and optimize ferroelectric functional characteristics, giving more possibility of 2D ferroelectric materials for applications in micro-nano optoelectronic devices.

Near-Infrared Emissive B-N Lewis Pair-Functionalized Anthracenes via Selective LUMO Delocalization in Extended Conjugated Dimer and Polymer.

Acenes are attractive as building blocks for low gap organic materials with applications, for example, in organic light emitting diodes, solar cells, bioimaging and diagnostics. Previously, we have shown that modification of dipyridylanthracene via B-N Lewis pair fusion (BDPA) strongly redshifts the emission, while facilitating self-sensitized reactivity toward O2 to reversibly generate the corresponding endoperoxides. Herein, we report on the further expansion of the p-system of BDPA to a vinyl-substituted monomer, vinylene-bridged dimer, and a polymer with an average of 20 chromophores. The extension of π-conjugation results in largely reduced band gaps of 1.8 eV for the dimer and 1.7 eV for the polymer, the latter giving rise to NIR emission with a maximum at 731 nm and an appreciable quantum yield of 7%. Electrochemical and computational studies reveal efficient delocalization of the lowest unoccupied molecular orbital (LUMO) along the pyridyl-anthracene-pyridyl axis, which results in effective electronic communication between BDPA units, selectively lowers the LUMO, and ultimately narrows the band gap. Time-resolved emission and transient absorption (TA) measurements offer insights into the pertinent photophysical processes. Extension of π-conjugation also slows down the self-sensitized formation of endoperoxides, while significantly accelerating the thermal release of singlet oxygen to regenerate the parent acenes.

Deciphering the dual role of persistent luminescence materials: Toxicity and photoreception effects on rice development.

Studies on the toxicity of micro- and nanomaterials in plants have primarily focused on their intrinsic effects. However, there is often oversight when considering the potential perceptual responses that plants may exhibit in response to these materials. In this investigation, we assessed the impact of three commercially available persistent luminescence materials (PLMs) that emit red, green, or blue light under various environmental conditions. We subjected rice (Oryza sativa L.), a short-day plant, to nine distinct treatments, including exposure to particles in isolation, their nocturnal afterglow, or a combination of both. We thoroughly examined rice seedling morphology, photosynthesis patterns, metabolite dynamics, and flowering gene expression to determine the biological responses of plants to these particles. These findings demonstrated that PLMs stably interact with rice, and their emitted afterglow precisely matches the perceptual bandwidth of rice photoreceptors. Notably, the nocturnal afterglow from the red and blue PLMs enhanced the vegetative growth of rice seedlings while inhibiting their reproductive development. The blue PLMs exhibited the most pronounced positive effects, while the red PLMs exhibited inhibitory effects. When exposed to a combination of red and blue PLMs, rice displays enhanced growth and development. The observed alterations in the expression patterns of genes responsible for flowering supported these effects. We concluded that PLMs influence rice growth and development due to their inherent properties and intermittent illumination during dark periods. Both factors collectively shape rice growth and development.

Investigating the Mechanism of Triboluminescence: Insights from Structural and Electrostatic Characterization of Copper Thiocyanate Complexes.

Triboluminescence is a phenomenon in which light is generated through mechanical stress; it has emerging applications in stress-sensing devices. Although the prevailing mechanistic model indicates that light emits from charge separation and recombination in fracture planes arising from polar structures, its application in designing triboluminescent materials remains limited owing to numerous exceptions. This study provides insights into the essential requirements for triboluminescence by investigating the structural and electrostatic properties of fractured crystals of copper thiocyanate complexes. The examined fracture plane indicated that charge pairs (which are essential for light emission) form when intermolecular interactions are disrupted during fracturing. On the basis of the nature of these charges, we successfully suppressed triboluminescence by inhibiting the formation of intermolecular interactions disrupted in the examined complexes. Furthermore, we induced its re-emergence by creating an alternative fracture plane through controlled manipulation of the molecular network. This demonstrative deactivation and reactivation of triboluminescence underscores the critical role of intermolecular disruption in generating charge pairs, a prerequisite for triboluminescence.

A [2.2]Isoindolinophanyl-Based Carbene (iPC) Ligand: Synthesis, Electronic and Photophysical Properties, and Application in Photocatalysis*.

