Recent advances in the approaches for improving the photovoltaic performance of porphyrin-based DSSCs.

Among other photovoltaic techniques including perovskite solar cells and organic solar cells, dye-sensitized solar cells (DSSCs) are considered to be a potential alternative to conventional silicon solar cells. Porphyrins are promising dyes with the properties of easy modification and superior light-harvesting capability. However, porphyrin dyes still suffer from a number of unfavorable aspects, which need to be addressed in order to improve the photovoltaic performance. This feature article briefly summarizes the recent progress in improving the Voc and Jsc of porphyrin-based DSSCs in terms of molecular engineering by modifying the porphyrin macrocycle, donor and acceptor moieties of the porphyrin dyes, coadsorption of the porphrin dyes with bulky coadsorbents like chenodeoxycholic acid (CDCA), and cosensitization of the porphyrin dyes with metal-free organic dyes. Notably, concerted companion (CC) dyes are described in detail, which have been constructed by linking a porphyrin dye subunit and a metal-free organic dye subunit with flexible alkoxy chains to achieve panchromatic absorption and concerted enhancement of Voc and Jsc. In one sentence, this article is expected to provide further insights into the development of high performance DSSCs through the design and syntheses of efficient porphyrin dyes and CC dyes in combination with device optimization to achieve simultaneously elevated Voc and Jsc, which may inspire and promote further progress in the commercialization of the DSSCs.

Astaxanthin Inhibits STING Carbonylation and Enhances Antiviral Responses.

STING-mediated DNA sensing pathway plays a crucial role in the innate antiviral immune responses. Clarifying its regulatory mechanism and searching STING agonists has potential clinical implications. Although multiple STING agonists have been developed to target cancer, there are few for the treatment of infectious diseases. Astaxanthin, a natural and powerful antioxidant, serves many biological functions and as a potential candidate drug for many diseases. However, how astaxanthin combats viruses and whether astaxanthin regulates the cyclic GMP-AMP synthase-STING pathway remains unclear. In this study, we showed that astaxanthin markedly inhibited HSV-1-induced lipid peroxidation and inflammatory responses and enhanced the induction of type I IFN in C57BL/6J mice and mouse primary peritoneal macrophages. Mechanistically, astaxanthin inhibited HSV-1 infection and oxidative stress-induced STING carbonylation and consequently promoted STING translocation to the Golgi apparatus and oligomerization, which activated STING-dependent host defenses. Thus, our study reveals that astaxanthin displays a strong antiviral activity by targeting STING, suggesting that astaxanthin might be a promising STING agonist and a therapeutic target for viral infectious diseases.

Mono- and bis-Pd(ii) complexes of N-confused dithiahexaphyrin(1.1.1.1.1.0) with the absorption and aromaticity modulated by Pd(ii) coordination, macrocycle contraction and ancillary ligands.

To further enrich the coordination chemistry of hexaphyrins and probe the underlying property-structural correlations, N-confused dithiahexaphyrin(1.1.1.1.1.0) (1) with 26 π-electron Hückel aromaticity was synthesized. Based on its unprecedented two unsymmetrical cavities, five palladium complexes 2, 3, 4-Ph, 4-Cl and 5 have been successfully synthesized under various coordinations. Thus, two mono-Pd(ii) complexes 2 and 3 with the Pd(ii) atom coordinated in the two different cavities were obtained by treating 1 with palladium reagents PdCl2, and (PPh3)2PdCl2 respectively. On this basis, bis-Pd(ii) complexes 4-Ph and 4-Cl were synthesized by treating 2 and 3 with (PPh3)2PdCl2 and PdCl2, respectively. As a result, both 4-Ph and 4-Cl contain two Pd(ii) atoms coordinated within the two cavities, with one of the Pd(ii) atoms further coordinated to a triphenylphosphine ligand in addition to an anionic ancillary ligand of Ph- and Cl-, respectively. Notably, a further contracted mono-Pd(ii) complex 5 was synthesized by treating 1 with Pd(PPh3)4 by eliminating one of the meso-carbon atoms together with the corresponding C6F5 moiety. These complexes present tunable 26 π aromaticity and NIR absorption up to 1060 nm. This work provides an effective approach for developing distinctive porphyrinoid Pd(ii) complexes from a single porphyrinoid, without resorting to tedious syntheses of a series of porphyrinoid ligands.

