Universal Murray's law for optimised fluid transport in synthetic structures.

Materials following Murray's law are of significant interest due to their unique porous structure and optimal mass transfer ability. However, it is challenging to construct such biomimetic hierarchical channels with perfectly cylindrical pores in synthetic systems following the existing theory. Achieving superior mass transport capacity revealed by Murray's law in nanostructured materials has thus far remained out of reach. We propose a Universal Murray's law applicable to a wide range of hierarchical structures, shapes and generalised transfer processes. We experimentally demonstrate optimal flow of various fluids in hierarchically planar and tubular graphene aerogel structures to validate the proposed law. By adjusting the macroscopic pores in such aerogel-based gas sensors, we also show a significantly improved sensor response dynamics. In this work, we provide a solid framework for designing synthetic Murray materials with arbitrarily shaped channels for superior mass transfer capabilities, with future implications in catalysis, sensing and energy applications.

Structure-Piezoelectric Property Relationships of Thin Films Composed of Electrospun Aligned Poly(vinylidene fluoride) Nanofibers.

In the past two decades, many studies on piezoelectric nanofibers (NFs) prepared from poly(vinylidene fluoride) (PVDF) and its copolymers, including single NFs, randomly oriented nonwoven mats, and aligned NFs, have been reported. However, studies on the relationships between the PVDF NF diameter, the orientation of the ß-phase crystals inside NFs, and the piezoelectric properties of the NFs are still limited. In this study, the effect of the fiber diameter on the internal molecular packing/orientation and piezoelectric properties of aligned PVDF NF thin films was investigated. Herein, piezoelectric thin films composed of densely packed, uniaxially aligned, PVDF NFs with diameters ranging from 228 to 1315 nm were prepared by means of electrospinning with a rotating collector and successive hot-pressing and poling. The effect of the diameters of PVDF NFs on their internal structures, as well as the piezoelectric properties of the thin films, was investigated. All prepared NFs mainly contained ß-phase crystals with a similar total crystallinity. The orientation of the ß-phase crystals inside the NFs increased with an increase in the fiber diameter, resulting in an improved transverse piezoelectric coefficient (d31) for the thin films. The output voltage of the prepared thin films reached a maximum of 2.7 V at 104 Hz.

All-Perfluorosulfonated-Ionomer Composite Membranes Containing Blow-Spun Fibers: Effect of a Thin Fiber Framework on Proton Conductivity and Mechanical Properties.

In this study, thin fiber composite polymer electrolyte membranes (PEMs) were prepared using short side-chain perfluorosulfonic acid (PFSA) ionomers, Aquivion, to create composite PEMs with improved proton conductivity and improved mechanical properties. PFSA thin fiber webs prepared by blow spinning and successive hot pressing were used as the porous substrate. Herein, PFSA ionomers were used for both the substrate and the matrix of the composite PEMs, and their structures, properties, and fuel cell performance were characterized. By adding the PFSA thin fiber webs to the matrix, the proton conductivity was enhanced and the mechanical properties were slightly improved. The prepared PFSA thin fiber composite PEM showed better FC performance than that of the pristine PFSA one for the high-temperature low-humidity condition in addition to the low-temperature high-humidity one. To the best of our knowledge, this is the first report on the all PFSA composite membranes containing a PFSA thin fiber framework.

Effect of the Fiber Diameter of Polyamide 11 Nanofibers on Their Internal Molecular Orientation and Properties.

Herein, the effect of the diameter of polyamide 11 nanofibers (PA11 NFs) on their internal structures as well as thermal and mechanical properties is investigated. Aligned PA11 NFs with diameters ranging from 109 to 462 nm are prepared by the single-component solvent electrospinning of different PA11/1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) solutions (4-8 wt%) and subsequently characterized. Owing to the similar hydrogen bond formation within the NFs during electrospinning, all prepared NFs have δ'-phase crystals with similar crystallinities and crystallite sizes. However, the orientation of the δ'-phase crystals is disrupted in NFs with diameters less than 200 nm, due to the rapid solidification during electrospinning. The δ'-phase crystals are the most highly oriented within NFs having a fiber diameter of ≈300 nm, and the corresponding NF sheets exhibit the highest mechanical strength. A single PA11 NF with a fiber diameter of ≈300 nm also exhibits a good piezoelectric response (piezoelectric coefficient d33 = 2.1 pm V-1 ).

