DNA-Directed Assembly of Hierarchical MOF-Cellulose Nanofiber Microbioreactors with "Branch-Fruit" Structures.

Assembling metal-organic frameworks (MOFs) into ordered multidimensional porous superstructures promises the encapsulation of enzymes for heterogeneous biocatalysts. However, the full potential of this approach has been limited by the poor stability of enzymes and the uncontrolled assembly of MOF nanoparticles onto suitable supports. In this study, a novel and exceptionally robust Ni-imidazole-based MOF was synthesized in water at room temperature, enabling in situ enzyme encapsulation. Based on this MOF platform, we developed a DNA-directed assembly strategy to achieve the uniform placement of MOF nanoparticles onto bacterial cellulose nanofibers, resulting in a distinctive "branch-fruit" structure. The resulting hybrid materials demonstrated remarkable versatility across various catalytic systems, accommodating natural enzymes, nanoenzymes, and multienzyme cascades, thus showcasing enormous potential as universal microbioreactors. Furthermore, the hierarchical composites facilitated rapid diffusion of the bulky substrate while maintaining the enzyme stability, with ∼3.5-fold higher relative activity compared to the traditional enzyme@MOF immobilized in bacterial cellulose nanofibers.

Complete Glucose Electrooxidation Enabled by Coordinatively Unsaturated Copper Sites in Metal-Organic Frameworks.

The electrocatalytic oxidation of glucose plays a vital role in biomass conversion, renewable energy, and biosensors, but significant challenges remain to achieve high selectivity and high activity simultaneously. In this study, we present a novel approach for achieving complete glucose electrooxidation utilizing Cu-based metal-hydroxide-organic framework (Cu-MHOF) featuring coordinatively unsaturated Cu active sites. In contrast to traditional Cu(OH)2 catalysts, the Cu-MHOF exhibits a remarkable 40-fold increase in electrocatalytic activity for glucose oxidation, enabling exclusive oxidation of glucose into formate and carbonate as the final products. The critical role of open metal sites in enhancing the adsorption affinity of glucose and key intermediates was confirmed by control experiments and density functional theory simulations. Subsequently, a miniaturized nonenzymatic glucose sensor was developed showing superior performance with a high sensitivity of 214.7 µA mM-1 cm-2 , a wide detection range from 0.1 µM to 22 mM, and a low detection limit of 0.086 µM. Our work provides a novel molecule-level strategy for designing catalytically active sites and could inspire the development of novel metal-organic framework for next-generation electrochemical devices.

Selective Conversion of Propane by Electrothermal Catalysis in Proton Exchange Membrane Fuel Cell.

Electrochemical conversion of alkanes to high value-added oxygenated products under a mild condition is of significance. Herein, we effectively couple the electrocatalysis of H2 O2 with the thermo-catalysis of propane oxidation in the cathode of proton exchange membrane fuel cell. Specifically, H2 O2 is in-situ generated on the nitric acid-treated carbon black (C-acid) via 2e- process of oxygen reduction reaction, and then transports to the Fe active sites of MIL-53 (Al, Fe) metal-organic frameworks for propane oxidation. Based on this strategy, the space-time yield of C3 oxygenated products of propane oxidation reaches 2.65 µmol h-1 cm-2 , which represents a new benchmark for electrochemical alkane oxidation in the fuel-cell-type electrolyzer. This study highlights the importance of multifunctional composite catalysts in the field of electrosynthesis.

Dynamic Bond-Directed Synthesis of Stable Mesoporous Metal-Organic Frameworks under Room Temperature.

Stable metal-organic frameworks (MOFs) with mesopores (2-50 nm) are promising platforms for immobilizing nanosized functional compounds, such as metal-oxo clusters, metal-sulfide quantum dots, and coordination complexes. However, these species easily decompose under acidic conditions or high temperatures, hindering their in situ encapsulation in stable MOFs, which are usually synthesized under harsh conditions involving excess acid modulators and high temperatures. Herein, we report a route for the room-temperature and acid-modulator-free synthesis of stable mesoporous MOFs and MOF catalysts with acid-sensitive species encapsulated: (1) we initially construct a MOF template by connecting stable Zr6 clusters with labile Cu-bipyridyl moieties; (2) Cu-bipyridyl moieties are subsequently exchanged by organic linkers to afford a stable version of Zr-MOFs; (3) acid-sensitive species, including polyoxometalates (POMs), CdSeS/ZnS quantum dots, and Cu-coordination cages, can be encapsulated in situ into the MOFs during step 1. The room-temperature synthesis allows the isolation of mesoporous MOFs with 8-connected Zr6 clusters and reo topology as kinetic products, which are inaccessible by traditional solvothermal synthesis. Furthermore, acid-sensitive species remain stable, active, and locked within the frameworks during MOF synthesis. We observed high catalytic activity for VX degradation by the POM@Zr-MOF catalysts as a result of the synergy between redox-active POMs and Lewis-acidic Zr sites. The dynamic bond-directed method will accelerate the discovery of large-pore stable MOFs and offer a mild route to avoid the decomposition of catalysts during MOF synthesis.

