Ultrafiltration separation of Am(VI)-polyoxometalate from lanthanides.

Partitioning of americium from lanthanides (Ln) present in used nuclear fuel plays a key role in the sustainable development of nuclear energy1-3. This task is extremely challenging because thermodynamically stable Am(III) and Ln(III) ions have nearly identical ionic radii and coordination chemistry. Oxidization of Am(III) to Am(VI) produces AmO22+ ions distinct with Ln(III) ions, which has the potential to facilitate separations in principle. However, the rapid reduction of Am(VI) back to Am(III) by radiolysis products and organic reagents required for the traditional separation protocols including solvent and solid extractions hampers practical redox-based separations. Herein, we report a nanoscale polyoxometalate (POM) cluster with a vacancy site compatible with the selective coordination of hexavalent actinides (238U, 237Np, 242Pu and 243Am) over trivalent lanthanides in nitric acid media. To our knowledge, this cluster is the most stable Am(VI) species in aqueous media observed so far. Ultrafiltration-based separation of nanoscale Am(VI)-POM clusters from hydrated lanthanide ions by commercially available, fine-pored membranes enables the development of a once-through americium/lanthanide separation strategy that is highly efficient and rapid, does not involve any organic components and requires minimal energy input.

Multicomponent, Multicavity Metallacages That Contain Different Binding Sites for Allosteric Recognition.

The encapsulation of different guest molecules by their different recognition domains of proteins leads to selective binding, catalysis, and transportation. Synthetic hosts capable of selectively binding different guests in their different cavities to mimic the function of proteins are highly desirable but challenging. Here, we report three ladder-shaped, triple-cavity metallacages prepared by multicomponent coordination-driven self-assembly. Interestingly, the porphyrin-based metallacage is capable of heteroleptic encapsulation of fullerenes (C60 or C70) and coronene using its different cavities, allowing distinct allosteric recognition of coronene upon the addition of C60 or C70. Owing to the different binding affinities of the cavities, the metallacage hosts one C60 molecule in the central cavity and two coronene units in the side cavities, while encapsulating two C70 molecules in the side cavities and one coronene molecule in the central cavity. The rational design of multicavity assemblies that enable heteroleptic encapsulation and allosteric recognition will guide the further design of advanced supramolecular constructs with tunable recognition properties.

A High-Nuclearity Copper Sulfide Nanocluster [S-Cu50] Featuring a Double-Shell Structure Configuration with Cu(II)/Cu(I) Valences.

This work represents an important step in the quest for creating atomically precise binary semiconductor nanoclusters (BS-NCs). Compared with coinage metal NCs, the preparation of BS-NCs requires strict control of the reaction kinetics to guarantee the formation of an atomically precise single phase under mild conditions, which otherwise could lead to the generation of multiple phases. Herein, we developed an acid-assisted thiolate dissociation approach that employs suitable acid to induce cleavage of the S-C bonds in the Cu-S-R (R = alkyl) precursor, spontaneously fostering the formation of the [Cu-S-Cu] skeleton upon the addition of extra Cu sources. Through this method, a high-nuclearity copper sulfide nanocluster, Cu50S12(SC(CH3)3)20(CF3COO)12 (abbreviated as [S-Cu50] hereafter), has been successfully prepared in high yield, and its atomic structure was accurately modeled through single-crystal X-ray diffraction. It was revealed that [S-Cu50] exhibits a unique double-shell structural configuration of [Cu14S12]@[Cu36S20], and the innermost [Cu14] moiety displays a rhombic dodecahedron geometry, which has never been observed in previously synthesized Cu metal, hydride, or chalcogenide NCs. Importantly, [S-Cu50] represents the first example incorporating mixed Cu(II)/Cu(I) valences in reported atomically precise copper sulfide NCs, which was unambiguously confirmed by XPS, EPR, and XANES. In addition, the electronic structure of [S-Cu50] was established by a variety of optical investigations, including absorption, photoluminescence, and ultrafast transient absorption spectroscopies, as well as theoretical calculations. Moreover, [S-Cu50] is air-stable and demonstrates electrocatalytic activity in ORR with a four-electron pathway.

