bluuebunny/crossref_metadata_2025 huggingface dataset:
Evaluating the strengths of salt bridges in the CutA1 protein using molecular dynamic simulations: a comparison of different force fields
Authors: Matsuura Yoshinori , Joti Yasumasa , Bagautdinov Bagautdin , Yutani Katsuhide
Published: September 2019

Ion–ion interactions (salt bridges) between favorable pairs of charged residues are important for the conformational stability of proteins. Molecular dynamic (MD) simulations are useful for elucidating the interactions among charged residues fluctuating in solution. However, the quality of MD results depends strongly on the force fields used. In this study, we compared the strengths of salt bridges among force fields by performing MD simulations using the CutA1 protein (trimer) from the hyperthermophile Pyrococcus horikoshii (PhCutA1), which has an unusually large proportion of charged residues. The force fields Chemistry at HARvard Macromolecular Mechanics (Charmm)27, Assisted Model Building and Energy Refinement (Amber)99sb, Amber14sb, GROningen Molecular Simulation (Gromos)43a1, and Gromos53a6 were used in combination with two different water models, tip3p (for Charmm27, Amber99sb, and Amber14sb) and simple point charge/extended (for Amber99sb, Gromos43a1, and Gromos53a6), yielding a total of six combinations. The RMSDs of all Cα atoms of PhCutA1 were similar among force fields, except for Charmm27, during 400‐ns MD simulations at 300 K; however, the radius of gyration (Rg) was greater for Amber99sb and shorter for Gromos43a1. The average strengths of salt bridges for each positively charged residue did not differ greatly among force fields, but the strengths at specific sites within the structure depended sensitively on the force field used. In the case of the Gromos group, positively charged residues could engage in favorable interactions with many more charged residues than in the other force fields, especially in loop regions; consequently, the apparent strength at each site was lower.
Dominant collagen XII mutations cause a distal myopathy
Authors: Mohassel Payam , Liewluck Teerin , Hu Ying , Ezzo Daniel , Ogata Tracy , Saade Dimah , Neuhaus Sarah , Bolduc Véronique , Zou Yaqun , Donkervoort Sandra , Medne Livija , Sumner Charlotte J. , Dyck P. James B. , Wierenga Klaas J. , Tennekoon Gihan , Finkel Richard S. , Chen Jiani , Winder Thomas L. , Staff Nathan P. , Foley A. Reghan , Koch Manuel , Bönnemann Carsten G.
Published: September 2019

Objective

To characterize the natural history and clinical features of myopathies caused by mono‐allelic, dominantly acting pathogenic variants in COL12A1.

Methods

Patients with dominant COL12A1‐related myopathies were characterized by history and clinical examination, muscle imaging, and genetic analysis. Pathogenicity of the variants was assessed by immunostaining patient‐derived dermal fibroblast cultures for collagen XII.

Results

Four independent families with childhood‐onset weakness due to novel, dominantly acting pathogenic variants in COL12A1 were identified. Adult patients exhibited distal‐predominant weakness. Three families carried dominantly acting glycine missense variants, and one family had a heterozygous, intragenic, in‐frame deletion of exon 52 of COL12A1. All pathogenic variants resulted in increased intracellular retention of collagen XII in patient‐derived fibroblasts as well as loss of extracellular, fibrillar collagen XII deposition. Since haploinsufficiency for COL12A1 is largely clinically asymptomatic, we designed and evaluated small interfering RNAs (siRNAs) that specifically target the mutant allele containing the exon 52 deletion. Immunostaining of the patient fibroblasts treated with the siRNA showed a near complete correction of collagen XII staining patterns.

Interpretation

This study characterizes a distal myopathy phenotype in adults with dominant COL12A1 pathogenic variants, further defining the phenotypic spectrum and natural history of COL12A1‐related myopathies. This work also provides proof of concept of a precision medicine treatment approach by proposing and validating allele‐specific knockdown using siRNAs specifically designed to target a patient’s dominant COL12A1 disease allele.
Comparison of Three Classification Criteria Sets for Systemic Lupus Erythematosus: A Study Looking at Links to Outcome and Mortality
Authors: Carneiro Antonio Costa , Ruiz Marta Mozo , Freitas Sara , Isenberg David
Published: September 2019

Objective

To compare the ability of the American College of Rheumatology (ACR), Systemic Lupus International Collaborating Clinics (SLICC), and European League Against Rheumatism (EULAR)/ACR systemic lupus erythematosus (SLE) classification criteria sets to provide information regarding organ damage and mortality, over a 10‐year follow‐up period.

Methods

Using data from 100 patients, we completed each classification set at the time of diagnosis and recorded the SLICC/ACR Damage Index (SDI) score, renal damage, major cardiovascular events, and death, 10 years later. We reviewed the presence of other autoantibodies, linked to SLE but not included in the classification criteria sets, and assessed whether they impacted the predictive capacity of the classification sets.

Results

We found a statistically significant association between the EULAR/ACR set and renal damage and SDI score, the latter after adjustment for age and sex. In the patients negative for other autoantibodies, higher EULAR/ACR scores were associated with higher rates of organ damage.

