bluuebunny/crossref_metadata_2025 huggingface dataset:
TMS as a pharmacodynamic indicator of cortical activity of a novel anti‐epileptic drug, XEN1101
Authors: Premoli Isabella , Rossini Pierre G. , Goldberg Paul Y. , Posadas Kristina , Green Louise , Yogo Noah , Pimstone Simon , Abela Eugenio , Beatch Gregory N. , Richardson Mark P.
Published: October 2019

Objective

Transcranial magnetic stimulation (TMS) produces characteristic deflections in the EEG signal named TMS‐evoked EEG potentials (TEPs), which can be used to assess drug effects on cortical excitability. TMS can also be used to determine the resting motor threshold (RMT) for eliciting a minimal muscle response, as a biomarker of corticospinal excitability. XEN1101 is a novel potassium channel opener undergoing clinical development for treatment of epilepsy. We used TEPs and RMT to measure the effects of XEN1101 in the human brain, to provide evidence that XEN1101 alters cortical excitability at doses that might be used in future clinical trials.

Methods

TMS measurements were incorporated in this Phase I clinical trial to evaluate the extent to which XEN1101 modulates TMS parameters of cortical and corticospinal excitability. TEPs and RMT were collected before and at 2‐, 4‐, and 6‐hours post drug intake in a double‐blind, placebo‐controlled, randomized, two‐period crossover study of 20 healthy male volunteers.

Results

Consistent with previous TMS investigations of antiepileptic drugs (AEDs) targeting ion channels, the amplitude of TEPs occurring at early (15–55 msec after TMS) and at late (150–250 msec after TMS) latencies were significantly suppressed from baseline by 20 mg of XEN1101. Furthermore, the RMT showed a significant time‐dependent increase that correlated with the XEN1101 plasma concentration.

Interpretation

Changes from baseline in TMS measures provided evidence that 20 mg of XEN1101 suppressed cortical and corticospinal excitability, consistent with the effects of other AEDs. These results support the implementation of TMS as a tool to inform early‐stage clinical trials.
Brain lesion distribution criteria distinguish demyelinating diseases in China
Authors: Cai Meng‐Ting , Zhang Yin‐Xi , Zheng Yang , Yang Fan , Fang Wei , Shen Chun‐Hong , Ding Mei‐Ping
Published: October 2019

Objective

To verify the utility of brain lesion distribution criteria in distinguishing multiple sclerosis (MS) from aquaporin‐4 (AQP4)‐immunoglobulin G (IgG)‐positive/‐negative neuromyelitis optica spectrum disorder (NMOSD) and myelin oligodendrocyte glycoprotein IgG‐associated encephalomyelitis (MOG‐EM) in the Chinese population.

Methods

A total of 253 patients with MS (80), NMOSD (129 AQP4‐IgG positive, 34 AQP4‐IgG negative), and MOG‐EM (10) were enrolled. Anonymized magnetic resonance imaging results were scored on the previous reported criteria of “at least one lesion adjacent to the body of the lateral ventricle and in the inferior temporal lobe; or the presence of a subcortical U‐fiber lesion; or a Dawson’s finger‐type lesion.” Chi‐squared test (or Fisher’s exact test) was used to analyze the data.

Results

The distribution criteria were able to distinguish MS with a same sensitivity of 93.8% from all type of NMOSD and MOG‐EM, with a specificity of 89.7% from the whole NMOSD cohort, 89.1% from AQP4‐IgG‐positive NMOSD 91.2% from AQP4‐IgG‐negative NMOSD, and 70.0% from MOG‐EM. Dawson's finger‐type lesion was the most sensitive and specific feature, whereas the U‐fiber lesion was the least.

Conclusion

The brain lesion distribution criteria were helpful in distinguishing MS from NMOSD and MOG‐EM in the Chinese population. Dawson's finger‐type lesion was highly suggestive of MS.
A Simple Way to Simultaneously Release the Interface Stress and Realize the Inner Encapsulation for Highly Efficient and Stable Perovskite Solar Cells
Authors: Wu Jionghua , Cui Yuqi , Yu Bingchen , Liu Kuan , Li Yiming , Li Hongshi , Shi Jiangjian , Wu Huijue , Luo Yanhong , Li Dongmei , Meng Qingbo
Published: October 2019

The mixed halide perovskites have become famous for their outstanding photoelectric conversion efficiency among new‐generation solar cells. Unfortunately, for perovskites, little effort is focused on stress engineering, which should be emphasized for highly efficient solar cells like GaAs. Herein, polystyrene (PS) is introduced into the perovskite solar cells as the buffer layer between the SnO2 and perovskite, which can release the residual stress in the perovskite during annealing because of its low glass transition temperature. The stress‐free perovskite has less recombination, larger lattices, and a lower ion migration tendency, which significantly improves the cell's efficiency and device stability. Furthermore, the so‐called inner‐encapsulated perovskite solar cells are fabricated with another PS capping layer on the top of perovskite. As high as a 21.89% photoelectric conversion efficiency (PCE) with a steady‐state PCE of 21.5% is achieved, suggesting that the stress‐free cell can retain almost 97% of its initial efficiency after 5 days of “day cycle” stability testing.
Precisely Controlled Microsphere Design via Visible‐Light Cross‐Linking of Functional Prepolymers
Authors: Hooker Jordan P. , Feist Florian , Delafresnaye Laura , Barner Leonie , Barner‐Kowollik Christopher
Published: October 2019