UltrasonicGS: A Highly Robust Gesture and Sign Language Recognition Method Based on Ultrasonic Signals.

With the global spread of the novel coronavirus, avoiding human-to-human contact has become an effective way to cut off the spread of the virus. Therefore, contactless gesture recognition becomes an effective means to reduce the risk of contact infection in outbreak prevention and control. However, the recognition of everyday behavioral sign language of a certain population of deaf people presents a challenge to sensing technology. Ubiquitous acoustics offer new ideas on how to perceive everyday behavior. The advantages of a low sampling rate, slow propagation speed, and easy access to the equipment have led to the widespread use of acoustic signal-based gesture recognition sensing technology. Therefore, this paper proposed a contactless gesture and sign language behavior sensing method based on ultrasonic signals-UltrasonicGS. The method used Generative Adversarial Network (GAN)-based data augmentation techniques to expand the dataset without human intervention and improve the performance of the behavior recognition model. In addition, to solve the problem of inconsistent length and difficult alignment of input and output sequences of continuous gestures and sign language gestures, we added the Connectionist Temporal Classification (CTC) algorithm after the CRNN network. Additionally, the architecture can achieve better recognition of sign language behaviors of certain people, filling the gap of acoustic-based perception of Chinese sign language. We have conducted extensive experiments and evaluations of UltrasonicGS in a variety of real scenarios. The experimental results showed that UltrasonicGS achieved a combined recognition rate of 98.8% for 15 single gestures and an average correct recognition rate of 92.4% and 86.3% for six sets of continuous gestures and sign language gestures, respectively. As a result, our proposed method provided a low-cost and highly robust solution for avoiding human-to-human contact.

Application of Copper(II)-Organic Frameworks Bearing Dilophine Derivatives in Photocatalysis and Guest Separation.

The functionalized design of metal-organic frameworks (MOFs) has been rapidly developed in the last 20 years, and its broad applicability has been demonstrated in many fields. MOFs with desired functions can be assembled using predesigned organic linkers with specific metal nodes, which possess the ordered functional sites and open structures. Although a large number of carboxylic acid junctions have been used to construct MOFs, it is still a great challenge to realize their multifunctionality. In particular, there is a relative lack of research on MOFs as direct photocatalysts, which require not only abundant active sites and open structures but also adsorption groups and effective electron-hole separation performance. To this end, MOFs constructed from the carboxylic acid ligands derived from lophine-based derivatives and copper ions were deliberately used as a photocatalyst, and then, their application in dye degradation and aromatic alcohol conversion was investigated. In addition, in combination with the abundant Lewis sites of copper ions and imidazole sites, the material shows not only the adsorption and separation of C2 series and dyes but also the application of dye degradation and conversion of aromatic alcohols under illumination conditions. The corresponding results fully illustrate that the MOF constructed by using lophine derivatives can be an effective way to prepare photocatalysts. The subsequent research ideas will focus on designing a series of MOFs constructed with multilinked moieties of lophine groups and exploring their application strategies in the field of photocatalysis.

CT and MRI findings of intra-parenchymal and intra-ventricular schwannoma: a series of seven cases.

OBJECTIVE: To analyze the computed tomography (CT) and magnetic resonance imaging (MRI) features of patients with intra-parenchymal and intra-ventricular schwannoma. METHODS: The CT and MRI features of seven cases with intra-parenchymal and intra-ventricular schwannoma were analyzed retrospectively. RESULTS: There were four men and three women (median age, 25 years; range, 12-42 years) in this study. The median tumor size was 4.4 cm (range, 3.1-6.5 cm). The mass was, respectively, round in four cases (57.1%), lobulated in two cases (28.6%) and oval in one case (14.3%). All tumors were well-circumscribed. Septa in the mass could be observed in three cases (42.9%), and nodular calcification was observed in two cases (28.6%), which peritumoral edema (n = 3, 42.9%) and hydrocephalus (n = 3, 42.9%) could be observed. Most of these lesions (n = 6) presented iso-hypointensity on T1-weighted images and iso-hyperintensity on T2-weighted images, except one lesion showing low intensity on T2WI. In addition, a fluid-fluid level was observed in one case. After contrast agents' injection, all masses illustrated heterogeneously moderate to marked enhancement. CONCLUSIONS: A well-defined solid and cystic mass with calcification and moderate to marked delayed enhancement may be an objective account of intra-parenchymal or intra-ventricular schwannoma.