Conclusion

These data suggest that the EULAR/ACR set may offer useful prognostic information, because higher scores were associated with higher rates of organ damage. These findings were clearer in patients negative for nondiagnostic SLE autoantibodies, who may benefit more from the predictive capacity of the EULAR/ACR set.
Treatment Delays Associated With Prior Authorization for Infusible Medications: A Cohort Study
Authors: Wallace Zachary S. , Harkness Tyler , Fu Xiaoqing , Stone John H. , Choi Hyon K. , Walensky Rochelle P.
Published: September 2019

Objective

Prior authorizations (PAs) are commonly used by health payers as cost‐containment strategies for expensive medications, including infused biologics. There is scarce data about the effect of PA requirements on patient‐oriented outcomes.

Methods

We included patients for whom an infusible medication was prescribed for a rheumatologic condition. The exposures of interest were a PA requirement and whether or not the PA was denied. The primary outcome was the difference in days from medication request to infusion. Secondary outcomes included the proportion of denied PAs and differences in glucocorticoid exposure following a PA request.

Results

Of the 225 patients, the infusible medications of 160 (71%) required a PA. PAs were associated with a greater number of days to infusion compared to cases in which no authorization was required (median 31 days [interquartile range (IQR) 15–60 days] versus median 27 days [IQR 13–41 days];P= 0.045), especially among the 33 patients (21%) whose PA was denied initially (median 50 days [IQR 31–76 days] versus median 27 days [IQR 13–41 days];P< 0.001). PA denials were associated with greater prednisone‐equivalent glucocorticoid exposure in the 3 months following the request than when a PA was not required (median 605 mg [IQR 0–1,575] versus median 160 mg [IQR 0–675];P= 0.01). Twenty‐seven of the 33 PA requests that were initially denied (82%) were eventually approved. Thus, 96% of all PAs were ultimately approved.

Conclusion

PA requirements are associated with treatment delays and denials are associated with greater glucocorticoid exposure. Because the great majority of PA requests are ultimately approved, the value of PA requirements and their impact on patient safety should be reevaluated.
Template‐Electrodeposited and Imprint‐Transferred Microscale Metal‐Mesh Transparent Electrodes for Flexible and Stretchable Electronics
Authors: Khan Arshad , Liang Chuwei , Huang Yu-Ting , Zhang Cuiping , Cai Jingxuan , Feng Shien-Ping , Li Wen-Di
Published: September 2019

A scalable fabrication strategy is reported for the solution‐based electrochemical fabrication of microscale metal meshes from reusable, non‐sacrificial templates. This approach enables the reproducible fabrication of meshes, potentially made of any electrochemically depositable metal and transferable to a variety of polymeric substrates. Unlike other existing approaches, this benchtop method repetitively mass‐produces metal meshes whose geometric features are predefined by a template, without requiring lithography or any vacuum processes in each production cycle. Using this technique, a number of prototype‐flexible and stretchable transparent electrodes with an embedded metal mesh with micro‐sized linewidths are demonstrated with transmittance as high as 90% and sheet resistance as low as 0.036 Ω□−1, corresponding to a high figure of merit of 3.4 × 104 at 4 μm mesh linewidth, and the electrodeposition template showed no degradation after at least 20 production cycles. In addition to outstanding optical and electrical performances, the resulting electrodes show excellent mechanical robustness and stability against chemicals and harsh environment. The electrodes are further tested in flexible bifacial dye‐sensitized solar cells and stretchable transparent thin‐film heaters, confirming their suitability and reliability for practical applications.
2D Phononic Crystals: Progress and Prospects in Hypersound and Thermal Transport Engineering
Authors: Sledzinska Marianna , Graczykowski Bartlomiej , Maire Jeremie , Chavez‐Angel Emigdio , Sotomayor‐Torres Clivia M. , Alzina Francesc
Published: September 2019

The central concept in phononics is the tuning of the phonon dispersion relation, or phonon engineering, which provides a means of controlling related properties such as group velocity or phonon interactions and, therefore, phonon propagation, in a wide range of frequencies depending on the geometries and sizes of the materials. Phononics exploits the present state of the art in nanofabrication to tailor dispersion relations in the range of GHz for the control of elastic waves/phonons propagation with applications toward new information technology concepts with phonons as state variable. Moreover, phonons provide an adaptable approach for supporting a coherent coupling between different state variables, and the development of nanoscale optomechanical systems during the last decade attests this prospect. The most extended approach to manipulate the phonon dispersion relation is introducing an artificial periodic modulation of the elastic properties, which is referred to as phononic crystal (PnC). Herein, the focus is on the recent experimental achievements in the fabrication and application of 2D PnCs enabling the modification of the dispersion relation of surface and membrane modes, and presenting phononic bandgaps, waveguiding, and confinement in the hypersonic regime. Furthermore, these artificial materials offer the potential of modifying and controlling the heat flow to enable new schemes in thermal management.
Ultrathin Cobalt–Manganese Nanosheets: An Efficient Platform for Enhanced Photoelectrochemical Water Oxidation with Electron‐Donating Effect
Authors: Yang Gaoliang , Li Yunxiang , Pang Hong , Chang Kun , Ye Jinhua
Published: September 2019

An ultrathin cobalt–manganese (Co‐Mn) nanosheet, consisting of amorphous Co(OH)x layers and ultrasmall Mn3O4 nanocrystals, is designed as an efficient co‐catalyst on an α‐Fe2O3 film for photoelectrochemical (PEC) water oxidation. The uniformly distributed Co‐Mn nanosheets lead to a remarkable 2.6‐fold enhancement on the photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) and an impressive cathodic shift (≈200 mV) of onset potential compared with bare α‐Fe2O3 film. Furthermore, the decorated photoanode exhibits a prominent resistance against photocorrosion with excellent stability for over 10 h. Detailed mechanism investigation manifests that incorporation of Mn sites in the nanosheets could create electron donation to Co sites and facilitate the activation of the OH group, which drastically increases the catalytic activities for water oxidation. These findings provide valuable guidance for designing high‐performance co‐catalysts for PEC applications and open new avenues toward controlled fabrication of mixed metallic composites.
An Electrode Design Rule for Organic Photovoltaics Elucidated Using a Low Surface Area Electrode
Authors: Dabera G. Dinesha M. R. , Lee Jaemin , Hatton Ross A.
Published: September 2019