Syntheses of Thiophene-Thiophene-Linked Corrorin Dimers with Tunable Near-Infrared Absorption and Distinctive Reactivity.

Thiahexaphyrinone 1 and thia-dipyrrin-appended corrorin 2 have been synthesized. Surprisingly, further oxidation of compound 2 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in dichloromethane afforded dimer 3 with two molecules of compound 2 linked at the α-carbon atoms of the thienyl units. Treatment of compound 3 with DDQ in MeOH and SnCl2 in tetrahydrofuran/H2O afforded the dimethoxy-attached dimer 4 and hydrogenated dihydroxy-attached dimer 5, respectively. These results provide the first examples for synthesizing thiophene-linked porphyrinoid dimers with tunable near-infrared absorption and chirality.

Aromatic Ring-Fused Dipyrrins: Programmed [4 + 2]-Cycloaddition Pathway with Regio-selectivity upon Alkylamino-Substitution.

Sulfolenodipyrrins are employed as building blocks to concisely and efficiently construct aromatic rings (e.g., naphthoquinone, anthraquinone, fullerenes, and phthalimide) from fused dipyrrins by programmed [4 + 2]-cycloaddition reactions. Notably, alkylamino-substitution at the α-position not only enhances the reactivity of sulfolenodipyrrins but also results in the regio-selectivity of the cycloaddition reactions. Theoretical calculations in terms of frontier orbitals of dienes, energy of dienes, steric hindrance, and aromaticity have been conducted to understand the reason in depth. Additionally, the fusion of aromatic groups enables bathochromic absorption with up to ∼130 nm for the monoadducts and to ∼200 nm for the bis-adducts. The phthalimide annulation dipyrrin displays red emission, while the other mono- or bis-adducts do not, owing to the presence of typical acceptors such as quinone analogs or fullerene.

Efficient Solar Cells Based on Porphyrin and Concerted Companion Dyes Featuring Benzo 12-Crown-4 for Suppressing Charge Recombination and Enhancing Dye Loading.

In recent years, various porphyrin dyes have been designed to develop efficient dye-sensitized solar cells (DSSCs). Based on our previously reported porphyrin dye XW43, which contains a phenothiazine donor with two diethylene glycol (DEG)-derived substituents, we herein report a porphyrin dye XW89 by introducing a benzo 12-crown-4 (BCE) unit onto the N atom of the phenothiazine donor. On this basis, XW90 and XW91 have been synthesized by replacing a DEG chain in XW89 with two DEG chains and a 12-crown-4 unit, respectively. For iodine electrolyte-based DSSCs, dyes XW89-XW91 exhibit VOC values of 765-779 mV, higher than that of XW43 (755 mV), which may be related to the strong capability of the BCE group in binding Li+ and thus suppressing the downward shift of the TiO2 conduction band and interfacial charge recombination. Moreover, the smaller size of 12-crown-4 than the DEG unit enables higher adsorption amounts of the dyes than XW43, contributing to an enhanced JSC value. Due to the presence of two BCE units, dye XW91 exhibits the highest dye loading amount and JSC of 1.86 × 10-7 mol cm-2 and 19.79 mA cm-2, respectively, affording a high PCE of 11.1%. To further enhance the light-harvesting ability, a concerted companion (CC) dye XW92 has been constructed by linking the two subdye units corresponding to the porphyrin dye XW91 and an organic dye. As a result, XW92 affords an enhanced JSC and efficiency. Further coadsorption of XW92 with chenodeoxycholic acid achieved the highest efficiency of 12.1%. This work provides an effective approach for fabricating efficient DSSCs sensitized by porphyrin and CC dyes based on the introduction of crown ether units with smaller sizes and stronger Li+ affinities.

