Heat-Dissipation Design and 3D Printing of Ternary Silver Chalcogenide-Based Thermoelectric Legs for Enhancing Power Generation Performance.

Thermoelectric devices have received significant attention because of their potential for sustainable energy recovery. In these devices, a thermal design that optimizes heat transfer and dissipation is crucial for maximizing the power output. Heat dissipation generally requires external active or passive cooling devices, which often suffer from inevitable heat loss and heavy systems. Herein, the design of heat-sink integrated thermoelectric legs is proposed to enhance heat dissipation without external cooling devices, realized by finite element model simulation and 3D printing of ternary silver chalcogenide-based thermoelectric materials. Owing to the self-induced surface charges of the synthesized AgBiSe2 (n-type) and AgSbTe2 (p-type) particles, these particle-based colloidal inks exhibited high viscoelasticity, which enables the creation of complex heat-dissipation architectures via 3D printing. Power generators made from 3D-printed heat-dissipating legs exhibit higher temperature differences and output power than traditional cuboids, offering a new strategy for enhancing thermoelectric power generation.

Multiscale Control of Nanofiber-Composite Hydrogel for Complex 3D Cell Culture by Extracellular Matrix Composition and Nanofiber Alignment.

In order to manipulate the complex behavior of cells in a 3-dimensional (3D) environment, it is important to provide the microenvironment that can accurately portray the complexity of highly anisotropic tissue structures. However, it is technically challenging to generate a complex microenvironment using conventional biomaterials that are mostly isotropic with limited bioactivity. In this study, the gelatin-hyaluronic acid hydrogel incorporated with aqueous-dispersible, short nanofibers capable of in situ alignment is developed to emulate the native heterogeneous extracellular matrix consisting of fibrous and non-fibrous components. The gelatin nanofibers containing magnetic nanoparticles, which could be aligned by external magnetic field, are dispersed and embedded in gelatin-hyaluronic acid hydrogel encapsulated with dermal fibroblasts. The aligned nanofibers via magnetic field could be safely integrated into the hydrogel, and the process could be repeated to generate larger 3D hydrogels with variable nanofiber alignments. The aligned nanofibers in the hydrogel can more effectively guide the anisotropic morphology (e.g., elongation) of dermal fibroblasts than random nanofibers, whereas myofibroblastic differentiation is more prominent in random nanofibers. At a given nanofiber configuration, the hydrogel composition having intermediate hyaluronic acid content induces myofibroblastic differentiation. These results indicate that modulating the degree of nanofiber alignment and the hyaluronic acid content of the hydrogel are crucial factors that critically influence the fibroblast phenotypes. The nanofiber-composite hydrogel capable of directional nanofiber alignment and tunable material composition can effectively induce a wide array of phenotypic plasticity in 3D cell culture.

Nanoscale Vertical Resolution in Optical Printing of Inorganic Nanoparticles.

Direct optical printing of functional inorganics shows tremendous potential as it enables the creation of intricate two-dimensional (2D) patterns and affordable design and production of various devices. Although there have been recent advancements in printing processes using short-wavelength light or pulsed lasers, the precise control of the vertical thickness in printed 3D structures has received little attention. This control is vital to the diverse functionalities of inorganic thin films and their devices, as they rely heavily on their thicknesses. This lack of research is attributed to the technical intricacy and complexity involved in the lithographic processes. Herein, we present a generalized optical 3D printing process for inorganic nanoparticles using maskless digital light processing. We develop a range of photocurable inorganic nanoparticle inks encompassing metals, semiconductors, and oxides, combined with photolinkable ligands and photoacid generators, enabling the direct solidification of nanoparticles in the ink medium. Our process creates complex and large-area patterns with a vertical resolution of ∼50 nm, producing 50-nm-thick 2D films and several micrometer-thick 3D architectures with no layer height difference via layer-by-layer deposition. Through fabrication and operation of multilayered switching devices with Au electrodes and Ag-organic resistive layers, the feasibility of our process for cost-effective manufacturing of multilayered devices is demonstrated.

