A Flexible and Stretchable MXene/Waterborne Polyurethane Composite-Coated Fiber Strain Sensor for Wearable Motion and Healthcare Monitoring.

Fiber-based flexible sensors have promising application potential in human motion and healthcare monitoring, owing to their merits of being lightweight, flexible, and easy to process. Now, high-performance elastic fiber-based strain sensors with high sensitivity, a large working range, and excellent durability are in great demand. Herein, we have easily and quickly prepared a highly sensitive and durable fiber-based strain sensor by dip coating a highly stretchable polyurethane (PU) elastic fiber in an MXene/waterborne polyurethane (WPU) dispersion solution. Benefiting from the electrostatic repulsion force between the negatively charged WPU and MXene sheets in the mixed solution, very homogeneous and stable MXene/WPU dispersion was successfully obtained, and the interconnected conducting networks were correspondingly formed in a coated MXene/WPU shell layer, which makes the as-prepared strain sensor exhibit a gauge factor of over 960, a large sensing range of over 90%, and a detection limit as low as 0.5% strain. As elastic fiber and mixed solution have the same polymer constitute, and tight bonding of the MXene/WPU conductive composite on PU fibers was achieved, enabling the as-prepared strain sensor to endure over 2500 stretching-releasing cycles and thus show good durability. Full-scale human motion detection was also performed by the strain sensor, and a body posture monitoring, analysis, and correction prototype system were developed via embedding the fiber-based strain sensors into sweaters, strongly indicating great application prospects in exercise, sports, and healthcare.

A novel homozygous mutation in ACTL7A leads to male infertility.

Male infertility, a global public health problem, exhibits complex pathogenic causes and genetic factors deserve further discovery and study. We identified a novel homozygous missense mutation c.224A > C (p.D75A) in ACTL7A gene in two infertile brothers with teratozoospermia by whole-exome sequencing (WES). In vitro fertilization (IVF) and intracytoplasmic sperm injection (ICSI) showed fertilization failure of the two affected couples. The three-dimensional (3D) models showed that a small section of α-helix transformed into random coil in the mutant ACTL7A protein and mutant amino acid lacked a hydrogen bond with Ser170 amino acid. Immunofluorescence revealed that ACTL7A protein was degraded in sperms of patients. Transmission electron microscopy (TEM) analysis of sperms from the infertile patients showed that the irregular perinuclear theca (PT) and acrosomal ultrastructural defects. Furthermore, ACTL7A mutation caused abnormal localization and reduced the expression of PLCZ1 in sperms of the patients, which may be the key reasons for the fertilization failure after ICSI. Our findings expand the spectrum of ACTL7A mutations and provide novel theoretical basis for genetic counseling.

Negatively Charged Holey Titania Nanosheets Added Electrolyte to Realize Dendrite-Free Lithium Metal Battery.

Electrolyte modulation and electrode structure design are two common strategies to suppress dendrites growth on Li metal anode. In this work, a self-adaptive electrode construction method to suppress Li dendrites growth is reported, which merges the merits of electrolyte modulation and electrode structure design strategies. In detail, negatively charged titania nanosheets with densely packed nanopores on them are prepared. These holey nanosheets in the electrolyte move spontaneously onto the anode under electrical field, building a mesoporous structure on the electrode surface. The as-formed porous electrode has large surface area with good lithiophilicity, which can efficiently transfer lithium ion (Li+ ) inside the electrode, and induce the genuine lithium plating/stripping. Moreover, the negative charges and nanopores on the sheets can also regulate the lithium-ion flux to promote uniform deposition of Li metal. As a result, the symmetric and full cells using the holey titania nanosheets containing electrolyte, show much better performance than the ones using electrolyte without holey nanosheets inside. This work points out a new route for the practical applications of Li-metal batteries.

A Gradient Lithiophilic Structure for Stable Lithium Metal Anodes with Ultrahigh Rate and Ultradeep Capacity.