Pyrrolylmethylene Appended Corrorin: Peripheral Coordination and Transformation to Pyridyl Incorporated Hemiporphycene Analogue.

A pyrrolylmethylene appended corrorin 1 was synthesized and coordinated with [Rh(CO)2Cl]2 to afford 1-Rh with unique RhI-η2-CC bonding in addition to the coordination of the dipyrrin-like unit and a carbonyl ligand. Further oxidation of 1 afforded 2, exhibiting a hydrocorrorinone core, and it can be further transformed into pyrrolo[3,2-c]pyridine incorporated hemiporphycene analogue 3 upon treatment with HOAc. The side chain modifies the reactivity of corrorin and effectively tunes the NIR absorption of the resulting porphyrinoids.

Flavonoid Components, Distribution, and Biological Activities in Taxus: A review.

Taxus, also known as "gold in plants" because of the famous agents with emphases on Taxol and Docetaxel, is a genus of the family Taxaceae, distributed almost around the world. The plants hold an important place in traditional medicine in China, and its products are used for treating treat dysuria, swelling and pain, diabetes, and irregular menstruation in women. In order to make a further study and better application of Taxus plants for the future, cited references from between 1958 and 2022 were collected from the Web of Science, the China National Knowledge Internet (CNKI), SciFinder, and Google Scholar, and the chemical structures, distribution, and bioactivity of flavonoids identified from Taxus samples were summed up in the research. So far, 59 flavonoids in total with different skeletons were identified from Taxus plants, presenting special characteristics of compound distribution. These compounds have been reported to display significant antibacterial, antiaging, anti-Alzheimer's, antidiabetes, anticancer, antidepressant, antileishmaniasis, anti-inflammatory, antinociceptive and antiallergic, antivirus, antilipase, neuronal protective, and hepatic-protective activities, as well as promotion of melanogenesis. Flavonoids represent a good example of the utilization of the Taxus species. In the future, further pharmacological and clinical experiments for flavonoids could be accomplished to promote the preparation of relative drugs.

Antiaromatic Sapphyrin Isomer: Transformation into Contracted Porphyrinoids with Variable Aromaticity.

Sapphyrin is a pentapyrrolic expanded porphyrin with a 22π aromatic character. Herein, we report the synthesis of a 20π antiaromatic sapphyrin isomer 1 by oxidative cyclization of a pentapyrrane precursor P5 with a terminal ß-linked pyrrole. The resulting isomer 1, containing a mis-linked bipyrrole unit in the skeleton, exhibits a reactivity for further oxidation due to the distinct antiaromatic electronic structure, affording a fused macrocycle 2, possessing a spiro-carbon-containing [5.6.5.6]-tetracyclic structure. Subsequent treatment with an acid afforded a weakly aromatic pyrrolone-appended N-confused corrole 3, and thermal fusion gave a [5.6.5.7]-tetracyclic-ring-embedded 14π aromatic triphyrin(2.1.1) analog 4. The cyclization at the mis-linked pyrrole moiety of P5 played a crucial role in synthesizing the antiaromatic porphyrinoid susceptible to facile transformation to novel porphyrinoids with variable aromaticity.

Chain Length Modulated Dimerization and Cyclization of Terminal Thienyl-Blocked Oligopyrranes.

Oxidation of thienyl-blocked bilane and pentapyrrane afforded chain length dependent products of the symmetric dimer D1 and the thienyloligopyrrin-appended pentaphyrin analogue P2, respectively, with the latter formed by simultaneous dimerization and cyclization. Coordination of D1 and P2 with Cu(II) afforded di- and monometallic complexes D1-Cu2 and P2-Cu, respectively. These compounds exhibit distinct NIR absorption, with the absorption tail of D1-Cu2 extended to ca. 1900 nm despite its smaller conjugation framework than that of P2-Cu.