An Ultrastable 155-Nuclei Silver Nanocluster Protected by Thiacalix[4]arene and Cyclohexanethiol for Photothermal Conversion.

Thiacalix[4]arenes have emerged as a family of macrocyclic ligands to protect metal nanoparticles, but it remains a great challenge to solve the mystery of their structures at the atomic level, especially for those larger than 2 nm. Here, we report the largest known mixed-valence silver nanocluster [Ag155 (CyS)40 (TC4A)5 Cl2 ] (Ag155) protected by deprotonated cyclohexanethiol (CySH) and macrocyclic ligand p-tert-butylthiacalix[4]arene (H4 TC4A). Its single-crystal structure consists of a metallic core of four concentric shells, Ag13 @Ag42 @Ag30 @Ag70 , lined with a organic skin of 40CyS- and 5TC4A4- and 2Cl- . Ag155 manifests an unusual pseudo-5-fold symmetry dictated by the intrinsic metal atom packing and the regioselective distribution of mixed protective ligands. This work not only reveals a macrocyclic ligand effect on the formation of a large silver nanocluster, but also provides a new structural archetype for comprehensively perceiving their interface and metal kernel structures.

Gastrointestinal symptoms of 95 cases with SARS-CoV-2 infection.

OBJECTIVE: To study the GI symptoms in severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infected patients. DESIGN: We analysed epidemiological, demographic, clinical and laboratory data of 95 cases with SARS-CoV-2 caused coronavirus disease 2019. Real-time reverse transcriptase PCR was used to detect the presence of SARS-CoV-2 in faeces and GI tissues. RESULTS: Among the 95 patients, 58 cases exhibited GI symptoms of which 11 (11.6%) occurred on admission and 47 (49.5%) developed during hospitalisation. Diarrhoea (24.2%), anorexia (17.9%) and nausea (17.9%) were the main symptoms with five (5.3%), five (5.3%) and three (3.2%) cases occurred on the illness onset, respectively. A substantial proportion of patients developed diarrhoea during hospitalisation, potentially aggravated by various drugs including antibiotics. Faecal samples of 65 hospitalised patients were tested for the presence of SARS-CoV-2, including 42 with and 23 without GI symptoms, of which 22 (52.4%) and 9 (39.1%) were positive, respectively. Six patients with GI symptoms were subjected to endoscopy, revealing oesophageal bleeding with erosions and ulcers in one severe patient. SARS-CoV-2 RNA was detected in oesophagus, stomach, duodenum and rectum specimens for both two severe patients. In contrast, only duodenum was positive in one of the four non-severe patients. CONCLUSIONS: GI tract may be a potential transmission route and target organ of SARS-CoV-2.

Synthesis and high pressure studies of white luminescence host-guest complex nanocrystals based on C60 and p-But-calix[8]arene.

Host-guest structured nanocrystals consisting of p-But-calix[8]arene and fullerene C60 were fabricated with the facial solution deposition method. The as-prepared host-guest complex nanocrystals are well crystallized in a tetragonal structure, in which the guest C60 and host p-But-calix[8]arene molecules interact with each other via the van der Waals force. The host-guest crystal has a wider band gap compared to that of C60 crystals. The luminescence range of the host-guest structured nanocrystals was widely extended, and its photoluminescence (PL) intensity was highly enhanced by one order of magnitude. High pressure studies on such host-guest nanocrystals were carried out using the diamond anvil cell technique with the associated spectroscopic measurements. Raman and PL spectra show a phase transition occurred on the samples owing to the deformation of fullerene molecules. A PL behavior change was also observed synchronously with the phase transition. The host-guest structure strongly influences the structure and optical behaviors of C60 under pressure.