It is widely considered that charge carrier extraction in bulk‐heterojunction organic photovoltaics (BHJ OPVs) is most efficient when the area of contact between the semiconductor layers and the electrodes is maximized and the electrodes are electrically homogeneous. Herein, it is shown that ≈99% of the electrode surface can in fact be insulating without degrading the efficiency of charge carrier extraction, provided the spacing of the conducting areas is less than or equal to twice the optimal thickness of the BHJ layer. This striking result is demonstrated for BHJ OPVs with both conventional and inverted device architectures using two different types of BHJ OPVs, namely, PCDTBT:PC70BM and the ternary blend PBDB‐T:ITIC‐m:PC70BM. This finding opens the door to the use of a large pallet of materials for optical spacers and charge transport layers, based on a low density of conducting particles embedded in a wide bandgap insulating matrix.
Kids and Teens in Court (KTIC): A Model for Preparing Child Witnesses for Court
Authors: Peterson Leslie , Rolls Reutz Jennifer A. , Hazen Andrea L. , Habib Adrienne , Williams Rhonda
Published: September 2019

Each year, numerous children testify in the United States in either criminal, civil, or juvenile court cases. Typically, children who testify are alleged victims of sexual or physical abuse or neglect, witnesses to violent crime, or subjects in custodial hearings in civil court. As more maltreatment cases are prosecuted and child custody is contested, an increasing number of children are being called as witnesses in court. Many of these children have already been traumatized by the experiences that led to their need to testify, and participation in the court process can have additional negative effects. This article describes the development and recent formative evaluation of a court preparation program that provides psychoeducation and utilizes components of evidence‐based trauma treatment approaches, such as relaxation and in vivo exposure, to support child witnesses and reduce the risk of retraumatization. Children and adolescents participating in the program attend group sessions conducted by mental health clinicians and complete a court‐related anxiety measure before and after each session. Results from 175 participants are reported. Findings indicated significant decreases in court‐related anxiety with large program effects. Challenges encountered by the program and future directions are discussed.
The association between anthropometric measures and physical performance in black adults of the North West Province, South Africa
Authors: Mamphwe Phumudzo , Kruger Herculina S. , Moss Sarah J. , Cockeran Marike , Ricci Cristian , Ukegbu Patricia O. , Kruger Iolanthé M.
Published: September 2019

Objective

This study investigated associations between anthropometric measures and physical performance in black South African adults. It was hypothesized that noninvasive, simple anthropometric measurements, such as calf circumference (CC) and body mass index (BMI), may be useful predictors of physical performance and strength.

Methods

Black human immunodeficiency virus (HIV) negative men and women (aged 32‐93 years) participating in the Prospective Urban and Rural Epidemiology (PURE) study were enrolled at baseline in 2005 = 1428). Men and women's anthropometry, socio‐demographics and physical activity (PA) were assessed at baseline, 5‐ and 10‐year follow‐up. Physical performance (walk speed, chair stand and handgrip strength [HGS]) were assessed at 10‐year follow‐up. Linear regression models adjusted for potential confounders were used to evaluate the association between anthropometric measures and physical performance.

Results

The combined overweight and obesity prevalence among both men (P = .02) and women (P < .001) increased significantly over 10 years, with significant increases over time in BMI and CC in the women, whereas PA decreased significantly over time in both men and women (P < .0001). BMI and CC were positively associated with HGS in the men (P = .02, P < .0001) and women (P < .0001), while CC was positively associated with walk speed in men only (P = .006) in the cross‐sectional analysis of 2015 measurements.

Conclusion

BMI and CC in both men and women were positively associated with HGS, but CC was associated with walk speed in the men only. Our study suggests that CC may be a useful predictor of physical performance in black men and to a limited extent in black women.
Prenatal diagnosis of micrognathia in 41 fetuses: Retrospective analysis of outcome and genetic etiologies
Authors: Mouthon Linda , Busa Tiffany , Bretelle Florence , Karmous‐Benailly Houda , Missirian Chantal , Philip Nicole , Sigaudy Sabine
Published: September 2019

