bluuebunny/crossref_metadata_2025 huggingface dataset:
Clinical and molecular spectrum of CHOPS syndrome
Authors: Raible Sarah E. , Mehta Devanshi , Bettale Chiara , Fiordaliso Sarah , Kaur Maninder , Medne Livija , Rio Marlene , Haan Eric , White Susan M. , Cusmano‐Ozog Kristina , Nishi Eriko , Guo Yiran , Wu Honglin , Shi Xiaoqing , Zhao Qingjie , Zhang Xueqin , Lei Qi , Lu Aimei , He Xiyu , Okamoto Nobuhiko , Miyake Noriko , Piccione Joseph , Allen Julian , Matsumoto Naomichi , Pipan Mary , Krantz Ian D. , Izumi Kosuke
Published: May 2019

CHOPS syndrome is a multisystem disorder caused by missense mutations in AFF4. Previously, we reported three individuals whose primary phenotype included cognitive impairment and coarse facies, heart defects, obesity, pulmonary involvement, and short stature. This syndrome overlaps phenotypically with Cornelia de Lange syndrome, but presents distinct differences including facial features, pulmonary involvement, and obesity. Here, we provide clinical descriptions of an additional eight individuals with CHOPS syndrome, as well as neurocognitive analysis of three individuals. All 11 individuals presented with features reminiscent of Cornelia de Lange syndrome such as synophrys, upturned nasal tip, arched eyebrows, and long eyelashes. All 11 individuals had short stature and obesity. Congenital heart disease and pulmonary involvement were common, and those were seen in about 70% of individuals with CHOPS syndrome. Skeletal abnormalities are also common, and those include abnormal shape of vertebral bodies, hypoplastic long bones, and low bone mineral density. Our observation indicates that obesity, pulmonary involvement, skeletal findings are the most notable features distinguishing CHOPS syndrome from Cornelia de Lange syndrome. In fact, two out of eight of our newly identified patients were found to have AFF4 mutations by targeted AFF4 mutational analysis rather than exome sequencing. These phenotypic findings establish CHOPS syndrome as a distinct, clinically recognizable disorder. Additionally, we report three novel missense mutations causative for CHOPS syndrome that lie within the highly conserved, 14 amino acid sequence of the ALF homology domain of the AFF4 gene, emphasizing the critical functional role of this region in human development.
SLC18A3 variants lead to fetal akinesia deformation sequence early in pregnancy
Authors: Hakonen Anna H. , Polvi Anne , Saloranta Carola , Paetau Anders , Heikkilä Päivi , Almusa Henrikki , Ellonen Pekka , Jakkula Eveliina , Saarela Janna , Aittomäki Kristiina
Published: May 2019

Fetal akinesia deformation sequence (FADS) and lethal multiple pterygium syndrome (LMPS) are clinically overlapping syndromes manifesting with reduced or absent fetal movement, arthrogryposis, and several anomalies during fetal life. The etiology of these syndromes is heterogeneous, and in many cases it remains unknown. In order to determine the genetic etiology of FADS in two fetuses with fetal akinesia, arthrogryposis, edema, and partial cleft palate, we utilized exome sequencing. Our investigations revealed a homozygous nonsense variant [c.1116C>A, p.(Cys372Ter)] in the SLC18A3 gene, which encodes for the vesicular acetylcholine transporter (VAChT) responsible for active transport of acetylcholine in the neuromuscular junction. This is the first description of a nonsense variant in the SLC18A3 gene, as only missense variants and whole gene deletions have been previously identified in patients. The previously detected SLC18A3 defects have been associated with congenital myasthenic syndromes, and therefore our findings extend the clinical spectrum of SLC18A3 defects to severe prenatal phenotypes. Our findings suggest that nonsense variants in SLC18A3 cause a more severe phenotype than missense variants and are in line with previous studies showing a lethal phenotype in VAChT knockout mice. Our results underline the importance of including SLC18A3 sequencing in the differential diagnostics of fetuses with arthrogryposis, FADS, or LMPS of unknown etiology.
Synthetische Analoga zeigen die essentiellen Strukturmotive von Lugdunin und seinen Protonentransport
Authors: Schilling Nadine A. , Berscheid Anne , Schumacher Johannes , Saur Julian S. , Konnerth Martin C. , Wirtz Sebastian N. , Beltrán‐Beleña José M. , Zipperer Alexander , Krismer Bernhard , Peschel Andreas , Kalbacher Hubert , Brötz‐Oesterhelt Heike , Steinem Claudia , Grond Stephanie
Published: May 2019

Lugdunin, ein neues Thiazolidin‐Cyclopeptid, weist gegenüber Methicillin‐resistentem Staphylococcus aureus (MRSA) antimikrobielle Wirkung im mikromolaren Bereich auf. Für die Untersuchung von Struktur‐Aktivitätsbeziehungen (SAR) wurden synthetische Alanin‐ und Stereo‐Derivate sowie Peptide mit modifiziertem Thiazolidinring auf ihre antimikrobielle Aktivität getestet. Sowohl das Thiazolidin als auch die d‐, l‐alternierende Konfiguration stellen essentielle Strukturmotive dar. Bemerkenswert ist die identische Aktivität des Enantiomers, was eine stereospezifische Wechselwirkung mit einem Zielmolekül ausschließt. Die antibakterielle Wirkung korreliert stark mit dem Einbrechen des Membranpotentials von S. aureus. Lugdunin gleicht pH‐Gradienten in künstlichen Membranvesikeln unter Erhalt der Membranintegrität aus. Der Wirkmechanismus (MoA) beruht somit auf Protonentransport. Der Einbau eines zusätzlichen Tryptophans oder einer Propargylfunktion erweitert die Diversität dieser neuen Substanzklasse der Thiazolidin‐Cyclopeptide.
Rapid Detection of Exosomal MicroRNAs Using Virus‐Mimicking Fusogenic Vesicles
Authors: Gao Xihui , Li Sha , Ding Fei , Fan Hongjia , Shi Leilei , Zhu Lijuan , Li Jing , Feng Jing , Zhu Xinyuan , Zhang Chuan
Published: May 2019

