bluuebunny/crossref_metadata_2025 huggingface dataset:
Murine leukemia provirus‐mediated activation of the Notch1 gene leads to induction of HES‐1 in a mouse T lymphoma cell line, DL‐3
Authors: Lee Jong-Seo , Ishimoto Akinori , Honjo Tasuku , Yanagawa Shin-ichi
Published: July 2002

Constitutive activation of Notch signaling is known to be associated with tumorigenesis. In a mouse T lymphoma cell line, DL‐3, we found that a murine leukemia provirus was inserted in the Notch1 locus, which led to marked expression of a virus‐Notch1 fusion mRNA encoding an intracellular portion of the Notch1 protein. Furthermore, expression and nuclear localization of this constitutively active form of Notch1 protein were confirmed. Corresponding to this finding, the transcription of the hairy/enhancer of split (HES‐1) gene, a known target of Notch1 signaling, was elevated in this cell line. A potential role for overexpressed HES‐1 in the development of the lymphoma was discussed.
Regulation by 1α,25‐dihydroxyvitamin D3 of expression of stanniocalcin messages in the rat kidney and ovary
Authors: Honda Shinji , Kashiwagi Masahide , Ookata Kayoko , Tojo Akihiro , Hirose Shigehisa
Published: July 2002

Regulation by vitamin D3 of expression of the genes for stanniocalcins 1 and 2 (STC‐1 and STC‐2) was studied and their levels were shown to be oppositely regulated in the kidney and to remain unaffected in the ovary. Female rats were treated with calcitriol, the active form of vitamin D3, and alterations in the levels of STC‐1 and STC‐2 mRNA were determined by Northern blot analysis in the kidney and ovary where the STC‐1‐expressing cells have previously been identified by in situ hybridization histochemistry. In the kidney, calcitriol treatment increased the STC‐1 mRNA levels more than 3‐fold, but decreased the STC‐2 message to trace levels. In the ovary, however, both STC‐1 and STC‐2 mRNA levels were not significantly affected by the calcitriol treatment. These results support the hypotheses that (1) STC‐1 and STC‐2 have opposite effects on calcium and phosphate homeostasis, namely anti‐hypercalcemic and anti‐hypocalcemic actions, respectively, and (2) the mammalian stanniocalcin system acquired, in addition to the role in the systemic mineral metabolism, a role in the reproduction system that operates independently of the systemic condition.
Cross‐reaction of chalcone synthase and stilbene synthase overexpressed in Escherichia coli
Authors: Yamaguchi Toshio , Kurosaki Fumiya , Suh Dae-Yeon , Sankawa Ushio , Nishioka Mizue , Akiyama Takumi , Shibuya Masaaki , Ebizuka Yutaka
Published: July 2002

Chalcone synthase (CHS) and stilbene synthase (STS) are related plant polyketide synthases belonging to the CHS superfamily. CHS and STS catalyze common condensation reactions of p‐coumaroyl‐CoA and three C2‐units from malonyl‐CoA but different cyclization reactions to produce naringenin chalcone and resveratrol, respectively. Using purified Pueraria lobata CHS and Arachis hypogaea STS overexpressed in Escherichia coli, bisnoryangonin (BNY, the derailed lactone after two condensations) and p‐coumaroyltriacetic acid lactone (the derailed lactone after three condensations) were detected from the reaction products. More importantly, we found a cross‐reaction between CHS and STS, i.e. resveratrol production by CHS (2.7–4.2% of naringenin) and naringenin production by STS (1.4–2.3% of resveratrol), possibly due to the conformational flexibility of their active sites.
Insulin and insulin antagonists evoke phosphorylation of P20 at serine 157 and serine 16 respectively in rat skeletal muscle
Authors: Wang Yu , Xu Aimin , Pearson Richard B. , Cooper Garth J.S.
Published: July 2002

We show here that insulin and insulin antagonists differentially modify phosphorylation of three phospho‐isoforms of P20 (termed S1, S2 and S3) in rat skeletal muscle. Precise phosphorylation sites of S1 and S2 were mapped to serine 157 and serine 16 respectively. Insulin evoked phosphorylation of P20 at serine 157 through the phosphatidylinositol (PI) 3‐kinase pathway. Epinephrine and calcitonin gene‐related peptide decreased phosphorylation at serine 157 and increased phosphorylation at serine 16 and other unidentified sites. These results demonstrate that the PI‐3‐kinase pathway of anabolic insulin and the cAMP pathway of catabolic hormones converge on P20 and suggest a potential role of this protein in regulating energy metabolism of skeletal muscle.
Functional properties of complement factor H‐related proteins FHR‐3 and FHR‐4: binding to the C3d region of C3b and differential regulation by heparin
Authors: Hellwage Jens , Jokiranta T.Sakari , Koistinen Vesa , Vaarala Outi , Meri Seppo , Zipfel Peter F.
Published: July 2002