A case study of pyloric stenosis caused by metastatic lobular carcinoma of breast.

Metastasis to the gastrointestinal tract is rare. A 59-year-old woman who had a history of an invasive lobular carcinoma of breast with clinical complete response visited our hospital and complained of an upper abdominal pain and distension. We performed an upper gastrointestinal endoscopy which showed only a gastric ulcer without any malignant findings. She experienced a recurrence of symptoms 2 months after this visit. An endoscopy revealed pyloric stenosis, which did not improve with balloon dilatation. We performed a gastro-jejunal and cecal-transverse colonic bypass surgery. Diffuse wall thickening of the antrum was verified during the surgery, and a biopsy sample was collected. The diagnosis of gastric metastasis from breast was confirmed since it showed the same immunohistochemistry pattern as the prior breast lesion. Pyloric stenosis has still been confirmed with an endoscopy, she has been alive with satisfactory oral food intake for >10 years.

Current-Voltage Characteristics and Solvent Dissociation of Bipolar Membranes in Organic Solvents.

In this work, the chronopotentiometric responses, pH changes, and current-voltage (I-V) characteristics of bipolar membrane (BPM)/LiCl-organic solvent systems were measured and compared with those of the BPM/LiCl-water system. Monohydric alcohols, polyhydric alcohols, and amides were used as organic solvents. The chronopotentiograms and pH changes supported that the organic solvents can dissociate into cations and anions at the BPM interface. It is found that amides cannot dissociate easily at the BPM compared with alcohols. The I-V characteristics showed that both the viscosity and acid-base property of organic solvents substantially influences the dissociation behaviors in addition to the autoprotolysis constant and relative permittivity of the solvents.

Laparoscopic repair of diaphragmatic hernia associating with radiofrequency ablation for hepatocellular carcinoma: A case report.

BACKGROUND: Radiofrequency ablation (RFA) is an effective treatment for early-stage hepatocellular carcinoma (HCC). Although RFA is a relatively safe technique compared with surgery, several complications have been reported to be following/accompanying this treatment. Delayed diaphragmatic hernia caused by RFA is rare; however, the best surgical approach for its treatment is uncertain. We present a case of laparoscopic repair of diaphragmatic hernia due to RFA. CASE SUMMARY: An 80-year-old woman with segment VIII HCC was treated twice in 5 years with RFA; 28 mo after the second RFA, the patient complained of right hypochondriac pain. Computed tomography revealed that the small intestine was incarcerated in the right thorax. The patient was diagnosed with diaphragmatic hernia and underwent laparoscopic repair by non-absorbable running sutures. The patient's postoperative course was favorable, and the patient was discharged on postoperative day 12. The diaphragmatic hernia has not recurred 24 mo after surgery. CONCLUSION: Laparoscopic treatment of iatrogenic diaphragmatic hernia is effective and minimally invasive.

Benzothiadiazole versus Thiazolobenzotriazole: A Structural Study of Electron Acceptors in Solution-Processable Organic Semiconductors.

Despite the rapid progress of organic electronics, developing high-performance n-type organic semiconductors is still challenging. Donor-acceptor (D-A) type conjugated structures have been an effective molecular design strategy to achieve chemically-stable semiconductors and the appropriate choice of the acceptor units determines the electronic properties and device performances. We have now synthesized two types of A1 -D-A2 -D-A1 type conjugated molecules, namely, NDI-BTT-NDI and NDI-TBZT-NDI, with different central acceptor units. In order to investigate the effects of the central acceptor units on the charge-transporting properties, organic field-effect transistors (OFETs) were fabricated. NDI-TBZT-NDI had shallower HOMO and deeper LUMO levels than NDI-BTT-NDI. Hence, the facilitated charge injection resulted in ambipolar transistor performances with the optimized hole and electron mobilities of 0.00134 and 0.151 cm2 V-1 s-1 , respectively. In contrast, NDI-BTT-NDI displayed only an n-channel OFET performance with the electron mobility of 0.0288 cm2 V-1 s-1 . In addition, the device based on NDI-TBZT-NDI showed a superior air stability to that based on NDI-BTT-NDI. The difference in these OFET performances was reasonably explained by the contact resistance and film morphology. Overall, this study demonstrated that the TBZ acceptor is a promising building block to create n-type organic semiconductors.

De Novo Ion-Exchange Membranes Based on Nanofibers.

