A portable smartphone platform utilizing dual-sensing signals for visual determination of semicarbazide in food samples.

Semicarbazide (SEM) is a metabolite of antibiotic nitrofurazone and a food contaminant in food production, showing potential carcinogenic, mutagenic, teratogenic, and toxic effects on human health. It is urgent to develop a highly efficient and sensitive assay for visual detection of SEM. In this paper, a pyrrolopyrrole cyanine fluorescent probe (PPCy-1) was reported for visualization and quantitative analysis of SEM through a chromophore reaction sensing mechanism for the first time. The probe towards SEM exhibited a fast response (10 min), a low detection limit (0.18 µM), high selectivity, and distinct dual ratiometric fluorescence turn-on and colorimetric modes. Its practicability was further verified by detecting SEM in meat, water, and honey samples with satisfactory recovery values. More importantly, a smartphone-assisted portable testing platform was constructed based on a PPCy-1-immobilized test paper or a polyamide thin film with a color scanning APP for real-time and on-site detection of SEM. This work provides low-cost, convenient, and rapid assays for visual SEM detection, which have potential applications in food safety monitoring.

Combination of disulfiram and Copper-Cysteamine nanoparticles induces mitochondria damage and promotes apoptosis in endometrial cancer.

Endometrial cancer (EC) stands as one of the most prevalent gynecological malignancies affecting women, with its incidence and disease-related mortality steadily on the rise. Disulfiram (DSF), an FDA-approved medication primarily used for treating alcohol addiction, has exhibited promising anti-tumor properties. Studies have revealed DSF's capacity for enhanced anti-tumor activity, particularly when combined with copper. The novel Copper-Cysteamine (CuCy) compound, Cu3Cl(SR)2 (R[bond, double bond]CH2CH2NH2), showcases photodynamic effects and demonstrates significant anti-tumor potential under various conditions, including exposure to ultraviolet light, X-ray, microwave, and ultrasound. This study delves into exploring the synergistic anti-tumor effects and underlying mechanisms by utilizing copper-cysteamine in conjunction with DSF against endometrial cancer. The investigation involved comprehensive analyses encompassing in vitro experiments utilizing Ishikawa cells, in vivo studies, and transcriptomic analyses. Remarkably, the combined administration of both compounds at a low dose of 0.5 µM exhibited pronounced efficacy in impeding tumor growth, inhibiting blood vessel formation, and stimulating cell apoptosis. Notably, experiments involving transplanted tumors in nude mice vividly demonstrated the significant in vivo anti-tumor effects of this combination treatment. Detailed examination through transmission electron microscopy unveiled compelling evidence of mitochondrial damage, cellular swelling, and rupture, indicative of apoptotic changes in morphology due to the combined treatment. Moreover, transcriptomic analysis unveiled substantial downregulation of mitochondrial-related genes at the molecular level, coupled with a significant hindrance in the DNA repair pathway. These findings strongly suggest that the combined application of CuCy and DSF induces mitochondrial impairment in Ishikawa cells, thereby fostering apoptosis and ultimately yielding potent anti-tumor effects.

A Strategy for Controlling the Polymerizations of Thiyl Radical Propagation by RAFT Agents.

The ability to extend the polymerizations of thiyl radical propagation to be regulated by existing controlled methods would be highly desirable, yet remained very challenging to achieve because the thiyl radicals still cannot be reversibly controlled by these methods. In this article, we reported a novel strategy that could enable the radical ring-opening polymerization of macrocyclic allylic sulfides, wherein propagating specie is thiyl radical, to be controlled by reversible addition-fragmentation chain transfer (RAFT) agents. The key to the success of this strategy is the propagating thiyl radical can undergo desulfurization with isocyanide and generate a stabilized alkyl radical for reversible control. Systematic optimization of the reaction conditions allowed good control over the polymerization, leading to the formation of polymers with well-defined architectures, exemplified by the radical block copolymerization of macrocyclic allylic sulfides and vinyl monomers and the incorporation of sequence-defined segments into the polymer backbone. This work represents a significant step toward directly enabling the polymerizations of heteroatom-centered radical propagation to be regulated by existing reversible-deactivation radical polymerization techniques.

Sorafenib-Based Drug Delivery Systems: Applications and Perspectives.