The human factor H‐related proteins FHR‐3 and FHR‐4 are members of a family of proteins related to the complement factor H. Here, we report that the two proteins bind to the C3d region of complement C3b. The apparent K
A values for the interactions of FHR‐3 and FHR‐4 with C3b are 7.5×106 M−1 and 2.9×106 M−1, respectively. Binding studies performed with C3b‐coated pneumococci confirmed the results obtained with the biosensor system. A C‐terminal construct of factor H showed similar binding characteristics. The interaction of FHR‐3, but not of FHR‐4, with opsonised pneumococci was inhibited by heparin.
Modification of Cys‐418 of pyruvate formate‐lyase by methacrylic acid, based on its radical mechanism
Authors: Plaga Wulf , Vielhaber Gabriele , Wallach Jochen , Knappe Joachim
Published: July 2002

The recently determined crystal structure of pyruvate formate‐lyase (PFL) suggested a new view of the mechanism of this glycyl radical enzyme, namely that intermediary thiyl radicals of Cys‐418 and Cys‐419 participate in different ways [Becker, A. et al. (1999) Nat. Struct. Biol. 6, 969–975]. We report here a suicide reaction of PFL that occurs with the substrate‐analog methacrylate with retention of the protein radical (K
I=0.42 mM, k
i=0.14 min−1). Using [1‐14C]methacrylate (synthesized via acetone cyanhydrin), the reaction end‐product was identified by peptide mapping and cocrystallization experiments as S‐(2‐carboxy‐(2S)‐propyl) substituted Cys‐418. The stereoselectivity of the observed Michael addition reaction is compatible with a radical mechanism that involves Cys‐418 thiyl as nucleophile and Cys‐419 as H‐atom donor, thus supporting the functional assignments of these catalytic amino acid residues derived from the protein structure.
Intrafascial abdominal hysterectomy: outcomes and complications of 867 operations
Authors: Conde‐Agudelo A
Published: July 2002

Objective: To prospectively evaluate the results and complications of the surgical technique of intrafascial abdominal hysterectomy. Methods: From March 1993 to February 1998, 867 women at four institutions from the Department of Valle del Cauca, Colombia, underwent intrafascial abdominal hysterectomy. Information on sociodemographic and clinical characteristics before hysterectomy, indications for hysterectomy, surgical outcomes and intra‐ and post‐operative complications were collected. Patients were evaluated at 1, 3, and 12 months post‐operatively and annually thereafter. Results: The follow‐up period ranged from 6 to 63 months (median=45 months). The mean blood loss was 286±112 ml. Operative time averaged 71±11 min. The overall operative site infection rate was 4%. Intra‐ and post‐operative hemorrhage occurred in 0.2 and 1.0% of patients, respectively. The transfusion rate was 0.7%. The incidences of ureteral, bladder, and bowel injury were 0.1, 0.4 and 0.0%, respectively. To date, none of the patients followed up between 1 and 5 years have had evidence of vaginal vault prolapse. Conclusions: Intrafascial abdominal hysterectomy is a safe technique with a low rate of complications.
The contribution of MD–PhD training to academic orthopaedic faculties
Authors: Clark John M. , Hanel Douglas P.
Published: July 2002

Little is known about the distribution of research‐trained physicians across the various specialties. To document the extent to which MD—PhD programs are a source of research‐trained faculty for orthopaedic departments, this study examined the specialty choices of graduates of the Medical Scientist Training Program (MSTP) from 1964 to 1994. The MSTP, a combined MD—PhD program supported by the National Institute of General Medical Sciences, (NIGMS), produces roughly 25% of all MD—PhDs in the US.

Methods. Copies of the appendices from training grant applications containing information on MSTP graduates were obtained from the NIGMS. Also, a questionnaire was mailed to 116 university‐affiliated orthopaedic surgery departments asking how many faculty were MD's, PhDs or MD—PhDs.