Using three-dimensional current collectors (3DCC) as frameworks for lithium metal anodes (LMAs) is a promising approach to inhibit dendrite growth. However, the intrinsically accumulated current density on the top surface and limited Li-ion transfer in the interior of 3DCC still lead to the formation of lithium dendrites, which can pose safety risks. In this study, it reports that gradient lithiophilic structures can induce uniform lithium deposition within the interior of the 3DCC, greatly suppressing dendrite formation, as confirmed by COMSOL simulations and experimental results. With this concept, a gradient-structured zinc oxide-loaded copper foam (GSZO-CF) is synthesized via an easy solution-combustion method at low cost. The resulting Li@GSZO-CF symmetric cells demonstrate stable cycling performance for over 800 cycles, with an ultra-deep capacity of 10 mAh cm-2 even under an ultra-high current density of 50 mA cm-2 , the top results reported in the literature. Moreover, when combined with a LiFePO4 (LFP) cathode under a low negative/positive (N/P) capacity ratio of 2.9, the Li@GSZO-CF||LFP full cells exhibit stable performance for 200 cycles, with a discharge capacity of 130 mAh g-1 and retention of 85.5% at a charging/discharging rate of 1C. These findings suggest a promising strategy for the development of new-generation LMAs.

In-Situ Construction of V2 O5 Nanosheet/Nitrogen-Doped Carbon Nanosheet Heterostructures with Interfacial C─O Bridging Bonds as the Cathode Material for Zn Ion Batteries.

Layered oxides are widely used as the electrode materials for metal ion batteries. However, for large radius size ions, such as Zn2+ and Al3+ , the tightly stacked layers and poor electrical conductivity of layered oxides result in restricted number of active sites and sluggish reaction kinetics. In this work, a facile in-situ construction strategy is provided to synthesize layered oxide nanosheets/nitrogen-doped carbon nanosheet (NC) heterostructure, which shows larger interlayer spacing and better electrical conductivity than the layered oxides. As a result, the Zn2+ ion diffusion inside the interlayer gallery is greatly enhanced and the storage sites inside the gallery can be better used. Meanwhile, the NC layers and oxide nanosheets are bridged by the C─O bonds to form a stable structure, which contributes to a better cycling stability than the pure layered oxides. The optimal V2 O5 @NC-400 cathode shows a capacity of 467 mA h g-1 at 0.1 A g-1 for 300 cycles, and long-term cyclic stability of 4000 cycles at 5 A g-1 with a capacity retention of 92%. All these performance parameters are among the best for vanadium oxide-based cathode materials.

Multi-layer 3D Chirality and Double-Helical Assembly in a Copper Nanocluster with a Triple-Helical Cu15 Core.

Conceptually mimicking biomolecules' ability to construct multiple-helical aggregates with emergent properties and functions remains a long-standing challenge. Here we report an atom-precise 18-copper nanocluster (NC), Cu18 H(PET)14 (TPP)6 (NCS)3 (Cu18 H) which contains a pseudo D3 -symmetrical triple-helical Cu15 core. Structurally, Cu18 H may be also viewed as sandwich type of sulfur-bridged chiral copper cluster units [Cu6 -Cu6 -Cu6 ], endowing three-layered 3D chirality. More importantly, the chiral NCs are aggregated into an infinite double-stranded helix supported by intra-strand homonuclear C-H⋅⋅⋅H-C dihydrogen contacts and inter-strand C-H/π and C-H/S interactions. The unique multi-layered 3D chirality and the double-helical assembly of Cu18 H are evocative of DNA. Moreover, the collective behaviours of the aggregated NCs not only exhibit crystallization-induced emission enhancement (CIEE) and aggregation-induced emission enhancement (AIEE) effects in the deep-red region, but also efficiently catalyze electron transfer (ET) reaction. This study thus presents that hierarchical assemblies of atomically defined copper NCs could be intricate as observed for important biomolecules like DNA with emergent properties arising from aggregated behaviours.

Total Structure, Electronic Structure and Catalytic Hydrogenation Activity of Metal-Deficient Chiral Polyhydride Cu57 Nanoclusters.