The unique functions of nanofibers (NFs) are based on their nanoscale cross-section, high specific surface area, and high molecular orientation, and/or their confined polymer chains inside the fibers. The introduction of ion-exchange (IEX) groups on the surface and/or inside the NFs provides de novo ion-exchangers. In particular, the combination of large surface areas and ionizable groups in the IEX-NFs improves their performance through indices such as extremely rapid ion-exchange kinetics and high ion-exchange capacities. In reality, the membranes based on ion-exchange NFs exhibit superior properties such as high catalytic efficiency, high ion-exchange and adsorption capacities, and high ionic conductivities. The present review highlights the fundamental aspects of IEX-NFs (i.e., their unique size-dependent properties), scalable production methods, and the recent advancements in their applications in catalysis, separation/adsorption processes, and fuel cells, as well as the future perspectives and endeavors of NF-based IEMs.

Tension Sensor Based on Fluorescence Resonance Energy Transfer Reveals Fiber Diameter-Dependent Mechanical Factors During Myelination.

Oligodendrocytes (OLs) form a myelin sheath around neuronal axons to increase conduction velocity of action potential. Although both large and small diameter axons are intermingled in the central nervous system (CNS), the number of myelin wrapping is related to the axon diameter, such that the ratio of the diameter of the axon to that of the entire myelinated-axon unit is optimal for each axon, which is required for exerting higher brain functions. This indicates there are unknown axon diameter-dependent factors that control myelination. We tried to investigate physical factors to clarify the mechanisms underlying axon diameter-dependent myelination. To visualize OL-generating forces during myelination, a tension sensor based on fluorescence resonance energy transfer (FRET) was used. Polystyrene nanofibers with varying diameters similar to neuronal axons were prepared to investigate biophysical factors regulating the OL-axon interactions. We found that higher tension was generated at OL processes contacting larger diameter fibers compared with smaller diameter fibers. Additionally, OLs formed longer focal adhesions (FAs) on larger diameter axons and shorter FAs on smaller diameter axons. These results suggest that OLs respond to the fiber diameter and activate mechanotransduction initiated at FAs, which controls their cytoskeletal organization and myelin formation. This study leads to the novel and interesting idea that physical factors are involved in myelin formation in response to axon diameter.

Persistent Water Repellency of Syndiotactic Polymethylene with Perfluoroethyl Hexyloxycarbonyl Side Chains.

Polyacrylates bearing long fluoroalkyl (Rf) side chains are known to have ultralow surface energies that are appropriate for functional coating and fabric finishing. However, these long Rf chains cause health concerns because of the risk of toxic and bioaccumulative perfluoroalcanoic acid emission via oxidative degradation. This work demonstrates that incorporating a short Rf chain of perfluoroethylene at the end of the side chains of syndiotactic poly(substituted methylene) (PM) produces hydrophobicity. A contact angle of 105° of PM remains constant for more than 50 s, whereas that of the polyacrylate (PA) with the same side chain rapidly decreases from 85° to 44° over the same period. Such persistent water repellency of the PM is ascribed to a liquid crystal structure comprised the main chains arranged in a 2D hexagonal lattice and side chains that extend perpendicularly from these main chains.

Microstructure Investigation of Polymer Electrolyte Fuel Cell Catalyst Layers Containing Perfluorosulfonated Ionomer.

Perfluorosulfonated ionomers are the most successful ion-exchange membranes at an industrial scale. One recent, cutting-edge application of perfluorosulfonated ionomers is in polymer electrolyte fuel cells (PEFCs). In PEFCs, the ionomers are used as a component of the catalyst layer (CL) in addition to functioning as a proton-exchange membrane. In this study, the microstructures in the CLs of PEFCs were characterized by combined synchrotron X-ray scattering and transmission electron microscopy (TEM) analyses. The CL comprised a catalyst, a support, and an ionomer. Fractal dimensional analysis of the combined ultrasmall- and small-angle X-ray scattering profiles indicated that the carbon-black-supported Pt catalyst (Pt/CB) surface was covered with the ionomer in the CL. Anomalous X-ray scattering revealed that the Pt catalyst nanoparticles on the carbon surfaces were aggregated in the CLs. These findings are consistent with the ionomer/catalyst microstructures and ionomer coverage on the Pt/CB surface obtained from TEM observations.

Preparation of Perfluorosulfonated Ionomer Nanofibers by Solution Blow Spinning.