Porphyrindiene-Based Tandem Diels-Alder Reaction for Preparing Low-Symmetry π-Extended Porphyrins with Push-Pull Skeletons.

Tandem Diels-Alder reactions of masked porphyrindienes (i.e., sulfolenoporphyrins) with benzoquinones and stilbenes, followed by aromatization, have been developed to load porphyrin with mixed annulation units (i.e., terphenyl and naphthoquinone), furnishing the low-symmetry π-extended porphyrins (DxAy) with push-pull skeletons. All low-symmetrical chromophores display panchromatic absorption spectra, which look like a spectral combination of symmetrical congeners (D4/A4) in a certain ratio. Among them, tD2A2 with trans-arrangement of push/pull units possesses the largest maximum centered at 766 nm with the onset around 900 nm. The fusion of the electron-deficient naphthoquinone moiety on the porphyrin core results in the approximately quantitative regulation of the Eox1 and HOMOs (i.e., 0.10-0.13 V increase for the Eox1 and 0.14-0.16 eV decrease for the HOMOs per naphthoquinone unit). In brief, this work provides a new way to construct low-symmetry π-extended porphyrins with tunable properties resorting to the ratios and locations of the annulated push-pull units.

Global burden and attributable risk factors of acute lymphoblastic leukemia in 204 countries and territories in 1990-2019: Estimation based on Global Burden of Disease Study 2019.

To provide a foundational guideline for policy-makers to efficiently allocate medical resources in the context of population aging and growth, the latest spatial distribution and temporal trend of acute lymphoblastic leukemia (ALL) along with attributable risk factors by sex and age were mapped. Based on the Global Burden of Disease Study 2019, estimated annual percentage change (EAPC) was calculated according to the relativity between age-standardized rate and calendar year, to quantify temporal trends in morbidity and mortality of ALL. We used applied Spearman rank correlation to estimate the relationship between the EAPC and potential influence factors. The population attributable fraction of potential risk factors for ALL-related disability-adjusted life years were estimated by the comparative risk assessment framework. As a result, we found that new ALL cases increased significantly by 1.29% worldwide, and the age-standardized incidence rate increased by 1.61% annually. The proportion of elder patients sharply increased, especially within the higher socio-demographic index (SDI) region. Smoking and high body mass index remained the predominant risk factors for ALL-related mortality. Notably, the contribution of high body mass index presented an increasing trend. In conclusion, the global burden of ALL has steadily increased, especially in Middle SDI region. Health measures and new drugs should be taken into consideration to improve the management and treatment of elders with ALL due to an increasing proportion in the higher SDI region. For Low SDI areas, attention should be paid to the environmental problems caused by industrial development.

Confusion Approach Modulated Syntheses of Corrorin Parasitized Hexaphyrins(1.1.1.1.1.0) and the Oxidative Ring Cleavage Behavior.

A corrorin parasitized hexaphyrin(1.1.1.1.1.0) 1 was synthesized by [4 + 4] condensation, and subsequent treatment with PbO2 afforded hexaphyrin 2 appended with a dipyrrinone moiety via regioselective opening of the corrorin ring. In contrast, oxidation of the corresponding corrorin-N-confused hexaphyrin(1.1.1.1.1.0) hybrid 3 afforded only a keto adduct 4. As a result, the planarity and aromaticity of the hexaphyrin moiety can be modulated.

Magnitude and Temporal Trend of the Chronic Myeloid Leukemia: On the Basis of the Global Burden of Disease Study 2019.