As a Food and Drug Administration (FDA)-approved molecular-targeted chemotherapeutic drug, sorafenib (SF) can inhibit angiogenesis and tumor cell proliferation, leading to improved patient overall survival of hepatocellular carcinoma (HCC). In addition, SF is an oral multikinase inhibitor as a single-agent therapy in renal cell carcinoma. However, the poor aqueous solubility, low bioavailability, unfavorable pharmacokinetic properties and undesirable side effects (anorexia, gastrointestinal bleeding, and severe skin toxicity, etc.) seriously limit its clinical application. To overcome these drawbacks, the entrapment of SF into nanocarriers by nanoformulations is an effective strategy, which delivers SF in a target tumor with decreased adverse effects and improved treatment efficacy. In this review, significant advances and design strategies of SF nanodelivery systems from 2012 to 2023 are summarized. The review is organized by type of carriers including natural biomacromolecule (lipid, chitosan, cyclodextrin, etc.); synthetic polymer (poly(lactic-co-glycolic acid), polyethyleneimine, brush copolymer, etc.); mesoporous silica; gold nanoparticles; and others. Co-delivery of SF and other active agents (glypican-3, hyaluronic acid, apolipoprotein peptide, folate, and superparamagnetic iron oxide nanoparticles) for targeted SF nanosystems and synergistic drug combinations are also highlighted. All these studies showed promising results for targeted treatment of HCC and other cancers by SF-based nanomedicines. The outlook, challenges and future opportunities for the development of SF-based drug delivery are presented.

A novel chromophore reaction-based pyrrolopyrrole aza-BODIPY fluorescent probe for H2S detection and its application in food spoilage.

In this work, we developed an aggregation-induced emission enhancement (AIEE) active and NIR emissive pyrrolopyrrole aza-BODIPY (PPAB) polymer (P1) for H2S detection for the first time. P1 showed obvious colorimetric change from green to yellow-green and ratiometric fluorescence "turn on" phenomenon with 167 nm blue-shift (from dark red to bright green). The sensing mechanism revealed a novel chromophore reaction between imine in PPAB core and H2S was involved, leading to less conjugated product. It exhibited distinct advantages of good selectivity, high sensitivity, and low detection limit of 0.66 µM. The potential applicability of P1 for H2S detection in the real samples (tap water, lake water and milk) was demonstrated. In addition, the solid sensor prepared by loading P1 on the PMMA film was successfully realized the visual detection of gaseous H2S gas produced from egg spoilage. Therefore, this work provides a promising approach based on novel sensing mechanism for monitoring H2S in complicated biological systems and practical food samples.

Recent advances in type I organic photosensitizers for efficient photodynamic therapy for overcoming tumor hypoxia.

Photodynamic therapy (PDT) with an oxygen-dependent character is a noninvasive therapeutic method for cancer treatment. However, its clinical therapeutic effect is greatly restricted by tumor hypoxia. What's more, both PDT-mediated oxygen consumption and microvascular damage aggravate tumor hypoxia, thus, further impeding therapeutic outcomes. Compared to type II PDT with high oxygen dependence and high oxygen consumption, type I PDT with less oxygen consumption exhibits great potential to overcome the vicious hypoxic plight in solid tumors. Type I photosensitizers (PSs) are significantly important for determining the therapeutic efficacy of PDT, which performs an electron transfer photochemical reaction with the surrounding oxygen/substrates to generate highly cytotoxic free radicals such as superoxide radicals (˙O2-) as type I ROS. In particular, the primary precursor (˙O2-) would progressively undergo a superoxide dismutase (SOD)-mediated disproportionation reaction and a Haber-Weiss/Fenton reaction, yielding higher cytotoxic species (˙OH) with better anticancer effects. As a result, developing high-performance type I PSs to treat hypoxic tumors has become more and more important and urgent. Herein, the latest progress of organic type I PSs (such as AIE-active cationic/neutral PSs, cationic/neutral PSs, polymer-based PSs and supramolecular self-assembled PSs) for monotherapy or synergistic therapeutic modalities is summarized. The molecular design principles and strategies (donor-acceptor system, anion-π+ incorporation, polymerization and cationization) are highlighted. Furthermore, the future challenges and prospects of type I PSs in hypoxia-overcoming PDT are proposed.

Recent Advances of Diketopyrrolopyrrole Derivatives in Cancer Therapy and Imaging Applications.

