Efficient Tin-Based Perovskite Solar Cells Enabled by Precisely Synthesized Single-Isomer Fullerene Bisadducts with Regulated Molecular Packing.

Designing and synthesizing fullerene bisadducts with a higher-lying conduction band minimum is promising to further improve the device performance of tin-based perovskite solar cells (TPSCs). However, the commonly obtained fullerene bisadduct products are isomeric mixtures and require complicated separation. Moreover, the isomeric mixtures are prone to resulting in energy alignment disorders, interfacial charge loss, and limited device performance improvement. Herein, we synthesized single-isomer C60- and C70-based diethylmalonate functionalized bisadducts (C60BB and C70BB) by utilizing the steric-hindrance-assisted strategy and determined all molecular structures involved by single crystal diffraction. Meanwhile, we found that the different solvents used for processing the fullerene bisadducts can effectively regulate the molecular packing in their films. The dense and amorphous fullerene bisadduct films prepared by using anisole exhibited the highest electron mobility. Finally, C60BB- and C70BB-based TPSCs showed impressive efficiencies up to 14.51 and 14.28%, respectively. These devices also exhibited excellent long-term stability. This work highlights the importance of developing strategies to synthesize single-isomer fullerene bisadducts and regulate their molecular packing to improve TPSCs' performance.

Soluble Nanographene C222: Synthesis and Applications for Synergistic Photodynamic/Photothermal Therapy.

Nanographene C222, which consists of a planar graphenic plane containing 222 carbon atoms, holds the record as the largest planar nanographene synthesized to date. However, its complete insolubility makes the processing of C222 difficult. Here we addressed this issue by introducing peripheral substituents perpendicular to the graphene plane, effectively disrupting the interlayer stacking and endowing C222 with good solubility. We also found that the electron-withdrawing substituents played a crucial role in the cyclodehydrogenation process, converting the dendritic polyphenylene precursor to C222. After disrupting the interlayer stacking, the introduction of only a few peripheral carboxylic groups allowed C222 to dissolve in phosphate buffer saline, reaching a concentration of up to 0.5 mg/mL. Taking advantage of the good photosensitizing and photothermal properties of the inner C222 core, the resulting water-soluble C222 emerged as a single-component agent for both photothermal and photodynamic tumor therapy, exhibiting an impressive tumor inhibition rate of 96%.

Epidemiological characteristics and antibody kinetics of elderly population with booster vaccination following both Omicron BA.5 and XBB waves in China.

After the termination of zero-COVID-19 policy, the populace in China has experienced both Omicron BA.5 and XBB waves. Considering the poor antibody responses and severe outcomes observed among the elderly following infection, we conducted a longitudinal investigation to examine the epidemiological characteristics and antibody kinetics among 107 boosted elderly participants following the Omicron BA.5 and XBB waves. We observed that 96 participants (89.7%) were infected with Omicron BA.5, while 59 (55.1%) participants were infected with Omicron XBB. Notably, 52 participants (48.6%) experienced dual infections of both Omicron BA.5 and XBB. The proportion of symptomatic cases appeared to decrease following the XBB wave (18.6%) compared to that after the BA.5 wave (59.3%). Omicron BA.5 breakthrough infection induced lower neutralizing antibody titers against XBB.1.5, BA.2.86, and JN.1, while reinfection with Omicron XBB broadened the antibody responses against all measured Omicron subvariants and may alleviate the wild type-vaccination induced immune imprinting. Boosted vaccination type and comorbidities were the significant factors associated with antibody responses. Updated vaccines based on emerging severe acute respiratory syndrome coronavirus 2 variants are needed to control the Coronavirus Disease 2019 pandemic in the elderly.

Cross-Linkable Fullerene Enables Elastic and Conductive Grain Boundaries for Efficient and Wearable Tin-Based Perovskite Solar Cells.