PURPOSE: To map the magnitudes and temporal trends of chronic myeloid leukemia (CML) along with its attributable risk factors, providing the essential foundation for targeted public policies at the national, regional, and global levels. MATERIALS AND METHODS: We retrieved annual data on CML burden in 204 countries and regions from the Global Burden of Disease Study 2019 in 1990-2019. The estimated annual percentage change (EAPC) was calculated to quantify the temporal trends of CML burden by region, sex, and age group. RESULTS: Globally, the age-standardized incidence rate of CML declined weakly over the past few years (EAPC: -1.04), but the number of incident cases increased by 54.1% to 65.8 × 103 in 2019. By contrast, a dramatic drop in death and disability-adjusted life years (DALYs) rate (EAPCs: -2.55; -2.69) led to a reduction in deaths and DALYs, especially in high-income regions. In 2019, the highest age-standardized death rate was observed in Ethiopia (1.89 per 100,000). The death rate of CML was pronounced among the population age above 70 years. DALYs of CML worldwide were primarily attributable to smoking (12.2%), high body mass index (5.0%), occupational exposure to benzene (0.9%), and occupational exposure to formaldehyde (0.3%) in 2019. CONCLUSION: Although the mortality rate of CML has decreased significantly, the management of patients with CML cannot be neglected, especially in elders and developing regions.

N-Confused Hexapyrrolic Phlorinoid with NIR Absorption: Synthesis, Fusion, Oxidation, and Copper(II) Coordination.

An N-confused hexapyrrolic phlorinoid 1 and its isomer N-fused hexapyrrolic phlorinoid 2 were synthesized through [4 + 2] condensation. Both 1 and 2 can be readily transformed into N-confused hexapyrrolic phlorinone 3 under aerobic conditions. Coordination of 1 with Cu(acac)2 afforded two different mono-Cu(II) complexes 4 and 5 with CNNN and ONNN coordination environments, respectively. The NIR absorption bands can be effectively modulated up to 1265 nm through the oxidation, fusion, and metalation reactions.

UAF1 deubiquitinase complexes facilitate NLRP3 inflammasome activation by promoting NLRP3 expression.

NOD-like receptor protein 3 (NLRP3) detects microbial infections or endogenous danger signals and activates the NLRP3 inflammasome, which has important functions in host defense and contributes to the pathogenesis of inflammatory diseases, and thereby needs to be tightly controlled. Deubiquitination of NLRP3 is considered a key step in NLRP3 inflammasome activation. However, the mechanisms by which deubiquitination controls NLRP3 inflammasome activation are unclear. Here, we show that the UAF1/USP1 deubiquitinase complex selectively removes K48-linked polyubiquitination of NLRP3 and suppresses its ubiquitination-mediated degradation, enhancing cellular NLRP3 levels, which are indispensable for subsequent NLRP3 inflammasome assembly and activation. In addition, the UAF1/USP12 and UAF1/USP46 complexes promote NF-κB activation, enhance the transcription of NLRP3 and proinflammatory cytokines (including pro-IL-1ß, TNF, and IL-6) by inhibiting ubiquitination-mediated degradation of p65. Consequently, Uaf1 deficiency attenuates NLRP3 inflammasome activation and IL-1ß secretion both in vitro and in vivo. Our study reveals that the UAF1 deubiquitinase complexes enhance NLRP3 and pro-IL-1ß expression by targeting NLRP3 and p65 and licensing NLRP3 inflammasome activation.

Twisted-Planar-Twisted expanded porphyrinoid dimer as a rudimentary reaction-based methanol indicator.

Directly linked porphyrin dimers have attracted considerable attention because of their intriguing electronic features. Most emphasis has been placed on either dimers with large dihedral angles between the constituent planar monomeric subunits or those with overall planarity, referred to as "Planar-Twisted-Planar" and "Planar-Planar-Planar", respectively. Herein, we report a "Twisted-Planar-Twisted" framework, the hexaphyrin dimer D that exists in a trans configuration. Treatment of D with MeOH affords two isomeric dimers, MD1 and MD2, both of which incorporate a methoxy moiety and exist in cis orientations with respect to the tethering linkage. The methanol-promoted conversion is accompanied by a readily discernible color change from green to brown and is not induced to an appreciable level by other alcohols. Dimer D thus acts as a rudimentary, albeit highly selective, reaction-based methanol indicator. This work provides a promising approach for constructing reaction-based chemosensors using porphyrinoid dimers of nonplanar subunits with biased reactivity.