Accurate identifying and in-depth understanding of the defect sites in a working nanomaterial could hinge on establishing specific defect-activity relationships. Yet, atomically precise coinage-metal nanoclusters (NCs) possessing surface vacancy defects are scarce primarily owing to challenges in the synthesis and isolation of such defective NCs. Herein we report a mixed-ligand strategy to synthesizing an intrinsically chiral and metal-deficient copper hydride-rich NC [Cu57 H20 (PET)36 (TPP)4 ]+ (Cu57 H20 ). Its total structure (including hydrides) and electronic structure are well established by combined experimental and computational results. Crystal structure reveals Cu57 H20 features a cube-like Cu8 kernel embedded in a corner-missing metal-ligand shell of Cu49 (PET)36 (TPP)4 . Single Cu vacancy defect site occurs at one corner of the shell, evocative of mono-lacunary polyoxometalates. Theoretical calculations demonstrate that the above-mentioned point vacancy causes one surface hydride exposed as an interfacial capping µ3 -H- , which is accessible in chemical reaction, as proved by deuterated experiment. Moreover, Cu57 H20 shows catalytic activity in the hydrogenation of nitroarene. The success of this work opens the way for the research on well-defined chiral metal-deficient Cu and other metal NCs, including exploring their application in asymmetrical catalysis.

Unusual Intramolecular Motion of ReH92- in K2ReH9 Crystal: Circle Dance and Three-Arm Turnstile Mechanisms Revealed by Computational Studies.

The nonahydridorhenate dianion ReH92- is a unique rhenium polyhydride complex due to its remarkably high coordination number; however, its detailed polytopal rearrangement process in either solution or crystal is so far unclear. In this work, our quantum chemical calculations have identified two previously unreported fluxional mechanisms for the ReH92- dianion in the K2ReH9 crystal: three-arm turnstile rotation and circle dance mechanism. These two polytopal rearrangements in the crystal offer an alternative interpretation to the pulse and wide-line NMR spectra (Farrar et al. J. Chem. Phys. 1969, 51, 3595). The previously postulated hindered rotation of the whole ReH92- dianion in K2ReH9 (White et al. J. Chem. Soc., Faraday Trans. 2 1972, 68, 1414) turns out to be a combination of the above-mentioned two elementary fluxional processes. In addition, our calculations have confirmed the Muetterties' D3h⇌C4v rearrangement as the intramolecular motion for the ReH92- dianion in solution.

Describing Polytopal Rearrangement Processes of Octacoordinate Structures. I. Renewed Insights into Fluxionality of the Rhenium Polyhydride Complex ReH5(PPh3)2(Pyridine).

Hydride ligands of transition metal polyhydride complexes with a high coordination number are prone to fluxionality leading to interesting structural dynamics. However, the underlying polytopal rearrangement pathways have been rarely studied. Based on quantum chemical calculations carried out in this work with density functional theory and coupled-cluster theory, two new fluxional mechanisms have been identified for the rhenium polyhydride complex ReH5(PPh3)2(pyridine) to jointly account for two consecutive coalescence events in the variable-temperature NMR spectra upon heating: lateral and basal three-arm turnstile rotation. The frequently cited pseudorotation in ReH5(PPh3)2(pyridine) (Lee et al. Inorg. Chem. 1996, 35, 695) turns out to be a three-step process including two lateral three-arm turnstile steps and one basal turnstile step in between. The new fluxional mechanisms discovered in this work may also exist in other transition metal polyhydrides.

Mid-term Results of Coil Embolization Alone and Stent-assisted Coil Embolization for Renal Artery Aneurysms.

