bluuebunny/crossref_metadata_2025 huggingface dataset:
Disease Burden of Patients With Osteoarthritis: Results of a Cross‐Sectional Survey Linked to Claims Data
Authors: Callhoff Johanna , Albrecht Katinka , Redeker Imke , Lange Toni , Goronzy Jens , Günther Klaus‐Peter , Zink Angela , Schmitt Jochen , Saam Joachim , Postler Anne
Published: September 2019

Objective

Osteoarthritis (OA) is a major reason for chronic pain, stiffness, and functional limitation. This study was undertaken to analyze factors associated with the burden of OA, taking the pattern of joint involvement into account.

Methods

From a random sample of 8,995 patients with OA (International Statistical Classification of Diseases and Related Health Problems, Tenth Revision, German Modification codes M15 [polyarticular], M16 [hip], or M17 [knee]) from a German statutory health insurance database, 3,564 patients completed a survey including the Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC). Patients with knee, hip, concomitant hip and knee, or polyarticular manifestation were compared concerning pain, stiffness, function, and impact on work and personal life. Data were linked to dispensation records. The association of age, sex, body mass index (BMI), symptom duration, and the World Health Organization–5 Well‐Being Index (WHO‐5) with WOMAC results was assessed in multiple linear regression models.

Results

Patients with knee (n = 1,448), hip (n = 959), hip and knee (n = 399), or polyarthritic (n = 758) OA were included. Concomitant hip and knee OA was accompanied by the highest WOMAC values (mean 44), frequent impairment of personal life (75%), and the highest use of analgesics (52% nonsteroidal antiinflammatory drugs, 22% opioids, and 37% others). In the regression analyses, BMI per 5 units and WHO‐5 per 10% worsening were associated with an increase in WOMAC values of 4–5 points, irrespective of the joint manifestations.

Conclusion

Disease burden is high in patients with concomitant hip and knee OA and is connected with frequent prescription of analgesics. Involvement of several joints, BMI, and depressive symptoms need to be considered when using the WOMAC as an outcome instrument.
Control Co‐Design: An engineering game changer
Authors: Garcia‐Sanz Mario
Published: September 2019

Over the last few decades, control engineers have focused on developing innovative control theories and algorithms to regulate systems. These control efforts are usually at the last stage of a sequential strategy that allows engineering departments to work independently and consecutively toward the design of new products and systems. Control algorithms are usually developed at the end of that sequential process, once the mechanical, electrical, and other subsystems are completely defined. This paper discusses a different approach, named Control Co‐Design (CCD). Following a concurrent engineering strategy that considers multidisciplinary subsystem interactions from the beginning of the design process, CCD applies control concepts to design the entire system and reach optimal solutions that are not achievable otherwise. This approach is a game changer for the control engineer, who will be not only the designer of advanced control algorithms but also the natural leader of the design of new products and systems. This paper describes some historic engineering breakthroughs achieved by applying CCD and explores some relevant application areas. It also presents three complementary CCD methodologies that include control‐inspired paradigms, formal mathematical co‐optimization techniques, and co‐simulation campaigns to enhance engineering creativity and achieve radically new optimal designs.
Novel Multicomponent Powders from the AlCrFeMnMo Family Synthesized by Mechanical Alloying
Authors: Stasiak Tomasz , Kumaran Surya Nilamegam , Touzin Matthieu , Béclin Franck , Cordier Catherine
Published: September 2019

High‐entropy alloys (HEAs) and multicomponent alloys are known for their promising properties and the almost infinite possibilities of the design of new compositions. The Al–Cr–Fe–Mn–Mo family of HEAs is chosen to promote the formation of a body‐centered cubic (bcc) structure that exhibits high hardness and yield strength. Powder metallurgy is preferred to the liquid route to avoid segregation problems. Two compositions of alloyed powder, equiatomic and optimized, are successfully prepared by mechanical alloying. X‐ray diffraction (XRD) indicates the formation of two major bcc phases: bcc#1 (a1 = 3.13–3.14 Å) and bcc#2 (a2 = 2.87–2.94 Å). Energy transferred during milling depends greatly on the milling device and process conditions. Scanning electron microscopy–energy‐dispersive X‐ray spectroscopy (SEM–EDX) images reveal that high‐energy shocks of balls enable to elaborate homogeneous powder with controlled Fe contamination coming from the grinding vial and balls, whereas low‐energy shocks enable to produce powder free of contamination by Fe, with heterogeneous particles. Finally, the milling process is optimized to obtain a homogeneous alloyed powder with as little contamination as possible.
Simultaneously Enhanced Permittivity and Electric Breakdown Strength of Polyacrylonitrile Composites by Introducing Ultralow Content BaSrTiO3 Nanofibers
Authors: Xu Pengpeng , Luo Suibin , Yu Junyi , Cao Liqiang , Yu Shuhui , Sun Rong , Wong Ching-Ping
Published: September 2019

Introducing nanoparticles in a polymer matrix to simultaneously enhance permittivity and electric breakdown strength is a challenge for the polymer‐based dielectric films to obtain improved energy‐storage density and efficiency. Herein, it is demonstrated that both of the aforementioned properties are enhanced by using an ultralow content of BaSrTiO3 nanofibers (BST NFs) with high aspect ratios (9–18) in the polyacrylonitrile (PAN) matrix. As the filler loading is 0.1–0.9 wt%, the permittivities of the composites are increased from 6.3 of the pure PAN to 6.93–7.92 at 1 kHz. The maximum electrical breakdown strength achieved at 0.3 wt% is 3865 kV cm−1, which is much higher than that of the pure PAN of ≈2987 kV cm−1. Significantly enhanced discharged energy density of 8.25 J cm−3 at a high charge–discharge efficiency of 83% is achieved. The electrical breakdown mechanism at ultralow filler content is investigated based on the simulation of space charges distribution.
Encapsulating Trogtalite CoSe2 Nanobuds into BCN Nanotubes as High Storage Capacity Sodium Ion Battery Anodes
Authors: Tabassum Hassina , Zhi Chenxu , Hussain Tanveer , Qiu Tianjie , Aftab Waseem , Zou Ruqiang
Published: September 2019