Cyclic amino(alkyl) and cyclic amino(aryl) carbenes (cAACs/cAArCs) have been established as very useful ligands for catalytic and photonic applications of transition metal complexes. Herein, we describe the synthesis of a structurally related sterically demanding, electrophilic [2.2]isoindolinophanyl-based carbene (iPC) with a [2.2]paracyclophane moiety. The latter leads to more delocalized frontier orbitals and intense green fluorescence of (HiPC)OTf (2) from an intra-ligand charge transfer (1ILCT) state in the solid state. Base-promoted synthesis of the free carbene led to an unusual ring expansion and subsequent dimerization reaction, but the beneficial ligand properties can be exploited by trapping in situ at a metal center. The iPC ligand is a very potent π-chromophore, which participates in low energy metal-to-ligand (ML)CT transitions in [RhCl(CO)2(iPC)] (4) and IL-"through-space"-CT transitions in [Au(iPC)2]OTf (5). The steric demand of the iPC leads to high stability of 5 against air, moisture, or solvent attack, and ultralong-lived green phosphorescence with a lifetime of 185 µs is observed in solution. The beneficial photophysical and electronic properties of the iPC ligand, including a large accessible π surface area, were exploited by employing highly efficient energy transfer (EnT) photocatalysis in a [2+2] styrene cycloaddition reaction using 5, which outperformed other established photocatalysts in comparison.

Narrowband Blue Circularly Polarized Luminescence Emitter based on BN-Doped Benzo[6]helicene with Stimuli-Responsive Properties.

Boron-doped helicenes, known for their unique electronic and photophysical properties, are of great interest for numerous applications. This research introduces two new azabora[6]helicenes, H[6]BN1 and H[6]BN2, synthesized through an efficient method. These molecules have boron and nitrogen atoms in opposing positions, enhancing their distinctive attributes. Both helicenes show excellent emission properties, with H[6]BN1 and H[6]BN2 exhibiting narrowband blue fluorescence and circularly polarized luminescence (CPL), achieving glum values of 4~5 ×10-4 which is beneficial for chiroptical applications. The addition of a donor group, 3, 6-di-tert-butyl-9H-carbazole, in H[6]BN2 improves luminescence, likely due to enhanced molecular orbital overlap and electron delocalization. H[6]BN1's needle-like single crystals exhibit mechanochromism, changing luminescent color from yellow to green under mechanical stress, which is promising for stimulus-responsive materials. In conclusion, this study presents a novel class of BN[6]helicenes with superior chiroptical properties. Their combination of electronic features and mechanochromism makes them ideal for advanced chiroptical materials, expanding the potential of helicene-based compounds and offering new directions for the synthesis of molecules with specific chiroptical characteristics.

Living Hybrid Exciton Materials: Enhanced Fluorescence and Chiroptical Properties in Living Supramolecular Polymers with Strong Frenkel/Charge-Transfer Exciton Coupling.

A family of chiral perylene diimides (PDIs) was newly developed as excellent circularly polarized luminescence (CPL) materials. They are asymmetrically derivatized with a double-alkyl-chained L- or D-glutamate unit and a linear or branched alkyl chain. When water is added to the tetrahydrofuran (THF) solution of glutamate-PDI-linear-alkyl chain compounds, kinetically formed H-aggregates are formed in globular nanoparticles (NPs). These NPs undergo spontaneous transformation into thermodynamically stable nanotubes via helical nanostructures, which showed structured broad spectra originating from the strong coupling of delocalized Frenkel excitations (FE) and charge transfer excitations (CTE). Significant enhancement of circular dichroism (CD), fluorescence quantum yield, and circularly polarized luminescence (CPL) with luminescence dissymmetry factor (glum) are observed during the transformation of NPs to the FE/CTE-coupled helical and tubular structures. This transformation process is significantly accelerated by applying physical stimuli, i.e., ultrasonication or adding helical aggregates as seed crystals, a feature unique to living supramolecular polymerization. Meanwhile, the branched chain-containing PDIs only form H-aggregates and did not show FE/CTE hybrid exciton states with living supramolecular polymerization properties. This study unveils that suitably designed chiral PDI derivatives show FE/CTE coupling accompanied by high fluorescence quantum yields, enhanced chiroptical properties, and supramolecular living polymerization characteristics.

Synthesis and structural characterizations of three carbonyl(α-diimine)hydrido(triphenylphosphine)ruthenium(II) complexes with derivatives of 1,10-phenanthroline.