BACKGROUND: Coil embolization (CE) alone and stent-assisted coil embolization (SCE) are two major endovascular techniques to treat renal artery aneurysms (RAAs). This study aimed at providing safety and efficacy data of CE and SCE for RAAs. METHODS: Between August 2015 and June 2019, 40 RAA patients treated with CE or SCE were included in the retrospective study. Patients' demographics, clinical manifestations, aneurysm characteristics, treatment strategies, and follow-up results were collected and analyzed. RESULTS: There were 26 and 14 patients in the CE and SCE group, respectively. The mean aneurysm diameter was 2.5 ± 1.5 cm and 2.2 ± 0.8 cm (CE versus SCE, P = 0.52). The neck width of the aneurysm was 0.63 ± 0.37 cm and 1.07 ± 0.42 cm (CE versus SCE, P = 0.021). Technical success was achieved in 97.5% patients. No death or aneurysm rupture occurred. During the perioperative period, 12% and 7.1% patients suffered partial renal infarction (CE versus SCE, P = 0.45). The mean duration of follow-up was 8.8 ± 9.4 months and 16.1 ± 16.3 months (CE versus SCE, P = 0.158) by imaging and 20.8 ± 11.3 and 22.7 ± 16.5 months by visit/telephone (CE versus SCE, P = 0.703). During the follow-up, 17.4% patients in the CE group and 30.8% patients in the SCE group suffered partial renal infarction, while their overall renal function remained normal. In addition, there was no aneurysm recurrence, sac enlargement, or death in both groups. CONCLUSIONS: Both CE and SCE were safe and effective to treat RAAs. In addition, SCE may prevent coil migration in the wide neck aneurysm in selected patients.

Deficiency of SCAMP5 leads to pediatric epilepsy and dysregulation of neurotransmitter release in the brain.

Secretory carrier membrane proteins (SCAMPs) play an important role in exocytosis in animals, but the precise function of SCAMPs in human disease is unknown. In this study, we identified a homozygous mutation, SCAMP5 R91W, in a Chinese consanguineous family with pediatric epilepsy and juvenile Parkinson's disease. Scamp5 R91W mutant knock-in mice showed typical early-onset epilepsy similar to that in humans. Single-neuron electrophysiological recordings showed that the R91W mutation significantly increased the frequency of miniature excitatory postsynaptic currents (mEPSCs) at a resting state and also increased the amplitude of evoked EPSCs. The R91W mutation affected the interaction between SCAMP5 and synaptotagmin 1 and may affect the function of the SNARE complex, the machinery required for vesicular trafficking and neurotransmitter release. Our work shows that dysfunction of SCAMP5 shifted the excitation/inhibition balance of the neuronal network in the brain, and the deficiency of SCAMP5 leads to pediatric epilepsy.

Recent Progress in Inorganic Anions Templated Silver Nanoclusters: Synthesis, Structures and Properties.

Over recent years, research on the ligand-protected silver clusters have gained significant interest owing to their unique potential applications in catalysis, organic optoelectronics, and luminescent materials. However, the synthesis of structurally precise high-nuclearity silver nanoclusters is still challenging and become one of the prime interests of chemists. The controllable synthesis of high-nuclearity silver nanoclusters involves the ingenious use of capping ligands or/and templating agents. Thereinto, the main role of the templating agents is to promote the order arrangement of silver ions around them to form discrete molecules. Our lab has performed comprehensive studies on the ligand-protected silver clusters in the past eight years. This review highlights recent progress in the use of inorganic template anions, silver precursors, solvents, and the ligand types in synthesizing high-nuclearity silver nanoclusters. Furthermore, some interesting photo- and electrochemical properties revealed by silver clusters including luminescent thermochromism, electrical conductivity, and electrochemical reduction of H2 O2 have been also summarized.

Novel mutations in ZP1 and ZP2 cause primary infertility due to empty follicle syndrome and abnormal zona pellucida.

PURPOSE: Mutations in the zona pellucida glycoprotein genes have been reported to be associated with empty follicle syndrome (EFS) and abnormal zona pellucida (ZP). In this study, we performed genetic analysis in the patients with female infertility due to abnormal zona pellucida and empty follicle syndrome to identify the disease-causing gene mutations in these patients. METHODS: We characterized three patients from two independent families who had suffered from empty follicle syndrome or abnormal zona pellucida. Whole exome sequencing and Sanger sequencing were used to identify the mutations in the families. Western blot was used to check the expression of wild type and mutant disease genes. RESULTS: We identified two novel mutations in these patients, including a novel compound heterozygous mutation (c.507delC, p. His170fs; c.239 G>A, p. Cys80Tyr and c.241 T>C, p. Tyr81His) in ZP1 gene and a compound mutation in ZP2 gene (c.860_861delTG, p.Val287fs and c.1924 C>T, p.Arg642Ter). Expression of the mutant ZP1 protein (p. Cys80Tyr and p. Tyr81His) is significantly decreased compared with the wild-type ZP1. Other three mutations produce truncated proteins. CONCLUSIONS: Our findings expand the mutational spectrum of ZP1 and ZP2 genes associated with EFS and abnormal oocytes and provide new support for the genetic diagnosis of female infertility.