Different Silver Nanoparticles in One Crystal: Ag210 (i PrPhS)71 (Ph3 P)5 Cl and Ag211 (i PrPhS)71 (Ph3 P)6 Cl.

Two pure silver nanoparticles (Ag210 (i PrPhS)71 (Ph3 P)5 Cl and Ag211 (i PrPhS)71 (Ph3 P)6 Cl labeled as SD/Ag210 and SD/Ag211 (SD=SunDi), were found to co-crystallize in forming compound 1. Single-crystal X-ray diffraction (SCXRD) revealed that they differ by only one Ag(PPh3 ). Their four-shell nanoparticles consist of three pure Ag metal shells (Ag19 @Ag52 @Ag45 ) shielded by a silver-organic Ag89 (i PrPhS)71 Cl[Ag(Ph3 P)]n outermost shell. The number (n) of Ag(Ph3 P) is five for SD/Ag210 and six for SD/Ag211. The pseudo-fivefold symmetric Ag nanoparticles exhibit surface plasmon absorption similar to a true metallic state but at the nanoscale. This work exemplifies the important effects of phosphine in stabilizing large silver nanoparticles; and offers a platform to investigate the origin of differences in nanoscale metal materials, even differing by only one metal atom; it also sheds light on the regioselective binding of auxiliary Ph3 P on the surface of silver nanoparticles.

Thermally Induced Reversible Double Phase Transitions in an Organic-Inorganic Hybrid Iodoplumbate C4H12NPbI3 with Symmetry Breaking.

A one-dimensional (1D) organic-inorganic hybrid iodoplumbate crystal (1, C4H12NPbI3, TMAPbI3) can undergo two reversible phase transitions as the temperature decreases. Its dynamic phase-transition behaviors were carefully studied by dielectric measurements, thermal analysis, and variable-temperature crystallographic studies. These results indicate that the phase transitions possess a disorder-order feature with a noncentrosymmetrical intermediate phase structure. Due to the existence of the ordered motion and reorientation of the C4H12N(+) cation, 1 undergoes two phase transitions: the first one from space group P63/m at room temperature to Pm at 163 K with symmetry breaking, and the second one from space group Pm at 163 K to P61 at 142 K with partial symmetry restoration. Our results indicate that there is an existence of a transitional structure with a low symmetry space group during the disorder-order-type phase transitions, which can provide us valuable information to deeply understand the disorder-order phase transition in organic-inorganic hybrids.

Structural insights into the specific recognition of N-heterocycle biodenitrogenation-derived substrates by microbial amide hydrolases.

N-heterocyclic compounds from industrial wastes, including nicotine, are environmental pollutants or toxicants responsible for a variety of health problems. Microbial biodegradation is an attractive strategy for the removal of N-heterocyclic pollutants, during which carbon-nitrogen bonds in N-heterocycles are converted to amide bonds and subsequently severed by amide hydrolases. Previous studies have failed to clarify the molecular mechanism through which amide hydrolases selectively recognize diverse amide substrates and complete the biodenitrogenation process. In this study, structural, computational and enzymatic analyses showed how the N-formylmaleamate deformylase Nfo and the maleamate amidase Ami, two pivotal amide hydrolases in the nicotine catabolic pathway of Pseudomonas putida S16, specifically recognize their respective substrates. In addition, comparison of the α-ß-α groups of amidases, which include Ami, pinpointed several subgroup-characteristic residues differentiating the two classes of amide substrates as containing either carboxylate groups or aromatic rings. Furthermore, this study reveals the molecular mechanism through which the specially tailored active sites of deformylases and amidases selectively recognize their unique substrates. Our work thus provides a thorough elucidation of the molecular mechanism through which amide hydrolases accomplish substrate-specific recognition in the microbial N-heterocycles biodenitrogenation pathway.

Structural and computational studies of the maleate isomerase from Pseudomonas putida S16 reveal a breathing motion wrapping the substrate inside.