A new strategy for particle synthesis is enabled by utilizing modern synthetic, polymer, and photochemical techniques to facilitate the synthesis of highly narrow–disperse multifunctional microspheres from visible‐light induced crosslinking of prepolymers in both a single and dual polymer system. The approach requires no stabilizers, bases, or initiators, and proceeds at ambient temperature to yield microspheres with a tunable size range (0.25–5 µm) in less than 4 h, depending largely on solvent composition, but also polymer concentration (2–10 mg mL−1), ratio, and irradiation intensity (3–20 W). Critically, the visible‐light induced dimerization reaction exploited herein enables simple functional particle syntheses via a single polymer system. Underpinned by an in‐depth kinetic analysis of the particle formation as well as a detailed small molecule study, the mechanism for particle formation is also elucidated. Importantly, inherent advantages of the system are exploited for surface functionalization of residual acrylate and hydroxyl groups (generating inherently fluorescent particles).
Nanowire Genome: A Magic Toolbox for 1D Nanostructures
Authors: He Zhen , Yang Yuan , Liang Hai‐Wei , Liu Jian‐Wei , Yu Shu‐Hong
Published: October 2019

1D nanomaterials with high aspect ratio, i.e., nanowires and nanotubes, have inspired considerable research interest thanks to the fact that exotic physical and chemical properties emerge as their diameters approach or fall into certain length scales, such as the wavelength of light, the mean free path of phonons, the exciton Bohr radius, the critical size of magnetic domains, and the exciton diffusion length. On the basis of their components, aspect ratio, and properties, there may be imperceptible connections among hundreds of nanowires prepared by different strategies. Inspired by the heredity system in life, a new concept termed the “nanowire genome” is introduced here to clarify the relationships between hundreds of nanowires reported previously. As such, this approach will not only improve the tools incorporating the prior nanowires but also help to precisely synthesize new nanowires and even assist in the prediction on the properties of nanowires. Although the road from start‐ups to maturity is long and fraught with challenges, the genetical syntheses of more than 200 kinds of nanostructures stemming from three mother nanowires (Te, Ag, and Cu) are summarized here to demonstrate the nanowire genome as a versatile toolbox. A summary and outlook on future challenges in this field are also presented.
Rekindling RNAi Therapy: Materials Design Requirements for In Vivo siRNA Delivery
Authors: Kim Byungji , Park Ji‐Ho , Sailor Michael J.
Published: October 2019

With the recent FDA approval of the first siRNA‐derived therapeutic, RNA interference (RNAi)‐mediated gene therapy is undergoing a transition from research to the clinical space. The primary obstacle to realization of RNAi therapy has been the delivery of oligonucleotide payloads. Therefore, the main aims is to identify and describe key design features needed for nanoscale vehicles to achieve effective delivery of siRNA‐mediated gene silencing agents in vivo. The problem is broken into three elements: 1) protection of siRNA from degradation and clearance; 2) selective homing to target cell types; and 3) cytoplasmic release of the siRNA payload by escaping or bypassing endocytic uptake. The in vitro and in vivo gene silencing efficiency values that have been reported in publications over the past decade are quantitatively summarized by material type (lipid, polymer, metal, mesoporous silica, and porous silicon), and the overall trends in research publication and in clinical translation are discussed to reflect on the direction of the RNAi therapeutics field.
Revealing the Cooperative Relationship between Spin, Energy, and Polarization Parameters toward Developing High‐Efficiency Exciplex Light‐Emitting Diodes
Authors: Wang Miaosheng , Huang Yi‐Hsuan , Lin Kai‐Siang , Yeh Tzu‐Hung , Duan Jiashun , Ko Tzu‐Yu , Liu Shun‐Wei , Wong Ken‐Tsung , Hu Bin
Published: October 2019

Experimental studies to reveal the cooperative relationship between spin, energy, and polarization through intermolecular charge‐transfer dipoles to harvest nonradiative triplets into radiative singlets in exciplex light‐emitting diodes are reported. Magneto‐photoluminescence studies reveal that the triplet‐to‐singlet conversion in exciplexes involves an artificially generated spin‐orbital coupling (SOC). The photoinduced electron parametric resonance measurements indicate that the intermolecular charge‐transfer occurs with forming electric dipoles (D+•→A−•), providing the ionic polarization to generate SOC in exciplexes. By having different singlet‐triplet energy differences (ΔEST) in 9,9′‐diphenyl‐9H,9′H‐3,3′‐bicarbazole (BCzPh):3′,3′″,3′″″‐(1,3,5‐triazine‐2,4,6‐triyl)tris(([1,1′‐biphenyl]‐3‐carbonitrile)) (CN‐T2T) (ΔEST = 30 meV) and BCzPh:bis‐4,6‐(3,5‐di‐3‐pyridylphenyl)‐2‐methyl‐pyrimidine (B3PYMPM) (ΔEST = 130 meV) exciplexes, the SOC generated by the intermolecular charge‐transfer states shows large and small values (reflected by different internal magnetic parameters: 274 vs 17 mT) with high and low external quantum efficiency maximum, EQEmax (21.05% vs 4.89%), respectively. To further explore the cooperative relationship of spin, energy, and polarization parameters, different photoluminescence wavelengths are selected to concurrently change SOC, ΔEST, and polarization while monitoring delayed fluorescence. When the electron clouds become more deformed at a longer emitting wavelength due to reduced dipole (D+•→A−•) size, enhanced SOC, increased orbital polarization, and decreased ΔEST can simultaneously occur to cooperatively operate the triplet‐to‐singlet conversion.
Nanomedicine‐Based Immunotherapy for the Treatment of Cancer Metastasis
Authors: Zhang Pengcheng , Zhai Yihui , Cai Ying , Zhao Yuliang , Li Yaping
Published: October 2019