Results. Records were obtained for all MST programs. Information on postdoctoral training and/or a current position was reported for 1615 graduates who earned both MD and PhD. Of these graduates, 277 chose non‐clinical paths. The other 1338 entered a residency or internship. Of these, 593 were still in residency training, 566 were academic faculty members and 130 were in private practice. In the records, 12 (0.9%) were listed as orthopaedic surgical residents (6) or faculty (6). At this time, all 12 have completed training, and 11 are in academic practice. Eighty‐three departments replied to the questionnaire. In that sample of 1761 faculty positions, 1478 were MDs, 217 were PhDs and 36 (2.0%) were MD‐PhDs.

Conclusion. Despite robust support of MD—PhD programs, the number of dual degree recipients on orthopaedic faculties is small when compared to the relative size of the specialty. Other sources of research‐trained staff should perhaps be developed. © 2001 Orthopaedic Research Society. Published by Elsevier Science Ltd. All rights reserved.
Association of D2 dopamine receptor and alcohol dehydrogenase 2 genes with Polynesian alcoholics
Authors: Amadéo S. , Noble E.P. , Fourcade-Amadéo M.L. , Tetaria C. , Brugiroux M.F. , Nicolas L. , Deparis X. , Elbaz A. , Zhang X. , Ritchie T. , Martin P.V. , Mallet J.
Published: July 2002

Alleles of the D2 dopamine receptor (DRD2) and the alcohol dehydrogenase 2 (ADH2) genes were determined in 69 French Polynesian alcoholic patients and 57 controls matched for racial origin. Three racial groups were studied: pure Polynesians (PP), Polynesians mixed with Caucasian (PCA) ancestry and Polynesians mixed with Chinese (PCH) ancestry. DRD2 A1 allele frequencies in the alcoholics compared to their controls in these groups were: PP,.26 vs .32 (P= .69); PCA, .44 vs .35 (P= .46); PCH, .40 vs 0.39 (P= .88). ADH2 1 allele frequencies in alcoholics compared to their controls groups were: PP, .56 vs .62 (P= .66); PCA, .75 vs .56 (P= .09); PCH, .78 vs .32 (P= .009). In the PCA group, the combination of the DRD2 A1 genotypes and the ADH2 1 homozygotes was strongly associated with alcoholism (P= .0027). This preliminary study shows the importance of ascertaining racial ancestry in molecular genetic association studies. Moreover, it suggests that a combination of genes are involved in susceptibility to the development of alcoholism.
Evaluation of the supervisory system in elderly subjects with and without disinhibition
Authors: Gokalsing E , Robert P.H. , Lafont V , Medecin I , Baudu C , Boyer P , Pringuey D , Darcourt G
Published: July 2002

Disinhibition and irritability, defined as loss of behavioral and emotional control, are frequent in the elderly. The working hypothesis for this study was that these disorders are associated with a cognitive alteration of control processes that manifests as non-routine behavior because of the dysfunction of a general executive component known as the supervisory attentional system (SAS).

Methods

A total of 28 elderly subjects with mild cognitive impairment were recruited and divided into two groups using the Neuropsychiatric Inventory. Fourteen subjects were allocated to the disinhibited group and 14 subjects matched for age, sex and educational level formed a disinhibition-free control group. The neuropsychological battery included the following tests: Mini Mental Score Evaluation, Boston Naming test, Token test, Trail Making and Verbal Fluency. Two tasks were specifically designed to stress the SAS: 1) A specific verbal sentence arrangement task in which subjects had to use sequential reasoning with verbal material. Each test sequence consisted of a series of words shown in jumbled order. The construction of some sequences had to be done by using familiar routine associations (valid conditions). In contrast, other sequences required the overriding selection of familiar routine associations, which were inappropriate within the general context of the task (invalid conditions). 2) Using the Continuous Performance Test, four aspects were evaluated: sustained, selective, preparation and suppressive attention.

Results

The only group differences in neuropsychological test results were the following: 1) the sentence arrangement task. In comparison with the control group, the disinhibited group was impaired in invalid conditions and the calculated difference between the number of correct responses in invalid conditions minus that in valid conditions was significantly higher; and 2) the CPT. Disinhibited subjects had a significantly lower number of hits, exclusively in the ‘suppressive attention’ paradigm.