Fetal micrognathia can be detected early in pregnancy. Prognosis of micrognathia depends on the risk of respiratory distress at birth and on the long‐term risk of intellectual disability. The purpose of this study was to evaluate the long‐term prognosis of fetuses with prenatal diagnosis of micrognathia by estimating the prevalence and the severity of confirmed genetic diagnosis in our cohort. Our retrospective study included 41 fetuses with prenatal diagnosis of micrognathia referred to the multidisciplinary centers for prenatal diagnosis in Nice and Marseille, France, between 2006 and 2016. Fetal micrognathia was associated with cleft palate in 27 cases. A genetic cause was confirmed in 21 cases (67%). A chromosomal abnormality was present in 12 cases, including three copy‐number variations diagnosed by array CGH. Monogenic disorders were identified in nine cases, most often after birth. Fetuses with family history of micrognathia or Pierre Robin sequence had a favorable outcome. Prognosis was good for the fetuses without associated findings and normal chromosomal analysis, with the exception of one case with a postnatal diagnosis of mandibulofacial dysostosis with microcephaly. Prognostic was poor for the fetuses with additional ultrasound anomalies, as only 5 out of 28 children had a good outcome. Prenatal diagnosis of micrognathia is an indicator of a possible fetal pathology justifying multidisciplinary management. Our study confirms the necessity of performing prenatal array CGH. Use of high‐throughput gene sequencing in prenatal period could improve diagnostic performance, prenatal counseling, and adequate postnatal care.
Amyloid, Vascular, and Resilience Pathways Associated with Cognitive Aging
Authors: Vemuri Prashanthi , Lesnick Timothy G. , Knopman David S. , Przybelski Scott A. , Reid Robert I. , Mielke Michelle M. , Graff‐Radford Jonathan , Lowe Val J. , Machulda Mary M. , Petersen Ronald C. , Jack Clifford R.
Published: September 2019

Objective

To investigate the multifactorial processes underlying cognitive aging based on the hypothesis that multiple causal pathways and mechanisms (amyloid, vascular, and resilience) influence longitudinal cognitive decline in each individual through worsening brain health.

Methods

We identified 1,230 elderly subjects (aged ≥50 years) with an average of 4.9 years of clinical follow‐up and with amyloid positron emission tomography, diffusion tensor imaging, and structural magnetic resonance imaging scans from the population‐based Mayo Clinic Study of Aging. We examined imaging markers of amyloid and brain health (white matter microstructural integrity and cortical thinning), systemic vascular health preceding the imaging markers, and early to midlife intellectual enrichment to predict longitudinal cognitive trajectories. We used latent growth curve models for modeling longitudinal cognitive decline.

Results

All the pathways (amyloid, vascular, resilience) converged through their effects on cortical thinning and worsening cognition and together explained patterns in cognitive decline. Resilience and vascular pathways (aging process, sex differences, education/occupation, and systemic vascular health) had significant impact on white matter microstructural integrity. Education/occupation levels contributed to white matter integrity through systemic vascular health. Worsening white matter integrity contributed to significant cortical thinning and subsequently longitudinal cognitive decline. Baseline amyloidosis contributed to a significant proportion of cognitive decline that accelerated with longer follow‐up times, and its primary impact was through cortical thinning.

Interpretation

We developed an integrated framework to help explain the dynamic and complex process of cognitive aging by considering key causal pathways. Such an approach is important for both better comprehension of cognitive aging processes and will aid in the development of successful intervention strategies. ANN NEUROL 2019;86:866–877
A Novel DNA Helical Wire Containing HgII‐Mediated T:T and T:G Pairs
Authors: Ono Akira , Kanazawa Hiroki , Ito Hikari , Goto Misato , Nakamura Koudai , Saneyoshi Hisao , Kondo Jiro
Published: September 2019

Numerous applications of metal‐mediated base pairs (metallo‐base‐pairs) to nucleic acid based nanodevices and genetic code expansion have been extensively studied. Many of these metallo‐base‐pairs are formed in DNA and RNA duplexes containing Watson–Crick base pairs. Recently, a crystal structure of a metal–DNA nanowire with an uninterrupted one‐dimensional silver array was reported. We now report the crystal structure of a novel DNA helical wire containing HgII‐mediated T:T and T:G base pairs and water‐mediated C:C base pairs. The Hg‐DNA wire does not contain any Watson–Crick base pairs. Crystals of the Hg‐DNA wire, which is the first DNA wire structure driven by HgII ions, were obtained by mixing the short oligonucleotide d(TTTGC) and HgII ions. This study demonstrates the potential of metallo‐DNA to form various structural components that can be used for functional nanodevices.
Adsorption behavior and kinetics of CO2 on amine‐functionalized hyper‐crosslinked polymer
Authors: Liu Fenglei , Fu Wenhao , Chen Shuixia
Published: September 2019

A hyper‐crosslinked polymer (XAD‐4‐pc) was developed by modifying the commercial polystyrene resin (XAD‐4) through a Friedel–Crafts reaction, followed by impregnation with polyethyleneimine (PEI) for CO2 capture. The physicochemical properties of the as‐synthesized adsorbents were analyzed by different characterization techniques, and the adsorption behavior of CO2 on these adsorbents was evaluated in a self‐assembled adsorption setup with gas chromatography. Experimental results found that the Brunauer–Emmett–Teller surface area and pore volume of XAD‐4‐pc were significantly higher than that of XAD‐4, which was favorable to the improvement of PEI loading and CO2 adsorption. The maximum CO2 uptake for PEI‐functionalized XAD‐4‐pc was 3.24 mmol g−1 at 25 °C. The adsorption isotherm of CO2 on the adsorbent was well described by the Langmuir equation, and the kinetics data could be accurately described by Avrami model over the entire adsorption range. The diffusion mechanism study showed that the film diffusion and intraparticle diffusion were mainly the rate‐limiting steps. Moreover, this adsorbent could be well regenerated at relatively low temperature and exhibited stable regenerability after five adsorption‐regeneration cycles, showing its high potential for the capture of CO2 from flue gases. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48479.
Size‐Dependent Vulnerability of Lumbar Motor Neuron Dendritic Degeneration in SOD1G93A Mice
Authors: Fogarty Matthew J. , Mu Erica W.H. , Lavidis Nickolas A. , Noakes Peter G. , Bellingham Mark C.
Published: September 2019