Nicotine is an environmental toxicant in tobacco waste, imposing a serious hazard for human health. Some bacteria including Pseudomonas spp. strains are able to metabolize nicotine to non-toxic compounds. The pyrrolidine pathway of nicotine degradation in Pseudomonas putida S16 has recently been revealed. The maleate isomerase (Pp-Iso) catalyses the last step in nicotine degradation of P. putida S16, the cis-trans isomerization of maleate to fumarate. In this study, we determined the crystal structures of both wild type isomerase by itself and its C200A point mutant in complex with its substrate maleate, to resolutions of 2.95 Å and 2.10 Å respectively. Our structures reveal that Asn17 and Asn169 play critical roles in recognizing the maleate by site-directed mutants' analysis. Surprisingly, our structure shows that the maleate is completely wrapped inside the isomerase. Examination of the structure prompted us to hypothesize that the ß2-α2 loop and the ß6-α7 loop have a breathing motion that regulates substrate/solvent entry and product departure. Our results of molecular dynamics simulation and enzymatic activity assay are fully consistent with this hypothesis. The isomerase probably uses this breathing motion to prevent the solvent from entering the active site and prohibit unproductive side reactions from happening.

Efficient CO2 capture and photoreduction by amine-functionalized TiO2.

Amine-functionalization of TiO2 nanoparticles, through a solvothermal approach, substantially increases the affinity of CO2 on TiO2 surfaces through chemisorption. This chemisorption allows for more effective activation of CO2 and charge transfer from excited TiO2 , and significantly enhances the photocatalytic rate of CO2 reduction into methane and CO.

Therapeutic effect of Periploca forrestii on collagen-induced arthritis in rats through JAK2/Nf-κB pathway.

Background: Rheumatoid arthritis (RA) is a chronic autoimmune disease that affects the body. Periploca forrestii was a miao ethnic drug in China that was used to treat arthritis for hundreds of years. But, the therapeutic mechanism is so far unknown. Therefore, the chemical component and effect of Periploca forrestii on arthritis in rats were studied using HPLC-QTOF MS, micro-CT, and other experiments in this paper. Method: Male Sprague-Dawley rats were used to assess the in vivo activity. HPLC QTOF-MS was used to analyze the chemical profile of the P. forrestii (PF). Bovine type II collagen and Complete Freund's Adjuvant were used to stimulate and construct the collagen-induced arthritis (CIA) model. Three dosages of PF (100 mg/kg, 200 mg/kg, 400 mg/kg) were used to evaluate in vivo activity. Methotrexate was used as the positive drug. H/E staining and micro-CT methods were used to monitor the pathological changes of CIA rats. ELISA method was used to assess the serum level of immune- and inflammation-related cytokines. Immunohistochemical experiments were used to test the gene expression in JAK and Nf-κB pathways. Results: 42 compounds were identified from PF. PF administration lowered the increased spleen index compared with that of control and MTX groups, and partially restored body weight, reduced paw swelling, and arthritis score compared with the model group. Macroscopic assessment indicated inflamed paw with significant swelling in the model group, while the extent of inflammation and swelling was attenuated by both MTX and PF. H/E staining experiments demonstrated that pathological changes of synovial cells and infiltration of inflammatory cells were observed in the model group. In contrast, the MTX and PF treatment partially reversed these pathological changes. Micro-CT examination showed severe injuries and scars caused by inflammation for the model group, and in the high-dosage group (400 mg/kg) the inflammation-caused injuries and scars were dramatically ameliorated. Mechanism study showed that PF restored Nf-κB phosphorylation and JAK2 expression compared with the model group. Conclusion: P. forrestii possesses a potent effect on CIA rats. Nf-κB and JAK2 pathways are involved in its protective effect on CIA.

Engineering Semi-Reversed Quantum Well Photocatalysts for Highly-Efficient Solar-to-Fuels Conversion.