These results suggest that subjects with disinhibition have impaired supervisory system function.
Methodological considerations and empirical data to the onset of efficacy of antidepressants and to the prediction of therapy outcome
Authors: Müller H , Möller H.J.
Published: July 2002

Is the onset of efficacy of antidepressants always delayed and which early clinical signs predict final outcome of therapy ? Our analyses show that strict response criteria produce necessarily later onset estimations rather than less strict ones. In two large-scale clinical samples we compared different estimation methods of the day of onset. Patients' direct ratings produced the earliest onset estimations. Because of the strong dependency of onset estimations on measurement methods, we argue that it is still open to debate, in which degree drug response is delayed. Concerning early clinical signs of final outcome we compared early changes of the Hamilton Rating Scale for Depression (HAM-D) items with several measures of final outcome. From the data we analyzed, there are no sufficiently precise signs of final outcome within the first 2 weeks of therapy.
Optimized low‐dose combinatorial drug treatment boosts selectivity and efficacy of colorectal carcinoma treatment
Authors: Zoetemelk Marloes , Ramzy George M. , Rausch Magdalena , Koessler Thibaud , van Beijnum Judy R. , Weiss Andrea , Mieville Valentin , Piersma Sander R. , de Haas Richard R. , Delucinge‐Vivier Céline , Andres Axel , Toso Christian , Henneman Alexander A. , Ragusa Simone , Petrova Tatiana V. , Docquier Mylène , McKee Thomas A. , Jimenez Connie R. , Daali Youssef , Griffioen Arjan W. , Rubbia‐Brandt Laura , Dietrich Pierre‐Yves , Nowak‐Sliwinska Patrycja
Published: October 2020

The current standard of care for colorectal cancer (CRC) is a combination of chemotherapeutics, often supplemented with targeted biological drugs. An urgent need exists for improved drug efficacy and minimized side effects, especially at late‐stage disease. We employed the phenotypically driven therapeutically guided multidrug optimization (TGMO) technology to identify optimized drug combinations (ODCs) in CRC. We identified low‐dose synergistic and selective ODCs for a panel of six human CRC cell lines also active in heterotypic 3D co‐culture models. Transcriptome sequencing and phosphoproteome analyses showed that the mechanisms of action of these ODCs converged toward MAP kinase signaling and cell cycle inhibition. Two cell‐specific ODCs were translated to in vivo mouse models. The ODCs reduced tumor growth by ~80%, outperforming standard chemotherapy (FOLFOX). No toxicity was observed for the ODCs, while significant side effects were induced in the group treated with FOLFOX therapy. Identified ODCs demonstrated significantly enhanced bioavailability of the individual components. Finally, ODCs were also active in primary cells from CRC patient tumor tissues. Taken together, we show that the TGMO technology efficiently identifies selective and potent low‐dose drug combinations, optimized regardless of tumor mutation status, outperforming conventional chemotherapy.
Higher Checkpoint Inhibitor Arthritis Disease Activity may be Associated With Cancer Progression: Results From an Observational Registry
Authors: Chan Karmela Kim , Tirpack Aidan , Vitone Gregory , Benson Caroline , Nguyen Joseph , Ghosh Nilasha , Jannat‐Khah Deanna , Bykerk Vivian , Bass Anne R.
Published: October 2020

Objective

To describe clinical features associated with cancer outcomes of patients with immune checkpoint inhibitor (ICI)‐associated arthritis.

Methods

Observational study of patients with ICI‐arthritis enrolled in a single‐center registry. Arthritis phenotype and activity, medications, and cancer status were recorded at every visit. We used descriptive statistic, and Kaplan‐Meier curves using two‐sided log‐rank test and Cox regression analysis were used to identify factors associated with cancer progression‐free survival (PFS).

Results

Forty‐two patients with ICI‐arthritis were followed for a median (interquartile range [IQR]) of 7.4 (1.7, 14.7) months. Fifty‐seven percent were female, 33% had melanoma, and 69% received anti–programmed death ligand 1 monotherapy. Median time from ICI initiation to arthritis onset was 2.8 (0.8, 11.2) months. Sixty‐two percent had a rheumatoid arthritis (RA)‐like small‐joint presentation; 27% of all patients were rheumatoid factor and/or cyclic citrullinated peptide positive. Median (IQR) Clinical Disease Activity Index (CDAI) on presentation was 15 (8, 24); 62% required systemic glucocorticoids, 55% required disease‐modifying antirheumatic drugs (DMARDs), and 69% had ongoing arthritis at 6 months. Arthritis led to ICI discontinuation in five patients. In univariate analysis, baseline CDAI, DMARD use, earlier arthritis onset, and longer duration of follow‐up were associated with shorter PFS. In multivariable Cox regression analysis controlling for DMARD use and time to arthritis onset, CDAI was a significant predictor of cancer progression (hazard ratio 1.09, 95% confidence interval [CI] 1.00‐1.19, P = 0.05)