Trogtalite CoSe2 nanobuds encapsulated into boron and nitrogen codoped graphene (BCN) nanotubes (CoSe2@BCN‐750) are synthesized via a concurrent thermal decomposition and selenization processes. The CoSe2@BCN‐750 nanotubes deliver an excellent storage capacity of 580 mA h g−1 at current density of 100 mA g−1 at 100th cycle, as the anode of a sodium ion battery. The CoSe2@BCN‐750 nanotubes exhibit a significant rate capability (100–2000 mA g−1 current density) and high stability (almost 98% storage retention after 4000 cycles at large current density of 8000 mA g−1). The reasons for these excellent storage properties are illuminated by theoretical calculations of the relevant models, and various possible Na+ ion storage sites are identified through first‐principles calculations. These results demonstrate that the insertion of heteroatoms, B–C, N–C as well as CoSe2, into BCN tubes, enables the observed excellent adsorption energy of Na+ ions in high energy storage devices, which supports the experimental results.
The phenotype of Sotos syndrome in adulthood: A review of 44 individuals
Authors: Foster Alison , Zachariou Anna , Loveday Chey , Ashraf Tazeen , Blair Edward , Clayton‐Smith Jill , Dorkins Huw , Fryer Alan , Gener Blanca , Goudie David , Henderson Alex , Irving Melita , Joss Shelagh , Keeley Vaughan , Lahiri Nayana , Lynch Sally Ann , Mansour Sahar , McCann Emma , Morton Jenny , Motton Nicole , Murray Alexandra , Riches Katie , Shears Deborah , Stark Zornitza , Thompson Elizabeth , Vogt Julie , Wright Michael , Cole Trevor , Tatton‐Brown Katrina
Published: September 2019

Sotos syndrome is an overgrowth‐intellectual disability (OGID) syndrome caused by NSD1 pathogenic variants and characterized by a distinctive facial appearance, an intellectual disability, tall stature and/or macrocephaly. Other associated clinical features include scoliosis, seizures, renal anomalies, and cardiac anomalies. However, many of the published Sotos syndrome clinical descriptions are based on studies of children; the phenotype in adults with Sotos syndrome is not yet well described. Given that it is now 17 years since disruption of NSD1 was shown to cause Sotos syndrome, many of the children first reported are now adults. It is therefore timely to investigate the phenotype of 44 adults with Sotos syndrome and NSD1 pathogenic variants. We have shown that adults with Sotos syndrome display a wide spectrum of intellectual ability with functioning ranging from fully independent to fully dependent. Reproductive rates are low. In our cohort, median height in adult women is +1.9 SD and men +0.5 SD. There is a distinctive facial appearance in adults with a tall, square, prominent chin. Reassuringly, adults with Sotos syndrome are generally healthy with few new medical issues; however, lymphedema, poor dentition, hearing loss, contractures and tremor have developed in a small number of individuals.
A Facilities Roundtable: Feinberg, Green and McGovern Analyze their Own Approaches to Intractable Disputes
Authors: Bleemer Russ
Published: September 2019

During the CPR Institute's 2019 Annual Meeting earlier this year, three of the nation's top neutrals—all best known for tackling mass torts and cases involving the government—spoke in a roundtable discussion, in person and by telephone, with Alternatives' then‐publisher Noah Hanft and editor Russ Bleemer.
Real‐Time In‐Situ Monitoring of a Tunable Pentapeptide Gel–Crystal Transition
Authors: Guterman Tom , Levin Maayan , Kolusheva Sofiya , Levy Davide , Noor Nadav , Roichman Yael , Gazit Ehud
Published: September 2019

Supramolecular gels often become destabilized by the transition of the gelator into a more stable crystalline phase, but often the long timescale and sporadic localization of the crystalline phase preclude a persistent observation of this process. We present a pentapeptide gel–crystal phase transition amenable for continuous visualization and quantification by common microscopic methods, allowing the extraction of kinetics and visualization of the dynamics of the transition. Using optical microscopy and microrheology, we show that the transition is a sporadic event in which gel dissolution is associated with microcrystalline growth that follows a sigmoidal rate profile. The two phases are based on β‐sheets of similar yet distinct configuration. We also demonstrate that the transition kinetics and crystal morphology can be modulated by extrinsic factors, including temperature, solvent composition, and mechanical perturbation. This work introduces an accessible model system and methodology for studying phase transitions in supramolecular gels.
Metal‐Free Synthesis of Benzothiophenes by Twofold C−H Functionalization: Direct Access to Materials‐Oriented Heteroaromatics
Authors: Yan Jiajie , Pulis Alexander P. , Perry Gregory J. P. , Procter David J.
Published: September 2019

Due to their ubiquity in nature and frequent use in organic electronic materials, benzothiophenes are highly sought after. Here we set out an unprecedented procedure for the formation of benzothiophenes by the twofold vicinal C−H functionalization of arenes that does not require metal catalysis. This one‐pot annulation proceeds through an interrupted Pummerer reaction/[3,3]‐sigmatropic rearrangement/cyclization sequence to deliver various benzothiophene products. The procedure is particularly effective for the rapid synthesis of benzothiophenes from non‐prefunctionalized polyaromatic hydrocarbons (PAHs).
A Supramolecular Radical Dimer: High‐Efficiency NIR‐II Photothermal Conversion and Therapy
Authors: Tang Bohan , Li Wan‐Lu , Chang Yincheng , Yuan Bin , Wu Yukun , Zhang Ming‐Tian , Xu Jiang‐Fei , Li Jun , Zhang Xi
Published: September 2019

