bluuebunny/crossref_metadata_2025 huggingface dataset:
Tumor‐Microenvironment‐Activated In Situ Self‐Assembly of Sequentially Responsive Biopolymer for Targeted Photodynamic Therapy
Authors: Wang Xuan , Li Menghuan , Hou Yanhua , Li Yanan , Yao Xuemei , Xue Chencheng , Fei Yang , Xiang Yang , Cai Kaiyong , Zhao Yanli , Luo Zhong
Published: August 2020

A sequentially responsive photosensitizer‐integrated biopolymer is developed for tumor‐specific photodynamic therapy, which is capable of forming long‐retained aggregates in situ inside tumor tissues. Specifically, the photosensitizer zinc phthalocyanine (ZnPc) is conjugated with polyethylene glycol (PEG) via pH‐labile maleic acid amide linker and then immobilized onto the hyaluronic acid (HA) chain using a redox‐cleavable disulfide linker. The PEG segment can enhance blood circulation of the molecular carrier after intravenous administration and be shed after reaching the acidic tumor microenvironment, allowing the remaining fragment to self‐assemble into large clusters in situ to avoid backward diffusion and improve tumor retention. This process is driven by hydrophobic interactions and does not require additional external actuation. The aggregates are then internalized by the tumor cells via HA‐facilitated endocytosis, and the high glutathione level in tumor cells eventually leads to the intracellular release of ZnPc to facilitate its interaction with the subcellular lipid structures. This tumor‐triggered morphology‐based delivery platform is constructed with clinically tested components and could potentially be applied to other hydrophobic therapeutics.
Self‐Adaptive All‐In‐One Delivery Chip for Rapid Skin Nerves Regeneration by Endogenous Mesenchymal Stem Cells
Authors: Peng Li‐Hua , Xu Xue‐Han , Huang Yan‐Fen , Zhao Xiao‐Li , Zhao Bo , Cai Sheng‐Ying , Xie Ming‐Jun , Wang Mao‐Ze , Yuan Tie‐Jun , He Yong , Xu Zhen , Gao Jian‐Qing , Gao Chao
Published: August 2020

Skin wound therapy aims not only to restore skin protection but also to recover excitation functions through nerve regeneration. During the restoration of skin nerves, the recruitment of endogenous stem cells and promotion of neuronal regeneration on site work stepwise are foundations of in situ regeneration. However, current therapeutic systems usually execute each process separately, leading to limited regeneration and recovery of excitation functions. Herein, a novel self‐adaptive all‐in‐one delivery chip (G:P:Al‐Chip) is constructed that combines therapeutic protein release, gene delivery, and electrical conduction in a single microfluidic chip by 3D coaxial printing. G:P:Al‐Chip consists of an outer conductive hydrogel shell anchored with chemokine and an inner microchannel filled with enzyme‐initiated vector/plasmid DNAs microcomplexes. G:P:Al‐Chip delivers chemokine, functional plasmid DNAs, and promotes electrical conduction with a self‐adaptive program that significantly enhances the recruitment of endogenous mesenchymal stem cells and promotes neuronal regeneration. G:P:Al‐Chip is shown to enhance nerve regeneration with excitation functions within 23 days. G:P:Al‐Chip organizes recruitment and neuronal regeneration cues along with bioelectrical signal in one degradable chip for accelerated skin nerve regeneration.
Promoting Cell Migration and Neurite Extension along Uniaxially Aligned Nanofibers with Biomacromolecular Particles in a Density Gradient
Authors: Xue Jiajia , Wu Tong , Qiu Jichuan , Rutledge Sarah , Tanes Michael L. , Xia Younan
Published: August 2020

A simple method based upon masked electrospray is reported for directly generating both unidirectional and bidirectional density gradients of biomacromolecular particles on uniaxially aligned nanofibers. The method has been successfully applied to different types of biomacromolecules, including collagen and a mixture of collagen and fibronectin or laminin, to suit different types of applications. Collagen particles in a unidirectional or bidirectional gradient are able to promote the linear migration of bone marrow stem cells or NIH‐3T3 fibroblasts along the direction of increasing particle density. In the case of particles made of a mixture of collagen and fibronectin, their deposition in a bidirectional gradient promotes the migration of Schwann cells from two opposite sides toward the center, matching the scenario in peripheral nerve repair. As for a mixture of collagen and laminin, the particles in a unidirectional gradient promote the extension of neurites from embryonic chick dorsal root ganglion in the direction of increasing particle density. Taken together, the scaffolds featuring a combination of uniaxially aligned nanofibers and biomacromolecular particles in density gradient can be applied to a range of biological studies and biomedical applications.
Optoelectronic In‐Ga‐Zn‐O Memtransistors for Artificial Vision System
Authors: Qiu Weijie , Huang Yulong , Kong Ling‐An , Chen Yang , Liu Wanrong , Wang Zhen , Sun Jia , Wan Qing , Cho Jeong Ho , Yang Junliang , Gao Yongli
Published: August 2020

An artificial vision system that can simulate the visual functions of human eyes is required for biological robots. Here, In‐Ga‐Zn‐O memtransistors using a naturally oxidized Al2O3 and an ion gel as a common gate stacking dielectric is proposed. Positive charge trapping in the Al2O3 layer can be induced by modulating the gate voltage, which causes the back sweep subthreshold swing (SS) of the device to break the physical limit (≥60 mV per decade at room temperature), and the minimum SS is as low as 26.4 mV per decade. In addition, photogenerated charges in the device are captured at the In‐Ga‐Zn‐O channel/ion gel interface due to the superposition of the additional electric field generated by positive charges trapped in the Al2O3 layer and the external gate electric field. Thus, persistent photoconductivity is observed in the In‐Ga‐Zn‐O memtransistors. Finally, by employing the optoelectronic memristive functions of In‐Ga‐Zn‐O memtransistors, an artificial vision system based on artificial retinal array (ARA) and artificial neural network is proposed. An obvious improvement in the recognition rate and efficiency with the use of ARA for the image preprocessing is achieved. This study provides a new strategy for the realization of artificial vision systems.
In Situ Formation of Multiple Schottky Barriers in a Ti3C2 MXene Film and its Application in Highly Sensitive Gas Sensors
Authors: Choi Junghoon , Kim Yong‐Jae , Cho Soo‐Yeon , Park Kangho , Kang Hohyung , Kim Seon Joon , Jung Hee‐Tae
Published: August 2020