3D microprinting of inorganic porous materials by chemical linking-induced solidification of nanocrystals.

Three-dimensional (3D) microprinting is considered a next-generation manufacturing process for the production of microscale components; however, the narrow range of suitable materials, which include mainly polymers, is a critical issue that limits the application of this process to functional inorganic materials. Herein, we develop a generalised microscale 3D printing method for the production of purely inorganic nanocrystal-based porous materials. Our process is designed to solidify all-inorganic nanocrystals via immediate dispersibility control and surface linking-induced interconnection in the nonsolvent linker bath and thereby creates multibranched gel networks. The process works with various inorganic materials, including metals, semiconductors, magnets, oxides, and multi-materials, not requiring organic binders or stereolithographic equipment. Filaments with a diameter of sub-10 µm are printed into designed complex 3D microarchitectures, which exhibit full nanocrystal functionality and high specific surface areas as well as hierarchical porous structures. This approach provides the platform technology for designing functional inorganics-based porous materials.

Association between vitamin D level and respiratory distress syndrome: A systematic review and meta-analysis.

BACKGROUND: Growing evidence suggests an association between the vitamin D levels and respiratory outcomes of preterm infants. The objective of this systematic review and meta-analysis was to explore whether premature neonates with a vitamin D deficiency have an increased risk of respiratory distress syndrome (RDS). METHODS: We searched PubMed, EMBASE, and the Cochrane Library up through July 20, 2021. The search terms were 'premature infant', 'vitamin D', and 'respiratory distress syndrome'. We retrieved randomized controlled trials and cohort and case-control studies. For statistical analysis, we employed the random-effects model in Comprehensive Meta-Analysis Software ver. 3.3. We employed the Newcastle-Ottawa Scales for quality assessment of the included studies. RESULTS: A total of 121 potentially relevant studies were found, of which 15 (12 cohort studies and 3 case-control studies) met the inclusion criteria; the studies included 2,051 preterm infants. We found significant associations between RDS development in such infants and vitamin D deficiency within 24 h of birth based on various criteria, thus vitamin D levels < 30 ng/mL (OR 3.478; 95% CI 1.817-6.659; p < 0.001), < 20 ng/mL (OR 4.549; 95% CI 3.007-6.881; p < 0.001), < 15 ng/mL (OR 17.267; 95% CI 1.084-275.112; p = 0.044), and < 10 ng/ml (OR 1.732; 95% CI 1.031-2.910; p = 0.038), and an even lower level of vitamin D (SMD = -0.656; 95% CI -1.029 to -0.283; p = 0.001). CONCLUSION: Although the vitamin D deficiency definitions varied and different methods were used to measure vitamin D levels, vitamin D deficiency or lower levels of vitamin D within 24 h of birth were always associated with RDS development. Monitoring of neonatal vitamin D levels or the maintenance of adequate levels may reduce the risk of RDS.

Self-Assembly of Matchstick-Shaped Inorganic Nano-Surfactants with Controlled Surface Amphiphilicity.

Molecular and nanoscale amphiphiles have been extensively studied as building blocks for organizing macroscopic matter through specific and local interactions. Among various amphiphiles, inorganic Janus nanoparticles have attracted a lot of attention owing to their ability to impart multifunctionalities, although the programmability to achieve complicated self-assembly remains a challenge. Here, we synthesized matchstick-shaped Janus nano-surfactants that mimic organic surfactant molecules and studied their programmable self-assembly. High amphiphilicity was achieved through the hard-soft acid-base-based ligand-exchange reaction with strong selectivity on the surface of nano-matchsticks consisting of Ag2S heads and CdS stems. The obtained nano-surfactants spontaneously assembled into diverse ordered structures such as lamellar, curved, wrinkled, cylindrical, and micellar structures depending on the vertical asymmetry and the interfacial tension controlled by their geometry and surface ligands. The correlation between the phase selectivity of suprastructures and the characteristics of nano-surfactants is discussed. This study realized the molecular amphiphile-like programmability of inorganic Janus nanostructures in self-assembly with the precise control on the surface chemistry.