Metastasis is the leading cause of cancer‐associated death, with poor prognosis even after extensive treatment. The dormancy of metastatic cancer cells during dissemination or after colony formation is one major reason for treatment failure, as most drugs target cells of active proliferation. Immunotherapy has shown great potential in cancer therapy because the activity of effector cells is less affected by the metabolic status of cancer cells. In addition, metastatic cells out of immunosuppressive tumor microenvironment (TME) are more susceptible to immune clearance, although these cells can achieve immune surveillance evasion via strategies such as platelet and macrophage recruitment. Since nanomaterials themselves or their carried drugs have the capability to modulate the immune system, a great amount of focus has been placed on nanomedicine strategies that leverage immune cells participating the metastatic cascade. These nanomedicines successfully inhibit the tumor metastasis and prolong the survival of model animals. Immune cells that are involved in the metastasis cascade are first summarized and then recent and inspiring strategies and nanomaterials in this growing field are highlighted.
Engineered Fibrillar Fibronectin Networks as Three‐Dimensional Tissue Scaffolds
Authors: Jordahl Stacy , Solorio Luis , Neale Dylan B. , McDermott Sean , Jordahl Jacob H. , Fox Alexandra , Dunlay Christopher , Xiao Annie , Brown Martha , Wicha Max , Luker Gary D. , Lahann Joerg
Published: October 2019

Extracellular matrix (ECM) proteins, and most prominently, fibronectin (Fn), are routinely used in the form of adsorbed pre‐coatings in an attempt to create a cell‐supporting environment in both two‐ and three‐dimensional cell culture systems. However, these protein coatings are typically deposited in a form which is structurally and functionally distinct from the ECM‐constituting fibrillar protein networks naturally deposited by cells. Here, the cell‐free and scalable synthesis of freely suspended and mechanically robust three‐dimensional (3D) networks of fibrillar fibronectin (fFn) supported by tessellated polymer scaffolds is reported. Hydrodynamically induced Fn fibrillogenesis at the three‐phase contact line between air, an Fn solution, and a tessellated scaffold microstructure yields extended protein networks. Importantly, engineered fFn networks promote cell invasion and proliferation, enable in vitro expansion of primary cancer cells, and induce an epithelial‐to‐mesenchymal transition in cancer cells. Engineered fFn networks support the formation of multicellular cancer structures cells from plural effusions of cancer patients. With further work, engineered fFn networks can have a transformative impact on fundamental cell studies, precision medicine, pharmaceutical testing, and pre‐clinical diagnostics.
Plasmonic Pt Superstructures with Boosted Near‐Infrared Absorption and Photothermal Conversion Efficiency in the Second Biowindow for Cancer Therapy
Authors: Wang Qishun , Wang Huan , Yang Yang , Jin Longhai , Liu Yang , Wang Ying , Yan Xiangyu , Xu Jing , Gao Ruoqian , Lei Pengpeng , Zhu Junjie , Wang Yinghui , Song Shuyan , Zhang Hongjie
Published: October 2019

Photothermal therapy triggered by near‐infrared light in the second biowindow (NIR‐II) has attracted extensive interest owing to its deeper penetration depth of biological tissue, lower photon scattering, and higher maximum permissible exposure. In spite of noble metals showing great potential as the photothermal agents due to the tunable localized surface plasmon resonance, the biological applications of platinum are rarely explored. Herein, a monocomponent hollow Pt nanoframe (“Pt Spirals”), whose superstructure is assembled with three levels (3D frame, 2D layered shells, and 1D nanowires), is reported. Pt Spirals exhibit outstanding photothermal conversion efficiency (52.5%) and molar extinction coefficients (228.7 m2 mol−1) in NIR‐II, which are much higher than those of solid Pt cubes. Simulations indicate that the unique superstructure can be a significant cause for improving both adsorption and the photothermal effect simultaneously in NIR‐II. The excellent photothermal effect is achieved and subsequently verified in in vitro and in vivo experiments, along with superb heat‐resistance properties, excellent photostability, and a prominent effect on computed tomography (CT) imaging, demonstrating that Pt Spirals are promising as effective theranostic platforms for CT imaging‐guided photothermal therapy.
Room Temperature Detection of NO2 at ppb Level and Full Recovery by Effective Modulation of the Barrier Height for Titanium Oxide/Graphene Schottky Heterojunctions
Authors: Falak Attia , Tian Yi , Yan Lanqin , Zhao Min , Zhang Xianfeng , Dong Fengliang , Chen Peipei , Wang Hanfu , Chu Weiguo
Published: October 2019

Simultaneous achievement of high response, high sensitivity, low detection limit, and full recovery at room temperature (RT) is quite challenging for gas sensors. Herein, ultrathin titanium oxide/graphene Schottky heterojunction sensors (SHS) are fabricated with varying junction areas. Increasing junction area favors the sensing performance. A change of 11.822 meV in Schottky barrier height (SBH) is induced by 3 ppm NO2 exposure, accompanied by a change of −36.54% in current, ≈18 and 36 times that for bare titanium oxide and graphene sensors at RT, respectively. A high sensitivity of 10.430% ppm−1, low detection limit of 28 ppb, and complete recovery for 100 ppb NO2 are simultaneously achieved at RT. 100 ppm NH3 can be detected with full recovery as well. The superior performance of SHS is predominantly attributed to the effective modulation of SBH (exponential change in current) by gas adsorption and the charge transfer to interfaces enhanced by the presence of ultrathin continuous oxide layers. The sensing mechanism can be understood via energy band diagrams. This study proposes an idea of designing SHS with ultrathin n‐metal oxides and p‐graphene to simultaneously achieve high sensitivity, low detection limit, and full recovery for NO2 and other gases at RT.
Rationalization of Diversity in Spinel MgFe2O4 Surfaces
Authors: Guo Haoyue , Marschilok Amy C. , Takeuchi Kenneth J. , Takeuchi Esther S. , Liu Ping
Published: October 2019