The motor neuron (MN) soma surface area is correlated with motor unit type. Larger MNs innervate fast fatigue‐intermediate (FInt) or fast‐fatiguable (FF) muscle fibers in type FInt and FF motor units, respectively. Smaller MNs innervate slow‐twitch fatigue‐resistant (S) or fast fatigue‐resistant (FR) muscle fibers in type S and FR motor units, respectively. In amyotrophic lateral sclerosis (ALS), FInt and FF motor units are more vulnerable, with denervation and MN death occurring for these units before the more resilient S and FR units. Abnormal MN dendritic arbors have been observed in ALS in humans and rodent models. We used a Golgi‐Cox impregnation protocol to examine soma size‐dependent changes in the dendritic morphology of lumbar MNs in SOD1G93A mice, a model of ALS, at pre‐symptomatic, onset and mid‐disease stages. In wildtype control mice, the relationship between MN soma surface area and dendritic length or dendritic spine number was highly linear (i.e., increased MN soma size correlated with increased dendritic length and spines). By contrast, in SOD1G93A mice, this linear relationship was lost and dendritic length reduction and spine loss were observed in larger MNs, from pre‐symptomatic stages onward. These changes correlated with the neuromotor symptoms of ALS in rodent models. At presymptomatic ages, changes were restricted to the larger MNs, likely to comprise vulnerable FInt and FF motor units. Our results suggest morphological changes of MN dendrites and dendritic spines are likely to contribute ALS pathogenesis, not compensate for it. Anat Rec, 303:1455–1471, 2020. © 2019 American Association for Anatomy
The Ontogeny of Masticatory Muscle Architecture in Microcebus murinus
Authors: Leonard Kaitlyn C. , Boettcher Marissa L. , Dickinson Edwin , Malhotra Neha , Aujard Fabienne , Herrel Anthony , Hartstone‐Rose Adam
Published: September 2019

The masticatory apparatus has been the focus of many studies in comparative anatomy—especially analyses of skulls and teeth, but also of the mandibular adductor muscles which are responsible for the production of bite force and the movements of the mandible during food processing and transport. The fiber architecture of these muscles has been correlated to specific diets (e.g., prey size in felids) and modes of foraging (e.g., tree gouging in marmosets). Despite the well‐elucidated functional implications of this architecture, little is known about its ontogeny. To characterize age‐related myological changes, we studied the masticatory muscles in a large (n = 33) intraspecific sample of a small, Malagasy primate, Microcebus murinus including neonatal through geriatric individuals. We removed each of the mandibular adductors and recorded its mass as well as other linear measurements. We then chemically dissected each muscle to study its architecture—fascicle length and physiological cross‐sectional area (PCSA) which relate to stretch (gape) and force capabilities, respectively. We observed PCSA and muscle mass to increase rapidly and plateau in adulthood through senescence. Fascicle lengths remained relatively constant once maximal length was reached, which occurred early in life, suggesting that subsequent changes in PCSA are driven by changes in muscle mass. Quadratic curvilinear models of each of the architectural variables of all adductors combined as well as individual muscles regressed against age were all significant. Anat Rec, 303:1364–1373, 2020. © 2019 American Association for Anatomy
Nanoreactors for Chemical Synthesis and Biomedical Applications
Authors: Zhou Hua , Tan Jingyun , Zhang Xuanjun
Published: September 2019

With the rapid development of nanoscience and nanotechnology, various types of functional nanoreactors have been designed for diverse applications. Here, the recent evolution of the rational design of nanoreactors for chemical synthesis and biomedical applications are briefly summarized and discussed. The presence of nanoreactors provides constrained space isolated from the surrounding environment. Scientists are committed to studying changes in chemical reactions when the reaction system is confined to the nanosized space. Nanoreactors accelerate the reaction rate and even change mechanism of some chemical reactions. Cells and organelles as natural nanoreactors are also discussed. The development of intracellular synthesis makes it possible to realize various applications in biomedicine. The challenges on the rational design of nanoreactors and perspectives are also discussed.
Augmented TP model transformation‐based parallel distributed compensation control design
Authors: Zhao Guoliang , Wang Degang
Published: September 2019

The usual sampled hyper grid points of uniform sampling method are distributed equally in the TP model transformation, thus, the sampling results often omit the local extrema when the sampling step is not fine‐tuned. Then the resultant tensor which is used for controller design can not fully cover the state space, although the gain which is the feasible solution of the linear matrix inequalities. In this paper, we proposed a non‐uniform sampling method for tensor product model transformation, local extrema are considered in the sampling step, while the sampling step can vary dynamically for different function entries. In this paper, TP model transformation‐based parallel distributed compensation (PDC) controller is extended in three folds: (i) The existing TP model transformation‐based PDC controller with uniform sampling method is extended to TP model transformation‐based PDC tracking controller with the uniform sampling method and an extended signal. (ii) A new TP model transformation‐based PDC tracking controller is proposed based on a new sampling method, that is, the Hammersley sampling method. (iii) TP model transformation‐based PDC tracking controller is also proposed based on the non‐uniform sampling method. The proposed adaptive TP model transformation‐based PDC tracking controller is able to enhance the performance of the TP model transformation‐based PDC controller, and the adaptive TP model transformation‐based PDC controller obtains the best results due to the nearly exact sampling of the system.
Back‐stepping stabilization of fractional‐order triangular system with applications to chaotic systems
Authors: Peng Chenchen , Zhang Weihai
Published: September 2019