Generalised optical printing of photocurable metal chalcogenides.

Optical three-dimensional (3D) printing techniques have attracted tremendous attention owing to their applicability to mask-less additive manufacturing, which enables the cost-effective and straightforward creation of patterned architectures. However, despite their potential use as alternatives to traditional lithography, the printable materials obtained from these methods are strictly limited to photocurable resins, thereby restricting the functionality of the printed objects and their application areas. Herein, we report a generalised direct optical printing technique to obtain functional metal chalcogenides via digital light processing. We developed universally applicable photocurable chalcogenidometallate inks that could be directly used to create 2D patterns or micrometre-thick 2.5D architectures of various sizes and shapes. Our process is applicable to a diverse range of functional metal chalcogenides for compound semiconductors and 2D transition-metal dichalcogenides. We then demonstrated the feasibility of our technique by fabricating and evaluating a micro-scale thermoelectric generator bearing tens of patterned semiconductors. Our approach shows potential for simple and cost-effective architecturing of functional inorganic materials.

Cu2Se-based thermoelectric cellular architectures for efficient and durable power generation.

Thermoelectric power generation offers a promising way to recover waste heat. The geometrical design of thermoelectric legs in modules is important to ensure sustainable power generation but cannot be easily achieved by traditional fabrication processes. Herein, we propose the design of cellular thermoelectric architectures for efficient and durable power generation, realized by the extrusion-based 3D printing process of Cu2Se thermoelectric materials. We design the optimum aspect ratio of a cuboid thermoelectric leg to maximize the power output and extend this design to the mechanically stiff cellular architectures of hollow hexagonal column- and honeycomb-based thermoelectric legs. Moreover, we develop organic binder-free Cu2Se-based 3D-printing inks with desirable viscoelasticity, tailored with an additive of inorganic Se82- polyanion, fabricating the designed topologies. The computational simulation and experimental measurement demonstrate the superior power output and mechanical stiffness of the proposed cellular thermoelectric architectures to other designs, unveiling the importance of topological designs of thermoelectric legs toward higher power and longer durability.

Solution-Processed Stretchable Ag2 S Semiconductor Thin Films for Wearable Self-Powered Nonvolatile Memory.

Compared with the large plastic deformation observed in ductile metals and organic materials, inorganic semiconductors have limited plasticity (<0.2%) due to their intrinsic bonding characters, restricting their widespread applications in stretchable electronics. Herein, the solution-processed synthesis of ductile α-Ag2 S thin films and fabrication of all-inorganic, self-powered, and stretchable memory devices, is reported. Molecular Ag2 S complex solution is synthesized by chemical reduction of Ag2 S powder, fabricating wafer-scale highly crystalline Ag2 S thin films. The thin films show stretchability due to the intrinsic ductility, sustaining the structural integrity at a tensile strain of 14.9%. Moreover, the fabricated Ag2 S-based resistive random access memory presents outstanding bipolar switching characteristics (Ion /Ioff ratio of ≈105 , operational endurance of 100 cycles, and retention time >106 s) as well as excellent mechanical stretchability (no degradation of properties up to stretchability of 52%). Meanwhile, the device is highly durable under diverse chemical environments and temperatures from -196 to 300 °C, especially maintaining the properties for 168 h in 85% relative humidity and 85 °C. A self-powered memory combined with motion sensors for use as a wearable healthcare monitoring system is demonstrated, offering the potential for designing high-performance wearable electronics that are usable in daily life in a real-world setting.

Synthesis of high quality 2D carbide MXene flakes using a highly purified MAX precursor for ink applications.