Conclusion

ICI‐arthritis most commonly presents with an RA‐like phenotype. High disease activity, as measured by CDAI, may portend cancer progression.
Continuous Synthesis of Hollow High‐Entropy Nanoparticles for Energy and Catalysis Applications
Authors: Wang Xizheng , Dong Qi , Qiao Haiyu , Huang Zhennan , Saray Mahmoud Tamadoni , Zhong Geng , Lin Zhiwei , Cui Mingjin , Brozena Alexandra , Hong Min , Xia Qinqin , Gao Jinlong , Chen Gang , Shahbazian‐Yassar Reza , Wang Dunwei , Hu Liangbing
Published: October 2020

Mixing multimetallic elements in hollow‐structured nanoparticles is a promising strategy for the synthesis of highly efficient and cost‐effective catalysts. However, the synthesis of multimetallic hollow nanoparticles is limited to two or three elements due to the difficulties in morphology control under the harsh alloying conditions. Herein, the rapid and continuous synthesis of hollow high‐entropy‐alloy (HEA) nanoparticles using a continuous “droplet‐to‐particle” method is reported. The formation of these hollow HEA nanoparticles is enabled through the decomposition of a gas‐blowing agent in which a large amount of gas is produced in situ to “puff” the droplet during heating, followed by decomposition of the metal salt precursors and nucleation/growth of multimetallic particles. The high active sites per mass ratio of such hollow HEA nanoparticles makes them promising candidates for energy and electrocatalysis applications. As a proof‐of‐concept, it is demonstrated that these materials can be applied as the cathode catalyst for Li–O2 battery operations with a record‐high current density per catalyst mass loading of 2000 mA gcat.−1, as well as good stability and durable catalytic activity. This work offers a viable strategy for the continuous manufacturing of hollow HEA nanomaterials that can find broad applications in energy and catalysis.
Physiological effects of humic acid in peanut growing in continuous cropping soil
Authors: Li Yan , Fang Feng , Wei Jianlin , Cui Rongzong , Li Guosheng , Zheng Fuli , Tan Deshui
Published: October 2020

Although humic acid has been demonstrated to improve the yield of some crops, the long‐term effects of continuous cropping on peanut (Arachis hypogaea L.) remain largely undetermined. In the present study, we aimed to compare the continuous effects of different concentrations of humic acid on the continuously cropped peanut. A 3‐yr experiment was conducted in the North China Plain. Treatments of 50 kg ha−1 (T1), 100 kg ha−1 (T2), and 150 kg ha−1 (T3) humic acid were applied with inorganic fertilizer along with the equal N, P, and K inputs. Compared with the control group, humic acid increased the yield and oxidative stress tolerance of continuously cropped peanut. To elucidate the mechanism, various physiological indicators were evaluated and compared in this study. First, humic acid increased chlorophyll content and the ability to incorporate nutrients, and the maximum effect was achieved by T3 in 2016. Second, the activities of nitrate reductase and sucrose phosphate synthase in peanut leaves were significantly increased after humic acid treatment, and the most increase was achieved by T2. Third, the activities of antioxidant enzymes were increased, the malondialdehyde (MDA) content was reduced in 2016–2018 by T3, and the same effects were observed in roots and leaves. Fourth, the content of the hormone was changed after humic acid treatment. Collectively, humic acid improved the yield and tolerance of continuously cropped peanut due to the above‐mentioned four reasons, which were conducive to alleviating the obstacles of continuously cropped peanut.
Mental Health Identification Practices of Jails: The Unmet Needs of the “Silent” Population
Authors: Comartin Erin B. , Milanovic Edita , Nelson Victoria , Kubiak Sheryl
Published: October 2020