Spinel magnesium ferrite (MgFe2O4) is a prospective anode material for lithium ion batteries (LIBs). Here, using density functional theory the first systematic study of diverse MgFe2O4 surfaces is reported in three types of spinel structures: normal, mixed, inverse, which can have significant impact on the initial lithiation. The results show that the faceting and therefore the shape of MgFe2O4 crystals strongly depend on the bulk structures. Upon going from normal, mixed to inverse spinel, the energetically preferred facets of MgFe2O4 vary from the combination of (1 0 0) and (3 1 1), soly {1 0 0} to a combination of (1 0 0), (0 0 1), (1 1 1), and (3 1 1), respectively, depending on the distribution of Mg2+ in the spinel structure. However, there is one common descriptor to the stable surfaces among all three MgFe2O4 systems: high density of Mg2+ exposed to the surface. This study rationalizes the essential effect of the substitution of Zn2+ for Mg2+ in ferrites and provides new insights on how to control the shape of ferrite materials and thus tune the performances of LIBs.
Customizable Nonplanar Printing of Lithium‐Ion Batteries
Authors: Yu Xiaowei , Liu Yangtao , Pham Hiep , Sarkar Susmita , Ludwig Brandon , Chen I‐Meng , Everhart Wesley , Park Jonghyun , Wang Yan , Pan Heng
Published: October 2019

Lithium‐ion batteries (LIBs) are widely used in consumer electronics due to their rechargeability and high energy density. Commercial LIBs are fabricated in fixed geometries such as cylinder, coin, and pouch. However, for specialized applications such as wearable electronics and on‐device power systems, customizable LIBs with arbitrary geometry on three‐dimensional (3D) structures need to be developed. For this purpose, aerosol printing is uniquely suitable due to its flexible working distance, allowing deposition on nonplanar substrates with multiscale surface topologies. Aerosol printing of LiFePO4 cathodes and Li4Ti5O12 anodes for LIBs is presented. Electrodes with an arbitrary geometry, tailorable thickness and on nonplanar substrates can be realized. The highest areal capacity achieved is ≈7.1 mAh cm−2, which is at least twice that of conventional electrodes. Furthermore, to package the printed electrodes, 3D enclosures are fabricated via fused deposition modeling of polyvinylidene fluoride. The printed electrodes packaged in 3D enclosures exhibit 78.4% capacity retention after 30 cycles. With the two additive manufacturing processes, customizable LIBs on targeted objects can be realized. A nonplanar LIB conformably covering the edge of a block with specific capacity of 135 mAh g−1 is demonstrated.
Ultrastretchable Hybrid Electrodes of Silver Nanowires and Multiwalled Carbon Nanotubes Realized by Capillary‐Force‐Induced Welding
Authors: Wang Yangyang , Zhang Liang , Wang Dongrui
Published: October 2019

The paucity of soft materials with both high electrical conductivity and the capability to maintain their superior conductance under large and complex mechanical deformations is a crucial barrier hindering the development of stretchable electronics toward practical applications. A type of ultrastretchable hybrid electrodes composed of silver nanowires (AgNWs) and multiwalled carbon nanotubes (CNTs) are reported, which show sheet resistance as low as 7.1 Ω sq.−1 and a small resistance increase of only 42% when uniaxially stretched to a strain of 580%. The hybrid electrodes can also withstand equibiaxial stretching, showing a resistance increase of 100% at a strain of 200%, and survive at least 1500 stretching/releasing cycles with negligible resistance change. The key to such performance is welding the loosely stacked AgNWs and CNTs into one integrated network with the aid of capillary force. When coated onto both sides of a polyacrylate‐based elastomer, VHB, the AgNW/CNT hybrid films can serve as excellent compliant electrodes of a dielectric elastomer actuator, causing a maximum actuated areal strain of 190% with a relatively low starting electric field of 11.6 V µm−1. These ultrastretchable AgNW/CNT electrodes will pave the way for the rapid development of high‐end stretchable electronics.
Intermetallic PtBi Nanoplates Boost Oxygen Reduction Catalysis with Superior Tolerance over Chemical Fuels
Authors: Feng Yonggang , Shao Qi , Lv Fan , Bu Lingzheng , Guo Jun , Guo Shaojun , Huang Xiaoqing
Published: October 2019

The crossover issue of small‐molecule organic fuels usually makes the Pt‐based nanocatalysts exhibit low efficiency, and poor tolerance and durability under the practical fuel cell operating conditions. Here, a new approach to prepare a class of intermetallic hexagonal PtBi nanoplates with superior tolerance over chemical fuels for boosting oxygen reduction catalysis is reported. The time‐dependent morphology studies reveal that the well‐defined hexagonal PtBi nanoplates are transformed from a new reaction immediate (triangular/truncated triangular bismuth oxides nanoplates). Different from conventional Pt‐based catalysts, the hexagonal PtBi nanoplates exhibit much improved tolerance over CH3OH, HCOOH, and CO. X‐ray photoelectron spectroscopy results reveal that the charge displacement resulting from Pt–Bi bonding is the main factor in enhancing the tolerance. The PtBi nanoplates also exhibit much higher ORR activity than all the reported PtBi nanoparticles. Considering their exceptional antipoisoning ability and high activity, these hexagonal nanoplates show great potential in the development of commercial fuel cells.
CD4+ T Cell‐Released Extracellular Vesicles Potentiate the Efficacy of the HBsAg Vaccine by Enhancing B Cell Responses
Authors: Lu Jian , Wu Jing , Xie Feiting , Tian Jie , Tang Xinyi , Guo Hongye , Ma Jie , Xu Ping , Mao Lingxiang , Xu Huaxi , Wang Shengjun
Published: October 2019

