Travel changes and equitable access to urban parks in the post COVID-19 pandemic period: Evidence from Wuhan, China.

COVID-19 has spread worldwide, leading to a significant impact on daily life. Numerous studies have confirmed that people have changed their travel to urban green spaces during the COVID-19 pandemic. However, in China, where COVID-19 has been effectively controlled, how the travel behavior of visitors to urban parks has changed under different risk levels (RLs) of COVID-19 is unclear. Faced with these gaps, we took a highly developed city, Wuhan, as a case study and a questionnaire survey was conducted with 3276 respondents to analyze the changes in park visitors' travel behaviors under different COVID-19 RLs. Using a stated preference (SP) survey method, four RLs were assigned: new cases in other provinces (RL1), Hubei province (RL2), Wuhan (RL3), and in the district of the park (RL4). The results indicated that visitors reduced their willingness to visit urban parks, with 78.39%, 37.97%, and 13.34% of visitors remaining under RL2, RL3, and RL4, respectively. Furthermore, the service radius of urban parks also shrank from 4230 m under no new cases of COVID-19 to approximately 3000 m under RL3. A higher impact was found for visitors using public transport, those with a higher income and higher education, and female visitors. Based on the modified travel behaviors, the Gaussian-based two-step floating catchment area (2SFCA) method was used to evaluate the accessibility and the Gini coefficient was calculated to represent the equality of the urban parks. A higher RL led to lower accessibility and greater inequitable access. The results should help the government guide residents' travel behaviors after COVID-19.

3D Porous Liquid Crystal Elastomer Foams Supporting Long-term Neuronal Cultures.

3D liquid crystal elastomer (3D-LCE) foams are used to support long-term neuronal cultures for over 60 days. Sequential imaging shows that cell density remains relatively constant throughout the culture period while the number of cells per observational area increases. In a subset of samples, retinoic acid is used to stimulate extensive neuritic outgrowth and maturation of proliferated neurons within the LCEs, inducing a threefold increase in length with cells displaying morphologies indicative of mature neurons. Designed LCEs' micro-channels have a similar diameter to endogenous parenchymal arterioles, ensuring that neurons throughout the construct have constant access to growth media during extended experiments. Here it is shown that 3D-LCEs provide a unique environment and simple method to longitudinally study spatial neuronal function, not possible in conventional culture environments, with simplistic integration into existing methodological pipelines.

Hole-punching for enhancing electrocatalytic activities of 2D graphene electrodes: Less is more.

Using a polymer-masking approach, we have developed metal-free 2D carbon electrocatalysts based on single-layer graphene with and without punched holes and/or N-doping. A combined experimental and theoretical study on the resultant 2D graphene electrodes revealed that a single-layer graphene sheet exhibited a significantly higher electrocatalytic activity at its edge than that over the surface of its basal plane. Furthermore, the electrocatalytic activity of a single-layer 2D graphene sheet was significantly enhanced by simply punching microholes through the graphene electrode due to the increased edge population for the hole-punched graphene electrode. In a good consistency with the experimental observations, our density function theory calculations confirmed that the introduction of holes into a graphene sheet generated additional positive charge along the edge of the punched holes and hence the creation of more highly active sites for the oxygen reduction reaction. The demonstrated concept for less graphene material to be more electrocatalytically active shed light on the rational design of low-cost, but efficient electrocatalysts from 2D graphene for various potential applications ranging from electrochemical sensing to energy conversion and storage.

Direct Intertube Cross-Linking of Carbon Nanotubes at Room Temperature.

Carbon nanotubes (CNTs) have long been regarded as an efficient free radical scavenger because of the large-conjugation system in their electronic structures. Hence, despite abundant reports on CNT reacting with incoming free radical species, current research has not seen CNT itself displaying the chemical reactivity of free radicals. Here we show that reactive free radicals can in fact be generated on carbon nanotubes via reductive defluorination of highly fluorinated single-walled carbon nanotubes (FSWNTs). This finding not only enriches the current understanding of carbon nanotube chemical reactivity but also opens up new opportunities in CNT-based material design. For example, spacer-free direct intertube cross-linking of carbon nanotubes was previously achieved only under extremely high temperature and pressure or electron/ion beam irradiation. With the free radicals on defluorinated FSWNTs, the nanotubes containing multiple radicals on the sidewall can directly cross-link with each other under ambient temperature through intertube radical recombination. It is demonstrated that carbon nanotube fibers reinforced via direct cross-linking displays much improved mechanical properties.