The main gas‐sensing mechanisms of 2D materials are surface charge transfer by analytes and Schottky barrier (SB) modulation at the interface between the metallic and semiconducting surfaces. In particular, dramatic differences in the gas‐sensing performances of 2D materials originate from SB modulation. However, SB sites typically exist only at the interface between the semiconducting channel material and the metal electrode. Herein, in situ formed multiple SBs in a single gas‐sensing channel are demonstrated, which are derived from the heterojunction of metallic Ti3C2 and semiconducting TiO2. In stark contrast with previous techniques, edge‐oxidized Ti3C2 flakes are synthesized by solution oxidation, allowing the uniform formation of TiO2 crystals on all flakes that comprise the gas sensing channel. Oxidized colloidal solutions are subjected to vacuum filtration to automatically form SB sites at the multiple inter‐flake junctions in both the outer surface and inner bulk regions of the film. The TiO2/Ti3C2 composite sensor shows 13.7 times higher NO2 sensitivity as compared with pristine Ti3C2 MXene, while the responses of the reducing gases are almost unchanged. The results suggest a new strategy for improving gas‐sensing performance by maximizing the density of SB sites through a simple method.
2D Material Enabled Offset‐Patterning with Atomic Resolution
Authors: Chen Szu‐Hua , Hofmann Mario , Yen Zhi‐Long , Hsieh Ya‐Ping
Published: August 2020

Atomic‐precision patterning at large scale is a central requirement for nanotechnology and future electronics that is hindered by the limitations of lithographical techniques. Historically, imperfections of the fabrication tools have been compensated by multi‐patterning using sequential lithography processes. The realization of nanometer‐scale features from much larger patterns through offset stacking of atomically thin masks is demonstrated. A unique mutual stabilization effect between two graphene layers produces atomically abrupt transitions that selectively expose single‐layer covered regions. Bilayer regions, on the other hand, protect the underlying substrate from removal for several hours permitting transfer of atomic thickness variations into lateral features in various semiconductors. Nanoscopic offsets between two 2D materials layers could be introduced through bottom‐up and top‐down approaches, opening up new routes for high‐resolution patterning. A self‐aligned templating approach yields nanometer‐wide bilayer graphene nanoribbons with macroscopic length that produces high‐aspect‐ratio silicon nanowalls. Moreover, offset‐transfer of lithographically patterned graphene layers enables multipatterning of large arrays of semiconductor features whose resolution is not limited by the employed lithography and could reach <10 nm feature size. The results open up a new route to combining design flexibility with unprecedented resolution at large scale.
In Situ Designing a Gradient Li+ Capture and Quasi‐Spontaneous Diffusion Anode Protection Layer toward Long‐Life Li−O2 Batteries
Authors: Yu Yue , Huang Gang , Wang Jia‐Zhi , Li Kai , Ma Jin‐Ling , Zhang Xin‐Bo
Published: August 2020

Lithium metal is the only anode material that can enable the Li−O2 battery to realize its high theoretical energy density (≈3500 Wh kg−1). However, the inherent uncontrolled dendrite growth and serious corrosion limitations of lithium metal anodes make it experience fast degradation and impede the practical application of Li−O2 batteries. Herein, a multifunctional complementary LiF/F‐doped carbon gradient protection layer on a lithium metal anode by one‐step in situ reaction of molten Li with poly(tetrafluoroethylene) (PTFE) is developed. The abundant strong polar C‐F bonds in the upper carbon can not only act as Li+ capture site to pre‐uniform Li+ flux but also regulate the electron configuration of LiF to make Li+ quasi‐spontaneously diffuse from carbon to LiF surface, avoiding the strong Li+‐adhesion‐induced Li aggregation. For LiF, it can behave as fast Li+ conductor and homogenize the nucleation sites on lithium, as well as ensure firm connection with lithium. As a result, this well‐designed protection layer endows the Li metal anode with dendrite‐free plating/stripping and anticorrosion behavior both in ether‐based and carbonate ester‐based electrolytes. Even applied protected Li anodes in Li−O2 batteries, its superiority can still be maintained, making the cell achieve stable cycling performance (180 cycles).
Cu‐Catalysed Three‐Component Reaction of Aryldiazonium Salts with Fluorinated Diazo Reagents and Nitriles: Access to Difluoro‐ and Trifluoromethylated N1‐Aryl‐1,2,4‐triazoles
Authors: Peng Xing , Zhang Fa‐Guang , Ma Jun‐An
Published: August 2020

A copper‐catalysed three‐component reaction of aryldiazonium salts with fluorinated diazo reagents and nitriles is described. This formal [1+2+2] annulation protocol provides rapid access to a diverse array of difluoro‐ and trifluoromethylated N1‐aryl‐1,2,4‐triazoles under simple conditions. The synthetic applicability to divergent drug‐like 1,2,4‐triazoles is also demonstrated.

magnified image
A Novel Targeted and High‐Efficiency Nanosystem for Combinational Therapy for Alzheimer's Disease
Authors: Yang Han , Mu Weihang , Wei Daohe , Zhang Yue , Duan Yue , Gao Jun‐xiao , Gong Xiao‐qun , Wang Han‐jie , Wu Xiao‐li , Tao Huaying , Chang Jin
Published: August 2020