Expanded N-Confused Phlorin: A Platform for a Multiply Fused Polycyclic Ring System via Oxidation within the Macrocycle.

Novel interrupted π-conjugated macrocycles derived from expanded porphyrinoids were synthesized, and their unique reactivity was investigated in this work. The specific porphyrin analogs, so-called phlorins and isoporphyrins, possess a meso-sp3 methylene moiety, showing inner 3NH and 1NH pyrrolic cores, respectively, and extended near-infrared (NIR) absorption. Expanded N-confused pentapyrrolic phlorin analog 1 bears an interrupted cyclic π-conjugated system that is featured by a distinct higher HOMO and a lower LUMO. Oxidation of 1 allowed structural transformations through the expanded isoporphyrin-like species 2. One of the representative products is a spiro-carbon-bridged multiply N-fused product 3 comprising a fused [5.6.5.7.6.5]-hexacyclic ring obtained by oxidation with 2,3-dichloro-5,6-dicyano-p-benzoquinone. When magic blue was used as the oxidant, an aromatic N-confused pentaphyrin 4 was obtained via migration of one of the meso-phenyl groups to the ß-position of the neighboring pyrrolic ring. By employing the flexible cavity of 1 for metal coordination, Pd(II) complexation occurred with a specific meso oxygenation to give a bimetallic complex 5. In contrast to the rich oxidation reactions, reduction of 1 with NaBH4 resulted in the regioselective nucleophilic hydrogen substitution reaction at the para position of one of the meso-C6F5 groups. These results provide a practical approach for synthesizing novel interrupted or aromatic π-conjugated frameworks showing NIR absorptions.

Aggregation Enhanced Responsiveness of Rationally Designed Probes to Hydrogen Sulfide for Targeted Cancer Imaging.

Activatable molecular probes hold great promise for targeted cancer imaging. However, the hydrophobic nature of most conventional probes makes them generate precipitated agglomerate in aqueous media, thereby annihilating their responsiveness to analytes and precluding their practical applications for bioimaging. This study reports the development of two small molecular probes with unprecedented aggregation enhanced responsiveness to H2S for in vivo imaging of H2S-rich cancers. The subtle modulation of the equilibrium between hydrophilicity and lipophilicity by N-methylpyridinium endows these designed probes with the capability of spontaneously self-assembling into nanoprobes under physiological conditions. Such probes in an aggregated state, rather than a molecular dissolved state, show NIR fluorescence light up and photoacoustic signals turn on upon H2S specific activation, allowing in vivo visualization and differentiation of cancers based on differences in H2S content. Thus, our study presents an effective design strategy which should pave the way to molecular design of optimized probes for precision cancer diagnostics.

Extracellular vesicle-mediated transfer of miR-21-5p from mesenchymal stromal cells to neurons alleviates early brain injury to improve cognitive function via the PTEN/Akt pathway after subarachnoid hemorrhage.

Patients with subarachnoid hemorrhage (SAH) often suffer from cognitive function impairments even when they have received proper treatment, such as the clipping or coiling of aneurysms, and this causes problems with returning to work and burdens the family. Increasing attention has been paid to mesenchymal stem cell (MSC)-derived extracellular vesicle (MSC-EV) as promising therapeutic vesicles for stroke management. In this study, we explored the potential role of MSC-EV in a rat model of SAH. We observed that MSC-EV ameliorated early brain injury (EBI) after SAH by reducing the apoptosis of neurons and that SAH induced an increase in the expression level of miR-21 in the prefrontal cortex and hippocampus. In addition, using miRNA profiling and CSF sequencing data from the exRNA Atlas, we demonstrated that EV-derived miR-21 protected neurons from apoptosis and alleviated SAH-induced cognitive dysfunction. The neuroprotective role of MSC-EV was abrogated by miR-21 knockdown or the administration of MK2206, a PTEN/Akt inhibitor. Overall, our results suggest that MSC-EV promotes neuronal survival and alleviates EBI after SAH through transferring miR-21 to recipient neurons.