Novel homozygous mutations in PATL2 lead to female infertility with oocyte maturation arrest.

PURPOSE: To identify the disease gene in 40 patients with female infertility due to oocyte maturation arrest. METHODS: Genomic DNA was extracted from peripheral blood of 40 patients and their family members. Whole-exome sequencing was performed on the patients, and the PATL2 mutations were identified and confirmed by Sanger sequencing. Harmfulness of the mutations was analyzed by SIFT, Polyphen-2, Mutation Taster, and M-CAP software, and we used western immunoblotting analysis to check the effect of mutations on PATL2 protein expression in vitro. RESULTS: Two novel missense mutations c.1528C>A (p.Pro510Thr) and c.1376C>A (p.Ser459Tyr) in PATL2 were identified in three patients (7.5%) from two consanguineous families in our cohort. We found that mutations in PATL2 resulted in variable oocyte phenotypes, including GV arrest, MI arrest, and morphologic abnormalities. Western immunoblotting analysis showed that the expression levels of the two novel mutant PATL2 proteins decreased significantly. CONCLUSIONS: We identified two novel PATL2 mutations that caused oocyte maturation arrest and abnormal morphology, and variable phenotypes in patients.

The Difference Se Makes: A Bio-Inspired Dppf-Supported Nickel Selenolate Complex Boosts Dihydrogen Evolution with High Oxygen Tolerance.

Inspired by the metal active sites of [NiFeSe]-hydrogenases, a dppf-supported nickel(II) selenolate complex (dppf=1,1'-bis(diphenylphosphino)ferrocene) shows high catalytic activity for electrochemical proton reduction with a remarkable enzyme-like H2 evolution turnover frequency (TOF) of 7838 s-1 under an Ar atmosphere, which markedly surpasses the activity of a dppf-supported nickel(II) thiolate analogue with a low TOF of 600 s-1 . A combined study of electrochemical experiments and DFT calculations shed light on the catalytic process, suggesting that selenium atom as a bio-inspired proton relay plays a key role in proton exchange and enhancing catalytic activity of H2 production. For the first time, this type of Ni selenolate-containing electrocatalyst displays a high degree of O2 and H2 tolerance. Our results should encourage the development of the design of highly efficient oxygen-tolerant Ni selenolate molecular catalysts.

Silver-Sulfur Hybrid Supertetrahedral Clusters: The Hitherto Missing Members in the Metal-Chalcogenide Tetrahedral Clusters.

The synthesis of Group 11 metal chalcogenide supertetrahedral clusters (SCs) still remains a great challenge mainly due to the high tendency of metal aggregation through metallophilicity and global charge balance. Demonstrated herein are the preparation, crystallographic characterization, and optical properties of two stable silver-sulfur SCs through ligand-control; one as a discrete zero-dimensional (0D) V3,4-type cluster and the other as a one-dimensional (1D) zigzag chain extended by alternating V3,2-type clusters. The notation Vn,m (where n is the number of metal layers, and m is the number of vacant corners) is used to describe a new series of vacant-corner SCs, which can be derived from the regular Tn clusters. The existence of vacant-corner-type SCs may be ascribed to the low valence and tri-coordinated environment of silver ions. These are the first representatives of structurally determined silver-sulfur tetrahedral clusters thus far. This work enriches the coinage-metal chalcogenide tetrahedral cluster portfolio, discovers vacant-corner SCs present in silver-sulfur hybrid tetrahedral clusters, and provides effective means for further development of Group 11 coinage-metal chalcogenide SCs.