In this work, we report the preparation of high-purity perfluorosulfonated ionomer (Nafion) nanofibers (NFs) via solution blow spinning (SBS). Fiber formation in solution jet spinning is strongly dependent on the structure of the spinning solution. Upon adding a small amount of poly(ethyleneoxide) (PEO) as a spinning aid to Nafion dispersion, most of the highly ordered Nafion aggregate disappeared, allowing the stable production of bead-free and smooth high-purity NFs (Nafion/PEO = 99/1) by SBS. The microstructure of the blowspun Nafion NFs differed from that of electrospun NFs. In the blowspun NFs, incomplete microphase separation between hydrophilic (ionic) and hydrophobic domains was observed, but the crystallization of CF2-CF2 chains was enhanced owing to the high extensional strain rate and rapid solidification during SBS. These findings provide fundamental information for the preparation and characterization of blowspun Nafion NFs.

Absence of HOMO/LUMO Transition in Charge-Transfer Complexes of Thienoacenes.

In charge-transfer complexes, transition from the donor highest occupied molecular orbital (HOMO) to the acceptor lowest unoccupied molecular orbital (LUMO) gives the charge-transfer absorption. However, in tetracyanoquinodimethane (TCNQ) complexes of thienoacenes, comparison of the observed and calculated charge-transfer absorption demonstrates that the HOMO/LUMO transition is absent in the solid state owing to the orbital symmetry, and the first near-infrared band comes from the transition from the donor next HOMO to the TCNQ LUMO. Maps of the oscillator strength in rotated and translated molecular geometries are calculated on the basis of the time-dependent density functional theory, in which the absence of the HOMO/LUMO transition is approximately maintained even in the general molecular geometry.

Incidence, diagnosis and treatment of popliteal artery entrapment syndrome in current vascular practice in Japan.

Few data regarding popliteal artery entrapment syndrome (PAES) is available in Japan. In this study, we investigated incidence, diagnosis and treatment of PAES in current vascular practice. A retrospective analysis of all patients with PAES visiting 31 participating institutes between 2003 and 2015 was conducted. Thirty-five limbs (28 patients) were identified during the 13-year study period, and the incidence of PAES was 0.12% of all peripheral artery disease cases revascularized. Mean age was 32.0 ± 16.9 years old, and 60 and more years old was 10.7%. Also, 92.9% were male and 39.3% were athletes. Most frequent initial symptoms were intermittent claudication in 23 limbs (65.7%); 4 limbs (11.4%) had chronic limb-threatening ischemia. CT scan was most frequently (94.3%) used for the diagnostic imaging followed by MRI (45.7%) and duplex ultrasound (45.7%). Stress test such as dorsal flexion during duplex ultrasound was used only in 28.6%. Thirty-two limbs (91.4%) received surgical treatment, including 23 arterial reconstructions (71.9%); there were no major perioperative complications. All patients achieved improvement of their symptoms, and the average ankle brachial index increased from 0.69 ± 0.22 to 1.00 ± 0.14 post-surgery. The average postoperative follow-up period was 26.0 months with only one reintervention during the follow-up. In conclusion, PAES was a rare condition and traditional surgical treatment was solid. However, given a broad spectrum of clinical feature of PAES and less usage of diagnostic duplex ultrasound with stress test, there might be a miss- or delayed diagnosis of PAES even in the current vascular practice.

Inflammatory breast cancer associated with amyopathic dermatomyositis: a case report.

BACKGROUND: Dermatomyositis is associated with malignant tumors including breast cancer, and inflammatory breast cancer is considered to have a poorer prognosis than most breast cancers. CASE PRESENTATION: A 74-year-old Asian woman, developed erythema on her face, back, and the back of her hands, 3 weeks before attending our department. At the same time, she had noticed a right breast mass and redness of the skin of the breast. The clinical findings and vacuum aspiration biopsy diagnosed inflammatory breast cancer and neoadjuvant chemotherapy was performed. The mass and enlarged axillary lymph nodes had shrunk, therefore a total mastectomy was performed. The sentinel lymph node biopsy was negative. She was discharged 7 days after surgery without any complications. She has received a postoperative aromatase inhibitor and is alive without recurrence. The dermatomyositis also began to improve with the start of her chemotherapy and has not recurred since the surgery. CONCLUSIONS: Neoadjuvant chemotherapy was performed for inflammatory breast cancer with dermatomyositis, and tumor shrinkage was confirmed. A total mastectomy without axillary lymph node dissection was performed. Dermatomyositis and breast cancer have not recurred. Dermatomyositis may have been a paraneoplastic syndrome due to breast cancer.