This paper addresses the stabilization of fractional‐order nonlinear lower triangular systems and applies the obtained results to the synchronization of fractional‐order chaotic systems (FOCSs). Three cases are considered as follows: (i) FOCSs have a lower triangular structure themselves. (ii) FOCSs can be converted into the form in full by appropriate nonsingular coordinate transformations. (iii) FOCSs can be transformed into the structure in part by the conversions. It is shown that the above three cases combining with back‐stepping approach are useful for the control of FOCSs. Different from the previous literature, the system structure studied is more concise with more applications. A numerical example is presented to show the validity of the proposed results.
Decompositions of finite games: From weighted inner product to standard inner product
Authors: Li Changxi , He Fenghua , Yao Haodi
Published: September 2019

To investigate the topological structure of finite games, various decomposions of finite games have been proposed. The inner product of vectors plays a key role in the decomposition of finite games. This paper considers the effect of different inner products on the orthogonal decomposition of finite games. We found that only when the compatible condition is satisfied, a common decomposition can be induced by the standard inner product and the weighted inner product simultaneously. To explain the result, we studied the existing decompositions, including potential based decomposition, zero‐sum based decomposition, and normalization based decomposition. For zero‐sum based decomposition and normalization based decomposition, we redefine their subspaces in a linear algebraic framework, which shows their physical meanings clearly. Bases of subspaces in these two decompositions are constructed.
From three‐dimensional morphology to effective diffusivity in filamentous fungal pellets
Authors: Schmideder Stefan , Barthel Lars , Müller Henri , Meyer Vera , Briesen Heiko
Published: September 2019

Filamentous fungi are exploited as cell factories in biotechnology for the production of proteins, organic acids, and natural products. Hereby, fungal macromorphologies adopted during submerged cultivations in bioreactors strongly impact the productivity. In particular, fungal pellets are known to limit the diffusivity of oxygen, substrates, and products. To investigate the spatial distribution of substances inside fungal pellets, the diffusive mass transport must be locally resolved. In this study, we present a new approach to obtain the effective diffusivity in a fungal pellet based on its three‐dimensional morphology. Freeze‐dried Aspergillus niger pellets were studied by X‐ray microcomputed tomography, and the results were reconstructed to obtain three‐dimensional images. After processing these images, representative cubes of the pellets were subjected to diffusion computations. The effective diffusion factor and the tortuosity of each cube were calculated using the software GeoDict. Afterwards, the effective diffusion factor was correlated with the amount of hyphal material inside the cubes (hyphal fraction). The obtained correlation between the effective diffusion factor and hyphal fraction shows a large deviation from the correlations reported in the literature so far, giving new and more accurate insights. This knowledge can be used for morphological optimization of filamentous pellets to increase the yield of biotechnological processes.
Taking sustainable fashion mainstream: Social media and the institutional celebrity entrepreneur
Authors: McKeown Carolyn , Shearer Linda
Published: September 2019

There is a growing imperative to address the negative environmental impact of fashion and an increased awareness of sustainability issues: the sustainable fashion concept (SFC). However, while consumers are becoming more aware and concerned about sustainability, this is not resulting in the purchase of sustainable fashion products in preference to “mainstream” goods. This so‐called attitude–behaviour gap is well documented in academic literature, and yet there is a lack of research into potential methods of disrupting this phenomenon. This study seeks to redress this by examining the potential influence of celebrity institutional entrepreneurs (CIEs) to raise awareness of the SFC and to therefore guide and change consumer behaviour towards more sustainable practice. CIEs are celebrities who use their social position to espouse their values with the intention of influencing institutional habits and behaviours. In this case, Emma Watson is identified as an appropriate and credible proponent, and her @the_press_tour Instagram account was used to examine her influence. A netnographic investigation of this account was conducted in combination with eight in‐depth interviews with account followers to examine attitudes and actions towards sustainable fashion. Findings showed that the account had partial impact on consumer engagement with the SFC in that it led to the participants being more likely to discuss and consider the issues around sustainable fashion; however, it had no significant impact on purchases of sustainable fashion. The study concludes that CIEs can impact the attitudes of mainstream consumers towards sustainable fashion; however, further research is required to determine any long‐term influence.
Insights into the Role of Ketoreductases in the Biosynthesis of Partially Reduced Bacterial Aromatic Polyketides*
Authors: Husain Syed Masood , Präg Andreas , Linnenbrink Anton , Bechthold Andreas , Müller Michael
Published: September 2019

Partially reduced aromatic polyketides are bioactive secondary metabolites or intermediates in the biosynthesis of deoxygenated aromatics. For the antibiotic GTRI‐02 (mensalone) in different Streptomyces spp., biosynthesis involving the reduction of a fully aromatized acetyltrihydroxynaphthalene by a naphthol reductase has been proposed and shown in vitro with a fungal enzyme. However, more recently, GTRI‐02 has been identified as a product of the ActIII biosynthetic gene cluster from Streptomyces coelicolor A3(2), for which the reduction of a linear polyketide precursor by ActIII ketoreductase, prior to cyclization and aromatization, has been suggested. We have examined three different ketoreductases from bacterial producer strains of GTRI‐02 for their ability to reduce mono‐, bi‐, and tricyclic aromatic substrates. The enzymes reduced 1‐ and 2‐tetralone but not other aromatic substrates. This strongly suggests a reduction of a cyclized but not yet aromatic polyketide intermediate in the biosynthesis of GTRI‐02. Implications of the results for the biosynthesis of other secondary polyketidic metabolites are discussed.
Hemodynamic assessment in heart failure
Authors: Jain Christopher Charles , Borlaug Barry A.
Published: September 2019