Three new ruthenium(II) polypyridyl complexes containing α-diimine ligands, namely, carbonylhydrido(1,10-phenanthroline-κ2N,N)bis(triphenylphosphine-κP)ruthenium(II) hexafluorophosphate, [RuH(C12H8N2)(C18H15P)2(CO)]PF6, carbonylhydrido(2,9-dimethyl-1,10-phenanthroline-κ2N,N)bis(triphenylphosphine-κP)ruthenium(II) hexafluorophosphate, and carbonylhydrido(4,7-dimethyl-1,10-phenanthroline-κ2N,N)bis(triphenylphosphine-κP)ruthenium(II) hexafluorophosphate, both [RuH(C14H12N2)(C18H15P)2(CO)]PF6, were synthesized and characterized by spectroscopic and X-ray diffraction methods. In these complexes, the ruthenium(II) ion adopts a distorted octahedral geometry. There are no intermolecular hydrogen bonds in the crystal structures of the analysed complexes and Hirshfeld surface analysis showed that the H...H contacts constitute a high percentage, close to 50%, of the intermolecular interactions.

Circularly Polarized Luminescence Without External Magnetic Fields from Individual CsPbBr3 Perovskite Quantum Dots.

Lead halide perovskite quantum dots (QDs), the latest generation of the colloidal QD family, exhibit outstanding optical properties, which are now exploited as both classical and quantum light sources. Most of their rather exceptional properties are related to the peculiar exciton fine-structure of band-edge states, which can support unique bright triplet excitons. The degeneracy of the bright triplet excitons is lifted with energetic splitting in the order of millielectronvolts, which can be resolved by the photoluminescence (PL) measurements of single QDs at cryogenic temperatures. Each bright exciton fine-structure-state (FSS) exhibits a dominantly linear polarization, in line with several theoretical models based on the sole crystal field, exchange interaction, and shape anisotropy. Here, we show that in addition to a high degree of linear polarization, the individual exciton FSS can exhibit a non-negligible degree of circular polarization even without external magnetic fields by investigating the four Stokes parameters of the exciton fine-structure in individual CsPbBr3 QDs through Stokes polarimetric measurements. We observe a degree of circular polarization up to ∼38%, which could not be detected by using the conventional polarimetric technique. In addition, we found a consistent transition from left- to right-hand circular polarization within the fine-structure triplet manifold, which was observed in magnetic-field-dependent experiments. Our optical investigation provides deeper insights into the nature of the exciton fine structures and thereby drives the yet-incomplete understanding of the unique photophysical properties of this class of QDs for the benefit of future applications in chiral quantum optics.

Chromic soft crystals based on luminescent platinum(II) complexes.

Platinum(II) complexes of square-planar geometry are interesting from a crystal engineering viewpoint because they exhibit strong luminescence based on the self-assembly of molecular units. The luminescence color changes in response to gentle stimuli, such as vapor exposure or weak mechanical forces. Both the molecular and the crystal designs for soft crystals are critical to effectively generate the chromic luminescence phenomenon of Pt(II) complexes. In this topical review, strategies for fabricating chromic luminescent Pt(II) complexes are described from a crystal design perspective, focusing on the structural regulation of Pt(II) complexes that exhibit assembly-induced luminescence via metal-metal interactions and structural control of anionic Pt(II) complexes using cations. The research progress on the evolution of various chromic luminescence properties of Pt(II) complexes, including the studies conducted by our group, are presented here along with the latest research outcomes, and an overview of the frontiers and future potential of this research field is provided.

Phosphorylation site of L-alanyl-L-glutamine identified by Raman optical activity spectroscopy.

Phosphorylated peptides are instrumental in studying protein phosphorylation events. In the present study, Raman optical activity (ROA) is employed to elucidate the structure of a dipeptide, L-alanyl-L-glutamine (L-Ala-L-Gln) and its two differently alkylated N-phosphorylated derivatives. Theoretical simulations were conducted to aid the interpretation of peptide conformation variations upon phosphorylation, and of the measured Raman and ROA spectra. Induced circularly polarized luminescence (CPL) was also recorded in solution, in the presence of a simple europium aqua ion. As the spectra are peptide specific, this type of stereochemical analysis is expected to aid identification of the phosphorylation sites also in other peptides and possibly proteins.

Efficient chiral hydrogel template based on supramolecular self-assembly driven by chiral carbon dots for circularly polarized luminescence.

Since the chiral emission of excited states is observed on carbon dots (CDs), exploration towards the design and synthesis of chiral CDs nanomaterials with circularly polarized luminescence (CPL) properties has been at a brisk pace. In this regard, the "host and guest" co-assembly strategy based on the combination of CDs and chiral templates has been of unique interest recently for its convenient operation, multicolor tunable CPL, and wide application of prepared CDs-composited materials in optoelectronic devices and information encryption. However, the existing chiral templates that match perfectly with chiral CDs exhibiting optical activity both in ground and excited states are rather scarce. In this work, we synthesize the chiral CDs that could induce the spontaneous supramolecular self-assembly of N-(9-fluorenylmethox-ycarbonyl) (Fmoc)-protected glutamic acid to form chiral hydrogels with helical nanostructure. The co-assembled hydrogels show powerful chiral template function, which not only enable chiral CDs with a luminescence dissymmetry factor (glum) up to 10-2, but also have universal chiral transfer to inserted dye molecules, realizing full-color CPL and Förster resonance energy transfer (FRET) CPL as well as the distinction between left and right circularly polarized light. This CPL-active template based on chiral CDs enriches the design scenario of chiral functionalized nanomaterials.