Cancer is threatening the survival of human beings all over the world. Phototherapy (including photothermal therapy (PTT) and photodynamic therapy (PDT)) and bioimaging are important tools for imaging-mediated cancer theranostics. Diketopyrrolopyrrole (DPP) dyes have received more attention due to their high thermal and photochemical stability, efficient reactive oxygen species (ROS) generation and thermal effects, easy functionalization, and tunable photophysical properties. In this review, we outline the latest achievements of DPP derivatives in cancer therapy and imaging over the past three years. DPP-based conjugated polymers and small molecules for detection, bioimaging, PTT, photoacoustic imaging (PAI)-guided PTT, and PDT/PTT combination therapy are summarized. Their design principles and chemical structures are highlighted. The outlook, challenges, and future opportunities for the development of DPP derivatives are also presented, which will give a future perspective for cancer treatment.

Multifunctional Supramolecular Vesicles as Zn2+ -Triggered Microglial Modulator Alleviates Alzheimer's Disease.

Zn2+ -induced ß-amyloid protein (Aß) aggregation and microglia activation are the predominant contributors in Alzheimer's disease (AD). Regulating intracephalic excessive Zn2+ is a promising therapeutic strategy for AD treatment. However, only inhibition of Zn2+ is hardly to repair continuous damages caused by activated microglia. Herein, an intelligent resveratrol-loaded supramolecular vesicles (RES-loaded vesicles) with zinc ion chelation function and responsive release capability are constructed to alleviate Aß fibrillation, oxidative stress, and microglial dysfunction. The resveratrol encapsulation efficiency and drug loading efficiency are calculated to be 49.67% and 7.87%, respectively. In vitro studies demonstrate that the RES-loaded vesicles can modulate Zn2+ -dependent Aß aggregation. More importantly, the cargoes will be released in zinc environment and further reprograms microglia from proinflammatory M1 phenotype toward anti-inflammatory M2 phenotype, which prevents spontaneous neuroinflammation and alleviates cytotoxicity of cultured cells from 29% to 12%. With the stereotactic or intranasal administration, RES-loaded vesicles can overcome the blood brain barrier, alleviate neuronal apoptosis, neuroinflammation, and ultimately ameliorate cognitive impairment in two AD mouse models. This work provides a new sight for taking advantage of Zn2+ to treat CNS disorders.

Luminescence Nanomaterials and Applications.

We are pleased to introduce to you this Special Issue of Nanomaterials on 'Luminescence Nanomaterials and Applications' [...].

Green, Efficient Detection and Removal of Hg2+ by Water-Soluble Fluorescent Pillar[5]arene Supramolecular Self-Assembly.

Developing a water-soluble supramolecular system for the detection and removal of Hg2+ is extremely needed but remains challenging. Herein, we reported the facile construction of a fluorescent supramolecular system (H⊃G) in 100% water through the self-assembly of carboxylatopillar[5]arene sodium salts (H) and diketopyrrolopyrrole-bridged bis(quaternary ammonium) guest (G) by host-guest interaction. With the addition of Hg2+, the fluorescence of H⊃G could be efficiently quenched. Since Hg2+ showed synergistic interactions (coordination and Hg2+- cavity interactions with G and H, respectively), crosslinked networks of H⊃G@Hg2+ were formed. A sensitive response to Hg2+ with excellent selectivity and a low limit of detection (LOD) of 7.17 × 10-7 M was obtained. Significantly, the quenching fluorescence of H⊃G@Hg2+ can be recovered after a simple treatment with Na2S. The reusability of H⊃G for the detection of Hg2+ ions was retained for four cycles, indicating the H⊃G could be efficiently used in a reversible manner. In addition, the H⊃G could efficiently detect Hg2+ concentration in real samples (tap water and lake water). The developed supramolecular system in 100% water provides great potential in the treatment of Hg2+ detection and removal for environmental sustainability.

Recent Advances in Fluorescent Methods for Polyamine Detection and the Polyamine Suppressing Strategy in Tumor Treatment.