Hemodynamics play a central role in the pathophysiology of heart failure (HF), yet their proper assessment and optimization remains challenging. Heart failure is defined as the inability of the heart to deliver adequate perfusion (cardiac output) to the body at rest or exercise, or to require an elevation in cardiac filling pressures in order to do this. This bedrock definition is important because it relies on measurable quantities (filling pressures and output) that are readily assessed in the cardiac catheterization laboratory. Here we present three cases to illustrate how better understanding of the determinants of cardiac output and stroke volume: preload, afterload, contractility, and lusitropy, as well as the determinants of congestion (high filling pressures) may be used to guide optimization of hemodynamic status. The goal is that the readers will be able to think more critically when evaluating the hemodynamics of their patient in HF and recognize the complex interplay that determines the complex balance between cardiac ejection and filling capabilities, and how this alters symptoms and outcomes for patients with HF.

Key Points

Careful assessment of hemodynamics in the catheterization laboratory allows for actionable insight to a patient's volume status, cardiac function and can help prognosticate outcomes.

Exercise hemodynamics in heart failure is a powerful tool to better understand the cause of symptoms and predict outcomes.

Clinicians should aim to decrease biventricular filling pressures to normal values to improve morbidity and reduce risk for readmission.

In patients with heart failure and reduced ejection fraction, clinicians should aim to decrease afterload as much as can be tolerated by the renal function and patient's symptoms.

Low cardiac output can often be improved by optimizing preload and afterload rather than initiating inotropes, which should be reserved until needed.

In advanced heart failure, the right heart function becomes a key determinant of symptoms and outcomes.
Fast Cyclohexane Oxidation Under Mild Reaction Conditions Through a Controlled Creation of Redox‐Active Fe(II/III) Sites in a Metal−Organic Framework
Authors: Kim Ah‐Reum , Ahn Sol , Yoon Tae‐Ung , Notestein Justin M. , Farha Omar K. , Bae Youn‐Sang
Published: September 2019

MIL‐100(Fe), a metal−organic framework containing coordinatively unsaturated iron sites, was prepared by a solvothermal method and utilized in cyclohexane oxidation. Interestingly, the composition and fraction of redox‐active Fe(II/III) sites in MIL‐100(Fe) could be tuned by using different pretreatment temperatures. The obtained materials were characterized by means of field‐emission scanning electron microscopy (FE‐SEM), powder X‐ray diffraction (PXRD), N2 adsorption‐desorption isotherms, and X‐ray photoelectron spectroscopy (XPS). Due to the presence of redox‐active coordinatively unsaturated sites (CUS) at the iron atoms, MIL‐100(Fe) exhibited good performance for cyclohexane oxidation under mild reaction conditions. Oxidation rates were significantly enhanced when reduced FeII sites were generated by high‐temperature pretreatments. In either high‐temperature or low‐temperature pretreatment, the isolated Fe(II/III) sites in MIL‐100 were far more reactive in cyclohexane oxidation than were bulk iron oxide materials. Finally, possible reaction pathways were proposed based on radical, Haber‐Weiss routes.
Iridium Water Oxidation Catalysts Based on Pyridine‐Carbene Alkyl‐Substituted Ligands
Authors: Corbucci Ilaria , Zaccaria Francesco , Heath Rachel , Gatto Giordano , Zuccaccia Cristiano , Albrecht Martin , Macchioni Alceo
Published: September 2019

Iridium complexes bearing pyridine triazolylidene ligands with variable steric hindrance, derived by the presence of an R group (R=H, Me, Et, nPr, iPr, Bu, and Oct) onto the N1‐nitrogen, have been synthesized, fully characterized and tested as water oxidation catalysts (WOCs), using chemical sacrificial oxidants (CAN and NaIO4) or in photocatalytic experiments ([Ru(bpy)3]Cl2 as phosensitizer and Na2S2O8 as an electron acceptor). The catalytic activity is barely affected by the nature of R when WO is driven by NaIO4 (1 min−1<TOF<14 min−1) or light/[Ru(bpy)3]Cl2/Na2S2O8 (TOF≈0.15 min−1); on the contrary, a remarkable effect is observed with CAN. Particularly, in the latter case, complexes with R=H and Me exhibit similar activity (10 min−1<TOF<20 min−1), whereas all other complexes (R=Et, Pr, i‐Pr, Bu, and Oct) are significantly more active and exhibit comparable TOFs in the range 40–130 min−1. Thus, a marked discontinuity in performances occurs when passing from R=Me to R=Et. This can be hardly explained solely based on the previously proposed hypothesis, suggesting that an increased R‐dimension might favor the association of iridium complexes leading to the formation of highly active multimetallic species. An additional, more specific effect has to be present. It appears plausible that the steric hindrance introduced in close proximity of the iridium center, when R≥Et, hampers transfer of the hydroperoxo or peroxo moiety from iridium active species to cerium, a process that could slow down kinetics of O2 evolution.
Manganese‐Catalyzed Transfer Hydrogenation of Nitriles with 2‐Butanol as the Hydrogen Source
Authors: Garduño Jorge A. , Flores‐Alamo Marcos , García Juventino J.
Published: September 2019