Photothermal therapy at the NIR‐II biowindow (1000–1350 nm) is drawing increasing interest because of its large penetration depth and maximum permissible exposure. Now, the supramolecular radical dimer, fabricated by N,N′‐dimethylated dipyridinium thiazolo[5,4‐d]thiazole radical cation (MPT.+) and cucurbit[8]uril (CB[8]), achieves strong absorption at NIR‐II biowindow. The supramolecular radical dimer (2MPT.+‐CB[8]) showed highly efficient photothermal conversion and improved stability, thus contributing to the strong inhibition on HegG2 cancer cell under 1064 nm irradiation even penetrating through chicken breast tissue. This work provides a novel approach to construct NIR‐II chromophore by tailor‐made assembly of organic radicals. It is anticipated that this study provides a new strategy to achieve NIR‐II photothermal therapy and holds promises in luminescence materials, optoelectronic materials, and also biosensing.
Large‐Area Aminated‐Graphdiyne Thin Films for Direct Methanol Fuel Cells
Authors: Wang Fan , Zuo Zicheng , Li Liang , Li Kuo , He Feng , Jiang Zhongqing , Li Yuliang
Published: September 2019

A two‐dimensional (2D) carbon nanofilm with uniform artificial nanopores is an ideal material to ultimately suppress the fuel permeation in the proton exchange membrane fuel cells. Graphdiyne has great mechanical strength, high dimensional stability, and controllable nanopores, and has good prospects to play this crucial role. It is found that graphdiyne nanofilm with amino groups and natural nanopores can be easily prepared with high integrity. The aminated graphdiyne has good compatibility with the Nafion matrix owing to the acid–base interaction between them. The excellent comprehensive properties of graphdiyne in selectivity, dimensional stability, and integrity effectively improve the power performance and stability of fuel cells at wide temperature. Our results can be developed into a universal method that can easily realize the selective separation of ions and small molecules, and open a new way for the emerging applications in green energy.
Crosslinking Allosteric Sites on the Nucleosome
Authors: Batchelor Lucinda K. , De Falco Louis , von Erlach Thibaud , Sharma Deepti , Adhireksan Zenita , Roethlisberger Ursula , Davey Curt A. , Dyson Paul J.
Published: September 2019

Targeting defined histone protein sites in chromatin is an emerging therapeutic approach that can potentially be enhanced by allosteric effects within the nucleosome. Here we characterized a novel hetero‐bimetallic compound with a design based on a nucleosomal allostery effect observed earlier for two unrelated drugs—the RuII antimetastasis/antitumor RAPTA‐T and the AuI anti‐arthritic auranofin. The RuII moiety binds specifically to two H2A glutamate residues on the nucleosome acidic patch, allosterically triggering a cascade of structural changes that promote binding of the AuI moiety to selective histidine residues on H3, resulting in cross‐linking sites that are over 35 Å distant. By tethering the H2A‐H2B dimers to the H3‐H4 tetramer, the hetero‐bimetallic compound significantly increases stability of the nucleosome, illustrating its utility as a site‐selective cross‐linking agent.
A Mesoporous Nanorattle‐Structured Pd@PtRu Electrocatalyst
Authors: Li Chunjie , Yu Hongjie , Liu Songliang , Xu You , Wang Ziqiang , Li Xiaonian , Wang Liang , Wang Hongjing
Published: September 2019

Pt‐based nanomaterials play important roles in the catalytic process toward oxygen reduction reaction (ORR). Rationally regulating the composition and morphology of the catalysts could enhance the catalytic performance effectively. In this work, an effective method is presented to synthesize Pd@ mesoporous PtRu nanorattles (Pd@mPtRu NRs) containing a Pd core and a mesoporous PtRu shell. Owing to the unique structure and PtRu alloy composition, the prepared Pd@mPtRu NRs exhibit an enhanced catalytic performance and durability toward ORR relative to mesoporous PtRu hollow nanoparticles (mPtRu HNs) and commercial Pt/C. The proposed approach may provide a general way to synthesize Pt‐based yolk‐shell structures with different compositions.
Duplex‐forming Oligonucleotide of Triazole‐linked RNA
Authors: Fujino Tomoko , Suzuki Takeru , Ooi Tsugumi , Ikemoto Koki , Isobe Hiroyuki
Published: September 2019

An oligonucleotide of triazole‐linked RNA (TLRNA) was synthesized by performing consecutive copper‐catalyzed azide‐alkyne cycloaddition reactions for elongation. The reaction conditions that had been optimized for the synthesis of 3‐mer TLRNA were found to be inappropriate for longer oligonucleotides, and the conditions were reoptimized for the solid‐phase synthesis of an 11‐mer TLRNA oligonucleotide. Duplex formation of the 11‐mer TLRNA oligonucleotide was examined with the complementary oligonucleotide of natural RNA to reveal the effects of the 2′‐OH groups on the duplex stability.
Controlled Synthesis of CuCo2S4@Ni(OH)2 Hybrid Nanorod Arrays for Water Splitting at an Ultralow Cell Voltage of 1.47 V
Authors: Du Xiaoqiang , Fu Jianpeng , Zhang Xiaoshuang
Published: September 2019