Nonstoichiometry-Induced Self-Activated Phosphors for Dynamic Anti-counterfeiting Applications.

Optical signals with distinctive properties, such as contactless, fast response, and high identification, are harnessed to realize advanced anti-counterfeiting. However, the simultaneous attainment of multi-color, -temporal, and -modal luminescence performance remains a compelling and imperative pursuit. In our work, a temperature/photon-responded dynamic self-activated luminescence originating from nonstoichiometric Zn2GeO4 is developed with the modulation of intrinsic defects. The increased concentration of oxygen vacancies (VO••) contributes to an enhanced recombination of ZnGe″-VO••, ultimately improving the self-activated luminescence performance. Additionally, the photoluminescence (PL) color of the representative Zn2.2GeO4 sample changes from green to blue-white with the increased ultraviolet (UV) irradiation time. Concurrently, the emission color undergoes a variation from blue to green as the ambient temperature raises from 280 to 420 K. Remarkably, green long persistent luminescence (LPL) and photostimulated luminescence (PSL) behaviors are observed. Herein, this study elucidates a sophisticated anti-counterfeiting approach grounded in the dynamic luminescent attributes of nonstoichiometric Zn2GeO4, presenting a promising frontier for the evolution of anti-counterfeiting technologies.

Persistent Luminescence Nanosensors: A Generalized Optode-Based Platform for Autofluorescence-Free Sensing in Biological Systems.

Fluorescent nanosensors have revolutionized diagnostics and our ability to monitor cellular dynamics. Yet, distinguishing sensor signals from autofluorescence remains a challenge. Here, we merged optode-based sensing with near-infrared-emitting ZnGa2O4:Cr3+ persistent luminescence nanoparticles (PLNPs) to create nanocomposites for autofluorescence-free "glow-in-the-dark" sensing. Hydrophobic modification and incorporation of the persistent luminescence nanoparticles into an optode-based nanoparticle core yielded persistent luminescence nanosensors (PLNs) for five analytes (K+, Na+, Ca2+, pH, and O2) via two distinct mechanisms. We demonstrated the viability of the PLNs by quantifying K+ in fetal bovine serum, calibrating the pH PLNs in the same, and ratiometrically monitoring O2 metabolism in cultures of Saccharomyces cerevisiae, all the while overcoming their respective autofluorescence signatures. This highly modular platform allows for facile tuning of the sensing functionality, optical properties, and surface chemistry and promises high signal-to-noise ratios in complex optical environments.

Sensitive detection of choline and nicotine in real samples by switching upconversion luminescence.

Nicotine (3-(1-methyl-2-pyrrolidinyl)pyridine) is one of the most common addictive substances, causing the trace detection of nicotine to be very necessary. Herein, we designed and prepared a functionalized nanocomposite CS-PAA (NaYF4:19.5%Yb,0.5%Tm@NaYF4-PAA) using a simple method. The nicotine concentration was quantitatively detected through the inhibition of choline oxidase activity by nicotine and the luminescence intensity of CS-PAA being quenched by Fe3+. The mechanism of Fe3+ quenching CS-PAA emission was inferred by luminescence lifetime and UV-vis absorption spectra characterization. During the nicotine detection, both excitation (980 nm) and emission (802 nm) wavelengths of CS-PAA enable the avoidance of the interference of background fluorescence in complicated food objects, thus providing high selectivity and sensitivity with a linear range of 5-750 ng/mL and a limit of detection of 9.3 nM. The method exhibits an excellent recovery and relative standard deviation, indicating high accuracy and repeatability of the detection of nicotine.

Detection of ascorbic acid by persistent luminescent nanoparticles based on CoOOH nanosheets modification.