The biogenic aliphatic polyamines (spermine, spermidine, and putrescine) are responsible for numerous cell functions, including cell proliferation, the stabilization of nucleic acid conformations, cell division, homeostasis, gene expression, and protein synthesis in living organisms. The change of polyamine concentrations in the urine or blood is usually related to the presence of malignant tumors and is regarded as a biomarker for the early diagnosis of cancer. Therefore, the detection of polyamine levels in physiological fluids can provide valuable information in terms of cancer diagnosis and in monitoring therapeutic effects. In this review, we summarize the recent advances in fluorescent methods for polyamine detection (supramolecular fluorescent sensing systems, fluorescent probes based on the chromophore reaction, fluorescent small molecules, and fluorescent nanoparticles). In addition, tumor polyamine-suppressing strategies (such as polyamine conjugate, polyamine analogs, combinations that target multiple components, spermine-responsive supramolecular chemotherapy, a combination of polyamine consumption and photodynamic therapy, etc.) are highlighted. We hope that this review promotes the development of more efficient polyamine detection methods and provides a comprehensive understanding of polyamine-based tumor suppressor strategies.

Design, synthesis and applications of NIR-emissive scaffolds of diketopyrrolopyrrole-aza-BODIPY hybrids.

Herein, we report a facile synthetic method towards diketopyrrolopyrrole-aza-BODIPY hybrids by a two-step strategy. The three resulting fluorophores (LAB-TH4 ∼ LAB-TH6) showed absorption maxima up to 637 nm with molar extinction coefficients (ε) up to 32 300 M-1 cm-1 and emission maxima at 661 nm with a fluorescence quantum yield of 25.2% in solution. Due to good biocompatibility and strong ROS generation ability, they are useful fluorophores for bioimaging and photodynamic therapy (PDT). In addition, as a useful scaffold, a novel NIR-emissive conjugated polymer can be constructed by further bromination and Suzuki coupling polymerization.

Interfacial Engineering of PTAA/Perovskites for Improved Crystallinity and Hole Extraction in Inverted Perovskite Solar Cells.

Inverted perovskite solar cells (PSCs) have gained rapid progress and increasing research interest in recent years. The poly (triarylamine) (PTAA) is the most frequently used semiconductor in the hole-transporting layer (HTL) in inverted PSCs for its favorable highest occupied molecular orbital energy level (-5.2 eV), excellent carrier mobility, and low-temperature solution processability. However, its intrinsic hydrophobic property hinders the growth of high-quality perovskite on the PTAA film, which is one of the main obstacles that limits the further development of inverted PSCs. Herein, a donor-acceptor-donor type organic molecule, 4,4',4″-(1-hexyl-1H-dithieno [3',2':3,4; 2″,3″:5,6] benzo[1,2-d] imidazole-2,5,8-triyl) tris (N,N-bis(4-methoxyphenyl) aniline) (denoted as M2), is employed to modify the surface of PTAA. The PTAA/M2 composite hole transport layer facilitates the growth of perovskite films due to ameliorated hydrophobic property of PTAA. PTAA/M2 also exhibits enhanced hole mobility and conductivity than pristine PTAA. With enhanced crystallinity and hole extraction ability, using PTAA/M2 instead of pure PTAA as HTL, the power-conversion efficiency of inverted PSC increases from 18.67% to 20.23%. Furthermore, its operational stability is also enhanced. Our methodology carves out a novel path for addressing the hydrophobic issue of PTAA and improving the efficiency and photostability of inverted PSCs.

Bio-inspired AIE pillar[5]arene probe with multiple binding sites to discriminate alkanediamines.

Two functionalized pillar[5]arenes (H1 and H2) with significant AIE properties were synthesized. H2 is an excellent probe to selectively detect specific alkanediamines owing to its multiple binding sites, which result in the enhancement of emission based on the AIE mechanism and the induced-fit mechanism, and provides a new strategy to develop probes with high selectivity and sensitivity.

Development of a novel chromophore reaction-based fluorescent probe for biogenic amines detection.

Biogenic amines (BAs) are important biomarkers to monitor meat spoilage. However, the design of efficient BA fluorescent probes with distinct colorimetric and ratiometric fluorescent dual-channels is still a critical challenge because of similar chemical properties and basicity between BAs and other amines. Herein, pyrrolopyrrole cyanine (PPCy-1) is reported to display distinctly high reactivity toward BAs through an ultrasensitive irreversible chromophore reaction for the first time. The reaction mechanism is ascribed to synergistic aza-Michael addition and B-N detachment, followed by hydrolysis to produce low-conjugated diketopyrrolopyrrole and heteroaromatic acetonitrile compounds. As a result, colorimetric and ratiometric fluorescent dual-channel (Δλab = 188 nm and Δλem = 151 nm) signals and a limit of detection up to 62.1 nM level for BA solution are acquired. In addition, the colorimetric detection of volatile amine vapor using the PPCy-1-loaded filter paper, showing a color change from green to yellow, is feasible. A simple and cost-effective fluorescence "turn on" method using the filter paper or the CAD-40 resin loaded with PPCy-1 to detect TVB (total volatile bases) originating from shrimp spoilage is further demonstrated.