Exosomal microRNAs (miRNAs) are important biomarkers for clinical diagnosis and disease treatment monitoring. However, most approaches for exosomal miRNA detection are time‐consuming, laborious, and expensive. Herein, we report a virus‐mimicking fusogenic vesicle (Vir‐FV) that enables rapid, efficient, and high‐throughput detection of exosomal miRNAs within 2 h. Fusogenic proteins on Vir‐FVs can specifically target the sialic‐acid‐containing receptors on exosomes, inducing efficient fusion of Vir‐FVs and exosomes. Upon vesicle content mixing, the molecular beacons encapsulated in Vir‐FVs specifically hybridize with the target miRNAs in the exosomes, generating fluorescence. Combined with flow cytometry, the Vir‐FVs can not only detect exosomal miRNAs but also distinguish tumor exosomes from normal exosomes by sensing the tumor‐related miRNAs, paving the way towards the rapid and efficient detection of exosomal miRNAs for diagnosis and prognosis prediction of diseases.
π–π Interactions Between Aromatic Groups in Amphiphilic Molecules: Directing Hierarchical Growth of Porous Zeolites
Authors: Zhang Yunjuan , Che Shunai
Published: May 2019

The development of hierarchical macro‐ or mesoporous zeolites is essential in zeolite synthesis because the size of the micropores limits mass transport and their use as industrial catalysts for bulky molecules. Although major breakthroughs have been achieved, fabricating crystallographically ordered mesoporous zeolites using a templating strategy is still an unsolved challenge. This minireview highlights our recent efforts on the self‐assembly of amphiphilic molecules to obtain ordered hierarchical MFI zeolites by introducing aromatic groups into the hydrophobic tail of the amphiphilic molecules. Owing to the geometric matching between the self‐assembled aromatic tails and the MFI framework, a) single‐crystalline mesostructured zeolite nanosheets (SCZNs), b) SCZNs with a 90° rotational intergrowth structure, c) a hierarchical MFI zeolite with a two‐dimensional square P4mm mesostructure, and d) a single‐crystalline mesoporous ZSM‐5 with three‐dimensional pores and sheetlike mesopores layered along the a‐axis were successfully synthesized.
Robust Microporous Metal–Organic Frameworks for Highly Efficient and Simultaneous Removal of Propyne and Propadiene from Propylene
Authors: Peng Yun‐Lei , He Chaohui , Pham Tony , Wang Ting , Li Pengfei , Krishna Rajamani , Forrest Katherine A. , Hogan Adam , Suepaul Shanelle , Space Brian , Fang Ming , Chen Yao , Zaworotko Michael J. , Li Jinping , Li Libo , Zhang Zhenjie , Cheng Peng , Chen Banglin
Published: May 2019

Simultaneous removal of trace amounts of propyne and propadiene from propylene is an important but challenging industrial process. We report herein a class of microporous metal–organic frameworks (NKMOF‐1‐M) with exceptional water stability and remarkably high uptakes for both propyne and propadiene at low pressures. NKMOF‐1‐M separated a ternary propyne/propadiene/propylene (0.5 : 0.5 : 99.0) mixture with the highest reported selectivity for the production of polymer‐grade propylene (99.996 %) at ambient temperature, as attributed to its strong binding affinity for propyne and propadiene over propylene. Moreover, we were able to visualize propyne and propadiene molecules in the single‐crystal structure of NKMOF‐1‐M through a convenient approach under ambient conditions, which helped to precisely understand the binding sites and affinity for propyne and propadiene. These results provide important guidance on using ultramicroporous MOFs as physisorbent materials.
Platinum (II) N‐heterocyclic carbene complexes: Synthesis, characterization and cytotoxic properties
Authors: Karaca Emine Özge , Çiftçi Osman , Özdemir İlknur , Yakali Gül , Aygün Muhittin , Gürbüz Nevin , Özdemir İsmail
Published: May 2019

Platinum (II) complexes bearing N‐heterocyclic carbene (NHC) ligands have been widely used in catalytic chemistry, but there are very few reports of biological properties of this type of complexes. A series of [PtCl2(NHC)(PEt3)] complexes were synthesized. The structures of all compounds were characterized by 1H‐NMR, 13C‐NMR, IR and elemental analysis techniques, which supported the proposed structures. The single crystal structures of complexes 1a and 1e were determined. The title complexes show slightly distorted square‐planar coordination around the platinum (II) metal center. The cytotoxic properties of the platinum (II)–NHC complexes have been assessed in various human cancer lines, including cisplatin‐sensitive and resistant cells. IC50 values of these four complexes were determined by the MTS‐based assay on three human cell lines—brain (SHSY5Y), colon (HTC116) and liver (HEP3B). These complexes have been highlighted cancer therapeutic agent with unique structures and functions.
Synthesis, structural characterization and DNA binding affinity of new bioactive nano‐sized transition metal complexes with sulfathiazole azo dye for therapeutic applications
Authors: Saad Fawaz A. , El‐Ghamry Hoda A. , Kassem Mohammed A.
Published: May 2019