Alzheimer's disease (AD) remains the most prevalent neurodegenerative disease, and no effective treatment is available yet. Metal‐ion‐triggered aggregates of amyloid‐beta (Aβ) peptide and acetylcholine imbalance are reported to be possible factors in AD pathogenesis. Thus, a combination therapy that can not only inhibit and reduce Aβ aggregation but also simultaneously regulate acetylcholine imbalance that can serve as a potential treatment for AD is needed. Here, clioquinol (metal‐ion chelating agent) and donepezil (acetylcholinesterase (AChE) inhibitor) co‐encapsulated human serum albumin (HSA) nanoparticles (dcHGT NPs) are designed, which are modified with transcriptional activator protein (TAT) and monosialotetrahexosylganglioside (GM1). The GM1 lipid and TAT peptide endow this drug delivery nanosystem with high brain entry efficiency and long‐term retention capabilities through intranasal administration. It is found that dcHGT NPs can significantly inhibit and eliminate Aβ aggregation, relieve acetylcholine‐related inflammation in microglial cells, and protect primary neurons from Aβ oligomer‐induced neurotoxicity in vitro. The alleviation of Aβ‐related inflammation and AChE‐inhibited effect further synergistically adjust acetylcholine imbalance. It is further demonstrated that dcHGT NPs reduce Aβ deposition, ameliorate neuron morphological changes, rescue memory deficits, and greatly improve acetylcholine regulation ability in vivo. This multifunctional synergetic nanosystem can be a new candidate to achieve highly efficient combination therapy for AD.
Bioinspired DNA Nanointerface with Anisotropic Aptamers for Accurate Capture of Circulating Tumor Cells
Authors: Qin Weiwei , Chen Liang , Wang Zhiru , Li Qian , Fan Chunhai , Wu Minhao , Zhang Yuanqing
Published: August 2020

The capture and analysis of circulating tumor cells (CTCs) have provided a non‐invasive entry for cancer diagnosis and disease monitoring. Despite recent development in affinity‐based CTCs isolation, it remains challenging to achieve efficient capture toward CTCs with dynamic surface expression. Enlightened by the synergistic effect insideimmune synapses, the development of a nanointerface engineered with topology‐defined anisotropic aptamers programmed by DNA scaffold (DNA nanosynapse), for accurate CTCs isolation, is herein reported. As compared to isotropic aptamers, the DNA nanosynapse exhibits enhanced anchoring on the cell membrane with both high and low epithelial cell adhesion molecule (EpCAM) expression. This nanointerface enables accurate capture toward CTCs of heterogeneous EpCAM, without dramatically proportional change inside the mixture of diverse phenotypes. By applying this nanoplatform, CTCs detection as well as downstream analysis for measuring disease status can be achieved in clinical samples from breast cancer patients.
Zeolitic Imidazolate Frameworks as Zn2+ Modulation Layers to Enable Dendrite‐Free Zn Anodes
Authors: Liu Xiaoqing , Yang Fan , Xu Wei , Zeng Yinxiang , He Jinjun , Lu Xihong
Published: August 2020

Zinc (Zn) holds great promise as a desirable anode material for next‐generation rechargeable batteries. However, the uncontrollable dendrite growth and low coulombic efficiency of the Zn plating/stripping process severely impede further practical applications of Zn‐based batteries. Here, these roadblocks are removed by using in situ grown zeolitic imidazolate framework‐8 (ZIF‐8) as the ion modulation layer to tune the diffusion behavior of Zn2+ ions on Zn anodes. The well‐ordered nanochannels and N species of ZIF‐8 can effectively homogenize Zn2+ flux distribution and modulate the plating/stripping rate, ensuring uniform Zn deposition without dendrite growth. The Zn corrosion and hydrogen evolution are also alleviated by the insulating nature of ZIF‐8, resulting in high coulombic efficiency. Therefore, the Zn@ZIF anode shows highly reversible, dendrite‐free Zn plating/stripping behavior under a broad range of current densities, and a symmetric cell using this anode can work correctly up to 1200 h with a low polarization at 2 mA cm−2. Moreover, this ultrastable Zn@ZIF anode also enables a full Zn ion battery with outstanding cyclic stability (10 000 cycles).
Degradation of High‐Nickel‐Layered Oxide Cathodes from Surface to Bulk: A Comprehensive Structural, Chemical, and Electrical Analysis
Authors: Ko Dong‐Su , Park Jun‐Ho , Yu Byong Yong , Ahn Docheon , Kim Kihong , Han Heung Nam , Jeon Woo Sung , Jung Changhoon , Manthiram Arumugram
Published: August 2020

Multiple applications of lithium‐ion batteries in energy storage systems and electric vehicles require highly stable electrode materials for long‐term battery operation. Among the various cathode materials, high‐Ni cathode materials enable a high energy density. However, cathode degradation accompanied by complex chemical and structural changes results in capacity and voltage fading in batteries. Cathode degradation remains poorly understood; the majority of studies have only explored the oxidation states of transition‐metal ions in localized areas and have rarely evaluated chemical degradation in complete particles after prolonged cycling. This study systematically investigates the degradation of a high‐Ni cathode by comparing the chemical, structural, and electrical changes in pristine and 500 times‐cycled cathodes. Electron probe micro‐analysis and X‐ray energy dispersive spectroscopy reveal changes in the Ni:O ratio from 1:2 to 1:1 over a large area inside the secondary particle. Electron energy loss spectroscopy analysis related to structural changes is performed for the entire primary particle area to visualize the oxidation state of transition‐metal ions in two dimensions. The results imply that the observed monotonic capacity fade without unusual changes is due to the continuous formation of the Ni2+ phase from the surface to the bulk through chemical and structural degradation.
An Urgent Call to Spent LIB Recycling: Whys and Wherefores for Graphite Recovery
Authors: Natarajan Subramanian , Aravindan Vanchiappan
Published: August 2020