Development of a Tri-Axial Cutting Force Sensor for the Milling Process.

This paper presents a three-component fixed dynamometer based on a strain gauge, which reduces output errors produced by the cutting force imposed on different milling positions of the workpiece. A reformative structure of tri-layer cross beams is proposed, sensitive areas were selected, and corresponding measuring circuits were arranged to decrease the inaccuracy brought about by positional variation. To simulate the situation with a milling cutter moving on the workpiece and validate the function of reducing the output errors when the milling position changes, both static calibration and dynamic milling tests were implemented on different parts of the workpiece. Static experiment results indicate that with standard loads imposed, the maximal deviation between the measured forces and the standard inputs is 4.87%. The results of the dynamic milling test illustrate that with identical machining parameters, the differences in output variation between the developed sensor and standard dynamometer are no larger than 6.61%. Both static and dynamic experimental results demonstrate that the developed dynamometer is suitable for measuring milling force imposed on different positions of the workpiece, which shows potential applicability in machining a monitoring system.

A Quantum Mechanical MP2 Study of the Electronic Effect of Nonplanarity on the Carbon Pyramidalization of Fullerene C60.

Among C60's diverse functionalities, its potential application in CO2 sequestration has gained increasing interest. However, the processes involved are sensitive to the molecule's electronic structure, aspects of which remain debated and require greater precision. To address this, we performed structural optimization of fullerene C60 using the QM MP2/6-31G* method. The nonplanarity of the optimized icosahedron is characterized by two types of dihedral angles: 138° and 143°. The 120 dihedrals of 138° occur between two hexagons intersecting at C-C bonds of 1.42 Å, while the 60 dihedrals of 143° are observed between hexagons and pentagons at C-C bonds of 1.47 Å. NBO analysis reveals less pyramidal sp1.78 hybridization for carbons at the 1.42 Å bonds and more pyramidal sp2.13 hybridization for the 1.47 Å bonds. Electrostatic potential charges range from -0.04 a.u. to 0.04 a.u. on the carbon atoms. Second-order perturbation analysis indicates that delocalization interactions in the C-C bonds of 1.42 Å (143.70 kcal/mol) and 1.47 Å (34.98 kcal/mol) are 22% and 38% higher, respectively, than those in benzene. MP2/Def2SVP calculations yield a correlation energy of 13.49 kcal/mol per electron for C60, slightly higher than the 11.68 kcal/mol for benzene. However, the results from HOMO-LUMO calculations should be interpreted with caution. This study may assist in the rational design of fullerene C60 derivatives for CO2 reduction systems.

The Stability of UV-Defluorination-Driven Crosslinked Carbon Nanotubes: A Raman Study.

Carbon nanotubes (CNTs) are often regarded as semi-rigid, all-carbon polymers. However, unlike conventional polymers that can form 3D networks such as hydrogels or elastomers through crosslinking in solution, CNTs have long been considered non-crosslinkable under mild conditions. This perception changed with our recent discovery of UV-defluorination-driven direct crosslinking of CNTs in solution. In this study, we further investigate the thermal stability of UV-defluorination-driven crosslinked CNTs, revealing that they are metastable and decompose more readily than either pristine or fluorinated CNTs under Raman laser irradiation. Using Raman spectroscopy under controlled laser power, we examined both single-walled and multi-walled fluorinated CNTs. The results demonstrate that UV-defluorinated CNTs exhibit reduced thermal stability compared to their pristine or untreated fluorinated counterparts. This instability is attributed to the strain on the intertube crosslinking bonds resulting from the curved carbon lattice of the linked CNTs. The metallic CNTs in the crosslinked CNT networks decompose and revert to their pristine state more readily than the semiconducting ones. The inherent instability of crosslinked CNTs leads to combustion at temperatures approximately 100 °C lower than those required for non-crosslinked fluorinated CNTs. This property positions crosslinked CNTs as promising candidates for applications where mechanically robust, lightweight materials are needed, along with feasible post-use removal options.

Sensor arrays from multicomponent micropatterned nanoparticles and graphene.