T cells secrete bioactive extracellular vesicles (EVs), but the potential biological effects of CD4+ T cell EVs are not clear. The main purpose of this study is to investigate the effects of CD4+ T cell–derived EVs on B cell responses and examine their role in antigen‐mediated humoral immune responses. In this study, CD4+ T cell EVs are purified from activated CD4+ T cells in vitro. After immunization with the Hepatitis B surface antigen (HBsAg) vaccine, CD4+ T cell EVs‐treated mice show stronger humoral immune responses, which is indicated by a greater Hepatitis B surface antibody (HBsAb) level in serum and a greater proportion of plasma cells in bone marrow. In addition, it is found that EVs released from activated CD4+ T cells play an important role in B cell responses in vitro, which significantly promote B cell activation, proliferation, and antibody production. Interestingly, antigen‐specific CD4+ T cell EVs are found to be more efficient than control EVs in enhancing B cell responses. Furthermore, it is shown that CD40 ligand (CD40L) is involved in CD4+ T cell EVs‐mediated B cell responses. Overall, the results have demonstrated that CD4+ T cell EVs enhance B cell responses and serve as a novel immunomodulator to promote antigen‐specific humoral immune responses.
Nonleaching Antibacterial Concept Demonstrated by In Situ Construction of 2D Nanoflakes on Magnesium
Authors: Wang Guomin , Jiang Wenjuan , Mo Shi , Xie Lingxia , Liao Qing , Hu Liangsheng , Ruan Qingdong , Tang Kaiwei , Mehrjou Babak , Liu Mengting , Tong Liping , Wang Huaiyu , Zhuang Jie , Wu Guosong , Chu Paul K.
Published: October 2019

In bone implants, antibacterial biomaterials with nonleaching surfaces are superior to ones based on abrupt release because systemic side effects arising from the latter can be avoided. In this work, a nonleaching antibacterial concept is demonstrated by fabricating 2D nanoflakes in situ on magnesium (Mg). Different from the conventional antibacterial mechanisms that depend on Mg2+ release and pH increase, the nanoflakes exert mechanical tension onto the bacteria membranes to destroy microorganisms on contact and produce intracellular stress via physical interactions, which is also revealed by computational simulations. Moreover, the nanoflake layer decelerates the corrosion process resulting in mitigated Mg2+ release, weaker alkalinity in the vicinity, and less hydrogen evolution, in turn inducing less inflammatory reactions and ensuring the biocompatibility as confirmed by the in vivo study. In this way, bacteria are killed by a mechanical process causing very little side effects. This work provides information and insights pertaining to the design of multifunctional biomaterials.
Enhanced Thermoelectric and Mechanical Properties in Yb0.3Co4Sb12 with In Situ Formed CoSi Nanoprecipitates
Authors: Qin Dandan , Wu Haijun , Cai Songting , Zhu Jianbo , Cui Bo , Yin Li , Qin Haixu , Shi Wenjing , Zhang Yang , Zhang Qian , Liu Weishu , Cao Jian , Pennycook Stephen J. , Cai Wei , Sui Jiehe
Published: October 2019

Filled Skutterudites are one group of the most promising thermoelectric materials in real power generation applications. Herein, homogeneously dispersed multiscale CoSi nanostructures are successfully embedded into grains of the classic skutterudite system, Yb0.3Co4Sb12, by the in situ precipitation method. Such nanoprecipitates contribute much to the synergistic enhancement of thermoelectric and mechanical properties. On one hand, by the fine deployment of multiscale CoSi nanoparticles, the lattice thermal conductivity is significantly depressed almost to the theoretical limit because of the disrupted propagation of the heat‐carrying phonons at phase boundaries. On the other hand, low‐energy electrons are effectively screened due to the energy filtering effect by the interfacial potential barrier between the CoSi nanoprecipitate and the matrix, resulting in an enhanced power factor. Taken together, an enhanced peak ZT value of ≈1.5 at 873 K for the Yb0.3Co4Sb12/0.05CoSi composite is obtained with a high average ZT ≈0.95 between 300 and 873 K through decoupling the electrical and thermal transport parameters. Moreover, such a microstructure with multiscale CoSi nanoparticles shows significantly improved mechanical properties owing to particle hardening, making it more competitive for practical applications.
Fifty‐year history of biliary surgery
Authors: Nagino Masato
Published: October 2019

There has been enormous progress in the surgical treatment of biliary tract cancers in the past 50 years. In preoperative management, biliary drainage methods have changed from percutaneous transhepatic biliary drainage to endoscopic nasobiliary drainage, while the advent of multidetector‐row computed tomography in imaging diagnostics now enables visualization of three‐dimensional anatomy, extent of cancer progression, and hepatic segment volume. Portal vein embolization has also greatly improved the safety of extended hepatectomy, and indication of extended hepatectomy can now be objectively determined with a combination of the indocyanine green test and computed tomography volumetry. In terms of surgery, combined resection and reconstruction of the portal vein and/or hepatic artery can now be safely carried out at specialized centers. Further, long‐term survival can be attained with combined vascular resection if R0 resection can be achieved, even in locally advanced cancer. Hepatopancreatoduodenectomy, combined major hepatectomy with pancreatoduodenectomy, should be aggressively carried out for laterally advanced cholangiocarcinoma, whereas its indication for advanced gallbladder cancer should be carefully evaluated. Japanese surgeons have made a significant contribution to the progression of extended surgeries such as combined vascular resection and hepatopancreatoduodenectomy for biliary tract cancer.
Emotional functioning among children with neurofibromatosis type 1 or Noonan syndrome
Authors: McNeill Alana M. , Hudock Rebekah L. , Foy Allison M. H. , Shanley Ryan , Semrud‐Clikeman Margaret , Pierpont Mary Ella , Berry Susan A. , Sommer Katherine , Moertel Christopher L. , Pierpont Elizabeth I.
Published: October 2019