The relationship between the boron dipyrromethene (BODIPY) structure and the effectiveness of homogeneous and heterogeneous solar hydrogen-generating systems as well as DSSCs.

A series of boron dipyrromethene (BODIPY) dyes (B1­B5) having H atoms at 2,6-positions or heavy-atom I at 2-/2,6-positions, and an ortho- or a para-COOH substituted phenyl moiety at the 8-position on the BODIPY core were synthesized and characterized. These organic dyes were applied for investigating the relationship between the BODIPY structure and the effectiveness of homogeneous and heterogeneous visible-light-driven hydrogen production as well as dye-sensitized solar cells (DSSCs). For the homogeneous photocatalytic hydrogen production systems with a cobaloxime catalyst, the efficiency of hydrogen production could be tuned by substituting with heavy atoms and varying carboxyl group orientations of BODIPYs. As a result, B5 containing two I atoms and an ortho-COOH anchoring group was the most active one (TONs = 197). The activity of hydrogen generation followed the order B5 > B3 > B2 > B1 = B4 = 0. An interesting "ortho-position effect" was observed in the present homogeneous systems, i.e., substitution groups were located at the ortho-position and higher hydrogen production activities were obtained. For the heterogeneous hydrogen production systems with a platinized TiO2 catalyst, the effectiveness of hydrogen evolution was highly influenced by the intersystem crossing efficiency, molar absorptivity and positions of the anchoring group of dyes. Thus, B3 having two core iodine atoms and a para-COOH group with TONs of 70 excelled other BODIPYs and the TONs of hydrogen generation showed the trend of B3 > B5 > B2 > B1 = B4 = 0. The results demonstrate that the present photocatalytic H2 production proceeds with higher efficiency and stability in the homogeneity than in the heterogeneity. In the case of DSSCs, the overall cell performance of BODIPY chromophores was highly dependent on both the absence or the presence of iodine atoms on the BODIPY core and ­COOH anchoring positions. The B1­TiO2 system showed the best cell performance, because the most effective surface binding mode is allowed with this structure. This is also in contrast with the case of dye-sensitized solar H2 generation, in which B3 was the most efficient chromophore. The differences between dye-sensitized hydrogen-generating systems and DSSCs may be due to rates of electron transfer and the dye aggregation tendency.

Experimental and theoretical study of enol-keto prototropic tautomerism and photophysics of azomethine-BODIPY dyads.

In this study we report about two novel azomethine­BODIPY dyads 1 and 2. The two dyads have been, respectively, synthesized by covalent tethering of tautomeric ortho-hydroxy aromatic azomethine moieties including N-salicylideneaniline (SA) and N-naphthlideneaniline (NA) to a BODIPY fluorophore. Both of the two dyads 1 and 2 show enol-imine (OH) structures dominating in the crystalline state. Dyad 1 in the enol state is the most stable form at room temperature in most media, while enol­keto prototropic tautomerism of the NA moiety in solution is preserved in dyad 2, which can be reversibly converted between enol and keto forms in the environment's polarity. Visible illumination of dyad 2 in the enol state excites selectively the BODIPY fragment and then deactivates radiatively by emitting green light in the form of fluorescence, while the emission intensity of 2 in the keto state is quenched on the basis of the proton-coupled photoinduced electron transfer (PCPET) mechanism. This allows large fluorescence modulation between the two states of dyad 2 and generates a novel tautomerisable fluorescent switch. Theoretical calculations including calculated energies, potential energy surfaces (PESs) and intrinsic reaction coordinate (IRC) analysis further support that the single proton transfer reaction from an enol form to a transition state (TS) and from the TS to a keto form for 2 is easier to occur than that for 1, which accounts for the fluorescence quenching of 2 in methanol. The agreement of the experimental results and theoretical calculations clearly suggests that fluorescent and tautomeric components can be paired within the same molecular skeleton and the proton tautomerization of the latter can be designed to regulate the emission of the former. In addition, preliminary experiments revealed that 1 can be potentially used as a simple on/off fluorescent chemosensor which exhibited higher selectivity for Cu(2+) over other common cations.