The practical application of 2D MXenes in electronic and energy fields has been hindered by the severe variation in the quality of MXene products depending on the parent MAX phases, manufacturing techniques, and preparation parameters. In particular, their synthesis has been impeded by the lack of studies reporting the synthesis of high-quality parent MAX phases. In addition, controllable and uniform deposition of 2D MXenes on various large-scale substrates is urgently required to use them practically. Herein, a method of pelletizing raw materials could synthesize a stoichiometric Ti3AlC2 MAX phase with high yield and processability, and fewer impurities. The Ti3AlC2 could be exfoliated into 1-2-atom-thick 2D Ti3C2T x flakes, and their applicability was confirmed by the deposition and additional alignment of the 2D flakes with tunable thickness and electrical properties. Moreover, a practical MXene ink was fabricated with rheological characterization. MXene ink exhibited much better thickness uniformity while retaining excellent electrical performances (e.g., sheet resistance, electromagnetic interference shielding ability) as those of a film produced by vacuum filtration. The direct functional integration of MXenes on various substrates is expected to initiate new and unexpected MXene-based applications.

Ordered Mesoporous Carbons with Graphitic Tubular Frameworks by Dual Templating for Efficient Electrocatalysis and Energy Storage.

Ordered mesoporous carbons (OMCs) have attracted considerable interest owing to their broad utility. OMCs reported to date comprise amorphous rod-like or tubular or graphitic rod-like frameworks, which exhibit tradeoffs between conductivity and surface area. Here we report ordered mesoporous carbons constructed with graphitic tubular frameworks (OMGCs) with tunable pore sizes and mesostructures via dual templating, using mesoporous silica and molybdenum carbide as exo- and endo-templates, respectively. OMGCs simultaneously realize high electrical conductivity and large surface area and pore volume. Benefitting from these features, Ru nanoparticles (NPs) supported on OMGC exhibit superior catalytic activity for alkaline hydrogen evolution reaction and single-cell performance for anion exchange membrane water electrolysis compared to Ru NPs on other OMCs and commercial catalysts. Further, the OMGC-based full-carbon symmetric cell demonstrates excellent performances for Li-ion capacitors.

Association between vitamin D level and bronchopulmonary dysplasia: A systematic review and meta-analysis.

Neonatal vitamin D deficiency is common and is associated with development of pulmonary disease in children and adults. While the role of vitamin D in normal lung development is well established, the association between vitamin D deficiency and bronchopulmonary dysplasia (BPD) remains unclear. The present meta-analysis was conducted to evaluate the relationship between vitamin D and BPD. We identified relevant studies (n = 8) using the PubMed, EMBASE, Cochrane Library, and KoreaMed databases and applied the Newcastle-Ottawa Scale to assess the methodological components of each study, and used I2 statistic to evaluate heterogeneity. Comprehensive Meta-Analysis software version 3.3 was used for the statistical analysis. A total of 909 infants were included, of whom 251 (27.6%) were diagnosed with BPD. We found that both vitamin D deficiency at birth (four studies; OR 2.405; 95% CI 1.269 to 4.560; p = 0.007) and low levels of vitamin D at birth (four studies; standardized mean difference -1.463; 95% CI -2.900 to -0.027; p = 0.046) were associated with BPD. The compiled data suggest that antenatal vitamin D deficiency and low vitamin D levels are associated with neonatal BPD.

Thiometallate precursors for the synthesis of supported Pt and PtNi nanoparticle electrocatalysts: Size-focusing by S capping.

Herein, we report for the first time the successful preparation of thiometallate-based precursors for use in a bottom-up synthetic process of supported Pt and PtNi nanoparticle catalyst. This precursor enabled the monodisperse synthesis of supported Pt nanoparticles and the in situ formation of S, which were caught directly in a collection system by the nanoparticle synthetic processes consisting of impregnation and thermal processes. S is proven to act as a capping agent in generating highly stable nanoparticles with the size ranging from 2 nm to 3 nm and further favors the formation of monodispersed particles by solid-state digestive ripening. The proposed synthetic methodology can be applied to high-quality PtNi alloy nanoparticle systems. The current route is readily scalable, and multi-gram quantities can be prepared. The prepared carbon-supported Pt and PtNi nanoparticles were characterized as electrocatalysts for the oxygen reduction reaction and exhibited superior performance and durability to commercial Pt/C.

Clinical Features of Severely Constipated Children: Comparison of Infrequent Bowel Movement and Fecal Soiling Groups.