The overrepresentation of individuals with mental illness in the criminal/legal system is well documented. While professional associations urge diversion towards treatment, little is known about the practices these institutions use to identify this population. One understudied space in the criminal/legal continuum is jails. This exploratory study compares two types of mental health identification at jail booking to assess jail‐ and community‐based service outcomes by identification type (N = 2956): (a) staff observation and (b) a standardized screening instrument. Individuals identified through staff observation were significantly more likely to receive jail‐ and community‐based services, even though current symptomology and substance misuse were both significantly higher for individuals identified only by the screening instrument. These findings point to the importance of jails in providing stabilizing services during incarceration, but further, show the impact that identification practices have on individuals as they transition to the community. Community context showed varied rates of jail staff observations of mental illness, showing greater risks for individuals in rural communities. Implications include a need for system‐level changes by instituting evidence‐based identification practices in jails, and improving professional collaboration practices between mental health and criminal/legal practitioners as individuals enter and exit jails.
Disparities in the usage of maternity leave according to occupation, race/ethnicity, and education
Authors: Hawkins Devan
Published: October 2020

Background

Unlike almost all other countries, the United States does not mandate paid maternity leave for mothers. Lack of access to maternity leave may be a risk factor for adverse maternal and child health outcomes. This study sought to assess disparities in the usage of maternity leave according to maternal occupation, race/ethnicity, and education, and to explore the relationships between these factors.

Methods

We used data from the Pregnancy Risk Assessment Monitoring System from the years 2016 and 2017. We calculated the prevalence of usage of maternity leave and paid maternity leave according to the mother's age, race/ethnicity, education, state, and occupation. We constructed regression models to explore the bivariate and mutually adjusted associations between these factors and usage of maternal leave.

Results

Usage of maternity leave and paid maternity leave were estimated at 89.3% and 49.0%, respectively. Usage of paid maternity leave was lower in younger mothers, in Black and Hispanic mothers, and in mothers with fewer years of education. Workers in several occupations, including building and grounds cleaning and maintenance, personal care, and food preparation and serving, used maternity leave at rates significantly lower than the average of all workers. Adjustment for education and occupation reduced, but did not obviate, racial/ethnic differentials in usage of paid maternity leave.

Conclusions

There are substantial differentials in usage of maternity leave. Further research could examine whether these differences contribute to disparities in maternal and child health outcomes.
Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements
Authors: Shetty Manish , Wang Huamin , Chen Feng , Jaegers Nicholas , Liu Yue , Camaioni Donald M. , Gutiérrez Oliver Y. , Lercher Johannes A.
Published: October 2020

Alkanol dehydration rates catalyzed by hydronium ions are enhanced by the dimensions of steric confinements of zeolite pores as well as by intraporous intermolecular interactions with other alkanols. The higher rates with zeolite MFI having pores smaller than those of zeolite BEA for dehydration of secondary alkanols, 3‐heptanol and 2‐methyl‐3‐hexanol, is caused by the lower activation enthalpy in the tighter confinements of MFI that offsets a less positive activation entropy. The higher activity in BEA than in MFI for dehydration of a tertiary alkanol, 2‐methyl‐2‐hexanol, is primarily attributed to the reduction of the activation enthalpy by stabilizing intraporous interactions of the Cβ‐H transition state with surrounding alcohol molecules. Overall, we show that the positive impact of zeolite confinements results from the stabilization of transition state provided by the confinement and intermolecular interaction of alkanols with the transition state, which is impacted by both the size of confinements and the structure of alkanols in the E1 pathway of dehydration.
Metallo‐Helicoid with Double Rims: Polymerization Followed by Folding by Intramolecular Coordination
Authors: Yin Guang‐Qiang , Kandapal Sneha , Liu Chung‐Hao , Wang Heng , Huang Jianxiang , Jiang Shu‐Ting , Ji Tan , Yan Yu , Khalife Sandra , Zhou Ruhong , Ye Libin , Xu Bingqian , Yang Hai‐Bo , Nieh Mu‐Ping , Li Xiaopeng
Published: October 2020