A novel approach for multicomponent patterning metal/metal oxide nanoparticles on graphene was developed, which involves region-specific plasma treatment, followed by region-selective substrate-enhanced electroless deposition of Au nanoparticles and solution alkalization of ferrous chloride tetrahydrate in the presence of ammonia into Fe3O4 nanoparticles. The resultant Fe3O4/Au multicomponent micropatterned-graphene films were found to be highly selective sensor arrays for detecting low levels of chemical vapor molecules at ppm levels. This novel concept could be applied to the development of various multicomponent patterned nanomaterials for many potential applications, ranging from nanoscale region-specific chemical-/bio-sensor arrays to multifunctional optoelectronic devices.

The driving mechanism of passivator islands adsorbing and immobilizing heavy metals during chicken manure composting.

The aim of this study was to assess the effectiveness of biochar and montmorillonite islands on heavy metal adsorptive immobilization and identify crucial driving factors and pathways during chicken manure composting. Compared to montmorillonite (6.74 and 89.25 mg/kg), biochar exhibited an obviously higher ability of Cu and Zn enrichment (41.79 and 167.77 mg/kg), might be attributed to its abundant active functional groups. Network analysis showed that compared to Cu, core bacteria positively and negatively related to Zn was obviously more and less in passivator islands, respectively, which might explain significantly higher Zn concentration. Structural Equation Model displayed that dissolved organic carbon (DOC), pH and bacteria were critical driving factors. Pretreatment of passivator packages, such as soaking in the solution being rich in DOC and inoculating specific microbial agents accumulating heavy metals via extracellular adsorption /intracellular interception would significantly improve the effectiveness of adsorptive passivation on heavy metals.

Insight into the pathways of biochar/smectite-induced humification during chicken manure composting.

As representative organic and inorganic additives, both biochar and smectite exhibit an excellent capacity to improve humification efficiency during composting. Nevertheless, the mechanisms underlying biochar/smectite-induced compost humification have still not been fully explored from the perspective of overall organic substances. In this study, three composting treatments were performed as follows: 10 % biochar-amended composting, 10 % smectite-amended composting and natural composting without any additive. UV-visible parameters and synchronous hetero two-dimensional correlation spectra showed that biochar accelerated dissolved organic matter (DOM) complications, unsaturation and aromatization. For example, biochar promoted the C2 and simple C3 peaks to convert into a sophisticated C3/360 peak. However, the effect of smectite was negligible in complicating the DOM structure. Both biochar and smectite displayed an invigorating role in promoting humic substance (HS) formation. The strengthened relations between bacterial richness and physicochemical indicators and HS fractions might contribute to the positive action of biochar/smectite on HS synthesis. Network analysis showed that both bacterial functional omnipotence and specialization in response to the addition of catalysts may contribute to compost humification. The chemical pathway involved in DOM humification was intensified by enhancing the role of pH in biochar composting and weakening the degradation of unsaturated aromatic compounds of DOM with smectite addition. These findings benefit the practical application of biochar/smectite in promoting composting efficiency.

QM/MM study of N501 involved intermolecular interaction between SARS-CoV-2 receptor binding domain and antibody of human origin.

Intermolecular interaction between key residue N501 of the epitope on SARS-CoV-2 RBD and screening antibody B38 was studied using the QM/MM and QM approach. The QM/MM optimized geometry shows that angle X-H---Y is 165° for O-H---O between mAb light chain S30 and RBD N501. High level MP2 calculations indicated the interaction between RBD N501 and S30 of B38 Fab light chain provide a relatively strong attractive force of - 3.32 kcal/mol, whereas the hydrogen bond between RBD Q498 and S30 was quantified as 0.10 kcal/mol. The decrease in ESP partial charge on hydrogen atom of hydroxyl group on S30 drops from 0.38 a.u. to 0.31 a.u., exhibiting the sharing of 0.07 a.u. from the lone pair electron oxygen of N501 due to hydrogen bond formation. The NBO occupancy of hydrogen atom also decreases from 25.79 % to 22.93 % in the hydroxyl H-O NBO bond of S30. However, the minor change of NBO hybridization of hydroxyl oxygen of S30 from sp3.00 to sp3.05 implies the rigidity of hydrogen bond tetrahedral geometry in the relative dynamic protein complex. The O-H---O angle is 165° which is close but not exactly linear. The structural requirement for sp3 hybridization of oxygen for hydroxyl group on S30 and dimension of protein likely prevent O-H---O from adopting linear geometry. The hydrogen bond strengths were also calculated using a variety of DFT methods, and the result of - 3.33 kcal/mol from the M06L method is the closest to that of the MP2 calculation. Results of this work may aid in the COVID-19 vaccine and drug screening.