Organic Liquid Impregnation Behavior into Nanofibrous Membranes: Quantitative Analysis of the Effects of Structural Parameters.

This paper reports the effects of structural parameters on organic liquid impregnation behavior into nanofibrous (NF) polymer membranes. The NF membranes were prepared from organic liquidphilic polymers, poly(amide-imide)s (PAIs), by electrospinning. The impregnation velocity of the organic liquid, ethylmethylcarbonate, into the as-spun PAI NF membranes with diameters ranging from 400 to 900 nm was approximately 10-20 times higher than that into commercial cellulose nonwoven membranes. Our theoretical analyses based on the Kozeny-Carman equation and multivariate statistics clearly indicate that in addition to the porosity of the membranes, the variation in fiber diameter as well as the average fiber diameter is a crucial factor for controlling the liquid impregnation behavior.

Significant Difference in Semiconducting Properties of Isomeric All-Acceptor Polymers Synthesized via Direct Arylation Polycondensation.

The direct arylation polycondensation (DArP) appeared as an efficient method for producing semiconducting polymers but often requires acceptor monomers with orienting or activating groups for the reactive carbon-hydrogen (C-H) bonds, which limits the choice of acceptor units. In this study, we describe a DArP for producing high-molecular-weight all-acceptor polymers composed of the acceptor monomers without any orienting or activating groups via a modified method using Pd/Cu co-catalysts. We thus obtained two isomeric all-acceptor polymers, P1 and P2, which have the same backbone and side-chains but different positions of the nitrogen atoms in the thiazole units. This subtle change significantly influences their optoelectronic, molecular packing, and charge-transport properties. P2 with a greater backbone torsion has favorable edge-on orientations and a high electron mobility µe of 2.55 cm2 V-1 s-1 . Moreover, P2-based transistors show an excellent shelf-storage stability in air even after the storage for 1 month.

Dual Imide-Functionalized Unit-Based Regioregular D-A1-D-A2 Polymers for Efficient Unipolar n-Channel Organic Transistors and All-Polymer Solar Cells.

The demand for the development of more promising n-type semiconducting polymers with excellent electron mobilities and air stabilities is growing fast. In this study, we designed and synthesized a series of new dual imide-functionalized derivative-based regioregular D-A1-D-A2 copolymers with different side chains (namely, PNT-R, R = 2-decyltetradecyl (DT), 2-octadecyldodecyl (OD), and 2-hexyldecyl (HD)). These new polymers PNT-R showed strong electron affinities with deep lowest unoccupied molecular orbital (LUMO) levels down to -4.01 eV, indicating that they are promising electron-transporting materials. To optimize the electron mobility, side-chain engineering was adopted. Thus, the effects of the side-chain length on their optoelectronic and charge-transport properties as well as the performances of all-polymer solar cells (all-PSCs) were systematically investigated. Shortening the side-chain length significantly expanded the absorption range, deepened the LUMO energy level, strengthened the molecular packing properties, and developed more crystalline microstructures in the solid state, as evidenced by the ultraviolet-visible absorption spectra, cyclic voltammetry, synchrotron two-dimensional grazing-incidence wide-angle X-ray scattering, and atomic force microscopy measurements. Consequently, the highest electron mobility of 1.05 cm2 V-1 s-1 was achieved in PNT-HD-based organic thin-film transistors (OTFTs). Also, PNT-R polymers were successfully applied as electron acceptors in all-PSCs. In good agreement with the OTFT results, the highest power conversion efficiency of 6.62% was obtained for the PNT-HD-blend film due to its excellent short-circuit current ( Jsc) value (12.07 mA cm-2), which was much higher than that of the PNT-DT- and PNT-OD-based all-PSCs (7.67 and 10.19 mA cm-2, respectively). By further investigating the dependence of the Jsc and open-circuit voltage ( Voc) on the illuminated light intensity ( P), the high Jsc value of the PNT-HD-based device was found to originate from its highly suppressed mono- and bimolecular recombination as well as efficient exciton dissociation and charge transfer at the donor-acceptor interfaces. Overall, this study provides insights into the naphthalenediimide-based regioregular D-A1-D-A2 copolymers used in all-PSCs and offers important design guidelines for future development of n-type semiconducting polymers.