Spent lithium‐ion batteries (LIBs) are a key source for securing tons of raw materials that are valuable materials for LIB applications. However, the massive emerging volume of spent LIBs urgently needs a new management strategy to recycle/reuse all components of spent LIBs, particularly the graphite before it becomes a “future critical material” like Li and Co. Many elements in LIB electrodes can now be recycled, however graphite has till now, been largely overlooked. Some research groups have begun examining possible strategies for the reuse of graphite for energy storage applications. This work has delivered some promising results that may help to achieve this goal on an industrial scale
The Impact of Criminal Record Stigma on Quality of Life: A Test of Theoretical Pathways
Authors: McWilliams Elaina R. , Hunter Bronwyn A.
Published: August 2020

Across multiple stigmatized groups, research suggests that stigma may negatively impact individual wellbeing. This impact often occurs through a sequential pathway that includes perceiving societal stigma, a diminished and stereotyped self‐concept (i.e., internalized stigma), experiences of discrimination and rejection, and attempts to cope with stigma (e.g., secrecy or withdrawal). While prior research supports individual links within this pathway, no study has evaluated a model representing the relationships between all of these factors in relation to criminal record stigma. This study utilized cross‐sectional data from an online survey of 198 adults to test the pathways through which criminal record‐related stigma impacts individual quality of life. The results indicated that perceived stigma was a significant predictor of discrimination and rejection experiences, secrecy coping strategies, and decreased quality of life. There was also a significant indirect association between perceived stigma and quality of life through secrecy coping. Consistent with recent criminal record stigma research, internalized stigma was low among respondents. These findings point to the importance of reducing criminal record stigma and discrimination, so that individuals with criminal records have more opportunities to enhance their quality of life without having to withdraw from society or keep their record a secret.
The complex karyotype and chronic lymphocytic leukemia: prognostic value and diagnostic recommendations
Authors: Jondreville Ludovic , Krzisch Daphné , Chapiro Elise , Nguyen‐Khac Florence
Published: August 2020

Chromosomal abnormalities are frequently observed in patients with chronic lymphocytic leukemia (CLL) and have prognostic value. Deletions of the short arm of chromosome 17 (and/or mutations TP53) predict resistance to chemoimmunotherapy and shorter progression‐free survival after targeted therapies. Although the complex karyotype (CK) is strongly predictive of a poor prognosis in hematologic malignancies such acute myeloid leukemia or myelodysplastic syndrome, its value in CLL is subject to debate. Here, we review the literature on the CK in CLL and examine its prognostic value with different treatments. We also propose a standardized method for defining a CK in all types of hematopoietic neoplasm.
Biallelic loss of function variants in SYT2 cause a treatable congenital onset presynaptic myasthenic syndrome
Authors: Donkervoort Sandra , Mohassel Payam , Laugwitz Lucia , Zaki Maha S. , Kamsteeg Erik‐Jan , Maroofian Reza , Chao Katherine R. , Verschuuren‐Bemelmans Corien C. , Horber Veronka , Fock Annemarie J. M. , McCarty Riley M. , Jain Minal S. , Biancavilla Victoria , McMacken Grace , Nalls Matthew , Voermans Nicol C. , Elbendary Hasnaa M. , Snyder Molly , Cai Chunyu , Lehky Tanya J. , Stanley Valentina , Iannaccone Susan T. , Foley A. Reghan , Lochmüller Hanns , Gleeson Joseph , Houlden Henry , Haack Tobias B. , Horvath Rita , Bönnemann Carsten G.
Published: August 2020

Synaptotagmins are integral synaptic vesicle membrane proteins that function as calcium sensors and regulate neurotransmitter release at the presynaptic nerve terminal. Synaptotagmin‐2 (SYT2), is the major isoform expressed at the neuromuscular junction. Recently, dominant missense variants in SYT2 have been reported as a rare cause of distal motor neuropathy and myasthenic syndrome, manifesting with stable or slowly progressive distal weakness of variable severity along with presynaptic NMJ impairment. These variants are thought to have a dominant‐negative effect on synaptic vesicle exocytosis, although the precise pathomechanism remains to be elucidated. Here we report seven patients of five families, with biallelic loss of function variants in SYT2, clinically manifesting with a remarkably consistent phenotype of severe congenital onset hypotonia and weakness, with variable degrees of respiratory involvement. Electrodiagnostic findings were consistent with a presynaptic congenital myasthenic syndrome (CMS) in some. Treatment with an acetylcholinesterase inhibitor pursued in three patients showed clinical improvement with increased strength and function. This series further establishes SYT2 as a CMS‐disease gene and expands its clinical and genetic spectrum to include recessive loss‐of‐function variants, manifesting as a severe congenital onset presynaptic CMS with potential treatment implications.
Sharp Switching of DNAzyme Activity through the Formation of a CuII‐Mediated Carboxyimidazole Base Pair
Authors: Takezawa Yusuke , Hu Lingyun , Nakama Takahiro , Shionoya Mitsuhiko
Published: August 2020

DNAzymes are widely used as functional units for creating DNA‐based sensors and devices. Switching of DNAzyme activity by external stimuli is of increasing interest. Herein we report a CuII‐responsive DNAzyme rationally designed by incorporating one of the most stabilizing artificial metallo‐base pairs, a CuII‐mediated carboxyimidazole base pair (ImC‐CuII‐ImC), into a known RNA‐cleaving DNAzyme. Cleavage of the substrate was suppressed without CuII, but the reaction proceeded efficiently in the presence of CuII ions. This is due to the induction of a catalytically active structure by ImC‐CuII‐ImC pairing. The on/off ratio was as high as 12‐fold, which far exceeds that of the previously reported DNAzyme with a CuII‐mediated hydroxypyridone base pair. The DNAzyme activity can be regulated specifically in response to CuII ions during the reaction through the addition, removal, or reduction of CuII. This approach should advance the development of stimuli‐responsive DNA systems with a well‐defined sharp switching function.
Die Natur starker Chalkogenbindungen unter Beteiligung chalkogenhaltiger Heterocyclen
Authors: Haberhauer Gebhard , Gleiter Rolf
Published: August 2020