Versatile control of multiphase laminar flow for in-channel microfabrication.

We have improved the multiphase laminar flow based in-channel fabrication method to overcome diffusion-induced broadening. A sheathing phase with protecting molecules confines metal wire deposition and allows for flexible control of the location, width, and uniformity of deposited metal wires. Two-layered T-junctions are introduced to form vertically stacked multiphase laminar flow. Combining these techniques, we fabricate quadrupole silver electrodes on the four sidewalls of rectangular polydimethylsiloxane (PDMS) microchannels that are 3 cm in length.

Carbon Nano-Allotrope/Magnetic Nanoparticle Hybrid Nanomaterials as T2 Contrast Agents for Magnetic Resonance Imaging Applications.

Magnetic resonance imaging (MRI) is the most powerful tool for deep penetration and high-quality 3D imaging of tissues with anatomical details. However, the sensitivity of the MRI technique is not as good as that of the radioactive or optical imaging methods. Carbon-based nanomaterials have attracted significant attention in biomaterial research in recent decades due to their unique physical properties, versatile functionalization chemistry, as well as excellent biological compatibility. Researchers have employed various carbon nano-allotropes to develop hybrid MRI contrast agents for improved sensitivity. This review summarizes the new research progresses in carbon-based hybrid MRI contrast agents, especially those reported in the past five years. The review will only focus on T2-weighted MRI agents and will be categorized by the different carbon allotrope types and magnetic components. Considering the strong trend in recent bio-nanotechnology research towards multifunctional diagnosis and therapy, carbon-based MRI contrast agents integrated with other imaging modalities or therapeutic functions are also covered.

Synthesis of Biocompatible Liquid Crystal Elastomer Foams as Cell Scaffolds for 3D Spatial Cell Cultures.

Here, we present a step-by-step preparation of a 3D, biodegradable, foam-like cell scaffold. These scaffolds were prepared by cross-linking star block co-polymers featuring cholesterol units as side-chain pendant groups, resulting in smectic-A (SmA) liquid crystal elastomers (LCEs). Foam-like scaffolds, prepared using metal templates, feature interconnected microchannels, making them suitable as 3D cell culture scaffolds. The combined properties of the regular structure of the metal foam and of the elastomer result in a 3D cell scaffold that promotes not only higher cell proliferation compared to conventional porous templated films, but also better management of mass transport (i.e., nutrients, gases, waste, etc.). The nature of the metal template allows for the easy manipulation of foam shapes (i.e., rolls or films) and for the preparation of scaffolds of different pore sizes for different cell studies while preserving the interconnected porous nature of the template. The etching process does not affect the chemistry of the elastomers, preserving their biocompatible and biodegradable nature. We show that these smectic LCEs, when grown for extensive time periods, enable the study of clinically relevant and complex tissue constructs while promoting the growth and proliferation of cells.

Block-copolymer-controlled growth of CaCO3 microrings.

A novel way for directed solution growth of hollow superstructures of CaCO3 has been successfully developed on the basis of controlled self-assembly and polymer concentration gradients using a double-hydrophilic block copolymer with a hydrophobic modification as a directing agent. A formation mechanism of such rings is proposed on the basis of the formation of CaCO3 nanoparticles in unstructured block copolymer assemblies with subsequent aggregation of these primary nanoparticles. This leads to the formation of a polymer concentration gradient from the inside to the outside of the particle. As the polymer contains multiple chelating units, this leads to a selective dissolution of the center of the particle.

Biocompatible 3D Liquid Crystal Elastomer Cell Scaffolds and Foams with Primary and Secondary Porous Architecture.