Developing environmentally friendly and highly active water splitting catalysts would be of great significance for clean energy conversion and utilization processes. Heterogeneous CuCo2S4@Ni(OH)2 nanorod arrays with abundant oxygen vacancy firstly have been designed through a controllable hydrothermal and electrodeposition method. The synergies and open structures of the particular hierarchical structure together with the abundant oxygen vacancies offer more surface reactive centers, which can promote the electron transfer rate and reduce the activation energy of intermediate species. The CuCo2S4@Ni(OH)2–20 min nanorod arrays are considered as an excellent and robust electrocatalyst for the proton reduction under an alkaline condition with an extraordinary low overpotential of 117 mV at 10 mA cm−2. The CuCo2S4@Ni(OH)2–20 min heterostructures electrode is also stable and robust for the water oxidation reaction, needing an overpotential of only 250 mV to obtain 100 mA cm−2. Therefore, an alkaline electrolyzer was designed using CuCo2S4@Ni(OH)2–20 min nanorod arrays as bifunctional electrocatalyst, which can complete overall water splitting at a cell voltage of 1.47 V with 10 mA cm−2, suggesting a promising combination of the same material for efficient overall water splitting device. The cell voltage of 1.47 V, to our knowledge, is among the lowest values of the published support catalysts for electrocatalytic water splitting up to now.
Efficient production of S‐adenosyl‐l‐methionine from dl‐methionine in metabolic engineered Saccharomyces cerevisiae
Authors: Liu Wei , Tang Dandan , Shi Rui , Lian Jiazhang , Huang Lei , Cai Jin , Xu Zhinan
Published: September 2019

S‐Adenosyl‐l‐methionine (SAM) is an important small molecule compound widely used in treating various diseases. Although l‐methionine is generally used, the low‐cost dl‐methionine is more suitable as the substrate for industrial production of SAM. However, d‐methionine is inefficient for SAM formation due to the substrate‐specificity of SAM synthetase. In order to increase the utilization efficiency of dl‐methionine, intracellular conversion of d‐methionine to l‐methionine was investigated in the type strain Saccharomyces cerevisiae BY4741 and an industrial strain S. cerevisiae HDL. Firstly, via disruption of HPA3 encoding d‐amino acid‐N‐acetyltransferase, d‐methionine was accumulated in vivo and no N‐acetyl‐d‐methionine production was observed. Further, codon‐optimized d‐amino acid oxidase (DAAO) gene from Trigonopsis variabilis (Genbank MK280686) and l‐phenylalanine dehydrogenase gene (l‐PheDH) from Rhodococcus jostii (Genbank MK280687) were introduced to convert d‐methionine to l‐methionine, SAM concentration and content was increased by 110% and 72.1% in BY4741 (plasmid borne) and increased by 38.2% and 34.1% in HDL (genome integrated), by feeding 0.5 g/L d‐methionine. Using the recently developed CRISPR tools, the DAAO and l‐PheDH expression cassettes were integrated into the HPA3 and SAH1 loci while SAM2 expression was integrated into the SPE2 and GLC3 loci of HDL, and the resultant strain HDL‐R2 accumulated 289% and 192% more SAM concentration and content, respectively, by feeding 0.5 g/L dl‐methionine. Further, in a 10 L fed‐batch fermentation process, 10.3 g/L SAM were accumulated with the SAM content of 242 mg/g dry cell weight by feeding 16 g/L dl‐methionine. The strategies used here provided a promising approach to enhance SAM production using low‐cost dl‐methionine.
Biosynthesis of the human milk oligosaccharide 3‐fucosyllactose in metabolically engineered Escherichia coli via the salvage pathway through increasing GTP synthesis and β‐galactosidase modification
Authors: Choi Yun Hee , Park Bum Seok , Seo Joo‐Hyun , Kim Byung‐Gee
Published: September 2019

3‐Fucosyllactose (3‐FL) is one of the major fucosylated oligosaccharides in human milk. Along with 2′‐fucosyllactose (2′‐FL), it is known for its prebiotic, immunomodulator, neonatal brain development, and antimicrobial function. Whereas the biological production of 2′‐FL has been widely studied and made significant progress over the years, the biological production of 3‐FL has been hampered by the low activity and insoluble expression of α‐1,3‐fucosyltransferase (FutA), relatively low abundance in human milk oligosaccharides compared with 2′‐FL, and lower digestibility of 3‐FL than 2′‐FL by bifidobacteria. In this study, we report the gram‐scale production of 3‐FL using E. coli BL21(DE3). We previously generated the FutA quadruple mutant (mFutA) with four site mutations at S46F, A128N, H129E, Y132I, and its specific activity was increased by nearly 15 times compared with that of wild‐type FutA owing to the increase in kcat and the decrease in Km. We overexpressed mFutA in its maximum expression level, which was achieved by the optimization of yeast extract concentration in culture media. We also overexpressed L‐fucokinase/GDP‐
L‐fucose pyrophosphorylase to increase the supply of GDP‐fucose in the cytoplasm. To increase the mass of recombinant whole‐cell catalysts, the host E. coli BW25113 was switched to E. coli BL21(DE3) because of the lower acetate accumulation of E. coli BL21(DE3) than that of E. coli BW25113. Finally, the lactose operon was modified by partially deleting the sequence of LacZ (lacZΔm15) for better utilization of D‐lactose. Production using the lacZΔm15 mutant yielded 3‐FL concentration of 4.6 g/L with the productivity of 0.076 g·L−1·hr−1 and the specific 3‐FL yield of 0.5 g/g dry cell weight.
Myocardial tissue salvage is correlated with ischemic border region temperature at reperfusion
Authors: Merrill Thomas L. , Mitchell Jennifer E. , Merrill Denise R. , Gorman Joseph H. , Gorman Robert C. , Gillespie Matthew J.
Published: September 2019

Objectives

Our pilot study investigated the association between region‐specific myocardial tissue temperature and tissue salvage using a novel tri‐lumen cooling catheter to provide rapid localized cooling directly to the heart in an open‐chest porcine model of ischemia–reperfusion.