Tin-based perovskite solar cells (TPSCs) have received increasing attention due to their low toxicity, high theoretical efficiency, and potential applications as wearable devices. However, the inherent fast and uncontrollable crystallization process of tin-based perovskites results in high defect density in the film. Meanwhile, when fabricated into flexible devices, the prepared perovskite film exhibits inevitable brittleness and high Young's modulus, seriously weakening the mechanical stability. In this work, we design and synthesize a cross-linkable fullerene, thioctic acid functionalized C60 fulleropyrrolidinium iodide (FTAI), which has multiple interactions with perovskite components and can finely regulate the crystallization quality of perovskite film. The obtained perovskite film shows an increased grain size and a more matched energy level with the electron transport material, effectively improving the carrier extraction efficiency. The FTAI-based rigid device achieves a champion efficiency of 14.91 % with enhanced stability. More importantly, the FTAI located at the perovskite grain boundaries could spontaneously cross-link during the perovskite annealing process, which effectively improves the conductivity and elasticity of grain boundaries, thereby giving the film excellent bending resistance. Finally, the FTAI-based wearable device yields a record efficiency of 12.35 % and displays robust bending durability, retaining about 90 % of the initial efficiency after 10,000 bending times.

Synthesis and Interlayer Assembly of a Graphenic Bowl with Peripheral Selenium Annulation.

Pentagonal cyclization at the bay positions of armchair-edged graphenic cores can build molecular bowls without the destruction of hexagonal lattices. However, this synthesis remains challenging due to unfavorable strain and the multiple reactions required. Here, we show that a new type of graphenic molecular bowl with a depth of 1.7 Å and a diameter of 1.2 nm is constructed by sextuple Se annulation at the bay positions of armchair-edged hexa-peri-hexabenzocoronene. This graphenic bowl is functionalized with phenylseleno groups that stack into a discrete bilayer dimer in solution. Such a dimer exhibits high stability and survives in the gas phase after laser ablation. Strikingly, the asymmetric one-dimensional supramolecular columns of graphenic bowl with coherent stacking configuration are observed in the solid state, which results in a strong second harmonic generation with prominent polarization dependence. Our findings present a concise synthesis of a giant molecular bowl with a graphenic core and demonstrate the unique supramolecular assembly of extended graphenic bowls.

Hexa-Branched Nanographenes with Large Two-Photon Absorption.

The conventional approach toward molecules with large two-photon absorption (TPA) involves donor-acceptor conjugation. Herein we show a new strategy involving the use of hexa-branched nanographenes. We synthesized two hexa-branched nanographenes, one with six benzoaceanthrylene arms fused to the coronene core and the other with six pyrenyl arms fused to the coronene core. Neither of these hexa-branched nanographenes has a donor-acceptor structure, yet they exhibited high TPA values of 3.6 × 103 and 1.9 × 104 GM, respectively, which are the highest values recorded for heteroatom-free hydrocarbon molecules. Theoretical analysis suggests that the fused branched structures are responsible for the large TPA cross-section. These findings illustrate the importance of the topology of the fused conjugated skeleton in TPA and provide an alternative structural design toward large TPA.

Helical Trilayer Nanographenes with Tunable Interlayer Overlaps.

The synthesis of well-defined nanocarbon multilayers, beyond the bilayer structure, is still a challenging goal. Herein, two trilayer nanographenes were synthesized by covalently linking nanographene layers through helicene bridges. The structural characterization of the trilayer nanographenes revealed a compact trilayer-stacked architecture. The introduction of a furan ring into the helicene linker modulates the interlayer overlap and π-conjugation of the trilayer nanographenes, enabling the tuning of the interlayer coupling, as demonstrated by optical, electrochemical, and theoretical analyses. Both synthesized trilayer nanographenes are rigid chiral nanocarbons and show a chirality transfer from the helicene moiety to the stacked nanographene layers. These helical trilayer nanographenes reported here represent the covalently linked multilayer nanographenes rather than bilayer ones, showing the tunable multilayer stacking structure.

Remote-Triggered Domino-like Cyclodehydrogenation in Second-Layer Topological Graphene Nanoribbons.