While neurofibromatosis type 1 (NF1) and Noonan syndrome (NS) are clinically distinct genetic syndromes, they have overlapping features because they are caused by pathogenic variants in genes encoding molecules within the Ras‐mitogen‐activated protein kinase signaling pathway. Increased risk for emotional and behavioral challenges has been reported in both children and adults with these syndromes. The current study examined parent‐report and self‐report measures of emotional functioning among children with NF1 and NS as compared to their unaffected siblings. Parents and children with NS (n = 39), NF1 (n = 39), and their siblings without a genetic condition (n = 32) completed well‐validated clinical symptom rating scales. Results from parent questionnaires indicated greater symptomatology on scales measuring internalizing behaviors and symptoms of attention deficit hyperactivity disorder (ADHD) in both syndrome groups as compared with unaffected children. Frequency and severity of emotional and behavioral symptoms were remarkably similar across the two clinical groups. Symptoms of depression and anxiety were higher in children who were also rated as meeting symptom criteria for ADHD. While self‐report ratings by children generally correlated with parent ratings, symptom severity was less pronounced. Among unaffected siblings, parent ratings indicated higher than expected levels of anxiety. Study findings may assist with guiding family‐based interventions to address emotional challenges.
Phenotypic expansion of POFUT1 loss of function mutations in a disorder featuring segmental dyspigmentation with eczematous and folliculo‐centric lesions
Authors: Atzmony Lihi , Zaki Theodore D. , Antaya Richard J. , Choate Keith A.
Published: October 2019

Appearance of mosaic disorders in thin Blaschko lines suggests that somatic mutations in keratinocyte precursors underlie their pathogenesis. Germline heterozygous mutations in POFUT1 gene cause Dowling–Degos disease (DDD), a skin disease that features flexural reticulated hyperpigmentation and follicular‐based lesions. POFUT1 mosaicism has not been described to date. Here, we describe a 9‐year‐old female with segmental hyper‐ and hypopigmented patches with overlying eczematous plaques and follicular papules. Employing paired whole exome sequencing of saliva and keratinocytes isolated from affected skin, we found a novel germline heterozygous POFUT1 deletion causing frameshift and premature codon termination and somatic copy‐neutral loss of heterozygosity on chromosome 20 encompassing POFUT1. Expression levels of POFUT1 as well as other key regulators of the notch signaling pathway—NOTCH1, NOTCH2, and HES1—were reduced in affected keratinocytes compared with normal keratinocytes. Our findings provide the first evidence of POFUT1 postzygotic mutation and a phenotypic expansion of POFUT1 loss of function mutations. We show that a recessive loss of function mutation in POFUT1 produces a distinct clinical presentation with features (e.g., dermatitis) that are absent in the generalized form of DDD. This study demonstrates how analysis of mosaic disorders can reveal unexpected phenotypes for known genes.
Modifications of Electron States, Magnetization, and Persistent Current in a Quantum Dot by Controlled Curvature
Authors: Pereira Luís Fernando C. , Andrade Fabiano M. , Filgueiras Cleverson , Silva Edilberto O.
Published: October 2019

The thin‐layer quantization procedure is used to study the physical implications due to curvature effects on a quantum dot in the presence of an external magnetic field. Among the various physical implications due to the curvature of the system, the absence of the state is the most relevant one. This absence affects the Fermi energy and consequently the thermodynamic properties of the system. In the absence of magnetic fields, it is verified that the rotational symmetry in the lateral confinement is preserved in the electronic states of the system and its degeneracy concerning the harmonicity of the confining potential is broken. In the presence of a magnetic field, however, the energies of the electronic states in a quantum dot with curvature are greater than those obtained for a quantum dot in a flat space, and the profile of degeneracy changes when the field is varied. It is shown that the curvature of the surface modifies the number of subbands occupied in the Fermi energy. In the study of both magnetization and persistent currents, it is observed that Aharonov–Bohm‐type oscillations are present, whereas de Haas–van Alphen‐type oscillations are not well defined.
Coordinative Chain Transfer Polymerization of Butadiene with Functionalized Aluminum Reagents
Authors: Göttker‐Schnetmann Inigo , Kenyon Philip , Mecking Stefan
Published: October 2019

Functionalized aluminum alkyls enable effective coordinative chain transfer polymerization with selective chain initiation by the functionalized alkyl. (ω‐Aminoalkyl)diisobutylaluminum reagents (12 examples studied) obtained by hydroalumination of α‐amino‐ω‐enes with diisobutylaluminum hydride promote the stereoselective catalytic chain growth of butadiene on aluminum in the presence of Nd(versatate)3, Cp*2Nd(allyl), or Cp*2Gd(allyl) precatalysts and [PhNMe2H+]/[B(C6F5)4−]. Carbazolyl‐ and indolylaluminum reagents result in efficient molecular weight control and chain initiation by the aminoalkyl rather than the isobutyl substituent bound to aluminum. As confirmed for (3‐(9H‐carbazol‐9‐yl)propyl)‐initiated polybutadiene (PBD), for example, by deuterium quenching studies, polymer chain transfer by β‐hydride transfer is negligible in comparison to back‐transfer to aluminum.
Effiziente organokatalytische Dehydrierung von Amminboran
Authors: Hasenbeck Max , Becker Jonathan , Gellrich Urs
Published: October 2019

Wir berichten die effiziente Dehydrierung von Amminboran durch sterisch anspruchsvolle Pyridone als Organokatalysatoren. Mit 6‐tert‐Butylthiopyridon wurde eine Wechselzahl (Turnover Frequency, TOF) von 88 h−1 erreicht. Experimentelle mechanistische Untersuchungen, gestützt durch DLPNO‐CCSD(T) Rechnungen, deuten auf eine Protonierung der B‐H‐Bindungen durch den in der Mercaptopyridinform vorliegenden Katalysator als ersten Schritt des Katalysezyklus hin. Das durch diese initiale Protonierung gebildete Intermediat wurde NMR‐spektroskopisch detektiert und die Molekülstruktur einer Surrogat‐Verbindung mittels Einkristall‐Röntgendiffraktometrie ermittelt. Ein intramolekularer Protonentransfer von der NH3‐Gruppe zu dem Pyridinring in diesem Intermediat und das gleichzeitige Brechen der S‐B‐Bindung regeneriert das Thiopyridon und schließt somit einen katalytischen Zyklus. Dieser Schritt kann als eine anorganische Retro‐En‐Reaktion beschrieben werden.
Katalytische Difunktionalisierung von nichtaktivierten Alkenen mit reaktionsträgem Hexamethyldisilan durch Neubildung von Silyliumionen
Authors: Wu Qian , Roy Avijit , Irran Elisabeth , Qu Zheng‐Wang , Grimme Stefan , Klare Hendrik F. T. , Oestreich Martin
Published: October 2019