The azo dye ligand 4‐(5‐chloro‐2‐hydroxyphenylazo)‐N‐thiazol‐2‐ylbenzenesulfonamide (H2L) formed by the coupling reaction of sulfathiazole and p‐chlorophenol was synthesized and characterized using elemental analysis and Fourier transform infrared (FT‐IR) as well as UV–visible spectra. Nano‐sized divalent Cu, Co, Ni, Mn and Zn complexes of the synthesized azo dye ligand were prepared and investigated using various spectroscopic and analytical techniques. Elemental and thermal analyses indicated the formation of the Cu(II), Ni(II) and Mn(II) complexes in a molar ratio of 1:2 (L:M) while Co(II) and Zn(II) complexes exhibited a 1:1 (M:L) ratio. FT‐IR spectral studies confirmed the coordination of the ligand to the metal ions through the phenolic hydroxyl oxygen, azo nitrogen, sulfonamide oxygen and/or thiazole nitrogen. The geometric arrangements around the central metal ions were investigated applying UV–visible and electron spin resonance spectra, thermogravimetric analysis and molar conductance measurements. X‐ray diffraction patterns revealed crystalline nature of H2L and amorphous nature of all synthesized complexes. Transmission electron microscopy images confirmed nano‐sized particles and their homogeneous distribution over the complex surface. Antibacterial, antifungal and antitumour activities of the investigated complexes were screened compared with familiar standard drugs to confirm their potential therapeutic applications. The Cu(II) complex showed IC50 of 3.47 μg ml−1 (5.53 μM) against hepatocellular carcinoma cells, which means that it is a more potent anticancer drug compared with the standard cisplatin (IC50 = 3.67 μg ml−1 (12.23 μM)). Furthermore, the Co(II), Ni(II), Cu(II) and Zn(II) complexes displayed IC50 greater than that of an applied standard anticancer agent (5‐flurouracil) towards breast carcinoma cells. Hence, these complexes can be considered as promising anticancer drugs. The mode of binding of the complexes with salmon serum DNA was determined through electronic absorption titration and viscosity studies.
Facile one‐step synthesis of broken case‐like carbon‐doped g‐C3N4 for photocatalytic degradation of benzene
Authors: Xue Jinjuan , Huang Chengjuan , Xu Peng , Wang Mingxin , Ma Shuaishuai
Published: May 2019

Herein, a novel broken case‐like carbon‐doped g‐C3N4 photocatalyst was obtained via a facile one‐pot pyrolysis and cost‐effective method using glyoxal‐modified melamine as a precursor. The obtained carbon/g‐C3N4 photocatalyst showed remarkable enhanced photocatalytic activity in the degradation of gaseous benzene compared with that of pristine g‐C3N4 under visible light. The pseudo‐first‐order rate constant for gaseous benzene degradation on carbon/g‐C3N4 was 0.186 hr−1, 5.81 times as large as that of pristine g‐C3N4. Furthermore, a possible photocatalytic mechanism for the improved photocatalytic performance over carbon/g‐C3N4 nanocomposites was proposed.
Influence of expandable graphite on flame retardancy and thermal stability property of unsaturated polyester resins/organic magnesium hydroxide composites
Authors: He Jinnan , Zeng Wei , Shi Miaomiao , Lv Xinyao , Fan Hui , Lei Ziqiang
Published: May 2019

An eco‐friendly flame retardant unsaturated polyester resin (UPR) material was prepared by combination organic magnesium hydroxide (OMH) and expandable graphite (EG). Different from direct addition of magnesium hydroxide (MH) in UPR matrix‐like traditional method, OMH as a reactive monomer participates in the polycondensation reaction of UPR was more effective in improving the compatibility of flame retardant with matrix. Interestingly, the flame retardant UPR composites exhibited a more satisfactory flame retardant effect when a certain amount of 8 wt % EG was added into UPR/OMH matrix because of the synergistic effect between OMH and EG, resulted in the limited oxygen index from 21.7 to 28.5% and UL‐94 test passed V‐0 rating. Moreover, the peak heat release rate, total heat release, and smoke production rate of flame retardant UPR composites significantly reduced. The excellent flame retardancy was due to the formation of a dense and continuous carbon layer in the later stages of combustion. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 47881.
The effect of phonological processing on mathematics performance in elementary school varies for boys and girls: Fixed‐effects longitudinal analysis
Authors: Kuzmina Yulia , Ivanova Alina , Kaiky Diana
Published: May 2019

Investigations into the relations between phonological processing and math performance have yielded contradictory results. These contradictions might be related to small sample sizes and/or cross‐sectional designs of previous studies that limited the possibility of generalizing the findings obtained. The first goal of this study was to estimate the effect of phonological processing on number recognition and math performance during the first year of schooling, controlling for reading achievement. The second goal was to examine whether this effect varied for boys and girls. To achieve these goals, we used a large sample of first‐graders (N = 3296, 49% were girls) in Russia and applied fixed effects longitudinal analysis. Participants were assessed twice, at the beginning and at the end of the first grade (mean age was 7.3 years at Time 1). The item response theory scaling procedure was used to estimate individual scores for math performance, number recognition, phonological processing and reading performance. The results revealed that phonological processing had effects on number recognition and math performance. This effect was more salient for number recognition than for math performance, probably due to the greater involvement of the retrieval strategy in number recognition tasks. The results also demonstrated that the effect of phonological processing on number recognition was stronger for girls than for boys.
A simplified relationship between the femoral trochlea and the femoral condyle: A sagittal MRI analysis by an ellipse‐fitting approach
Authors: Wang Gang , Liu Mingyang , Zhang Zheng , Liu Shiwei , Zhang Guanpeng , Yang Chen
Published: May 2019