Persistent luminescent nanomaterials (PLNPs) Zn0.8Ga2O4: Cr3+, Zr3+ with high brightness and good dispersion were prepared by hydrothermal method. The PLNPs were used as luminescent units, and CoOOH nanosheets were used as quenching agents. Based on the fluorescence internal filtering effect, the luminescence of PLNPs were effectively quenched by CoOOH modification on the surface of PLNPs. However, the introduction of ascorbic acid (AA) restored the luminescence of PLNPs and successfully achieved highly sensitive and selective detection of AA. This was due to a selective redox reaction between CoOOH and AA, in which CoOOH was reduced to Co2+. The degree of luminescence recovery of PLNPs showed a good linear relationship with AA concentration in the range 5-250 µM, with a detection limit of 0.72 µM. The recovery of actual spiked samples were 97.9-102.2%. This method is expected to provide reference for the study of other redox substances in biological systems.

Multi-Mode Luminescence in Smart Near-Infrared Cr3+/Pr3+ Codoped SrGa12O19 Phosphors Induced by Three Distinct Excitation Mechanisms.

Near-infrared (NIR) phosphors have emerged as novel luminescent materials across various fields due to their unique advantages of high penetration and invisibility. However, there is currently a lack of intelligent NIR phosphors that can achieve multimode stimuli responsive for sensing applications. In this study, we employed a high-temperature solid-phase reaction to incorporate Pr3+ into Cr3+-doped gallate magnetite SrGa12O19 phosphor, yielding a multimode luminescent intelligent NIR phosphor. Also, due to the inherent cation vacancies and defects in the matrix, the material not only exhibits brighter photoluminescence but also exhibits distinct NIR mechanoluminescence at a lower load. Notably, Pr3+-doped SrGa12O19:Cr3+ also demonstrates extended persistent luminescence and thermoluminescence effects. Finally, we combined the phosphor with the blue LED chip to develop a new multifunctional NIR pc-LED. Leveraging NIR's unique penetrating ability, it can persist in biological tissues for prolonged periods, enabling optical inspection and offering a novel approach to password protection for anticounterfeiting measures. This intelligent NIR phosphor solution significantly expands the application potential of NIR light in food quality assessment and analysis.

Jellyfish-Inspired Self-Healing Luminescent Elastomers Based on Borate Nanoassemblies for Dual-Model Encryption.

Responsive luminescent materials that reversibly react to external stimuli have emerged as prospective platforms for information encryption applications. Despite brilliant achievements, the existing fluorescent materials usually have low information density and experience inevitable information loss when subjected to mechanical damage. Here, inspired by the hierarchical nanostructure of fluorescent proteins in jellyfish, we propose a self-healable, photoresponsive luminescent elastomer based on dynamic interface-anchored borate nanoassemblies for smart dual-model encryption. The rigid cyclodextrin molecule restricts the movement of the guest fluorescent molecules, enabling long room-temperature phosphorescence (0.37 s) and excitation wavelength-responsive fluorescence. The building of reversible interfacial bonding between nanoassemblies and polymer matrix together with their nanoconfinement effect endows the nanocomposites with excellent mechanical performances (tensile strength of 15.8 MPa) and superior mechanical and functional recovery capacities after damage. Such supramolecular nanoassemblies with dynamic nanoconfinement and interfaces enable simultaneous material functionalization and self-healing, paving the way for the development of advanced functional materials.

Probing the Antiplasmodial Properties of Plakortinic Acids C and D: An Uncommon Pair of Marine Peroxide-Polyketides Isolated from a Two-Sponge Association of Plakortis symbiotica and Xetospongia deweerdtae Collected near Puerto Rico.

Plakortinic acids C (1) and D (2), an unseparable pair of endoperoxide polyketides isolated and purified from the symbiotic association of Caribbean Sea sponges Plakortis symbiotica-Xestospongia deweerdtae, underwent in vitro evaluation for antiplasmodial activity against the malaria parasite Plasmodium berghei using a drug luminescence assay. Initial screening at 10 µM revealed 50% in vitro parasite growth inhibition. The title compounds displayed antiplasmodial activity with an EC50 of 5.3 µM toward P. berghei parasites. The lytic activity against erythrocytes was assessed through an erythrocyte cell lysis assay, which showed non-lytic activity at lower concentrations ranging from 1.95 to 3.91 µM. The antiplasmodial activity and the absence of hemolytic activity support the potential of plakortinic acids C (1) and D (2) as promising lead compounds. Moreover, drug-likeness (ADMET) properties assessed through the pkCSM server predicted high intestinal absorption, hepatic metabolism, and volume of distribution, indicating favorable pharmacokinetic profiles for oral administration. These findings suggest the potential suitability of these metabolites for further investigations of antiplasmodial activity in multiple parasitic stages in the mosquito and Plasmodium falciparum. Notably, this study represents the first report of a marine natural product exhibiting the unique 7,8-dioxatricyclo[4.2.2.02,5]dec-9-ene motif being evaluated against malaria.