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Self-assembly of noble metal nanobuilding blocks (NBBs) to hierarchical self-supported porous monoliths provides a great potential for achieving their wonderful properties along with practical applications. However, the self-assembly procedure for this kind of material reported in template and sol–gel approach is limited to specific conditions, and little interest was paid to the role of ligands in the self-assembly process to grasp the control of the structure and properties. Herein, two ligands (L1 and L2) containing thiol and glutamic acid moiety were synthesized and grafted to noble metallic nanowires and nanospheres. It had been shown that these kind of functional NBBs formed supramolecular gels in various solvents. Interestingly, these gels displayed stimulus-responsibility that has remained unreported with noble metal gels so far. In particular, the gels formed by Pt nanowires capped with L2 (PtNW-L2) demonstrated both thermo and shearing reversible gelation. Furthermore, aerogels can easily be pre...

Additional file 3: Table S2. Primer sequences used for donor construction and the detection of hDHFR gene identification.

Additional file 4: Table S3. Primer sequences used for Southern blot.

Additional file 8: Table S7. Gene expression of five differentially expressed genes at six time points.

Additional file 5: Table S4. Overview of the RNA-Seq data.

Additional file 2: Table S1. Primer sequences used for sgRNA synthesis.

Additional file 6: Table S5. The annotation of novel transcripts/genes.

TiO2 monoliths with hierarchical pores and three-dimensional (3-D) networks have attracted much interest due to their potential applications in photocatalysis, photovoltaic and electrical energy storage, etc. However, their present preparation procedures are complex and expensive. Herein, we report a novel, simple, scalable and low-cost strategy based on the self-assembly of a ligand attached to TiO2 nanoparticles (NPs) to prepare crystal TiO2 foam with micron channels and mesopores in its 3-D skeleton, which has been fabricated via centrifugation and subsequent freeze-drying of suspensions of TiO2 particles in benzene. Furthermore, FT-IR and SEM measurements demonstrated that the 3-D continuous skeleton and channels are formed in a synergistic way, which were facilitated by hydrogen bonding between ligands, and the size of these can be regulated by varying the centrifugal speed. The produced TiO2 foam acts as a good photocatalyst for the degradation of formaldehyde due to its good mass transport through the micron channels. This work provides a novel strategy for the synthesis of the hierarchical porous crystal TiO2 foam by ligand self-assembly and it would be widely used in preparing other crystal porous functional materials.

Rationale: de Winter electrocardiograph (ECG) pattern signifies proximal left anterior descending coronary artery (LAD) occlusion and extensive anterior myocardial infarction, and it is found in about 2% of patients with proximal LAD occlusion. However, it is often unrecognized by physicians. In this case report, we present a patient with chest pain but showing an atypical and delayed de Winter ECG pattern. Patient concerns: A previously healthy 61-year-old man attended our emergency department with chest pain radiating to the left arm and back for 4 hours, who was without serious cardiovascular risk factors. ECG at emergency department showed no significant changes. High-sensitivity cardiac troponin I (hs-cTnI) was within normal limit. Diagnosis: At 5 hours after onset, ECG showed significant upsloping ST depression at J point in precordial leads V3 to V6, slight ST elevation in aVR and depression in inferior leads, and hs-cTnI peaked at 2.610 μg/L. The diagnosis of de Winter ECG pattern was confirmed by coronary angiography with an occlusion of the proximal LAD. Interventions: A stent was implanted through percutaneous coronary intervention. Outcomes: The patient's chest pain was relieved without further increase of hs-cTnI. ECG after procedure showed ST segment back to baseline in leads V4 to V6, but persistent ST elevation in V1 to V3 with QS or Q wave. Lessons: Timely diagnosis of de Winter ECG pattern is very important, especially the atypical and delayed ECG changes. It should be treated as ST elevation myocardial infarction equivalent and deserves emergent revascularization therapy.

Arterial tissue failures lead to a number of clinical conditions that develop rapidly and unpredictably in vivo. Structural components and their interfacial mechanical strength of arterial tissue play a critical role in the process of arterail delamination. Therefore, there is a pressing need to understand the micromechanical mechanisms of arterial delamination. The objective of this study was to investigate various failure mechanisms (e.g. failure of collagen fibers) responsible for arterial interfacial delamination. In-situ tensile tests of fibers were performed on a micro-tester in the scanning electron microscope. A 3D unit cell model containing an individual fiber bridging two arterial tissue layers was constructed. An exponential cohesive zone model (CZM) was used to assess the stiffening and softening mechanical behaviors of collagen fiber bundles between the two arterial layers. An anisotropic constitutive model was implemented for characterizing the mechanical properties of the amorphous matrix which includes the fibrous cap and the underlying plaque tissue and a nonlinear elastic model was adopted for characterizing the mechanical properties of the fibers. The CZM and elastic parameter values of fibers were identified through an inverse boundary value approach that matches the load-displacement curves from simulation predictions of tensile test of collagen fibers with experimental measurements. The identified parameter values were then used as input in the 3D unit cell model, through which micromechanical factors affecting the resultant traction-separation relation for the unit cell were investigated via a parametric analysis. Results of the parametric analysis showed the applicability of the 3D unit cell model approach for evaluating the micromechanical mechanisms of arterial tissue failure processes., 33 pages, 11 figures