Cyclodehydrogenation reactions in the on-surface synthesis of graphene nanoribbons (GNRs) usually involve a series of Csp2-Csp2 and/or Csp2-Csp3 couplings and just happen on uncovered metal or metal oxide surfaces. It is still a big challenge to extend the growth of second-layer GNRs in the absence of necessary catalytic sites. Here, we demonstrate the direct growth of topologically nontrivial GNRs via multistep Csp2-Csp2 and Csp2-Csp3 couplings in the second layer by annealing designed bowtie-shaped precursor molecules over one monolayer on the Au(111) surface. After annealing at 700 K, most of the polymerized chains that appear in the second layer covalently link to the first-layer GNRs that have partially undergone graphitization. Following annealing at 780 K, the second-layer GNRs are formed and linked to the first-layer GNRs. Benefiting from the minimized local steric hindrance of the precursors, we suggest that the second-layer GNRs undergo domino-like cyclodehydrogenation reactions that are remotely triggered at the link. We confirm the quasi-freestanding behaviors in the second-layer GNRs by measuring the quasiparticle energy gap of topological bands and the tunable Kondo resonance from topological end spins using scanning tunneling microscopy/spectroscopy combined with first-principles calculations. Our findings pave the avenue to diverse multilayer graphene nanostructures with designer quantum spins and topological states for quantum information science.

Length-Dependent Magnetic Evolution of Anthenes on Au(111).

Nanographenes with zigzag edges, for example, anthenes, exhibit a unique nonbonding π-electron state, which can be described as a spin-polarized edge state that yields specific magnetic ground state. However, prior researches on the magnetism of anthenes with varying lengths on a surface is lacking. This study systematically fabricated anthenes with inherent zigzag carbon atoms of different lengths ranging from bisanthene to hexanthene. Their magnetic evolution on the Au(111) surface was analyzed through bond-resolved scanning probe techniques and density functional theory calculations. The analyses revealed a transition in magnetic properties associated with the length of the anthenes, arising from the imbalance between hybridization energy and the Coulomb repulsion between valence electrons. With the increasing length of the anthenes, the ground state transforms gradually from a closed-shell to an antiferromagnetic open-shell singlet, exhibiting a weak exchange coupling of 4 meV and a charge transfer-induced doublet. Therefore, this study formulated a chemically tunable platform to explore size-dependent π magnetism at the atomic scale, providing a framework for research in organic spintronics.

Step-Assisted On-Surface Synthesis of Graphene Nanoribbons Embedded with Periodic Divacancies.

The bottom-up approach through on-surface synthesis of porous graphene nanoribbons (GNRs) presents a controllable manner for implanting periodic nanostructures to tune the electronic properties of GNRs in addition to bandgap engineering by width and edge configurations. However, owing to the existing steric hindrance in small pores like divacancies, it is still difficult to embed periodic divacancies with a nonplanar configuration into GNRs. Here, we demonstrate the on-surface synthesis of atomically precise eight-carbon-wide armchair GNRs embedded with periodic divacancies (DV8-aGNRs) by utilizing the monatomic step edges on the Au(111) surface. From a single molecular precursor correspondingly following a trans- and cis-coupling, the DV8-aGNR and another porous nanographene are respectively formed at step edges and on terraces at 720 and 570 K. Combining scanning tunneling microscopy/spectroscopy, atomic force microscopy, and first-principles calculations, we determine the out-of-plane conformation, wide bandgap (∼3.36 eV), and wiggly shaped frontier orbitals of the DV8-aGNR. Nudged elastic band calculations further quantitatively reveal that the additional steric hindrance effect in the cyclodehydrogenative reactions has a higher barrier of 1.3 eV than that in the planar porous nanographene, which also unveils the important role played by the monatomic Au step and adatoms in reducing the energy barriers and enhancing the thermodynamic preference of the oxidative cyclodehydrogenation. Our results provide the first case of GNRs containing periodic pores as small as divacancies with a nonplanar configuration and demonstrate the strategy by utilizing the chemical heterogeneity of a substrate to promote the formation of novel carbon nanomaterials.

Nanographene Metallaprisms: Structure, Stimulated Transformation, and Emission Enhancement.