3D biodegradable and highly regular foamlike cell scaffolds based on biocompatible side-chain liquid crystal elastomers have been prepared. Scaffolds with a primary porosity characterized by spatially interlaced, interconnected microchannels or an additional secondary porosity featuring interconnected microchannel networks define the novel elastomeric scaffolds. The macroscale morphology of the dual porosity 3D scaffold resembles vascular networks observed in tissue. 3D elastomer foams show four times higher cell proliferation capability compared to conventional porous templated films and within the channels guide spontaneous cell alignment enabling the possibility of tissue construct fabrication toward more clinically complex environments.

Non-viral nanoparticle delivers small interfering RNA to macrophages in vitro and in vivo.

Macrophages are increasingly being viewed as therapeutic target for various cancers and many inflammatory diseases. Sequence specific gene reduction by siRNA represents an attractive approach to modulate macrophage function. However, delivery of the therapeutic siRNA into macrophages by non-viral nanoparticles has been a major technical challenge. In this study, we developed a glucan-based siRNA carrier system (BG34-10-Re-I) and demonstrated that the BG34-10-Re-I can effectively assemble siRNA into uniformly distributed nanoparticles of the novel core-shell structure. The BG34-10-Re-I/siRNA nanoparticles effectively reduced gene expression of macrophage migration inhibitory factor (MIF) in primary macrophages at both protein and mRNA level. The nanoparticles also mediated a sustained reduction of MIF within primary macrophages. Moreover, systemic injection of the nanoparticles into the Balb/c mice bearing 4T1 mammary tumors resulted in the MIF reduction in tumor-associated macrophages. Mechanistic studies demonstrated that the glucan-shell and the siRNA-core structure contribute to the effective delivery of MIF siRNA to macrophages both in vitro and in vivo. This study represents the first development of the primary macrophage MIF gene targeted non-viral nanoparticle system for both in vitro and in vivo applications.

Biocompatible, biodegradable and porous liquid crystal elastomer scaffolds for spatial cell cultures.

Here we report on the modular synthesis and characterization of biodegradable, controlled porous, liquid crystal elastomers (LCE) and their use as three-dimensional cell culture scaffolds. The elastomers were prepared by cross-linking of star block-co-polymers with pendant cholesterol units resulting in the formation of smectic-A LCEs as determined by polarized optical microscopy, DSC, and X-ray diffraction. Scanning electron microscopy revealed the porosity of the as-prepared biocompatible LCEs, making them suitable as 3D cell culture scaffolds. Biodegradability studies in physiological buffers at varying pH show that these scaffolds are intact for about 11 weeks after which degradation sets in at an exponential rate. Initial results from cell culture studies indicate that these smectic LCEs are compatible with growth, survival, and expansion of cultured neuroblastomas and myoblasts when grown on the LCEs for extended time periods (about a month). These preliminary cell studies focused on characterizing the elastomer-based scaffolds' biocompatibility and the successful 3D incorporation as well as growth of cells in 60 to 150-µm thick elastomer sheets.

Hole and electron extraction layers based on graphene oxide derivatives for high-performance bulk heterojunction solar cells.

By charge neutralization of carboxylic acid groups in graphene oxide (GO) with Cs(2)CO(3) to afford Cesium-neutralized GO (GO-Cs), GO derivatives with appropriate modification are used as both hole- and electron-extraction layers for bulk heterojunction (BHJ) solar cells. The normal and inverted devices based on GO hole- and GO-Cs electron-extraction layers both outperform the corresponding standard BHJ solar cells.

Double hydrophilic block copolymer controlled growth and self-assembly of CaCO3 multilayered structures at the air/water interface.

Double hydrophilic block copolymers PEG-b-PEI-linear with different PEI block lengths have been examined for CaCO3 mineralization at the air/water interface. The results demonstrated that either PEI length or the solution acidity had a significant influence on the morphogenesis of vaterite crystals at the air/water interface. A possible mechanism for the stratification of CaCO3 vaterite crystals has been proposed. Increasing either PEI length or the initial pH value of the solution will decrease the density of the PEG block anchored on the binding interface and result in exposing more space as binding interface to solution and favoring the subnucleation and stratification growth on the polymer-CaCO3 interface. In contrast, higher density of PEG blocks will stabilize the growing crystals more efficiently and inhibit subnucleation on the polymer-CaCO3 interface, and thus prevent the formation of stratified structures. This study provides an example that it is possible to access morphogenesis of calcium carbonate structures by a combination of a block copolymer with the air/water interface.