In this study, we established a feasible strategy to construct a new type of metallo‐polymer with helicoidal structure through the combination of covalent polymerization and intramolecular coordination‐driven self‐assembly. In the design, a tetratopic monomer (M) was prepared with two terminal alkynes in the outer rim for polymerization, and two terpyridines (TPYs) in the inner rim for subsequent folding by selective intramolecular coordination. Then, the linear covalent polymer (P) was synthesized by polymerization of M via Glaser‐Hay homocoupling reaction. Finally, intramolecular coordination interactions between TPYs and Zn(II) folded the backbone of P into a right‐ or left‐handed metallo‐helicoid (H) with double rims. Owing to multiple positive charges on the inner rim of helicoid, double‐stranded DNA molecules (dsDNA) could interact with H through electrostatic interactions. Remarkably, dsDNA allowed exclusive formation of H with right handedness by means of chiral induction.
Breaking the Linear Scaling Relationship by Compositional and Structural Crafting of Ternary Cu–Au/Ag Nanoframes for Electrocatalytic Ethylene Production
Authors: Xiong Likun , Zhang Xiang , Yuan Hao , Wang Juan , Yuan Xuzhou , Lian Yuebin , Jin Huidong , Sun Hao , Deng Zhao , Wang Dan , Hu Jiapeng , Hu Huimin , Choi Jinho , Li Jiong , Chen Yufeng , Zhong Jun , Guo Jun , Rümmerli Mark H. , Xu Lai , Peng Yang
Published: October 2020

Electrocatalytic conversion of carbon dioxide into high‐value multicarbon (C2+) chemical feedstocks offers a promising avenue to liberate the chemical industry from fossil‐resource dependence and eventually close the anthropogenic carbon cycle but is severely impeded by the lack of high‐performance catalysts. To break the linear scaling relationship of intermediate binding and minimize the kinetic barrier of CO2 reduction reactions, ternary Cu–Au/Ag nanoframes were fabricated to decouple the functions of CO generation and C−C coupling, whereby the former is promoted by the alloyed Ag/Au substrate and the latter is facilitated by the highly strained and positively charged Cu domains. Thus, C2H4 production in an H‐cell and a flow cell occurred with high Faradic efficiencies of 69±5 and 77±2 %, respectively, as well as good electrocatalytic stability and material durability. In situ IR and DFT calculations unveiled two competing pathways for C2H4 generation, of which direct CO dimerization is energetically favored.
Fragment Binding to Kinase Hinge: If Charge Distribution and Local pKa Shifts Mislead Popular Bioisosterism Concepts
Authors: Oebbeke Matthias , Siefker Christof , Wagner Björn , Heine Andreas , Klebe Gerhard
Published: October 2020

Medicinal‐chemistry optimization follows strategies replacing functional groups and attaching larger substituents at a promising lead scaffold. Well‐established bioisosterism rules are considered, however, it is difficult to estimate whether the introduced modifications really match the required properties at a binding site. The electron density distribution and pKa values are modulated influencing protonation states and bioavailability. Considering the adjacent H‐bond donor/acceptor pattern of the hinge binding motif in a kinase, we studied by crystallography a set of fragments to map the required interaction pattern. Unexpectedly, benzoic acid and benzamidine, decorated with the correct substituents, are totally bioisosteric just as carboxamide and phenolic OH. A mono‐dentate pyridine nitrogen out‐performs bi‐dentate functionalities. The importance of correctly designing pKa values of attached functional groups by additional substituents at the parent scaffold is rendered prominent.
Synthesis, characterization, and thermal decomposition kinetics of copper hydroxide sulfate (Cu4(SO4)(OH)6) synthesized by chemical precipitation method
Authors: Güner Eda Keleş , Kancan Duygu , Naktiyok Jale , Özer Abdulkadir
Published: October 2020

In this study, copper hydroxide sulfate (Cu4(OH)6SO4) was synthesized by chemical precipitation using CuSO4 as the precursor material and the first time borax as basic precipitating agent. The synthesized samples were characterized using XRD, FTIR, and SEM. The decomposition kinetics of Cu4(OH)6SO4 were examined by the thermoanalytical procedures. It was obtained from TG‐DTG data that Cu4(OH)6SO4 has two‐region decomposition at elevated temperatures. Kinetic parameters of these regions were calculated by using both the model‐fitting and model‐free methods. In the decomposition of copper hydroxy sulfate, the mean activation energy for first region was calculated as 90.88 kJ mol−1 from KAS method and 91.47 kJ mol−1 from FWO method. The mean activation energy for the second region was 207.20 kJ mol−1 from KAS and 213.34 kJ mol−1 from FWO. The activation energies for first and second regions were obtained from Ortega method as 56.3 and 198.3 kJ mol−1, respectively.
Sequence‐Based Screening of Patients With Idiopathic Polyarteritis Nodosa, Granulomatosis With Polyangiitis, and Microscopic Polyangiitis for Deleterious Genetic Variants in ADA2
Authors: Schnappauf Oskar , Sampaio Moura Natalia , Aksentijevich Ivona , Stoffels Monique , Ombrello Amanda K. , Hoffmann Patrycja , Barron Karyl , Remmers Elaine F. , Hershfield Michael , Kelly Susan J. ,   NISC Comparative Sequencing Program, Cuthbertson David , Carette Simon , Chung Sharon A. , Forbess Lindsy , Khalidi Nader A. , Koening Curry L. , Langford Carol A. , McAlear Carol A. , Monach Paul A. , Moreland Larry , Pagnoux Christian , Seo Philip , Springer Jason M. , Sreih Antoine G. , Warrington Kenneth J. , Ytterberg Steven R. , Kastner Daniel L. , Grayson Peter C. , Merkel Peter A. ,   for the Vasculitis Clinical Research Consortium
Published: October 2020