Background

Therapeutic hypothermia remains a promising strategy to limit reperfusion injury following myocardial ischemia.

Methods

Large swine underwent 60 min of coronary occlusion followed by 3 hr of reperfusion. Prior to inducing ischemia, six temperature probes were placed directly on the heart, monitoring myocardial temperatures in different locations. Hemodynamic parameters and core temperature were also collected. Approximately 15 min prior to reperfusion, the cooling catheter was inserted via femoral artery and the distal tip advanced proximal to the occluded coronary vessel under fluoroscopic guidance. Autologous blood was pulled from the animal via femoral sheath and delivered through the central lumen of the cooling catheter, delivering at 50 ml/min, 27°C at the distal tip. Cooling was continued for an additional 25 min after reperfusion followed by a 5‐min controlled rewarming. Hearts were excised and assessed for infarct size per area at risk.

Results

Although cooling catheter performance was consistent throughout the study (38 W), the resulting tissue cooling was not. Our results show a correlation between myocardial tissue salvage and ischemic border region (IBR) temperature at the time of reperfusion (R2 = 0.59, p = 0.027). IBR tissue is the tissue located at the boundary between healthy and ischemic tissues.

Conclusions

Our findings suggest that localized, rapid, short‐term myocardial tissue cooling has the potential to limit reperfusion injury in humans.
Innovative Moments in Career Construction Counseling: Proposal for an Integrative Model
Authors: Cardoso Paulo , Savickas Mark L. , Gonçalves Miguel M.
Published: September 2019

This article advances understanding of career construction counseling (CCC) by viewing it through the lens of the innovative moments model (IMM) of how clients construct change. The IMM conceives clients’ narrative transformations as resulting from counselors prompting and clients reflecting on exceptions to a problematic self‐narrative (i.e., innovative moments; IMs) that emerges in counseling dialogues. On the basis of intensive IMM analysis of CCC case studies, the authors propose an integration of the 2 models that describes the sequence of client change in IMs across the 3 phases of CCC. This proposal provides both conceptual and assessment tools that make it possible to describe and analyze the process of client change through life‐designing dialogues. The authors illustrate the integrated framework with vignettes from case studies and conclude by suggesting research to examine the validity and usefulness of the client change sequence and interventions for using this pattern of change to foster client transformation.
The Career Decision‐Making Difficulties Questionnaire: A Case for Item‐Level Interpretation
Authors: Rochat Shékina
Published: September 2019

The Career Decision‐Making Difficulties Questionnaire (CDDQ; Gati, Krausz, & Osipow, 1996) has long been demonstrated as a useful instrument for career counseling practice. Several case studies have demonstrated how and why using the CDDQ facilitates the career counseling process (e.g., Amir, Gati, & Kleiman, 2008; Gati & Levin, 2014; Levin & Gati, 2014). This study explores how an in‐depth analysis of a case study conducted at the item level can provide career counselors with a richer understanding of their clients’ needs. The case study also emphasizes how administering and providing feedback on the CDDQ in career counseling sessions is likely to foster working alliances. The study concludes by presenting an intervention map based on the CDDQ taxonomy.
Various Techniques for Preparation of Thin‐Film Composite Mixed‐Matrix Membranes for CO2 Separation
Authors: Fauzan Nur Aqilah Bt , Mannan Hafiz Abdul , Nasir Rizwan , Mohshim Dzeti Farhah Bt , Mukhtar Hilmi
Published: September 2019

The application of thin‐film composite mixed‐matrix membranes (TFC‐MMMs) for gas separation is widely considered as an efficient separation technology. The principal methods for the preparation of TFC‐MMMs are dip‐coating, phase inversion, and interfacial polymerization comprising different types of support layers. These methods influence the CO2 permeation over the selective and support layers. A comprehensive review is provided for capturing new details of progress achieved in developing TFC‐MMMs with detailed performance of gas separation in the previous few years. Various preparation techniques of TFC‐MMMs and their effect on the gas separation performance of the prepared membranes are described.
Regioisomeric BODIPY Benzodithiophene Dyads and Triads with Tunable Red Emission as Ratiometric Temperature and Viscosity Sensors
Authors: Aswathy P. R. , Sharma Sushil , Tripathi Narendra Pratap , Sengupta Sanchita
Published: September 2019

Regioisomeric acceptor‐donor (AD) molecular rotors (p‐AD, m‐AD and m‐ADA) were synthesized and characterized, wherein dyads p‐AD and m‐AD, and triad m‐ADA contained 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) and benzodithiophene (BDT) as electron‐acceptor and electron‐donor, respectively. In all the compounds, the donor and acceptor moieties are electronically decoupled by a phenyl spacer, either through a para coupling or through a meta coupling. The dyad counterparts p‐AD and m‐AD showed distinct photophysical characteristics in which dyad p‐AD showed TICT band at ca. 654 nm characterized by a Stokes shift of ca. 150 nm and prominent solvatochromism. However, meta regioisomeric triad m‐ADA showed well‐defined aggregation in solution. Notably, because of the temperature‐tunable and solvent‐viscosity‐dependent emission, efficient ratiometric temperature sensing with positive and negative temperature coefficients and viscosity sensing was observed for all compounds. Interestingly, the fluorescence of dyad m‐AD (in 10/90 v/v THF/water) revealed a near‐white light emission with CIE chromaticity coordinates (x, y) of (0.32, 0.29). Furthermore, the fluorescence emission of p‐AD in THF at 0 °C also showed a near‐white light emission with chromaticity coordinates (x, y) of (0.34, 0.27). Such multifunctional rotors with readily tunable emission in the red region and prominent temperature‐ and viscosity‐sensing abilities are promising for sensing and bioimaging applications.
Luminescent Mono‐, Di‐, and Triradicals: Bridging Polychlorinated Triarylmethyl Radicals by Triarylamines and Triarylboranes
Authors: Hattori Yohei , Michail Evripidis , Schmiedel Alexander , Moos Michael , Holzapfel Marco , Krummenacher Ivo , Braunschweig Holger , Müller Ulrich , Pflaum Jens , Lambert Christoph
Published: September 2019