Es wird über eine metallfreie, intermolekulare syn‐Addition von Hexamethyldisilan an einfache Alkene berichtet. Der Katalysezyklus wird durch die Übertragung einer Methylgruppe des Disilans auf eine Silyliumion‐artige Zwischenstufe eingeleitet und aufrechterhalten, was der (Neu)bildung des Silyliumion‐Katalysators gleichkommt. Das Hauptmerkmal der Reaktionssequenz ist die Spaltung der Si‐Si‐Bindung im Zuge einer 1,3‐Silylwanderung von Silicium nach Kohlenstoff. Eine zentrale Zwischenstufe der Katalyse wurde durch Röntgenbeugung strukturell charakterisiert, und der berechnete Reaktionsmechanismus steht in vollständigem Einklang mit den experimentellen Befunden.
Festkörper‐ und Gasphasenstrukturen sowie energetische Eigenschaften des gefährlichen Methyl‐ und Fluormethylnitrats
Authors: Reichel Marco , Krumm Burkhard , Vishnevskiy Yury V. , Blomeyer Sebastian , Schwabedissen Jan , Stammler Hans‐Georg , Karaghiosoff Konstantin , Mitzel Norbert W.
Published: October 2019

Eine verbesserte Synthese für den einfachsten Salpetersäureester, Methylnitrat, und eine neue Synthese für Fluormethylnitrat benutzen die Salzeliminierung der entsprechenden Iodmethane mit Silbernitrat. Beide Verbindungen wurden spektroskopisch und durch Strukturbestimmung im Festkörper von in situ erzeugten Kristallen mittels Röntgenbeugung sowie in der Gasphase mittels Elektronenbeugung identifiziert. Die Fluorierung führt zu Strukturen mit kürzeren C‐O‐ und N‐O‐Bindungen, hat eine energetisch destabilisierende Wirkung und erhöht die Reibungsempfindlichkeit, verringert aber die Detonationsleistung.
Supramolecular Photothermal Effects: A Promising Mechanism for Efficient Thermal Conversion
Authors: Zhao Luyang , Liu Yamei , Xing Ruirui , Yan Xuehai
Published: October 2019

Supramolecular assemblies have been very successful in regulating the photothermal conversion efficiency of organic photothermal materials in a simple and flexible way, compared with conventional molecular synthesis. In these assemblies, it is the inherent physiochemical mechanism that determines the photothermal conversion, rather than the assembly strategy. This Minireview summarizes supramolecular photothermal effects, which refer to the unique features of supramolecular chemistry for regulating the photothermal conversion efficiency. Emphasis is placed on the mechanisms of how self‐assembly affects the photothermal performance. The supramolecular photothermal effects on various types of light‐harvesting species are discussed in detail. The timely interpretation of supramolecular photothermal effects is promising for the future design of the photothermal materials with high efficiency, precision, and multiple functionalities for a wide array of applications.
Sacral plexus catheter analgesia in a patient with traumatic sacral fractures and Tarlov cysts
Authors: Ireland E. , Womack J. , Foley E.
Published: October 2019

We report the use of a sacral plexus catheter for continuous local anaesthetic infusion in a patient with a unilateral sacral ala fracture following a fall from a horse. Although sacral plexus blockade has been well described for lower limb surgery, an ultrasound‐guided continuous catheter technique for conservatively managed fractures has not been described. Despite appropriate oral analgesia, the patient reported severe pain, particularly in the right gluteal region, which meant she was unable to sit upright or take deep breaths. A sacral plexus catheter was inserted with ultrasound guidance and an initial bolus of 30 ml levobupivicaine 0.25% was delivered followed by infusion of 8 ml.h−1 levobupivicaine 0.125%. Daily follow‐up and assessment were provided by the acute pain team. We judged the procedure to be a success as measured by an improvement in mobilisation, deep breathing, cough and patient satisfaction.
Cavitation Clusters in Lipid Systems: The Generation of a Bifurcated Streamer and the Dual Collapse of a Bubble Cluster
Authors: Birkin Peter R. , Martin Hannah L. , Youngs Jack J. , Truscott Tadd T. , Merritt Andrew S. , Elison Ethan J. , Martini Silvana
Published: October 2019

Several studies have reported the use of high‐intensity ultrasound (HIU) to induce the crystallization of lipids. The effect that HIU has on lipid crystallization is usually attributed to the generation of cavities but acoustic cavitation has never been fully explored in lipids. The dynamics of a particular cavitation cluster next to a piston like emitter (PLE) in an oil was investigated in this study. The lipid systems, which are important in food processing, are studied with high‐speed camera imaging, laser scattering, and acoustic pressure measurements. A sequence of stable clusters was noted. In addition, a bifurcated streamer was detected, which exists within a sequence of clusters. This is shown to originate from two clusters on the PLE tip oscillating with a 180° phase shift in time with respect to one another. Finally, the collapse phase of the cluster is shown to involve a rapid (~10 μs) two‐stage process. These results show that the dynamics of cluster formation and collapse is driven by HIU power levels and might have implications in lipid sonocrystallization.
High‐performance composite photocatalytic membrane based on titanium dioxide nanowire/graphene oxide for water treatment
Authors: Yu Zongxue , Zeng Haojie , Min Xia , Zhu Xianfeng
Published: October 2019