We report herein the first example of a homogeneous manganese catalyzed transfer hydrogenation of nitriles using 2‐BuOH as the hydrogen source. Compound fac‐[(CO)3Mn{iPr2P(CH2)2PiPr2}Br] (Mn‐1, 3 mol %) exhibited catalytic activity in the presence of KOtBu (10 mol %) for the transfer hydrogenation of benzonitrile to yield a mixture of benzylamine (BA) and N‐sec‐butylidenebenzylamine (SBA). Subsequent acidic hydrolysis yielded isolated benzylamine hydrochloride in 96 %. The title system featured reversible formation of N‐benzylidenebenzylamine (BBA) prior to formation of SBA. A series of amine hydrochlorides was prepared following this methodology (39–92 % isolated yields, 4 examples). Best substrates for this transformation are electron‐rich aromatic nitriles, nonetheless electron‐deficient aromatic as well as aliphatic nitriles were also hydrogenated. Mechanistic studies suggested coordinatively unsaturated Mn‐hydride species performing catalytic turnover.
Effect of the sp3/sp2 Ratio in Boron‐Doped Diamond Electrodes on the Degradation Pathway of Aniline by Anodic Oxidation
Authors: Espinoza L. Carolina , Aranda Mario , Contreras David , Henríquez Adolfo , Salazar Ricardo
Published: September 2019

The sp3/sp2 ratio present in boron‐doped diamond (BDD) electrodes conditions the way in which organic compounds are oxidized and transformed to CO2 during anodic oxidation. A higher content of sp3 carbon on the surface favors the generation of hydroxyl radicals over the oxygen evolution reaction, which generates different degradation byproducts. In this work, we studied the degradation of aniline by anodic oxidation using five BDD electrodes with different sp3/sp2 ratios in sulfate and chloride media. Aniline was degraded using the five BDD electrodes in both electrolytes, and clear differences were observed in the intermediates produced during the electrolysis. BDD electrodes with higher sp3 proportions allowed for greater degradation and mineralization of aniline with lower molecular weight and the production of fewer toxic organic byproducts. Degradation pathways for aniline in sulfate and chloride media are proposed, evidencing the differences in the oxidation mechanisms for aniline and its byproducts due to the varying sp3/sp2 ratio in the BDD electrodes.
Star‐Shaped Gold Nanoparticles as Friendly Interfaces for Protein Electrochemistry: the Case Study of Cytochrome c
Authors: Silveira Célia M. , Zumpano Rosaceleste , Moreira Miguel , de Almeida Miguel Peixoto , Oliveira Maria João , Bento Marina , Montez Cláudia , Paixão Inês , Franco Ricardo , Pereira Eulália , Almeida M. Gabriela
Published: September 2019

Gold nanostars with an average tip‐to‐tip length of 52±6 nm were functionalized with different capping agents and used as electrode modification materials for protein electrochemistry. Direct electron transfer between cytochrome c and nanostar‐coated pyrolytic graphite electrodes was observed with the protein in solution. The electrochemical response was improved at nanostars functionalized with a 1 : 1 mixture of 11‐mercaptoundecanoic acid and 4‐mercaptobenzoic acid in comparison with gold nanospheres coated with a similar functionalization. Further immobilization of cytochrome c on pyrolytic graphite while conjugated with the same nanostars guaranteed the maintenance of the protein's native properties, whereas direct adsorption on the bare or nanostar‐modified electrodes resulted in an altered conformational state. The pseudo‐peroxidase activity of the altered cytochrome c was enhanced in the presence of the nanostars.
Unexpectedly Large Couplings Between Orthogonal Units in Anthraquinone Polymers
Authors: Fornari Rocco P. , de Silva Piotr
Published: September 2019

The unusual electronic properties of directly linked 1,4‐polyanthraquinones (14PAQs) are investigated. The dihedral angle between the molecular planes of anthraquinones (AQs) is found to be close to 90°. Contrary to the prevailing notion that the interaction between orthogonal units is negligible due to broken π‐electron conjugation, the coupling between neighboring AQ units does not have a minimum at 90° and is much larger than that expected. The unexpectedly large electronic coupling between orthogonal AQ units is explained by the interaction between the lone pairs of the carbonyl oxygen and the π system of the neighboring unit, which allows favorable overlap between frontier molecular orbitals at the orthogonal geometry. It is shown that this effect, which is described computationally for the first time, can be strengthened by adding more quinone units. The effect of thermal fluctuations on the couplings is assessed through ab initio molecular dynamics simulations. The distributions of the couplings reveal that electron transport is resilient to dynamic disorder in all systems considered, whereas the hole couplings are much more sensitive to disorder. Lone pair–π interactions are described, as a previously largely overlooked conjugation mechanism, for incorporation into a new class of disorder‐resilient semiconducting redox polymers.
Dearomatization of 3‐Nitroindoles with Highly γ‐Functionalized Allenoates in Formal (3+2) Cycloadditions
Authors: Birbaum Léo , Gillard Laurent , Gérard Hélène , Oulyadi Hassan , Vincent Guillaume , Moreau Xavier , De Paolis Michael , Chataigner Isabelle
Published: September 2019

3‐Nitroindoles are easily reacted with highly substituted γ‐allenoates in the presence of a commercially available phosphine catalyst. For instance, allenoates derived from biomolecules such as amino and deoxycholic acids are combined for the first time with 3‐nitroindole. The corresponding dearomatized (3+2) tricyclic cycloadducts are obtained as α‐regioisomers exclusively. DFT computations shed light on this multi‐step reaction mechanism and on the selectivities observed in the sequence.