Up to three polychlorinated pyridyldiphenylmethyl radicals bridged by a triphenylamine carrying electron withdrawing (CN), neutral (Me), or donating (OMe) groups were synthesized and analogous radicals bridged by tris(2,6‐dimethylphenyl)borane were prepared for comparison. All compounds were as stable as common closed‐shell organic compounds and showed significant fluorescence upon excitation. Electronic, magnetic, absorption, and emission properties were examined in detail, and experimental results were interpreted using DFT calculations. Oxidation potentials, absorption and emission energies could be tuned depending on the electron density of the bridges. The triphenylamine bridges mediated intramolecular weak antiferromagnetic interactions between the radical spins, and the energy difference between the high spin and low spin states was determined by temperature dependent ESR spectroscopy and DFT calculations. The fluorescent properties of all radicals were examined in detail and revealed no difference for high and low spin states which facilitates application of these dyes in two‐photon absorption spectroscopy and OLED devices.
Synthesis and Characterisation of Hierarchically Structured Titanium Silicalite‐1 Zeolites with Large Intracrystalline Macropores
Authors: Weissenberger Tobias , Leonhardt Rainer , Zubiri Benjamin Apeleo , Pitínová‐Štekrová Martina , Sheppard Thomas L. , Reiprich Bastian , Bauer Jürgen , Dotzel Ralf , Kahnt Maik , Schropp Andreas , Schroer Christian G. , Grunwaldt Jan‐Dierk , Casci John L. , Čejka Jiří , Spiecker Erdmann , Schwieger Wilhelm
Published: September 2019

The successful synthesis of hierarchically structured titanium silicalite‐1 (TS‐1) with large intracrystalline macropores by steam‐assisted crystallisation of mesoporous silica particles is reported. The macropore topology was imaged in 3D by using electron tomography and synchrotron radiation‐based ptychographic X‐ray computed tomography, revealing interconnected macropores within the crystals accounting for about 30 % of the particle volume. The study of the macropore formation mechanism revealed that the mesoporous silica particles act as a sacrificial macropore template during the synthesis. Silicon‐to‐titanium ratio of the macroporous TS‐1 samples was successfully tuned from 100 to 44. The hierarchically structured TS‐1 exhibited high activity in the liquid phase epoxidation of 2‐octene with hydrogen peroxide. The hierarchically structured TS‐1 surpassed a conventional nano‐sized TS‐1 sample in terms of alkene conversion and showed comparable selectivity to the epoxide. The flexible synthesis route described here can be used to prepare hierarchical zeolites with improved mass transport properties for other selective oxidation reactions.
Excited‐State Dynamics of Non‐Luminescent and Luminescent π‐Radicals
Authors: Teki Yoshio
Published: September 2019

Recently, the potential use of organic π‐radicals and related spin systems has been expanded to modern technological applications. The unique excited‐state dynamics of organic π‐radicals can be useful to improve the stability of photochemically unstable organic compounds, make the polarization transfer applicable to information technology, and achieve effective up‐conversion of interest for luminescence bioimaging, among others. Furthermore, highly luminescent stable π‐radicals have been recently reported, which are especially interesting for application in organic light‐emitting devices owing to their potential to provide an internal quantum efficiency of 100 %. Thus, the excited‐state nature of stable π‐radicals as well as the control of their excited‐state spin dynamics are emerging topics both in terms of fundamental science and related technological applications. In this minireview, we focus on the excited‐state dynamics of both photostable non(weakly)‐luminescent and luminescent π‐radicals, which are opposites of each other. In particular, we cover the following topics: 1) effective generation of high‐spin photoexcited states and control of the excited‐state dynamics by using non‐luminescent π‐radicals, 2) unique excited‐state dynamics of luminescent π‐radicals and radical excimers, and 3) applications utilizing excited‐state dynamics of π‐radicals.
Palladium‐Catalyzed C8‐Arylation of Naphthalenes through C−H Activation: A Combined Experimental and Computational Study
Authors: Garrec Julian , Cordier Marie , Frison Gilles , Prévost Sébastien
Published: September 2019

Herein, a direct C8‐arylation reaction of 1‐amidonaphthalenes is described. By using diaryliodonium salts as arylating agents, the palladium‐catalyzed C−H activation reaction showed perfect C8 regioselectivity and a wide functional group tolerance. In most cases, the desired polyaromatic compounds were isolated in good to excellent yields. To explain the observed regioselectivity, DFT calculations were performed and highlighted the crucial role of the amide directing group. Finally, the utility of this method is showcased by the synthesis of benzanthrone derivatives.
Highly Stable and Inert Complexation of Indium(III) by Reinforced Cyclam Dipicolinate and a Bifunctional Derivative for Bead Encoding in Mass Cytometry
Authors: Grenier Laura , Beyler Maryline , Platas‐Iglesias Carlos , Closson Taunia , Gómez David Esteban , Seferos Dwight S. , Liu Peng , Ornatsky Olga I. , Baranov Vladimir , Tripier Raphaël
Published: September 2019