We have introduced an ellipse‐fitting approach to express the shapes of trochlea and condyle on magnetic resonance imaging (MRI) and to analyze their relationship. Fifty healthy right knees were sagittal‐imaged by MRI at full extension. On the deepest trochlear groove slice, the articular surface was best‐fitted by a circle. Based on the center of this circle, both the most prominent slices of the medial and lateral trochleae were best‐fitted by ellipses. On the most distal slice of medial condyle, the articular surface was best‐fitted by a horizontal ellipse. Based on the center of this ellipse, the lateral condyle was best‐fitted by a rotational ellipse. The semimajor and semiminor axes of the trochlear ellipse and the condylar ellipse constituted a rectangle that represented the relationship between the trochlea and the condyle. The anteroposterior dimension (l) of this rectangle was 12.33 ± 1.41 mm, and the superoinferior dimension (w) was 7.21 ± 1.23 mm. The average tangent angle (θ) of the rectangle was 30.1° ± 2.6°. There were significant sex differences in l, w, and θ (all P ≤ 0.006), and all correlated significantly with the height of the subject (all P ≤ 0.001). The relationship between the femoral trochlea and the femoral condyle differed significantly between males and females, but this could have been a consequence of the significant correlation with subject height. Clin. Anat. 33:500–506, 2020. © 2019 Wiley Periodicals, Inc.
Subcutaneous Fat in the Upper Eyelids of Asians: Application to Blepharoplasty
Authors: Sun Lei , Chen Xi , Liu Guangpeng , Zhang Peng
Published: May 2019

The Asian eyelid has distinctive anatomical properties. Although the upper eyelid is reported in the literature to have no subcutaneous fat layer, we have often noticed adipose tissue below the upper eyelid skin during ophthalmic plastic surgeries. The aim of the present study was to examine the anatomical and histological features of subcutaneous adipose tissue in Asian upper eyelids using biopsies and microscopic morphological analysis. A total of 30 Chinese patients (60 upper eyelids) undergoing upper blepharoplasty were evaluated. The subcutaneous fat in the upper eyelids was surgically harvested and examined histologically. This study yielded two main findings. First, upper eyelid subcutaneous fat was found in 28 of the 30 patients. This fat layer was the inferior extension of the eyebrow subcutaneous fat layer, which descended and covered the superior half of the upper eyelid. Second, the lobules of subcutaneous fat in the upper eyelid were surrounded by dense fibrous tissues, and the fat cells were smaller than abdominal adipocytes but similar in size to orbital fat cells. Subcutaneous fat tissue is prominent in the upper eyelids of most Asians and is one important contributor to the bulky appearance of those eyelids. Clin. Anat. 33:338–342, 2020. © 2019 Wiley Periodicals, Inc.
Pediatric central venous catheterization
Authors: Hinton Lucy R. , Fischer Nicholas J. , Taghavi Kiarash , O'Hagan Lomani A. , Mirjalili Seyed Ali
Published: May 2019

The aortic valve (AV) has been used as a surrogate marker for the superior vena cava‐right atrium (SVC‐RA) junction during the placement of central venous catheters. There is a paucity of evidence to determine whether this is a consistent finding in children. Eighty‐seven computed tomography scans of the thorax acquired at local children's hospitals from April 2010 to September 2011 were retrospectively collected. The distance between the SVC‐RA junction and the AV was measured by dual consensus. The cranio‐caudal level of the junction and the AV were referenced to the costal cartilages (CCs) and anterior intercostal spaces (ICSs). The results confirmed that the SVC‐RA junction has a variable relationship to the AV. The junction was on average 3.1 mm superior to the AV. This distance increased with age. In the <1‐year‐old age group, the junction was on average 1.3 mm superior to the AV (range: −6 to 11 mm). In the 1–2 years old age group: 3.5 mm (range: −8 to 15 mm). In the 3–6 years old: 3.8 mm (range: −9 to 13 mm). In the >7 years old age group: 4 mm (range: −11 to 16 mm). The surface anatomy of the SVC‐RA junction was variable, ranging from the second ICS to sixth CC. The SVC‐RA junction has a predictable relationship to the AV, and this can be used as an adjunct marker for accurate placement of central venous catheters except in the smallest neonates. Clin. Anat. 32:778–782, 2019. © 2019 Wiley Periodicals, Inc.
Integrated and secure web‐based examination management system
Authors: Al‐Hawari Feras , Alshawabkeh Mai , Althawbih Haytham , Abu Nawas Omar
Published: May 2019

A web‐based examination management system that is implemented in‐house is discussed in this paper. It is designed based on the Java enterprise edition three‐tier architecture. It also allows defining and setting up exams according to a flexible tree‐based exams structure. Moreover, it integrates a rich text editor for composing exams suitable for different engineering and language disciplines. In addition, it automates the scheduling, grading, and reporting processes to relieve instructors from such cumbersome tasks. Furthermore, its capabilities and integration with different databases enable it to offer several security schemes that support strong multifactor authentication and authorization, detect impersonation, and prevent cheating. Besides, it provides an easy to use and informative wizard that enables students to take exams. Not to mention, the deployment results illustrate that the system has been successfully used to organize online exams in several semesters over the past 3 academic years. Finally, the conducted user surveys responses assert that the system is also user‐friendly, cutting edge, capable, reliable, fast, and highly available.
Getting absorbed in group therapy: Absorption and cohesion in integrative group treatment
Authors: Kealy David , McCloskey Katharine D. , Cox Daniel W. , Ogrodniczuk John S. , Joyce Anthony S.
Published: May 2019

Background

Absorption is a trait‐like dimension reflecting a tendency to immerse oneself in sensory and imaginative experiences. This characteristic has scarcely been investigated in group psychotherapy. The present study examined absorption in relation to clients′ experience of early group process, and as a moderator of group cohesion and improvement in psychiatric symptoms, in an integrative group treatment programme.