Chalkogenbindungen sind Sigma‐Hole‐Wechselwirkungen und kommen seit einiger Zeit als Alternative zu Wasserstoffbrückenbindungen zum Einsatz. In der Regel werden das elektrostatische Potential am Chalkogenatom und Delokalisierungseffekte für die Orientierung der Chalkogenbindung verantwortlich gemacht. Wir konnten jedoch mithilfe von SAPT‐Berechnungen zeigen, dass weder der induktive Term (Delokalisierungseffekte) noch der elektrostatische Term die räumliche Orientierung starker Chalkogenbindungen in tellurhaltigen Aromaten verursacht. Stattdessen sind sterische Wechselwirkungen (Pauli‐Abstoßung) für die Geometrie der Chalkogenbindung ausschlaggebend. Entgegen der chemischen Intuition sind die Dispersionsenergien der untersuchten tellurhaltigen Aromaten im Vergleich zu den Dispersionsenergien der entsprechenden Schwefel‐ und Selenverbindungen weitaus weniger relevant für die Gesamtanziehungskraft. Unsere Ergebnisse unterstreichen die Bedeutung der häufig übersehenen sterischen Wechselwirkungen (Pauli‐Repulsion) in der Konformationskontrolle von Sigma‐Hole‐Wechselwirkungen.
How Far Does Energy Migrate in DNA and Cause Damage? Evidence for Long‐Range Photodamage to DNA
Authors: Kuhlmann Arthur , Bihr Larissa , Wagenknecht Hans‐Achim
Published: August 2020

A new DNA architecture addresses the question, how far energy migrates in DNA and forms cyclobutane pyrimidine dimers (CPDs) as photodamages causing skin cancer. The 3‐methoxyxanthone nucleoside allows site‐selective photoenergy injection into DNA. The designated CPD site lacks the phosphodiester bond and can be placed in defined distances. The CPD formation links two oligonucleotides together and allows probing by gel electrophoresis. We obtained a sigmoidal distance dependence with R0 of 25±3 Å. Below R0, short‐range energy migration occurs with high CPD yields and shallow distance dependence, characteristic for a coherent process. 5‐methyl‐C as epigenetic modification on the 3′‐side facilitates CPD formation. Above R0, long‐range incoherent energy migration occurs over 30 A‐T pairs (105.4 Å). The evidence of long‐range CPD formation is fundamental for our understanding of DNA photodamaging. Open access funding enabled and organized by Projekt DEAL.
Permethylated dinuclear Mn(III) coordination nanostructure with stripe‐ordered magnetic domains
Authors: Shova Sergiu , Tiron Vasile , Vlad Angelica , Novitchi Ghenadie , Dumitrescu Dan G. , Damoc Madalin , Zaltariov Mirela‐Fernanda , Cazacu Maria
Published: August 2020

A di‐manganese(III) complex structure was built by an original approach consisting of a two‐step procedure. First, the mononuclear complex of the manganese(III) with the Schiff base of the salen‐type ligand (H2L) derived from 1,3‐bis(3‐aminopropyl)tetramethyldisiloxane and 3,5‐di‐tert‐butyl‐2‐hydroxybenzaldehyde was prepared. The main feature of note is the 12‐membered chelate ring formed upon coordination of the Schiff base to central atom, which adopts a distorted N2O4 octahedron environment. In the second step, the acetato co‐ligand in this complex is replaced by the carboxylate anion of a dicarboxilic acid, namely adipic acid. This metathesis reaction leads to the formation of dinuclear structure by connecting two manganese centers. The structure, as was determined by X‐ray single crystal diffractometry, elemental and spectral analysis, is permethylated dinuclear complex with long aliphatic bridge. Thermal and magnetic properties were studied. In addition, the formation of magnetically induced stripe‐ordered domains was highlighted by the magnetic force microscopy (MFM) on films born from diluted solution.
Ferroelectric Behavior of an Octahedral Metal‐Ligand Cage and Its 2D‐Connected Cage Framework
Authors: Prajesh Neetu , Yadav Ashok , Gourkhede Rani , Praveenkumar Balu , Steiner Alexander , Boomishankar Ramamoorthy
Published: August 2020

Supramolecular systems hold great potential as ferroelectric materials because they are easy to prepare and do not require toxic and environmentally damaging elements. However, directing the self‐assembly process of a supramolecular array to yield polarizable solids is still challenging. Here, we describe induced ferroelectricity in a supramolecular framework of metal‐organic cages that are supported by a flexible tripodal ligand (NHCH2‐(3‐Py))3PO (TPPA). Ferroelectric responses on the discrete cage [Cu6(H2O)12(TPPA)8](NO3)12 ⋅ 45H2O (1) and its 2D‐connected framework [{Cu6Cl4(H2O)6(TPPA)8}(NO3)8 ⋅ 60H2O]n (2) yielded well‐resolved rectangular hysteresis loops at room temperature with remnant polarization values of 27.27 and 29.09 μC/cm2, respectively. Thermal hysteresis measurements (THM) and capacitance‐voltage (C−V) plots further corroborate the ferroelectric behavior in these compounds. The polarization in them is due to the displacements of solvated molecules and nitrate ions in the pockets of these frameworks.
Defect‐Rich Co−CoOx‐Graphene Nanocatalysts for Efficient Hydrogen Production from Ammonia Borane
Authors: Guan Shuyan , Zhang Lina , Zhang Huanhuan , Guo Yong , Liu Baozhong , Wen Hao , Fan Yanping , Li Baojun
Published: August 2020