Hydrogen is a promising energy carrier and key agent for many industrial chemical processes1. One method for generating hydrogen sustainably is via the hydrogen evolution reaction (HER), in which electrochemical reduction of protons is mediated by an appropriate catalyst-traditionally, an expensive platinum-group metal. Scalable production requires catalyst alternatives that can lower materials or processing costs while retaining the highest possible activity. Strategies have included dilute alloying of Pt2 or employing less expensive transition metal alloys, compounds or heterostructures (e.g., NiMo, metal phosphides, pyrite sulfides, encapsulated metal nanoparticles)3-5. Recently, low-cost, layered transition-metal dichalcogenides (MX2)6 based on molybdenum and tungsten have attracted substantial interest as alternative HER catalysts7-11. These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges.8,10,11. Here we use theory to unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead derives from highly active basal-plane sites. Beyond excellent catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds. This leads to long cycle life and practical advantages for scalable processing. The resulting performance is comparable to Pt and exceeds all reported MX2 candidates.

The objective of this study is to design and optimize metamaterial, especially those functioning in the near-IR and visible light range, with alloy wire array in a dielectric material to be fabricated by thermal drawing, overcoming the long time challenge in scalable fabrication of optical metamaterials. The feature size, wire diameter, of the metamaterial made of the wire-array structure, is demanded to be less than one-fifth of the incident light wavelength. Therefore, metal wire arrays with a wire diameter and a pitch size both less than 500 nm are required. This type of metamaterial, due to its three dimensional nature, is very hard to fabricate using conventional nanofabrication technologies. Thermal drawing technology is widely considered to be the most suitable method for fabricating this type of particular structures. Yet long, continuous metal wires with a diameter less than 500 nm have not been achieved by thermal drawing, due to an unavoidable instability in molten metal, a fluid with low viscosity and a high interfacial energy with dielectric cladding materials. To tackle this problem, noble metal based alloys are proposed to replace pure noble metals because these alloys can become semi-solid with a much higher viscosity within specific temperature windows, possible allowing the thermal drawing of long continuous micro/nano metal wires. It is expected that the optical properties of the alloys would be not as satisfying as pure noble metals. However, since currently there are no other promising way to realize the novel type of metamaterial from theoretical designs, the alloy thermal drawing approach would be groundbreaking to overcome the long-standing fabrication limit.In this study, first a material selection criteria is established. The dielectric material needs to be transparent, and has low extinction coefficient and suitable refractive index. Metal has to have a large enough localized surface plasmon at the interested wavelength range. Not only optical properties should be considered. Several other aspects including phase diagram, potential reaction between the cladding material and the metal core, viscosity profile of the dielectric cladding, and oxidation under high temperature. Using this criteria, a proper combination of alloy and cladding materials could be determined for a successful thermal drawing. Then two noble metal based alloy systems, silver-gold and silver-copper alloys are selected to be embedded inside a dielectric cladding with a dielectric constant of 2.4. Matlab calculation based on Maxwell-Garnett Theory is used to theoretically predict the optical performance of alloy wire array structures with a metal filling fraction between 0.227 and 0.325. The results show that the optical metamaterial with aligned wire arrays made of these two alloy systems could yield the desired negative refractive index, as light bends 8 degrees away from the normal axis, not at the same plane as the reflected wave but at same plane as the incident wave. COMSOL simulations are also carried out and the results validate the Matlab predictions. The phenomena by the negative refractive index are visualized in the COMSOL results.One major source of defects and their effects during thermal drawing are studied as well. It is crucial to control temperature during the thermal drawing process. Yet in reality the furnace is never perfect to heat up the whole preform uniformly during drawing. Simulation of the process suggests that the temperature difference induced along the radial direction of the cylindrical preform is problematic since the viscosity of the alloys in the semi-solid state is highly temperature sensitive. Precautions should be taken to reduce the temperature difference as much as possible to prevent the failure of the metamaterial by defects such as missing wires.In summary, this study successfully conducted research in design and optimization of optical metamaterial with aligned alloy wire array fabricated by thermal drawing. It overcomes the long time fabrication limit for wire-array metamaterial functioning in near-IR and visible light region. Analytical and numerical approaches have been applied to verify that using alloy of noble metals, instead of pure metals, is highly promising to make a breakthrough into the currently stagnant fabrication of wire-array optical metamaterials. Experimental verification as well as wire arrangement optimization are recommended to be explored in the future.

Porous materials are commonly applied in sound absorption in different places. Transmission loss, one of the vital parameters determining the performance of the material, will change when the material is compressed. Usually the compression that might affect the properties to the greatest extent are normal compression and the deformation can be simplified as 1D compression model. In order to verify the prediction, some formulas taking several parameters (porosity, tortuosity, flow resistivity and characteristic lengths) into account are applied and also the Johnson et al’s model of limp structure. Dynamic density of limp model and bulk modulus are thus obtained and to get the mathematical expression of the transmission coefficient and transmission loss, acoustic equations including Euler equation are applied to the boundary conditions between the material and the fluid (air in the experiment). The numerical predictions are later compared with experimental data collected with 4-mic 2-load measurement on Kundt standard impedance tube. Both the mathematical prediction and the experimental results shows that the transmission loss would decrease under compression and increase if the material is extended.