PURPOSE: To compare the clinical features, diagnostic findings, and medications of children with infrequent bowel movements or fecal soiling. METHODS: This study enrolled 333 children (189 male; age range, 1 month to 18 years) diagnosed with functional constipation by Rome III or IV criteria. We classified them into 3 groups (infrequent bowel movement without fecal soiling [G3-a], infrequent bowel movement with fecal soiling [G3-b], and fecal soiling only [G3-c]) and into 2 subgroups of fecal soiling (G2-b) or not (G2-a). Retrospective data on clinical characteristics, colon transit time (CTT) test results, and medications were collected. The Wilcoxon rank-sum test, Kruskal-Wallis test, Chi-square test, and Fisher's exact test were used for the statistical analysis. RESULTS: The median age (months) and interquartile range (IQR) was 33 (45) in G3-a, 54 (40) in G3-b, and 73 (48) in G3-c (p<0.0001). G3-c had the latest onset (median, 18; IQR, 18; p=0.0219) and longest symptom duration (24 [24], p=0.0148). PEG 4000 was used in 60.6% (G3-a), 96.8% (G3-b), and 83.2% (G3-c) of patients (p<0.0001). The median age (months) and IQR were 33.0 (45.0) in G2-a and 63.5 (52.5) in G2-b (p<0.0001). G2-b had later onset (median, 12; IQR, 19.5; p=0.0062) and longer symptom duration than G2-a (24 [12], p=0.0070). PEG 4000 was used in 60.6% (G2-a) and 88.3% (G2-b) of children (p<0.0001). No statistically significant intergroup differences were seen in maintenance laxative dose, CTT, or CTT type. CONCLUSION: Infrequent bowel movement and fecal soiling represent the advanced stage of chronic functional constipation.

Controlled Grafting of Colloidal Nanoparticles on Graphene through Tailored Electrostatic Interaction.

Nanoparticle/graphene hybrid composites have been of great interest in various disciplines due to their unique synergistic physicochemical properties. In this study, we report a facile and generalized synthesis method for preparing nanoparticle/exfoliated graphene (EG) composites by tailored electrostatic interactions. EG was synthesized by an electrochemical method, which produced selectively oxidized graphene sheets at the edges and grain boundaries. These EG sheets were further conjugated with polyethyleneimine to provide positive charges at the edges. The primary organic ligands of the colloidal nanoparticles were exchanged with Cl- or MoS42- anions, generating negatively charged colloidal nanoparticles in polar solvents. By simple electrostatic interactions between the EG and nanoparticles in a solution, nanoparticles were controllably assembled at the edges of the EG. Furthermore, the generality of this process was verified for a wide range of nanoparticles, such as semiconductors, metals, and magnets, on the EG. As a model application, designed composites with size-controlled FeCo nanoparticle/EG were utilized as electromagnetic interference countermeasure materials that showed a size-dependent shift of the frequency ranges on the electromagnetic absorption properties. The current generalized process will offer great potential for the large-scale production of well-designed graphene nanocomposites for electronic and energy applications.

Composition change-driven texturing and doping in solution-processed SnSe thermoelectric thin films.

The discovery of SnSe single crystals with record high thermoelectric efficiency along the b-axis has led to the search for ways to synthesize polycrystalline SnSe with similar efficiencies. However, due to weak texturing and difficulties in doping, such high thermoelectric efficiencies have not been realized in polycrystals or thin films. Here, we show that highly textured and hole doped SnSe thin films with thermoelectric power factors at the single crystal level can be prepared by solution process. Purification step in the synthetic process produced a SnSe-based chalcogenidometallate precursor, which decomposes to form the SnSe2 phase. We show that the strong textures of the thin films in the b-c plane originate from the transition of two dimensional SnSe2 to SnSe. This composition change-driven transition offers wide control over composition and doping of the thin films. Our optimum SnSe thin films exhibit a thermoelectric power factor of 4.27 µW cm-1 K-2.

Synthesis of Inorganic-Organic 2D CdSe Slab-Diamine Quantum Nets.