H2cb‐te2pa, a cross‐bridged cyclam functionalized by two picolinate arms, was used for the formation of an incredible inert InIII chelate. The inertness of the complex was evaluated by UV/Vis experiments in several competitive media and was highlighted by the comparison with [In(dota)]− and [In(dtpa)]2− (H4dota = 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid, H5dtpa = diethylenetriamine pentaacetic acid), which are currently used in biological applications. For the first time, a bifunctional analogue of H2cb‐te2pa was prepared by C‐functionalization to keep its coordination properties intact. However, this strategy leads to the formation of two diastereoisomers as evidenced and studied by NMR experiments and DFT calculations. Kinetic studies proved nevertheless that both isomers of the complex are equally inert. They were therefore used without distinction for their covalent grafting on polystyrene beads. The so‐called metal‐encoded beads were tested for imaging mass cytometry. The detection of 115In allows the generation of images with high quality, proving the great potential of the bifunctional [In(cb‐te2pa)]+ derivatives for single‐cell analysis by mass cytometry.
Hue, chroma, and lightness preference in Chinese adults: Age and gender differences
Authors: Zhang Yujing , Liu Pingping , Han Buxin , Xiang Yang , Li Liqin
Published: September 2019

Recent studies have shown cultural differences in color preference. However, the color preference of people in China, which was found to have its own pattern, was yet to be studied in depth. The current study investigated color preference and the associated age and gender differences in an adult national sample (N = 1290) to provide a culture‐specific characteristic of color perception. Participants rated how much they liked each of 31 colors (four chroma‐lightness levels of red, orange, yellow, green, cyan, blue, and purple, plus three achromatic colors). We found a unique saturated color preference pattern characterized by red, cyan, and blue being preferred the most and orange as the least preferred chromatic color. The “red preference” phenomenon was observed in Chinese adults. Light colors were preferred the most in terms of chroma‐lightness level, followed by saturated, muted, and dark colors. The results of a principal component analysis of the 28 chromatic colors showed that blue‐green‐like colors (cool colors) constituted the largest proportion of color preference. The preference for orange and several dark colors increased with age, while that for bluish colors, purple, yellow, white, black, and light colors decreased. In terms of gender, women liked cyan, white, pink, and light colors and disliked red, orange, and dark colors more than men did. Our findings provide new empirical evidence about the color preference of Chinese and may offer some insight into the study of color preference and lay the foundations for future theoretical and practical research.
Working with Worms: Caenorhabditis elegans as a Model Organism
Authors: Meneely Philip M. , Dahlberg Caroline L. , Rose Jacqueline K.
Published: September 2019

Since its introduction as a laboratory organism 50 years ago, the nematode worm Caenorhabditis elegans has become one of the most widely used and versatile models for nearly all aspects of biological and genomic research. Many experiments in C. elegans begin with the generation and analysis of mutants that affect a specific biological process, so genetic techniques are the foundation of worm research. Many different aspects of biology are being studied in C. elegans, and three different recent Nobel Prizes have recognized six researchers working with worms. In addition, C. elegans was the first multicellular organism to have its genome sequenced, so many of the standard genomic methods have also been pioneered in C. elegans. In fact, many novel techniques and ideas are initially tested in C. elegans because of its versatility as a research organism. It is also appropriate for introducing undergraduate students to research, and some of its strengths and challenges for this purpose are discussed. © 2019 The Authors.
Identification of a thermal degradation product of CUMYL‐PEGACLONE and its detection in biological samples
Authors: Nash Christine , Glowacki Linda , Gerostamoulos Dimitri , Pigou Paul , Scott Timothy , Kostakis Chris
Published: September 2019

The structural diversity of synthetic cannabinoids makes it a challenging task to have a comprehensive screening method for this class of drugs. The difficulty is increased by the fact that some synthetic cannabinoids undergo thermal decomposition during common routes of administration, such as smoking or vaping. CUMYL‐PEGACLONE is a relatively new synthetic cannabinoid which has a structural variant from most other synthetic cannabinoids: a γ‐carbolinone core. To investigate its thermal stability, CUMYL‐PEGACLONE was heated in an oven at temperatures ranging from 200 to 350oC, and a major thermal degradation product, N‐pentyl‐γ‐carbolinone, was subsequently identified. Unlike some other synthetic cannabinoids, the thermal degradation product of CUMYL‐PEGACLONE is not one of its known metabolites, nor were any known metabolites detected during the thermal stability experiments. The degradation product was formed in significant amounts at temperatures above 250°C, and has been detected (along with CUMYL‐PEGACLONE) in case samples, including post‐mortem blood and urine, and residue found at a scene.
Parental genetic similarity and offspring performance in blue tits in relation to brood size manipulation
Authors: Arct Aneta , Drobniak Szymon M. , Mellinger Samantha , Gustafsson Lars , Cichoń Mariusz
Published: September 2019