Semiconductor quantum wells (QWs) exhibit high charge-utilization efficiency for light-emitting applications due to their strong charge confinement effect. Inspired by this effect, herein, this work proposes a new idea to significantly improve the photo-generated charge separation for attaining a highly-efficient solar-to-fuels conversion process through "semi-reversing" the conventional QWs to confine only the photo-generated electrons. This electron confinement-improved charge separation is implemented in the well-designed model of the CdS/TiO2/CdS semi-reversed QW (SRQW) structure. The latter is fabricated by selectively assembling CdS quantum dots (QDs) onto the {101} facets (ultra-thin edge regions) of the TiO2 nanosheets (NSs). Upon light excitation, the photo-generated electrons of SRQW can be confined on the TiO2-{101} facets in the vicinity of the CdS/TiO2 hetero-interface. Thereby, the continuous multi-electron injection to the adsorbed reactants on the interfacial active-sites is significantly accelerated. Thus, the CdS/TiO2/CdS SRQW exhibits ≈35.7 and ≈56.0-fold enhancements on the photocatalytic activities for water and CO2 reduction, respectively, compared to those of pure TiO2. Correspondingly, its CH4-product selectivity is increased by ≈180%. This work provides a novel charge separation mechanism, which is of great importance for the design of the next-generation quantum-sized photocatalysts for solar-to-fuels conversion.

Different regions and environments have critical roles on yield, main quality and industrialization of an industrial purple-fleshed sweetpotato (Ipomoea batatas L. (Lam.)) "Xuzishu8".

Purple-fleshed sweetpotato (PFSP) (Ipomoea batatas (L.) Lam), whose flesh is purple to dark purple, is a special variety type of sweetpotato, which has the characteristics of food crop, industrial crop and medicinal crop. The storage root (SR) of PFSP is rich in anthocyanins, starch, protein, soluble sugar, mineral elements, polyphenol, dietary fiber and so on, which has balanced and comprehensive nutritional value. And in recent years, its unique nutritional elements are increasingly known for their health functions. At present, there is no article on the characteristics and quality analysis of industrial xz8 variety. To explore the influence of different environments on the processing quality of xz8, we selected nine regions (Xuzhou, Jiawang, Pizhou, Xinyi, Peixian, Sihong, Yanchen, Xiangyang and Tianshui) to measure its yield and quality changes. The data demonstrated that xz8 has a very consistent high yield performance. In Tianshui, the anthocyanins, protein and minerals contents were significantly higher and yield also above average. Moreover, the variety with the lowest starch content exhibited the best taste. On the basis of the above results, it suggested that quite practicable to promote xz8 cultivation and suitable for processing in these areas. Thus, our present findings improve our understanding of xz8 variety and provide the basis for the industrial production of PFSP with strong prospects for success.

Artificial photosynthetic hydrogen evolution over g-C3N4 nanosheets coupled with cobaloxime.

We report an economic and noble-metal-free artificial photosynthetic system, consisting of g-C3N4 as a photosensitizer and a photocatalyst, and cobaloxime as a co-catalyst, for H2 generation. This system allows for effective electron transfer from excited g-C3N4 to Co(III)(dmgH)2pyCl to generate reduced cobaloxime intermediate species for efficient H2 evolution. Transient fluorescence studies reveal that the presence of cobaloxime and TEOA promotes the population of excited electrons to transfer from g-C3N4, which is responsible for the high photocatalytic activity of this g-C3N4-cobaloxime conjugation system.

Radon natural radioactivity measurements for evaluation of primary pollutants.

Radon is naturally released from the soil into the surface layer of the atmosphere, and by monitoring the natural radioactivity data of radon and its shot-live decay products we can get valuable information about the dilution properties of the lower boundary layer. This paper explores the dispersion characteristics of the lower layer of the atmosphere in Lanzhou, China, and the close relationship with the patterns of primary pollutants' concentrations. Measurements were conducted from July 2007 to May 2008 at one station and a fifty-day campaign was carried out at two stations in Lanzhou. The interpretation of radon radioactivity measurement showed that the measured atmospheric stability index (ASI) data at two stations in Lanzhou had statistically significant correlation, and well described the lower atmospheric layer mixing property in the area. The temporal trend of PM10 data was consistent with the temporal trend of ASI, with almost twice as high values in December than it in August. The results show that the ASI allows to highlight the dilution factor playing an important role in determining primary pollution events, and the mixing properties of the lower boundary layer is the key factor determining PM10 concentration in urban areas.