Noble-metal-free BODIPY-cobaloxime photocatalysts for visible-light-driven hydrogen production.

In this study a series of supramolecular BODIPY-cobaloxime systems Co-Bn (n = 1-4): [{Co(dmgH)2Cl}{4,4-difluoro-8-(4-pyridyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene}] (Co-B1), [{Co(dmgH)2Cl}{4,4-difluoro-8-(4-pyridyl)-1,3,5,7-tetramethyl-2,6-diiodo-4-bora-3a,4a-diaza-s-indacene}] (Co-B2), [{Co(dmgH)2Cl}{4,4-difluoro-8-(3-pyridyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene}] (Co-B3), and [{Co(dmgH)2Cl}{4,4-difluoro-8-(3-pyridyl)-1,3,5,7-tetramethyl-2,6-diiodo-4-bora-3a,4a-diaza-s-indacene}] (Co-B4) (BODIPY = boron dipyrromethene, dmgH = dimethylglyoxime) have been synthesized by replacing one axial chlorine of cobaloxime moieties with the pyridine residues of BODIPYs, and structurally characterized. Absorption spectra show that the optical properties of the BODIPY-cobaloximes are essentially the sum of their constituent components, indicating weak interactions between the cobaloxime units and BODIPY chromophores in the ground state. If any, electronic communications may take place through the intramolecular electron transfer across their orthogonal structures. The possibility of intramolecular electron transfer is further supported by the results of the density functional theory (DFT) calculations at UB3LYP/LANL2DZ levels on Co-B2˙(-) and Co-B4˙(-), which show that the highest occupied molecular orbitals (HOMOs) possess predominantly BODIPY character, while the lowest unoccupied molecular orbitals (LUMOs) are located on the cobalt centers. The HOMO → LUMO transition is an electron-transfer process (BODIPY˙(-) radical anions → cobaloxime fragments). In view of the possible occurrence of electron transfer, these noble-metal-free BODIPY-cobaloximes are studied as single-component homogeneous photocatalysts for H2 generation in aqueous media. Under optimized conditions, the 2,6-diiodo BODIPY-sensitized cobaloxime Co-B4 that contains a meta-pyridyl at the 8-position of BODIPY presents excellent H2 photoproduction catalytic activity with a turnover number (TON) of 85, which is comparable to that of its analogue Co-B2 that has a para-pyridyl attached onto 2,6-diiodo BODIPY (TON = 82); however, both of the noniodinated BODIPY-sensitizer cobaloximes (Co-B1, Co-B3) exhibit a complete lack of activity under the same experimental conditions. These results show that the presence of heavy atoms in the core of BODIPY is essential for the catalytic process and reductive quenching pathways (namely, the intramolecular electron transfers from BODIPY˙(-) species to the cobalt centers) for these photocatalytically active systems of Co-Bn (n = 2 and 4) are thermodynamically feasible for the hydrogen-evolving reaction.

Metagenomic analysis of individual mosquito viromes reveals the geographical patterns and drivers of viral diversity.

Mosquito transmitted viruses are responsible for an increasing burden of human disease. Despite this, little is known about the diversity and ecology of viruses within individual mosquito hosts. Here, using a meta-transcriptomic approach, we determined the viromes of 2,438 individual mosquitoes (81 species), spanning ~4,000 km along latitudes and longitudes in China. From these data we identified 393 viral species associated with mosquitoes, including 7 (putative) species of arthropod-borne viruses (that is, arboviruses). We identified potential mosquito species and geographic hotspots of viral diversity and arbovirus occurrence, and demonstrated that the composition of individual mosquito viromes was strongly associated with host phylogeny. Our data revealed a large number of viruses shared among mosquito species or genera, enhancing our understanding of the host specificity of insect-associated viruses. We also detected multiple virus species that were widespread throughout the country, perhaps reflecting long-distance mosquito dispersal. Together, these results greatly expand the known mosquito virome, linked viral diversity at the scale of individual insects to that at a country-wide scale, and offered unique insights into the biogeography and diversity of viruses in insect vectors.