Nanographenes are inclined to assemble into stacked columnar structures that are stabilized by π-π interactions, whereas other supramolecular structures of nanographenes, such as prisms and cages, are rarely investigated. Herein, a diazananographene was synthesized, and then assembled with a coordination unit, thereby producing a triangular metallaprism. After adding C60 or C70 , the triangular metallaprism was transformed into a square tetramer, which encapsulated a pair of C60 or C70 molecules. The formed host-guest complex demonstrated efficient energy transfer from the diazananographene shell to the C60 cores. The emission intensity of the capsulated C60 was enhanced remarkably, compared with free C60 , due to an increased quantum yield and optical absorption coefficient. This work demonstrates the versatility of nanographene-based supramolecular architectures beyond columnar stacking and their ability to enhance the emission of otherwise non-emissive fullerene.

Nanographene with Multiple Embedded Heptagons: Cascade Radical Photocyclization.

Although heptagons are widely found in graphenic materials, the precise synthesis of nanocarbons containing heptagons remains a challenge, especially for the nanocarbons containing multiple-heptagons. Herein, we show that photo-induced radical cyclization (PIRC) can be used to synthesize multi-heptagon-embedded nanocarbons. Notably, a nanographene containing six heptagons (1) was obtained via a six-fold cascade PIRC reaction. The structure of 1 was clearly validated and showed a Monkey-saddle-shaped conformation. Experimental bond analysis and theoretical calculations indicated that the heptagons in 1 were non-aromatic, whereas the peripheral rings were highly aromatic. Compared to planar nanographene with the same number of π electrons, 1 had a similar optical gap due to a compromise between the decreased conjugation in the wrapped structure and enhanced electronic delocalization at the rim. Electrochemical studies showed that 1 had low-lying oxidation potentials, which was attributed to the nitrogen-doping.

Ultrasmall Abundant Metal-Based Clusters as Oxygen-Evolving Catalysts.

The oxygen evolution reaction is a crucial step in water electrolysis to develop clean and renewable energy. Although noble metal-based catalysts have demonstrated high activity for the oxygen evolution reaction, their application is limited by their high cost and low availability. Here we report the use of a molecule-to-cluster strategy for preparing ultrasmall trimetallic clusters by using the polyoxometalate molecule as a precursor. Ultrafine (0.8 nm) transition-metal clusters with controllable chemical composition are obtained. The transition-metal clusters enable highly efficient oxygen evolution through water electrolysis in alkaline media, manifested by an overpotential of 192 mV at 10 mA cm-2, a low Tafel slope of 36 mV dec-1, and long-term stability for 30 h of electrolysis. We note, however, that besides the excellent performance as an oxygen evolution catalyst, our molecule-to-cluster strategy provides a means to achieve well-defined transition-metal clusters in the subnanometer regime, which potentially can have an impact on several other applications.

Change of intestinal microbiota in cerebral ischemic stroke patients.

BACKGROUND: Gut microbiota has been suggested to play a role in stroke patients. Nevertheless, little is known about gut microbiota and the clinical indexes in stroke patients. METHODS: Total of 30 cerebral ischemic stroke (CI) patients and 30 healthy control were enrolled in this study and the fecal gut microbiota was profiled via Illumina sequencing of the 16S rRNA V1-V2. The National Institutes of Health Stroke Scale (NIHSS) were used to quantify stroke severity and modified Rankin scale (mRS) to assess outcome for CI patients. The correlations between the clinical indexes and microbiota were evaluated. RESULTS: Though the microbial α-diversity and structure is similar between CI patients and healthy controls, the gut microbiota of CI patients had more short chain fatty acids producer including Odoribacter, Akkermansia, Ruminococcaceae_UCG_005 and Victivallis. We also found that the special microbes were correlation with serum index, such as norank_O_ _Mollicutes_RF9, Enterobacter, Ruminococcaceae_UCG-002 were negative correlation with LDL (r = - 0.401, P < 0.01), HDL (r = - 0.425, P < 0.01) and blood glucose (r = - 0.439, P < 0.001), while the HDL was significantly positive correlation with the genus Ruminococcus_1 (r = 0.443, P < 0.001). The Christensenellaceae_R-7_group and norank_f_Ruminococcaceae was significantly positive correlation with NIHSS1M (r = 0.514, P < 0.05; r = 0.449, P < 0.05) and mRS (r = 0.471, P < 0.05, r = 0.503, P < 0.01), respectively. On the other hand, the genus Enterobacter was significantly negative correlation with NIHSS1M (r = 0.449, P < 0.05) and mRS (r = 0.503, P < 0.01). CONCLUSIONS: This study suggests that CI patients showed significant dysbiosis of the gut microbiota with enriched short chain fatty acids producer, including Odoribacter, Akkermansia. This dysbiosis was correlation with the outcomes and deserves further study.