Methods

Participants included 81 clients, who completed an 18‐week programme of intensive, integrative, group treatment for personality dysfunction. Clients completed assessments of absorption and psychiatric symptom severity, and rated three aspects of group cohesion at week 5 of the programme.

Results

Absorption was significantly associated with stimulation from the group after controlling for severity of symptoms and personality dysfunction. Moderation analyses found a significant interaction effect for absorption and the stimulation component of group cohesion with regard to symptom improvement. Absorption thus had a moderating effect on the relationship between stimulation from the group and improvement in psychiatric symptoms; for clients with higher levels of absorption, stimulation from group therapy contributed significantly to reduced symptom severity at post‐treatment.

Discussion

Findings suggest that absorption may be a salient personality feature to consider in group therapy for clients with personality dysfunction.

Conclusion

Absorption may contribute to treatment outcome, in that clients′ absorption tendencies could interact with their enthusiasm for the group experience, thereby leading to reduced symptoms following intensive group treatment.
Exploring the Functional Consequences of Protein Backbone Alteration in Ubiquitin through Native Chemical Ligation
Authors: Werner Halina M. , Estabrooks Samuel K. , Preston G. Michael , Brodsky Jeffrey L. , Horne W. Seth
Published: May 2019

Ubiquitin (Ub) plays critical roles in myriad protein degradation and signaling networks in the cell. We report herein Ub mimetics based on backbones that blend natural and artificial amino acid units. The variants were prepared by a modular route based on native chemical ligation. Biological assays show that some are enzymatically polymerized onto protein substrates, and that the resulting Ub tags are recognized for downstream pathways. These results advance the size and complexity of folded proteins mimicked by artificial backbones and expand the functional scope of such agents.
Functional Characterization of 3‐Aminobenzoic Acid Adenylation Enzyme PctU and UDP‐N‐Acetyl‐d‐Glucosamine: 3‐Aminobenzoyl‐ACP Glycosyltransferase PctL in Pactamycin Biosynthesis
Authors: Kudo Fumitaka , Zhang Jiahao , Sato Shusuke , Hirayama Akane , Eguchi Tadashi
Published: May 2019

Pactamycin is an antibiotic produced by Streptomyces pactum with antitumor and antimalarial properties. Pactamycin has a unique aminocyclitol core that is decorated with 3‐aminoacetophenone, 6‐methylsaliciate, and an N,N‐dimethylcarbamoyl group. Herein, we show that the adenylation enzyme PctU activates 3‐aminobenzoic acid (3ABA) with adenosine triphosphate and ligates it to the holo form of the discrete acyl carrier protein PctK to yield 3ABA‐PctK. Then, 3ABA‐PctK is N‐glycosylated with uridine diphosphate‐N‐acetyl‐d‐glucosamine (UDP‐GlcNAc) by the glycosyltransferase PctL to yield GlcNAc‐3ABA‐PctK. Because 3ABA is known to be a precursor of the 3‐aminoacetophenone moiety, PctU appears to be a gatekeeper that selects the appropriate 3‐aminobenzoate starter unit. Overall, we propose that acyl carrier protein‐bound glycosylated 3ABA derivatives are biosynthetic intermediates of pactamycin biosynthesis.
Further delineation of the phenotype caused by a novel large homozygous deletion of GRID2 gene in an adult patient
Authors: Taghdiri Maryam , Kashef Atie , Abbassi Golemaryam , Moshtagh Azadeh , Sadatian Neda , Fardaei Majid , Najafi Kimia , Kariminejad Roxana
Published: May 2019

Key Clinical Message

Different mutations in glutamate receptor ionotropic delta 2 (GRID2) gene cause cerebellar ataxia in human. We report the largest homozygous deletion of the GRID2 gene reported to date, most probably causing complete loss of the gene product. Our patient presents mainly early onset cerebellar ataxia, cerebellar atrophy, nystagmus, and developmental delay with the least amount of intellectual disability.
Metal‐Organic‐Framework‐Derived Nitrogen‐Doped Hybrid Nickel‐Iron‐Sulfide Architectures on Carbon Cloth as Efficient Electrocatalysts for the Oxygen Evolution Reaction
Authors: Shen Yirui , Wang Ling , Jiang Pingping , Lee Wee Siang Vincent , Xue Junmin
Published: May 2019

Metal‐organic framework (MOF)‐derived nitrogen‐doped NiFe‐sulfides/carbon hybrid architectures were successfully constructed on carbon cloth (CC) with different n(Ni)/n(Fe) ratios through a simultaneous carbonization and sulfurization procedure from the corresponding bimetal NiFe‐based MOFs. The samples were directly utilized as the working electrodes for the oxygen evolution reaction (OER). The optimal sample N‐NiFe‐S/C‐8/2@CC possessed superior OER electrocatalytic activity with a remarkably low overpotential of 232 mV at a current density of 10 mA cm−2 in 1 M KOH aqueous solution. At the same time, a small Tafel slope of 58 mV dec−1 was achieved and excellent durability was also demonstrated. Such superior OER activity and durability of N‐NiFe‐S/C@CC may originate from a synergetic effect between Fe and Ni, the nitrogen‐doped carbon matrix derived from MOFs, and the direct growth of active materials on CC. This facile approach of preparing bimetal sulfide compounds derived from MOFs may be a viable method for designing and preparing high‐performing electrocatalytic materials for wider applications.
Mechanochemically Assisted Synthesis of Ruthenium Clusters Embedded in Mesoporous Carbon for an Efficient Hydrogen Evolution Reaction
Authors: Liu Xiaofei , Jin Tian Leo , Hood Zachary D. , Tian Chengcheng , Guo Yanglong , Zhan Wangcheng
Published: May 2019