Chemical hydrogen storage ammonia borane has attracted extensive attention as a method of efficient utilization of hydrogen energy. The high‐efficiency catalysts are the main factor restricting the hydrogen production of ammonia borane. In this paper, the synergistic effect of Co and CoOx supported on graphene (named Co−CoOx@GO‐II) promotes the efficient hydrogen production of ammonia borane, and its catalytic hydrogen production rate can reach 5813 mL min−1 gCo−1 at 298 K, the corresponding TOF is 15.33 min−1. After five stability tests, Co−CoOx @GO‐II maintained 65% of its original catalytic performance. The synergy of metal and metal oxide and the defects in the atomic arrangement ensure the catalytic activity, the large specific surface area of graphene ensures the dispersion and fixation. This strategy may provide a possibility to design high‐performance transition metal catalysts.
A Reverse Strategy to Restore the Moisture‐deteriorated Luminescence Properties and Improve the Humidity Resistance of Mn4+‐doped Fluoride Phosphors
Authors: Liu Lili , Wu Di , He Shengan , Ouyang Zejian , Zhang Junfei , Du Fu , Peng Jiaqing , Yang Fengli , Ye Xinyu
Published: August 2020

Fluoride phosphors as red components for warm white LEDs have attracted a tremendous amount of research attention. But these phosphors are extremely sensitive to moisture, which seriously limits their practical industrial applications. To tackle this problem, unlike all the straightforward preventive strategies, a reverse strategy “Good comes from bad” was successfully developed to treat the degraded K2SiF6 : Mn4+ (D‐KSFM) phosphor in the present study, which not only completely restores the luminescence properties, but also significantly enhances the moisture resistance at the same time. After treatment with an oxalic acid solution as restoration modifier, the emission intensity of the D‐KSFM phosphor can be restored to 103.7% of the original K2SiF6 : Mn4+ red phosphor (O‐KSFM), and the moisture resistance is remarkably improved. The restored K2SiF6 : Mn4+ (R‐KSFM) maintains approximately 62.3% of its initial relative emission intensity after immersing in deionized water for 300 min, while the reference commercial K2SiF6 : Mn4+ with a protective coating (C‐KSFM) is only 33.2%. As a proof of general applicability, this strategy was also conducted to K2TiF6 : Mn4+ phosphor, which is less moisture‐stable than K2SiF6 : Mn4+. The luminescence intensity of the degraded K2TiF6 : Mn4+ (D‐KTFM) phosphor can be restored to 162.6% of original level of the K2TiF6 : Mn4+ synthesized through a cation exchange approach without any treatment (O‐KTFM). The emission intensity of the restored K2TiF6 : Mn4+ (R‐KTFM) phosphor retains 62.8% of its initial emission intensity after soaking in deionized water for 300 min. Finally, the R‐KSFM phosphors were packaged into white light‐emitting diodes with blue InGaN chips and Y3Al5O12 : Ce3+ yellow phosphors. The WLEDs display excellent color rendition with higher color rendering index, lower color temperature (WLED‐II: Ra=83.6, R9=57.3, 3743 K, ηl=199.68 lm/W; WLED‐III: Ra=90.4, R9=94.2, 2892 K, ηl=183.3 1 m/W). The above results show that the reverse strategy can be applied in those phosphor materials with poor moisture resistance to restore luminescence properties and improve moisture resistance without excessively care about the deterioration during the production, storage and transportation.
Leader–follower consensus for multi‐agent systems with external disturbances generated by heterogeneous nonlinear exosystems
Authors: Mu Rui , Wei Airong , Li Haitao
Published: August 2020

In this paper, the leader–follower consensus problem is investigated for multi‐agent systems subject to external disturbances generated by heterogeneous nonlinear exosystems. First, the disturbance observers are developed for each follower to effectively estimate the nonlinear disturbances. Then, based on the presented observers, the distributed state and output feedback consensus protocols are proposed to guarantee that the consensus tracking errors converge to zero asymptotically, and meanwhile to reject the nonlinear disturbances. Particularly, the output feedback protocol can be designed and implemented without any global information about the whole network, which means it is fully distributed. Finally, two numerical examples are given to illustrate the effectiveness of the results.
Anatomical templates for tissue (re)generation and beyond
Authors: Mavaro Isabella , De Felice Elena , Palladino Antonio , D'Angelo Livia , de Girolamo Paolo , Attanasio Chiara
Published: August 2020

Induced pluripotent stem cells (iPSCs) represent a valuable alternative to stem cells in regenerative medicine overcoming their ethical limitations, like embryo disruption. Takahashi and Yamanaka in 2006 reprogrammed, for the first time, mouse fibroblasts into iPSCs through the retroviral delivery of four reprogramming factors: Oct3/4, Sox2, c‐Myc, and Klf4. Since then, several studies started reporting the derivation of iPSC lines from animals other than rodents for translational and veterinary medicine. Here, we review the potential of using these cells for further intriguing applications, such as “cellular agriculture.” iPSCs, indeed, can be a source of in vitro, skeletal muscle tissue, namely “cultured meat,” a product that improves animal welfare and encourages the consumption of healthier meat along with environmental preservation. Also, we report the potential of using iPSCs, obtained from endangered species, for therapeutic treatments for captive animals and for assisted reproductive technologies as well. This review offers a unique opportunity to explore the whole spectrum of iPSC applications from regenerative translational and veterinary medicine to the production of artificial meat and the preservation of currently endangered species.
A novel composition of two heterozygous GFM1 mutations in a Chinese child with epilepsy and mental retardation
Authors: You Cuiping , Xu Na , Qiu Shiyan , Li Yufen , Xu Liyun , Li Xia , Yang Li
Published: August 2020

Introduction

G elongation factor mitochondrial 1 (GFM1) encodes one of the mitochondrial translation elongation factors. GFM1 variants were reported to be associated with neurological diseases and liver diseases in a few cases. Here, we present a novel composition of two heterozygous mutations of GFM1 in a boy with epilepsy, mental retardation, and other unusual phenotypes.