In birds, as in many other taxa, higher genetic similarity of mates has long been known to reduce offspring fitness. To date, the majority of avian studies have focused on examination whether the genetic similarity of social mates predicts hatching success. Yet, increased genetic similarity of mates may also reduce offspring fitness during later life stages, including the nestling period and beyond. Here, we investigated whether parental genetic similarity influences offspring performance using data from free‐living blue tits (Cyanistes caeruleus) collected across three breeding seasons. Additionally, we tested whether brood size manipulation affects the magnitude and direction of the relationship between genetic similarity of mates and offspring performance. Sixteen microsatellite markers were used to measure genetic similarity between biological parents. We found that the genetic similarity of parents negatively affects offspring immune response and this effect was independent of the experimental brood size manipulation.
Ecosystem functioning of two marine food webs in the North‐Western Ionian Sea (Central Mediterranean Sea)
Authors: Ricci Pasquale , Libralato Simone , Capezzuto Francesca , D’Onghia Gianfranco , Maiorano Porzia , Sion Letizia , Tursi Angelo , Solidoro Cosimo , Carlucci Roberto
Published: September 2019

The ecosystem functioning of two marine food webs covering the north‐eastern (Salento) and south‐western (Calabria) sectors of the North‐Western Ionian Sea (NWIS) (Central Mediterranean Sea) was investigated through a food‐web model. Data inputs covered a wide set of ecological information applied to 58 functional groups (FGs). The sum of consumption and the mean predation mortality rate were calculated for benthic, demersal, and pelagic subsystems indicating the predator and prey roles of the FGs. A complex system of energy and biomass exchanges characterized the investigated food webs indicating an important benthic‐pelagic coupling. In the food webs of both areas, the regulation of flows between the benthic‐pelagic coupling seems to occur through the benthopelagic shrimps and the small pelagics due to their wasp‐waist control role. Differences were observed concerning the top predators. Odontocetes play this keystone role in the Salento food web. Anglers, bathyal squids, and sharks assume this functional role in Calabria. The geomorphology and hydrography in the NWIS could affect the biomass and energy exchanges in this coupling. The higher flows of consumption of the benthic system observed in the Calabria food web could be influenced by a widespread presence of canyons along the continental edge which increase the benthic productivity. In contrast, the flows of consumption in the Salento food web seem to be driven by the planktonic productivity supporting the pelagic, benthopelagic, and demersal compartments. This condition could be favored by the large extension of the shelf break zone. The food‐web models realized for the NWIS represent ideal platforms for the development of analysis with dynamic simulations. The comparative analysis of the two food webs by means of the FGs and their functional traits allowed the general pattern of ecosystem structure and functioning in the NWIS to be identified, making it an interesting approach to investigate the marine ecosystem.
Time since fire strongly and variously influences anthophilous insects in a fire‐prone landscape
Authors: Adedoja Opeyemi , Kehinde Temitope , Samways Michael J.
Published: September 2019

Drivers of species productivity and ecosystem function are of great ecological significance. In fire‐prone ecosystems, dispersion patterns of important pollinator species are driven by the various fire events over space and time. However, different species have varying responses to fire intensity and frequency. Here, we assess how time since last fire influences abundance, composition, and dispersion patterns of flowering plants and anthophiles in a highly fire‐prone landscape. We classified study area into age since last fire, which were <1 yr (short‐term burned), 2–3 yr (medium‐term burned), and 9–10 yr (long‐term burned). We collected insect anthophiles using yellow, blue, and white pan traps at sites established in each post‐fire class. We also estimated flower abundance at each study site. Overall, anthophile abundance was highest in medium‐term burned, while lowest in short‐term burned sites. Also, flower abundance was highest at medium‐term burned and lowest in long‐term burned sites. Species composition of flowering plants and anthophiles, especially bees and flies, differed significantly across post‐fire class. Overall, flower abundance had a significant positive effect on bee abundance. Of all the taxa, bees were the only group that showed dispersion patterns reflecting those of flower abundance. Other factors, especially requirements for other resources such as logs, drive the distribution of other anthophile taxa, especially flies. We conclude that fire drives the distribution patterns of bees through its direct effect on flower abundance and composition in a fire‐prone landscape. While high frequency of short‐term fire may reduce flower abundance, flower‐rich areas with moderate time since fire may increase diversity of anthophiles in this fire‐prone landscape.
Floodplains provide important amphibian habitat despite multiple ecological threats
Authors: Holgerson Meredith A. , Duarte Adam , Hayes Marc P. , Adams Michael J. , Tyson Julie A. , Douville Keith A. , Strecker Angela L.
Published: September 2019

Floodplain ponds and wetlands are productive and biodiverse ecosystems, yet they face multiple threats including altered hydrology, land use change, and non‐native species. Protecting and restoring important floodplain ecosystems requires understanding how organisms use these habitats and respond to altered environmental conditions. We developed Bayesian models to evaluate occupancy of six amphibian species across 103 off‐channel aquatic habitats in the Chehalis River floodplain, Washington State, USA. The basin has been altered by changes in land use, reduced river–wetland connections, and the establishment of non‐native American bullfrogs (Rana catesbeiana = Lithobates catesbeianus) and centrarchid fishes, all of which we hypothesized could influence native amphibian occupancy. Despite potential threats, the floodplain habitats had relatively high rates of native amphibian occupancy, particularly when compared to studies from non‐floodplain habitats within the species’ native ranges. The biggest challenge for native amphibians appears to be non‐native centrarchid fishes, which strongly reduced occupancy of two native amphibians: the northern red‐legged frog (Rana aurora) and the northwestern salamander (Ambystoma gracile). Emergent vegetative cover increased occupancy probability for all five native amphibian species, indicating that plant management may offer a strategy to counter the negative effect of centrarchids by providing refuge from predation. We found that temporary and permanent hydroperiod sites supported different species; hence, both should be conserved on the landscape. Lastly, human‐created and natural ponds had similar amphibian occupancy patterns, suggesting that pond construction offers a viable strategy for adding habitats to the floodplain landscape. Overall, floodplain ponds and wetlands provide important amphibian habitat, and we offer management strategies that will bolster amphibian occupancy in an altered floodplain landscape.