Encapsulation of Dyes in Luminescent Metal-Organic Frameworks for White Light Emitting Diodes.

The development of white light emitting diodes (WLEDs) holds great promise for replacing traditional lighting devices due to high efficiency, low energy consumption and long lifetime. Metal-organic frameworks (MOFs) with a wide range of luminescent behaviors are ideal candidates to produce white light emission in the phosphor-converted WLEDs. Encapsulation of emissive organic dyes is a simple way to obtain luminescent MOFs. In this review, we summarize the recent progress on the design and constructions of dye encapsulated luminescent MOFs phosphors. Different strategies are highlighted where white light emitting phosphors were obtained by combining fluorescent dyes with metal ions and linkers.

Characterization of nanoparticles combining polyamine detection with photodynamic therapy.

Polyamine detection and depletion have been extensively investigated for cancer prevention and treatment. However, the therapeutic efficacy is far from satisfactory, mainly due to a polyamine compensation mechanism from the systemic circulation in the tumor environment. Herein, we explore a new solution for improving polyamine detection as well as a possible consumption therapy based on a new photosensitizer that can efficiently consume polyamines via an irreversible chemical reaction. The new photosensitizer is pyrrolopyrroleaza-BODIPY pyridinium salt (PPAB-PyS) nanoparticles that can react with the over-expressed polyamine in cancer cells and produce two photosensitizers with enhanced phototoxicity on cancer destruction. Meanwhile, PPAB-PyS nanoparticles provide a simultaneous ratiometric fluorescence imaging of intracellular polyamine. This combination polyamine consumption with a chemical reaction provides a new modality to enable polyamine detection along with photodynamic therapy as well as a putative depletion of polyamines for cancer treatment and prevention.

A cucurbituril-pillararene ring-on-ring complex.

A new type of non-intertwined ring-on-ring assembly was formed by the portal binding between a perfunctionalized polycationic pillar[5]arene and a cucurbit[10]uril, demonstrating a facile approach to solubilize a large macrocycle in water. Different binding behaviors towards guests were observed for the high-order complex, enriching the functional supramolecular systems.

A novel and efficient chromophore reaction based on a lactam-fused aza-BODIPY for polyamine detection.

Polyamines (such as spermine, spermidine) play important roles in biomedical and food field. The elevated polyamines have been proposed to serve as target analytes for monitoring meat spoilage. Because of structural similarity and low concentration of polyamines in real samples, it is exceedingly challenging to design and develop sensitive probes for visual detection of polyamines. To address this issue, a highly efficient probe was reported based on a newly developed chromophore reaction between lactam-fused aza-BODIPY (abbreviation: LAB) and polyamines by virtue of unique multiple amino groups character of polyamines. This chromophore reaction includes a kinetic-controllable reaction of a B-N bond cleavage by polyamines followed by a fast hydrolysis reaction to yield much smaller conjugated molecules. With 130 nm hypsochromic shift of the absorption peak and up to 99% fluorescence quenching within 1 min, LAB can be used as a highly sensitive fluorescent probe for detection of polyamines solution and monitoring fish spoilage with synchronous colorimetric and fluorescent changes.

Modulating the molecular configuration by varying linking bridge for double-anchored dye-sensitized solar cells.

Three novel metal-free organic dyes (TPTZ1, TPTZ2, and TPTZ3) with an A-D-π-D-A configuration were synthesized and applied for dye-sensitized solar cells (DSSCs). The relationship between the photovoltaic properties and the different connection bridges of these organic dyes was studied systematically, showing that a strategical variation on the linkage ways of dithiophene can obviously affect the twisted degree of backbone and, thus, have a great effect on inhibiting the intermolecular aggregation. Compared with a bulky rigid group substituted on TPTZ3, introducing flexible side chains at suitable sites on the TPTZ1 and TPTZ2 seems to be a more effective strategy to achieve high photoelectric performance for double anchoring dye. Indeed, the DSSCs based on TPTZ2 exhibit a high efficiency of 7.50%, reaching 99% of an N719-based standard cell at the same condition. This study provides a new approach for highly efficient anti-aggregation organic sensitizers.