Methods

The patient was found to be blind and experienced recurrent convulsive seizures such as nodding and hugging at the age of 3 months. After antiepileptic treatment with topiramate, he had no obvious seizures but still had mental retardation. The patient vomited frequently at 16 months old, sometimes accompanied by epileptic seizures. Hematuria metabolic screening, mutation screening of mitochondrial gene, and mitochondrial nuclear gene were negative. Then, he was analyzed by whole‐exome sequencing (WES).

Results

Whole‐exome sequencing revealed a novel composition of two heterozygous mutations in GFM1, the maternal c.679G > A (has not been reported) and the paternal c.1765‐1_1765‐2del (previously reported). At present, there is no specific and effective treatment for the disease, and the prognosis is very poor.

Conclusion

The discovery of new phenotypes and new genotypes will further enrich the diagnosis information of the disease and provide more experiences for clinicians to quickly diagnose the disease and judge the prognosis.
In situ forming microporous gelatin methacryloyl hydrogel scaffolds from thermostable microgels for tissue engineering
Authors: Zoratto Nicole , Di Lisa Donatella , de Rutte Joseph , Sakib Md Nurus , Alves e Silva Angelo Roncalli , Tamayol Ali , Di Carlo Dino , Khademhosseini Ali , Sheikhi Amir
Published: August 2020

Converting biopolymers to extracellular matrix (ECM)‐mimetic hydrogel‐based scaffolds has provided invaluable opportunities to design in vitro models of tissues/diseases and develop regenerative therapies for damaged tissues. Among biopolymers, gelatin and its crosslinkable derivatives, such as gelatin methacryloyl (GelMA), have gained significant importance for biomedical applications due to their ECM‐mimetic properties. Recently, we have developed the first class of in situ forming GelMA microporous hydrogels based on the chemical annealing of physically crosslinked GelMA microscale beads (microgels), which addressed several key shortcomings of bulk (nanoporous) GelMA scaffolds, including lack of interconnected micron‐sized pores to support on‐demand three‐dimensional‐cell seeding and cell–cell interactions. Here, we address one of the limitations of in situ forming microporous GelMA hydrogels, that is, the thermal instability (melting) of their physically crosslinked building blocks at physiological temperature, resulting in compromised microporosity. To overcome this challenge, we developed a two‐step fabrication strategy in which thermostable GelMA microbeads were produced via semi‐photocrosslinking, followed by photo‐annealing to form stable microporous scaffolds. We show that the semi‐photocrosslinking step (exposure time up to 90 s at an intensity of ~100 mW/cm2 and a wavelength of ~365 nm) increases the thermostability of GelMA microgels while decreasing their scaffold forming (annealing) capability. Hinging on the tradeoff between microgel and scaffold stabilities, we identify the optimal crosslinking condition (exposure time ~60 s) that enables the formation of stable annealed microgel scaffolds. This work is a step forward in engineering in situ forming microporous hydrogels made up from thermostable GelMA microgels for in vitro and in vivo applications at physiological temperature well above the gelatin melting point.
Lipase activation by molecular bioimprinting: The role of interactions between fatty acids and enzyme active site
Authors: Brandão Luma M. de S. , Barbosa Milson S. , Souza Ranyere L. , Pereira Matheus M. , Lima Álvaro S. , Soares Cleide M. F.
Published: August 2020

Bioimprinting is an easy, sustainable and low‐cost technique that promotes a printing of potential substrates on enzyme structure, inducing a more selective and stable conformation. Bioimprinting promotes conformational changes in enzymes, resulting in better catalytic performance. In this work, the effect of bioimprinting of Burkholderia cepacia lipase (BCL) and porcine pancreatic extracts (PPE) with four different fatty acids (lauric acid (C12:0), myristic acid (C14:0), palmitic acid (C16:0), and stearic acid (C18:0)) was investigated. The results demonstrated that the better bioimprinting effect was in BCL with lauric acid in esterification reaction, promoting BCL activation in which relative enzyme activity was 70 times greater than nonimprinted BCL. Bioimprinting results were influenced by the carbon chain length of fatty acids imprinted in the BCL, in which the effects were weaker with the chain increase. Molecular docking was performed to better understand the bioimprinting method. The results of these simulations showed that indeed all fatty acids were imprinted in the active site of BCL. However, lauric acid presented the highest imprinting preference in the active site of BCL, resulting in the highest relative activity. Furthermore, Fourier transform infrared (FTIR) analysis confirmed important variations in secondary structure of bioimprinting BCL with lauric acid, in which there was a reduction in the α‐helix content and an increase in the β‐sheet content that facilitated substrate access to the active site of BCL and led higher rigidity, resulting in high activity. Bioimprinted BCL with lauric acid showed excellent operational stability in esterification reaction, maintaining its original relative activity after five successive cycles. Thus, the results show that bioimprinting of BCL with lauric acid is a successful strategy due to its high catalytic activity and reusability.
Predictive model for risk of gastric cancer using genetic variants from genome‐wide association studies and high‐evidence meta‐analysis
Authors: Qiu Lixin , Qu Xiaofei , He Jing , Cheng Lei , Zhang Ruoxin , Sun Menghong , Yang Yajun , Wang Jiucun , Wang Mengyun , Zhu Xiaodong , Guo Weijian
Published: August 2020