Enlarged responsivity-ZnO honeycomb nanomaterials UV photodetectors with light trapping effect.

The ability of ZnO photodetectors to absorb UV light plays a key role in enhancing responsivity and performance in electronic, optical, and photonic devices. Herein, the light trapping effect of ZnO is used to design and fabricate a novel honeycomb-like ZnO nanomaterial-based UV photodetector with an excellent photoelectric performance. Compared with the traditional ZnO film UV photodetector, the photoresponsivity of the film with honeycomb nanomaterials can reach up to 4.79 A W-1, which is an improvement of about 300 times. In addition, the honeycomb ZnO nanomaterials UV photodetectors exhibit an improved light absorption, a very photo-to-dark current ratio (2.46 × 103), and an excellent detectivity (4.61 × 1012 Jones). The ZnO honeycomb nanostructure synthesized in this work exhibits a strong trapping effect, providing new insights into the research of nanomaterials used for UV photodetectors.

[Analysis of clinical features and AGL gene mutations in a family with glycogen storage disease type IIIa].

OBJECTIVE: To investigate the clinical features and AGL gene mutations in a family with glycogen storage disease type IIIa (GSD IIIa). METHODS: Clinical data for diagnosis, treatment and follow-up of a sick child with GSD III was collected and analyzed. Genomic DNA was extracted from the peripheral blood samples from the patient and his parents. Polymerase chain reaction and direct DNA sequencing were utilized to analyze all of the exons of the AGL gene. RESULTS: The genotype of the child was found to be c.3710_3711delTA/IVS14+1G>T. The former was a maternally-inherited mutation, which has not been reported previously. The latter was an abnormal splice-site mutation inherited from the father. CONCLUSION: Based on its clinical and molecular evidences, the patient was diagnosed as GSD IIIa in conjunction with retrobular optic neuritis.

[Cloning and sequence analysis of SLC25A13 transcripts in human amniocytes].

OBJECTIVE: This research intends to amplify the entire coding region sequences of SLC25A13 mRNA which encodes citrin, and to investigate sequence features of the transcripts for this gene in cultured human amniocytes. This study will provide laboratory evidence for prenatal diagnosis of neonatal intrahepatic cholestasis caused by citrin deficiency (NICCD) at mRNA level. METHODS: One amniocyte sample was collected from a pregnant woman who underwent prenatal diagnosis of citrin deficiency and whose fetus has proven a carrier of 851del4 mutation by genomic DNA analysis. Another amniocyte sample, as a control, was from a fetus without family history of citrin deficiency. Total RNA was extracted from cultured amniocytes, cDNA was synthesized, and then nested-PCR was performed to amplify the entire coding region sequences of SLC25A13. The PCR products were cloned and analyzed by sequencing. RESULTS: The entire coding region of SLC25A13 gene was successful amplified from two cultured human amniocytes. The splice variant of SLC25A13, SLCA (normal mRNA), was identified in the two samples. SLCB (CAG insertion between exon 9-10) was identified in the control. SLCC (exon 5-11 skipping), but not transcriptional product from the allele with 851del4 mutation, was identified in the 851del4 mutation carrier. CONCLUSIONS: This study demonstrated that the entire coding region of SLC25A13 cDNA can be successfully amplified from two cultured human amniocytes, and revealed exon 5-11 skipping as a novel SLC25A13 transcript. Normal mRNA predominated in the transcripts in normal control and 851del4 mutation carrier, suggesting that the two fetuses were not at risk for NICCD. These SLC25A13 transcription features provided laboratory evidence for prenatal diagnosis of NICCD.

Caffeine reduces oxidative stress to protect against hyperoxia-induced lung injury via the adenosine A2A receptor/cAMP/PKA/Src/ERK1/2/p38MAPK pathway.