Ruthenium (Ru) clusters are reported as efficient electrocatalysts for the hydrogen evolution reaction (HER). However, a precise and facile synthetic protocol for preparing Ru clusters is still a challenge. Herein, a facile mechanochemically assisted strategy was proposed to synthesize ruthenium clusters embedded in mesoporous carbon (Ru‐CN/MC). Importantly, for the synthesis of Ru‐CN/MC, melamine was utilized not only as a capping agent to stabilize Ru clusters, but also to provide N sites for the carbon support. The well‐designed Ru‐CN/MC exhibits impressive HER performance in 1 M KOH, which shows an extremely low overpotential of 17 mV at a current density of 10 mA cm−2. More importantly, excellent long‐term electrochemical stability in both alkaline and acid electrolyte was achieved for Ru‐CN/MC. Therefore, the developed synthesis method for Ru clusters and the subsequent insightful investigations on the HER performance shed light on new opportunities for exploring highly efficient and renewable HER electrocatalysts.
Unraveling the Mechanisms of the Excited‐State Intermolecular Proton Transfer (ESPT) for a D‐π‐A Molecular Architecture
Authors: Hong Dan‐Li , Luo Yang‐Hui , He Xiao‐Tong , Zheng Zi‐Yue , Su Shan , Wang Jia‐Ying , Wang Cong , Chen Chen , Sun Bai‐Wang
Published: May 2019

Precise revealing the mechanisms of excited‐state intermolecular proton transfer (ESPT) and the corresponding geometrical relaxation upon photoexcitation and photoionization remains a formidable challenge. In this work, the compound (E)‐4‐(((4H‐1,2,4‐triazol‐4‐yl)imino)methyl)‐2,6‐dimethoxyphenol (TIMDP) adopting a D‐π‐A molecular architecture featuring a significant intramolecular charge transfer (ICT) effect has been designed. With the presence of perchloric acid (35 %), TIMDP can be dissolved through the formation of a HClO4–H2O–OH(TIMDP)–N(TIMDP) hydrogen‐bonding bridge. At the ground state, the ICT effect is dominant, giving birth to crystals of TIMDP. Upon external stimuli (e.g., UV light irradiation, electro field), the excited state is achieved, which weakens the ICT effect, and significantly promotes the ESPT effect along the hydrogen‐bonding bridge, resulting in crystals of [HTIMDP]+⋅[H2O]⋅[ClO4]−. As a consequence, the mechanisms of the ESPT can be investigated, which distorted the D‐π‐A molecular architecture, tuned the emission color with the largest Stokes shift of 242 nm, and finally, high photoluminescence quantum yields (12 %) and long fluorescence lifetimes (8.6 μs) have achieved. These results not only provide new insight into ESPT mechanisms, but also open a new avenue for the design of efficient ESPT emitters.
Radical‐Pair Formation in Hydrocarbon (Aut)Oxidation
Authors: Sandhiya Lakshmanan , Zipse Hendrik
Published: May 2019

The reaction profiles for the uni‐ and bimolecular decomposition of benzyl hydroperoxide have been studied in the context of initiation reactions for the (aut)oxidation of hydrocarbons. The unimolecular dissociation of benzyl hydroperoxide was found to proceed through the formation of a hydrogen‐bonded radical‐pair minimum located +181 kJ mol−1 above the hydroperoxide substrate and around 15 kJ mol−1 below the separated radical products. The reaction of toluene with benzyl hydroperoxide proceeds such that O−O bond homolysis is coupled with a C−H bond abstraction event in a single kinetic step. The enthalpic barrier of this molecule‐induced radical formation (MIRF) process is significantly lower than that of the unimolecular O−O bond cleavage. The same type of reaction is also possible in the self‐reaction between two benzyl hydroperoxide molecules forming benzyloxyl and hydroxyl radical pairs along with benzaldehyde and water as co‐products. In the product complexes formed in these MIRF reactions, both radicals connect to a centrally placed water molecule through hydrogen‐bonding interactions.
NMR Reveals That a Highly Reactive Nonheme FeIV=O Complex Retains Its Six‐Coordinate Geometry and S=1 State in Solution
Authors: Banerjee Saikat , Rasheed Waqas , Fan Ruixi , Draksharapu Apparao , Oloo Williamson N. , Guo Yisong , Que Lawrence
Published: May 2019

The [FeIV(O)(Me3NTB)]2+ (Me3NTB=tris[(1‐methyl‐benzimidazol‐2‐yl)methyl]amine) complex 1 has been shown by Mössbauer spectroscopy to have an S=1 ground state at 4 K, but is proposed to become an S=2 trigonal‐bipyramidal species at higher temperatures based on a DFT model to rationalize its very high C−H bond‐cleavage reactivity. In this work, 1H NMR spectroscopy was used to determine that 1 does not have C3‐symmetry in solution and is not an S=2 species. Our results show that 1 is unique among nonheme FeIV=O complexes in retaining its S=1 spin state and high reactivity at 193 K, providing evidence that S=1 FeIV=O complexes can be as reactive as their S=2 counterparts. This result emphasizes the need to identify factors besides the ground spin state of the FeIV=O center to rationalize nonheme oxoiron(IV) reactivity.
A multilevel graph approach for rainfall forecasting: A preliminary study case on London area
Authors: Clarizia Fabio , Colace Francesco , De Santo Massimo , Lombardi Marco , Pascale Francesco , Santaniello Domenico , Tuker Allan
Published: May 2019