Genome‐wide association studies (GWAS) have identified some single nucleotide polymorphisms (SNPs) associated with the risk of gastric cancer (GCa). However, currently, there is no published predictive model to assess the risk of GCa. In the present study, risk‐associated SNPs derived from GWAS and large meta‐analyses were selected to construct a predictive model to assess the risk of GCa. A total of 1115 GCa cases and 1172 controls from the eastern Chinese population were included. Logistic regression models were used to identify SNPs that correlated with the risk of GCa. A predictive model to assess the risk of GCa was established by receiver operating characteristic curve analysis. Multifactor dimensionality reduction (MDR) and classification and regression tree (CART) were applied to calculate the effect of high‐order gene‐environment interactions on risk of the cancer. A total of 42 SNPs were selected for further analysis. The results revealed that ASH1L rs80142782, PKLR rs3762272, PRKAA1 rs13361707, MUC1 rs4072037, PSCA rs2294008, and PLCE1 rs2274223 polymorphisms were associated with a risk of GCa. The area under curve considering both genetic factors and BMI was 3.10% higher than that of BMI alone. MDR analysis revealed that rs13361707 and rs4072307 variants and BMI had interaction effects on susceptibility to GCa, with the highest predictive accuracy (61.23%) and cross‐validation consistency (100/100). CART analysis also supported this interaction model that non‐overweight status and a six SNP panel could synergistically increase the susceptibility to GCa. The six SNP panel for predicting the risk of GCa may provide new tools for prevention of the cancer based on GWAS and large meta‐analyses derived genetic variants.
ACADSB regulates ferroptosis and affects the migration, invasion, and proliferation of colorectal cancer cells
Authors: Lu Di , Yang Zhiyu , Xia Qiaoyun , Gao Shanjun , Sun Suofeng , Luo Xiaoying , Li Zhen , Zhang XiuLei , Li Xiuling
Published: August 2020

Colorectal cancer (CRC) is one of the most pressing health issues in today's society. As such, it is imperative that the scientific community devise effective methods to inhibit the proliferation and metastasis of CRC cells. Ferroptosis is a recently discovered regulatory cell death mode mainly manifested by dysregulation of cellular iron metabolism and mitochondrial lipid peroxidation. ACADSB is a member of the acyl‐CoA dehydrogenase. This study finds that ACADSB is lowly expressed in CRC tissues. Its expression is negatively correlated with N‐ and M‐stage CRC but positively correlated with the overall survival rate of CRC patients. In addition, it finds that ACADSB is found in the mitochondria of cells. Overexpression of ACADSB inhibits CRC cell migration, invasion, and proliferation, while ACADSB knockdown has the opposite effect. More importantly, the study finds that ACADSB negatively regulates expression of glutathione reductase and glutathione peroxidase 4, the two main enzymes responsible for clearing glutathione (GSH) in CRC cells. ACADSB overexpression enhances the concentration of malondialdehyde, Fe+, superoxide dismutase, and lipid peroxidation in CRC cells, but reduces the concentration of GSH. This is significant, as all of these are important indicators of ferroptosis. Evaluating the data as a whole, this paper speculates that ACADSB affects CRC cell migration, invasion, and proliferation by regulating CRC cell ferroptosis.
Cell‐based noninvasive prenatal testing (cbNIPT) detects pathogenic copy number variations
Authors: Hatt Lotte , Singh Ripudaman , Christensen Rikke , Ravn Katarina , Christensen Inga B , Jeppesen Line Dahl , Nicolaisen Bolette Hestbek , Kølvraa Mathias , Schelde Palle , Andreassen Lotte , Farlie Richard , Uldbjerg Niels , Vogel Ida
Published: August 2020

In two cases, cell‐based noninvasive prenatal testing (cbNIPT) detected pathogenic copy number variations (CNVs) in the fetal genome. cbNIPT may potentially be an improved noninvasive alternative for the detection of smaller CNVs.
Asymmetric Synthesis of Multi‐substituted Prolines via a Catalytic 1,3‐Dipolar Cycloaddition Using a Monocationic ZnIIOAc Complex of a Chiral Bisamidine Ligand, Naph‐diPIM‐dioxo‐R
Authors: Chaithanya Kiran I. N. , Fujita Kazuki , Tanaka Shinji , Kitamura Masato
Published: August 2020

A monocationic zinc acetate complex of chiral bisamidine‐type bidentate ligand (R)‐ or (S)‐Naph‐diPIM‐dioxo‐iPr (LR or LS) catalyzes a 1,3‐dipolar cycloaddition between tridentate‐type imino esters and acrylates in the absence of an external base to give the corresponding multi‐substituted prolines with high reactivity, diastero‐/enantio‐/regio‐selectivity, productivity, and broad generality. An anionic acetate ligand of the Lewis acidic Zn complex acts as a Brønsted base to facilitate a smooth intramolecular deprotonation to generate an imino N,O‐cis‐Zn enolate. The oxygen atoms of two dioxolanes of the LR/LS ligand form a C2 chiral scaffold that coordinates the Zn enolate via a non‐bonding n‐π* interaction. This view is supported by the lack of enantioselectivity obtained with an sp2N‐based Ph‐BOX ligand that has no oxygen atom in the reaction site.
Functionalized Single‐Walled Carbon Nanohorns to Reinforce Sulfonated Poly(ether ether ketone) Electrolyte for Direct Methanol Fuel Cells
Authors: Turanelloormana Parameswaran , Sarmah Sudeshna , Torris Arun , Bhat Santoshkumar D. , Unni Sreekuttan M.
Published: August 2020

Carbon‐nanomaterial‐based additives are promising materials for improving the physicochemical properties of sulfonated polyether ether ketone (sPEEK) for its use as composite membrane electrolyte in direct methanol fuel cells (DMFCs). In this work, functionalized single‐wall carbon nanohorns (f‐SWNHs) are realized as an additive in sPEEK. The −COOH groups created on the SWNHs during peroxide treatment improve the dispersion of f‐SWNHs in sPEEK and boost the proton conductivity, ion exchange capacity, mechanical properties and reduce the methanol permeability of the electrolyte. The composite membrane with 0.50 wt.% f‐SWNHs shows improved electrochemical selectivity of 17.03×10−4 Scm−3s and delivers the highest peak power density of 230 mW cm−2 in DMFCs.