Porous semiconductors attract great interest due to their unique structural characteristics of high surface area as well as their intrinsic optical and electronic properties. In this study, synthesis of inorganic-organic 2D CdSe slabs-diaminooctane (DAO) porous quantum net structures is demonstrated. It is found that the hybrid 2D CdSe-DAO lamellar structures are disintegrated into porous net structures, maintaining an ultrathin thickness of ≈1 nm in CdSe slabs. Furthermore, the CdSe slabs in quantum nets show the highly shifted excitonic transition in the absorption spectrum, demonstrating their strongly confined electronic structures. The possible formation mechanism of this porous structure is investigated with the control experiments of the synthesis using n-alkyldiamines with various hydrocarbon chain lengths and ligand exchange of DAO with oleylamine. It is suggested that a strong van der Waals interaction among long chain DAO may exert strong tensile stress on the CdSe slabs, eventually disintegrating slabs. The thermal decomposition of CdSe-DAO quantum nets is further studied to form well-defined CdSe nanorods. It is believed that the current CdSe-DAO quantum nets will offer a new type of porous semiconductors nanostructures under a strong quantum-confinement regime, which can be applied to various technological areas of catalysts, electronics, and optoelectronics.

Ink Processing for Thermoelectric Materials and Power-Generating Devices.

The growing concern over the depletion of hydrocarbon resources, and the adverse environmental effects associated with their use, has increased the demand for renewable energy sources. Thermoelectric (TE) power generation from waste heat has emerged as a renewable energy source that does not generate any pollutants. Recently, ink-based processing for the preparation of TE materials has attracted tremendous attention because of the simplicity in design of power generators and the possibility of cost-effective manufacturing. In this progress report, recent advances in the development of TE inks, processing techniques, and ink-fabricated devices are reviewed. A summary of typical formulations of TE materials as inks is included, as well as a discussion on various ink-based fabrication methods, with several examples of newly designed devices fabricated using these techniques. Finally, the prospects of this field with respect to the industrialization of TE power generation technology are presented.

Prognostic Value of Serial Echocardiography in Hypoplastic Left Heart Syndrome.

BACKGROUND: Hypoplastic left heart syndrome (HLHS) carries a high mortality. The prognostic value of echocardiographic variables at presentation and the importance of serial data are poorly explored. METHODS AND RESULTS: We retrospectively analyzed longitudinal clinical and echocardiographic parameters of children with hypoplastic left heart syndrome. The primary outcome was time to death or transplant after stage-1 surgery, right censored at stage 3 surgery, accounting for sequential surgical procedures. Univariable and multivariable analysis identified risk factors for transplant or mortality. Time-dependent trends in echo parameters stratified by patient survival were explored using nonparametric methods. In total 67 children with hypoplastic left heart syndrome were included. The 10-week, 20-week, and 1-year survival proportions were 77.6% (66-86), 68.7% (56-78), and 54.1% (41-65), respectively. At presentation, multivariable analysis identified a thicker interventricular septum (hazard ratio [HR], 1.64; P=0.007) to be associated with increased risk for transplant/death, whereas higher tricuspid valve annular planar systolic excursion z score (HR, 0.61; P=0.003) was associated with reduced risk of mortality/transplant. After stage-1, higher body surface area-indexed right ventricular end-systolic area (HR, 1.52; P=0.02), lower fractional area change (HR, 1.18; P=0.01), and qualitatively decreased right ventricular function (HR, 2.55; P=0.08) were associated with increased risk of transplant-free mortality, censored at stage 3. Higher body surface area-indexed right ventricular end-diastolic area (HR, 0.76; P=0.04) and better tricuspid valve annular planar systolic excursion z score (HR, 0.49; P=0.01) were associated with lower mortality/transplant. During follow-up, right ventricular dilation, dysfunction, and tricuspid regurgitation improved in transplant-free survivors and worsened in those transplanted or who died. CONCLUSIONS: Conventional echocardiographic parameters at presentation and during follow-up are potential markers for transplant-free survival in children with hypoplastic left heart syndrome.