Objectives: Caffeine has been shown to reduce the incidence of bronchopulmonary dysplasia (BPD). To investigate the protective mechanism of caffeine in a hyperoxia-based cell model of BPD in vitro.Methods: Type II alveolar epithelial cells (AECs II) were isolated and randomly divided into 6 groups: the normal, hyperoxia, caffeine (50 µM caffeine), antagonist (5 µM ZM241385), agonist (5 µM CGS21680), and DMSO groups. Transfection with siRNA against adenosine A2A receptor (siA2AR) was performed in AECs II.Results: Caffeine alone or in combination with adenosine A2A receptor (A2AR) antagonist inhibited apoptosis, promoted proliferation and reduced oxidative stress (OS). The cyclic adenosine monophosphate (cAMP), protein kinase A (PKA) mRNA, A2AR mRNA and the protein levels of A2AR, phospho-Src, phospho-ERK1/2, phospho-P38 and cleaved caspase-3 were decreased in the caffeine and antagonist groups compared with that in the hyperoxia group. However, the effects of caffeine above were weakened by the A2AR agonist. Knockdown of A2AR showed similar results to caffeine.Discussion: Caffeine can reduce apoptosis, promote proliferation, and alleviate OS in hyperoxia-induced AECs II injury by inhibiting the A2AR/cAMP/PKA/Src/ERK1/2/p38MAPK signaling pathway. Caffeine and A2AR may serve as a promising therapeutic target for BPD in prematurity.

Charge transport through single-molecule bilayer-graphene junctions with atomic thickness.

The van der Waals interactions (vdW) between π-conjugated molecules offer new opportunities for fabricating heterojunction-based devices and investigating charge transport in heterojunctions with atomic thickness. In this work, we fabricate sandwiched single-molecule bilayer-graphene junctions via vdW interactions and characterize their electrical transport properties by employing the cross-plane break junction (XPBJ) technique. The experimental results show that the cross-plane charge transport through single-molecule junctions is determined by the size and layer number of molecular graphene in these junctions. Density functional theory (DFT) calculations reveal that the charge transport through molecular graphene in these molecular junctions is sensitive to the angles between the graphene flake and peripheral mesityl groups, and those rotated groups can be used to tune the electrical conductance. This study provides new insight into cross-plane charge transport in atomically thin junctions and highlights the role of through-space interactions in vdW heterojunctions at the molecular scale.

Prenatal diagnosis of citrin deficiency in a Chinese family with a fatal proband.

Citrin deficiency (CD) is an autosomal recessive disorder with SLC25A13 as causative gene that encodes citrin, the liver-type aspartate/glutamate carrier isoform 2 (AGC2). Neonatal intrahepatic cholestasis caused by citrin deficiency (NICCD), the major CD phenotype at pediatric age, has been previously reported as a self-limiting condition with clinical presentations resolving between 6 months and 1 year of life. We report the prenatal diagnosis of CD in a family with a fatal NICCD proband. The proband was a 10-month-old male presenting cough for 8 days and jaundiced skin 1 day. Physical examination revealed fever, dark jaundiced sclera and skin, hoarse breathing sounds, and hepatosplenomegaly. Laboratory tests uncovered elevated cholestatic indices, increased ammonia, and prolonged activated partial thromboplastin time and prothrombin time, and reduced fibrinogen. Sonography showed the features of liver cirrhosis. Metabolome analysis uncovered large quantity of 4-hydroxyphenyllactate and dicarboxylates in urine and increased citrulline and methionine in blood. The patient passed away due to liver failure at his age of 13.5 months. Mutation analysis revealed him a homozygote of 851del4, a four-base deletion in exon 9 of SLC25A13 gene. On request of the parents who had a second fetus, prenatal diagnosis of CD was performed by PCR-electrophoresis following amniocentesis and amniocyte culture, and demonstrated the fetus a carrier of the same mutation. The fatal proband in the present report has provided clinical evidence challenging the traditional concept on NICCD prognosis. Moreover, as the first trial on CD prenatal diagnosis, this study might open a novel area for clinical management of CD.