Increasing populations and rapid large‐scale urbanization has created a demand to increase the quality of life through economic development, social stability, and better quality environments. These issues are addressed in the field of Smart Cities where, through the Internet of Things, efforts are being made to support added‐value services for the administration of the city and for citizens. The continuous exchange of information inevitably produces a huge amount of data, which demands analyses of data using unconventional methods within a Big Data context. How can we properly process these data? How can we properly use these data in order to increase the competitiveness and efficiency of services, and how could they contribute to social development? Services that could be useful in this field include Early Warning Systems. Information management environments, or more generally pervasive data contexts, may be supported by context representation approaches and enhanced through adopting probabilistic approaches such as Context Dimension Tree, Ontology, and Bayesian Network. The aim of this work is to introduce and explain a methodology for merging CDTs and Ontologies, and probabilistic approach based on BNs in order to help expert users handle emergencies and provide suggestions for improving the liveability of cities for their inhabitants.
Structural Transformation of 2,7‐Dibromopyrene on Au(111) Mediated by Halogen‐Bonding Motifs
Authors: Hu Jinbang , Shen Kongchao , Hu Jinping , Sun Haoliang , Tian Qiwei , Zhaofeng  , Liang  , Huang Han , Jiang Zheng , Wells Justin W. , Song Fei
Published: May 2019

Fundamental understanding of the bonding motifs that elaborately mediate the formation of supramolecular nanostructures is essential for the rational design of stable artificial organic architectures. Herein, the structural transformation of the adsorption complex of 2, 7‐dibromopyrene (Br2Py) on the Au(111) surface has been investigated by scanning tunnelling microscopy combined with X‐ray photoemission spectroscopy and density function theory calculations. In the initial stage of self‐assembly, well ordered patterns are formed in the manner of extended supramolecular structures balanced by intermolecular halogen bonding motifs, whilst the Au(111) reconstruction is still fairly visible. Subsequent thermal annealing promotes the dehalogenation and on‐surface Ullmann coupling, and polymerized oligomers are consequently constructed. Interestingly, such polymerized chains are still stably mediated by the halogen bonding motif via dissociated Br atoms which are revealed to be absorbed on the bridge site of Au(111), while the number of halogen bonds increases significantly from self‐assembly to Ullmann coupling polymerization, indicating that the halogen bonding motif contributes significantly to the extended one‐dimensional polymers.
Investigating Variation of the Pnicogen Nucleophilic Heteroatom on Ionic Liquid Solvent Effects in Bimolecular Nucleophilic Substitution Processes
Authors: Schaffarczyk McHale Karin S. , Haines Ronald S. , Harper Jason B.
Published: May 2019

A series of nucleophiles containing Group 15 nucleophilic heteroatoms has been used to expand and develop the current understanding of ionic liquid solvent effects on bimolecular nucleophilic substitution processes. It was found that when using arsenic‐, antimony‐ and bismuth‐based nucleophiles, rate constant enhancement was observed for all solvent compositions containing ionic liquids. This rate constant enhancement was driven by ionic liquid/transition state interactions, which contrasts with previous studies on earlier Group 15 nucleophiles. This study provides a holistic understanding and augments the predictive framework for the effects of ionic liquids on bimolecular nucleophilic substitution processes, with the potential for these periodic trends to be broadly applied.
Diabatization by Localization in the Framework of Configuration Interaction Based on Floating Occupation Molecular Orbitals (FOMO−CI)
Authors: Accomasso Davide , Persico Maurizio , Granucci Giovanni
Published: May 2019

We present a diabatization method of general applicability, based on the localization of molecular orbitals on user specified groups of atoms. The method yields orthogonal molecular orbitals similar to the canonical ones for the isolated atom groups, that are the basis to build reference spin‐adapted configurations representing localized or charge transfer excitations. An orthogonal transformation from the adiabatic to the quasi‐diabatic basis is defined by requiring maximum overlap with the diabatic references. We present the diabatization algorithm as implemented in the framework of semiempirical configuration interaction based on floating occupation molecular orbitals (FOMO−CI), but the same transformation can also be applied to ab initio wavefunctions, obtained for instance with state‐average CASSCF. The diabatic representation so obtained and the associated hamiltonian matrix are particularly suited to assess quantitatively the interactions that account for charge and energy transfer transitions, and to analyze the results of nonadiabatic dynamics simulations involving such phenomena.
In Silico Investigation of the Aggregation‐Caused Quenching: the “Tolane‐Based Molecule” Case
Authors: Le Bras Laura , Adamo Carlo , Perrier Aurélie
Published: May 2019

A tolane‐based molecule, the 4‐fluorophenyl 4‐((4‐(octyloxy)phenyl)ethynyl)‐benzoate (FOEB), was recently reported to show Crystallisation‐Induced Emission (CIE) and Aggregation‐Caused Quenching (ACQ) [Tong et al., J. Phys. Chem. C, 2015, 119, 21875]. In this work, we rely on a combination of tailored computational methods based on molecular dynamics, (TD‐)DFT and ONIOM QM/QM′ calculations, to investigate the structural and optical properties of FOEB in solution, crystal and aggregate. First, the computation of the Huang‐Rhys factors and the reorganization energies can rationalize the modulation of the emission efficiency observed when changing the solvent polarity. The moderate fluorescence quenching observed in solution is due to the photophysical energy dissipation caused by low‐frequency vibrational modes involving the lateral groups, along with motions out of the plane of the molecule. In crystalline environment, due to the packing arrangment, there is a restrictriction of intramolecular vibration (RIV) mechanism which should open the radiative decay channels. On the opposite, within the aggregate, the observed ACQ arises from two different phenomena, the energy dissipation during the internal conversion process through the low‐frequency vibration mode identified in solution and a moderate energy loss through excitonic couplings.
A Copper Coordination Polymer with Matching Energy Level for Modifying Hole Transport Layers to Improve the Performance of Perovskite Solar Cells
Authors: Qiu Lele , Zheng Xubin , Yang Yulin , Dong Yayu , Dong Guohua , Xia Debin , Liu Xianda , Wu Qingyin , Fan Ruiqing
Published: May 2019