Monitoring the Activation of Open Metal Sites in [FexM3-x(µ3-O)] Cluster-Based Metal-Organic Frameworks by Single-Crystal X-ray Diffraction.

While trinuclear [FexM3-x(µ3-O)] cluster-based metal-organic frameworks (MOFs) have found wide applications in gas storage and catalysis, it is still challenging to identify the structure of open metal sites obtained through proper activations and understand their influence on the adsorption and catalytic properties. Herein, we use in situ variable-temperature single-crystal X-ray diffraction to monitor the structural evolution of [FexM3-x(µ3-O)]-based MOFs (PCN-250, M = Ni2+, Co2+, Zn2+, Mg2+) upon thermal activation and provide the snapshots of metal sites at different temperatures. The exposure of open Fe3+ sites was observed along with the transformation of Fe3+ coordination geometries from octahedron to square pyramid. Furthermore, the effect of divalent metals in heterometallic PCN-250 was studied for the purpose of reducing the activation temperature and increasing the number of open metal sites. The metal site structures were corroborated by X-ray absorption and infrared spectroscopy. These results will not only guide the pretreatment of [FexM3-x(µ3-O)]-based MOFs but also corroborate spectral and computational studies on these materials.

[Intrauterine growth curves for body weight, body length, head circumference, chest circumference, and crown-rump length in 16 887 neonates with a gestational age of 27-42 weeks in Shenzhen, China].

OBJECTIVE: To establish the intrauterine growth curves of neonates in Shenzhen, China and to investigate the intrauterine growth of neonates in Shenzhen. METHODS: Cross-sectional cluster sampling was performed for an on-the-spot investigation of 16 887 neonates (9 418 males and 7 469 females) with a gestational age of 27-42 weeks who were born in two hospitals in Shenzhen from April 2013 to September 2015. The Lambda Mu Sigma (LMS) method was used for the curve fitting of body weight, body length, head circumference, chest circumference, and crown-rump length. RESULTS: The 3rd-97th percentile intrauterine growth curves for body weight, body length, head circumference, chest circumference, and crown-rump length were plotted for the neonates with a gestational age of 27-42 weeks who were divided into three groups (male, female, and mixed). The male neonates had significantly higher curves for the five indices than the female counterparts. The pattern and changing trend of body weight curves of these neonates were basically consistent with those in China Neonatal Network. CONCLUSIONS: The percentile intrauterine growth curves for body weight, body length, head circumference, chest circumference, and crown-rump length in neonates with a gestational age of 27-42 weeks in Shenzhen which has been established can provide a reference for clinical practice in the department of neonatology.

[Study on height-weight indices in newborns of different gestational ages].

OBJECTIVE: To establish height-weight indices in newborns of different gestational ages and to provide reference data for evaluation of intrauterine fetal growth. METHODS: The weight, height, crown-rump length, head circumference, and chest circumference of 8 357 newborns were measured in Maternal and Child Health Care Hospital of Bao'an District of shenzhen between 2005 and 2006, with the method of fact-finding investigation with cross-sectional cluster sampling, to establish the height-weight indices in newborns of different gestational ages. RESULTS: Five gender-specific height-weight indices (Quetelet Index, QI; Kaup Index, KI; Rohrer Index, RI; Livi Index, LI; Polock Index, PI) in newborns of different gestational ages (28-44 weeks of gestation) in three different groups (boys+girls, boys, and girls) were established in Shenzhen, China, and were expressed as mean gestational weeks±SD. The five indices above all increased with increasing gestational age, and the highest values appeared at 41-43 gestational weeks, suggesting that body density and enrichment degree increased constantly with increasing gestational age. Three indices (QI, KI and PI) were higher in boys than in girls (P<0.05). CONCLUSIONS: With the increasing gestational age, the body density and enrichment degree of newborns increase, and the enrichment degree in boys is better than that in girls.