In this study, a novel dopamine‐modified TiO2 nanowire (NW)‐intercalated graphene‐oxide‐based photocatalytic (NWC) membrane was prepared by vacuum‐assisted filtration using a commercial cellulose acetate membrane as a support layer. At the same time, compared with the synthesized reduced graphene‐oxide/polydopamine/TiO2 nanoparticle composite (NPC) membrane, it was found that the NWC membrane has high water flux (273 L m−2 h−1) and removal rate (above 98%) on the dye‐oil emulsion. After 5 cycles of experiments, the NWC membrane maintained a relatively stable permeation flux and removal rate, which was significantly better than the NPC membrane. The results showed that the NWC membrane had a more uniform distribution of TiO2 NW, and had better antifouling ability, recyclability, and photocatalytic performance than NPC membrane. In summary, the NWC photocatalytic membrane of this study shows excellent water purification potential and provides a new path for photocatalytic water treatment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48488.
Preparation of chitosan‐modified core–shell SiO2‐acidic polymer multiple crosslinked membranes
Authors: Shang Jing‐Ran , Zhong Shuang‐Ling , Zhao Ye , Wang Bin , Gao Yu‐Shan , Xiang Wen‐Tao , Cui Xue‐Jun
Published: October 2019

This article prepares and studies a series of chitosan‐modified core–shell SiO2‐acidic polymer multiple crosslinked membranes (modified membranes). The preparation process is simple, low cost, and environmentally friendly. The multiple crosslinking enhances the thermal stability and mechanical strength of membranes. TGA shows that the 10% weight loss temperatures of modified membranes are above 300 °C. Compared with water uptake, the methanol absorption of modified membranes is lower and decreases with increasing methanol concentration, which is very beneficial to their use in direct‐methanol fuel cells. The lowest methanol diffusion coefficient of the modified membrane is 4.56 × 10−8 cm2 s−1, which is only about 1/50th of that of Nafion117. In addition, the membranes exhibit feasible proton conductivity and higher selectivity than Nafion117. These results indicate that the chitosan‐modified core–shell SiO2‐acidic polymer multiple crosslinked membranes have potential applications in direct‐methanol fuel cells. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48494.
In situ dispersion and polymerization of polyethylene cellulose nanocrystal‐based nanocomposites
Authors: Hendren Keith D. , Baughman Travis W. , Deck Paul A. , Foster E. Johan
Published: October 2019

This study describes a novel method of forming a nanocomposite comprising cellulose nanocrystals (CNCs) as the reinforcing filler and a high‐density polyethylene (PE) matrix. The method involves covalent attachment of a metallocene catalyst, 1,1′‐bis(bromodimethylsilyl)zirconocene dibromide 1, to the hydroxyl‐rich surfaces of the CNCs and subsequent slurry polymerization with excess alumoxane (MMAO‐12) as the cocatalyst. Polymerization proceeds with activities reaching 500 kg mol−1 atm−1 h−1, while the CNCs are simultaneously dispersed to afford robust, well‐dispersed nanocomposites. Films of these composites (about 7‐vol % CNC) showed excellent dispersal of the filler (optically translucent; no CNC aggregation observed by atomic force microscopy). The composites (about 7‐vol % CNC) also revealed an increase in Young's modulus (10–100%) and comparable yield strength relative to commercially produced PEs. The experimental simplicity of this approach suggests that our method could be scaled beyond the present laboratory scale and extended to reinforce other polyolefin grades. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48500.
A simple and effective approach to produce tubular polysaccharide‐based hydrogel scaffolds
Authors: Bombaldi de Souza Fernanda Carla , Camasão Dimitria Bonizol , Bombaldi de Souza Renata Francielle , Drouin Bernard , Mantovani Diego , Moraes Ângela Maria
Published: October 2019

The production of porous tubular scaffolds is of great interest in the field of tissue engineering, given the existence of several tubular structures in the human body. In this work, a methodology was developed for the fabrication of tubular‐shaped scaffolds based on the casting of polymeric solutions by controlled crosslinking mediated by a semipermeable cast. The fabrication of hydrogel tubular scaffolds from chitosan–pectin polymeric mixtures (tCh‐P, 3% w/v) was performed to attest the feasibility of the technique. Tubular structures with about 4.15 mm internal diameter and 1.55 mm wall thickness were produced. The structures are highly porous, presenting interconnected pores with average diameter of about 360 μm. Seeding of human smooth muscle cells on the material was successfully achieved by using collagen gel to facilitate cell migration and retention inside the structure of the scaffold. The methodology herein proposed was successfully validated for the production of tubular constructs, opening new perspectives for the fabrication of matrices based on polymers that are passive of crosslinking with small molecules. Besides being an interesting approach to produce tubular scaffolds, this methodology can be considered an useful platform to obtain materials for drug screening and diagnostic studies. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48510.
Influence of remote plasma on PEDOT:PSS‐coated carbon felt for improved activity of glucose oxidase
Authors: Kahoush May , Behary Nemeshwaree , Cayla Aurélie , Mutel Brigitte , Guan Jinping , Nierstrasz Vincent
Published: October 2019

Increasing wettability of carbon felts is an important strategy to improve their efficiency in bio‐electrochemical applications. Herein, influence of cold remote plasma (N2 + O2) treatment on surface properties of carbon felts with poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coating was tested, aiming to improve immobilizing of glucose oxidase enzyme (GOx). Spectra of N 1s and O 1s confirmed the integration of carbonyl and ether as well as amide and amine groups on bare carbon fiber surface, while on coated fibers, carbonyl groups were pre‐dominant. S 2p spectra confirmed oxidation of PEDOT:PSS coating with reduction of (S−) compared to (SO3−) group. GOx immobilized on different samples showed highest activity for PEDOT:PSS coating subjected to plasma with 2% O2, maintaining up to 60% after immobilization, and 37% of its activity after six cycles for some samples. Enzymes immobilized on samples without plasma treatment lost their activity after four cycles. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48521.