Spiro‐OMeTAD is currently the most widely used hole transport material for the preparation of high‐performance perovskite solar cells (PSCs), usually requiring the addition of additives to achieve the desired electronic conductivity. However, the quality of the film is degraded owing to the addition of additives. Holes and defects can be observed, and the dispersion of the additives are uneven inside. Here, a copper coordination polymer, Cu‐bix, with matching energy level and fluorescent properties was screened for use as an additional additive to dope Spiro‐OMeTAD. The doping of Cu‐bix effectively improved the dispersion state of the additives in the hole transport layers and alleviated the aggregation of LiTFSI (lithium bis(trifluoromethanesulfonyl)imide) or/and lithium salt complexes in the film. Owing to better dispersion of the additives, Spiro‐OMeTAD was more fully and uniformly oxidized whereas the possibility of charge recombination was reduced in the devices. Furthermore, the flat and tightly bonded film layer obtained by optimization of the doping amount can efficiently transfer holes from the perovskite layers to the hole transport layers. Possible interaction mechanisms between additives and the copper coordination polymer are proposed and discussed. The resulting power conversion efficiency (PCE) for Cu‐bix‐doped PSCs was improved from 16.52 % to 18.47 % compared to the pristine devices, and this type of PSCs also showed a long stability in air owing to the increased hydrophobicity of the Cu‐bix‐based hole transport layers.
A Polyoxometalate‐Based Microfluidic Device for Liquid‐Phase Oxidation of Glycerol
Authors: Tao Meilin , Li Yiming , Zhang Xueyan , Li Zonghang , Hill Craig L. , Wang Xiaohong
Published: May 2019

Peroxidation of glycerol has been carried out in a polyoxometalate (POM)‐based microfluidic reactor, which was fabricated on a capillary by using a layer‐by‐layer strategy. Lactic acid (LA) is produced selectively in high yield with a TOF as high as 20 000 h−1, compared to a TOF of 200 h−1 in batch mode. This POM microfluidic reactor is readily prepared, scalable, highly stable, reusable, and also potentially applicable to selective oxidation of other bio‐wastes.
A multilevel inverter based on cascade connection of submultilevel units with reduced switch count
Authors: Sedaghati Farzad , Majareh Seyed Hadi Latifi
Published: May 2019

In this paper, a multilevel inverter based on cascade connection of new submultilevel inverters is presented. The suggested submultilevel inverter is constructed using series connection of basic switching units. The proposed multilevel inverter uses fewer power switches in comparison with some similar topologies which results in reduction of switch gate drivers and also converter size and cost. The proposed multilevel inverter can be implemented in both symmetric and asymmetric configurations. The multilevel inverter configuration and operation principle are described in detail, and then, design methods of symmetric and asymmetric configurations are given. Determination of the optimal number of basic units and cascaded submultilevel inverters regarding criteria such as number of switches and total blocking voltage (TBV) of switches is studied. Power losses of the proposed multilevel inverter are calculated, and then, its symmetric and asymmetric configurations are compared with each other and also with similar cascaded multilevel inverters in various items. The validity of the suggested cascaded multilevel inverter is verified using both computer simulations and laboratory prototype implementation.
Lifetime productivity of tree cavities used by cavity‐nesting animals in temperate and subtropical forests
Authors: Cockle Kristina L. , Trzcinski Mark Kurtis , Wiebe Karen L. , Edworthy Amanda B. , Martin Kathy
Published: May 2019

Tree cavities are a critical multi‐annual resource that can limit populations and structure communities of cavity‐nesting vertebrates. We examined the regional and local factors influencing lifetime productivity (number and richness of occupants) of individual tree cavities across two divergent forest ecosystems: temperate mixed forest in Canada and subtropical Atlantic Forest, Argentina. We predicted that (1) species would accumulate more rapidly within cavities in the species‐rich system (Argentina: 76 species) than the poorer system (Canada: 31 species), (2) cavity characteristics associated with nest‐site selection in short‐term studies would predict lifetime cavity productivity, and (3) species would accumulate more rapidly across highly used cavities than across cavities used only once, and in Argentina than in Canada. We monitored and measured nesting cavities used by birds and mammals over 22 breeding seasons (1995–2016) in Canada and 12 breeding seasons (2006–2017) in Argentina. Cavities were used an average of 3.1 times by 1.7 species in Canada and 2.2 times by 1.4 species in Argentina. Species richness within cavities increased with number of nesting events at similar rates in Canada and Argentina, in both cases much slower than expected if within‐cavity species assemblages were random, suggesting that lifetime richness of individual cavities is more strongly influenced by local ecological factors (nest site fidelity, nest niche) than by the regional species pool. The major determinant of lifetime cavity productivity was the cavity's life span. We found only weak or inconsistent relationships with cavity characteristics selected by individuals in short‐term nest‐site selection studies. Turnover among (vs. within) cavities was the primary driver of diversity at the landscape scale. In Canada, as predicted, species accumulation was fastest when sampling across high‐use cavities. In Argentina, the rates of species accumulation were similar across high‐ and low‐use cavities, and fastest when both high‐ and low‐use cavities were pooled. These findings imply that biodiversity of cavity nesters is maintained by a mix of long‐lived (highly productive, legacy trees) and many high‐turnover (single‐use, fast decaying) tree cavities. Conservation of both long‐lasting and single‐use cavities should be incorporated into decisions about stand‐level forest management, regional land use policies, and reserve networks.