Objective

Deficiency of adenosine deaminase 2 (DADA2) is a monogenic form of vasculitis that can resemble polyarteritis nodosa (PAN). This study was undertaken to identify potential disease‐causing sequence variants in ADA2 in patients with idiopathic PAN, granulomatosis with polyangiitis (GPA), or microscopic polyangiitis (MPA).

Methods

Patients with idiopathic PAN (n = 118) and patients with GPA or MPA (n = 1,107) were screened for rare nonsynonymous variants in ADA2 using DNA sequencing methods. ADA‐2 enzyme activity was assessed in selected serum samples.

Results

Nine of 118 patients with PAN (7.6%) were identified as having rare nonsynonymous variants in ADA2. Four patients (3.4%) were biallelic for pathogenic or likely pathogenic variants, and 5 patients (4.2%) were monoallelic carriers for 3 variants of uncertain significance and 2 likely pathogenic variants. Serum samples from 2 patients with PAN with biallelic variants were available and showed markedly reduced ADA‐2 enzyme activity. ADA‐2 enzyme testing of 86 additional patients revealed 1 individual with strongly reduced ADA‐2 activity without detectable pathogenic variants. Patients with PAN and biallelic variants in ADA2 were younger at diagnosis than patients with 1 or no variant in ADA2, with no other clinical differences noted. None of the patients with GPA or MPA carried biallelic variants in ADA2.

Conclusion

A subset of patients with idiopathic PAN meet genetic criteria for DADA2. Given that tumor necrosis factor inhibition is efficacious in DADA2 but is not conventional therapy for PAN, these findings suggest that ADA‐2 testing should strongly be considered in patients with hepatitis B virus–negative idiopathic PAN.
The effects of environmental, social and governance disclosure on the cost of capital in small and medium enterprises: The role of family business status
Authors: Gjergji Rafaela , Vena Luigi , Sciascia Salvatore , Cortesi Alessandro
Published: October 2020

Environmental, social, and governance (ESG) disclosure has become a critical component of corporate reporting. However, the effectiveness of this type of disclosure remains poorly explored among small and medium enterprises (SMEs), despite the fact that these businesses represent the majority of firms around the world. By leveraging on a dataset of Italian listed SMEs, we fill this gap to shed new light on the effects of nonfinancial disclosure on the cost of capital. The study reveals that, in stark contrast with the evidence on large companies, environmental disclosure for SMEs is bound to provoke an increase in the cost of capital. Yet this pattern is capsized when the company is a family SME, as it benefits from environmental disclosure, as large companies do.
Regulation of the Peroxidase‐Like Activity of nGO, MoS2 and WS2 Nanozymes by Using Metal Cations
Authors: Nandu Nidhi , Smith Christopher W. , Kachwala Mahera J. , Yigit Mehmet V.
Published: October 2020

Two dimensional nanoparticles (2D‐NPs) along with other nanoscale materials have been deemed to be the next generation of artificial enzymes (nanozymes). The low‐cost bulk‐scale production, ease of storage and modification of such nanomaterials have given nanozymes an advantage over traditional enzymes. Many studies have been aimed at developing methods to increase the performance of these nanozymes, and also identify interfering agents. To investigate the interference of a number of metal cations, we studied the effect of Ti2+, Fe2+, Ag+, Hg2+, Co2+, Cu2+, Ni2+, Pb2+, Ca2+, Zn2+ and Mn2+ in a nanozyme assays of 2D‐NPs using ABTS radical formation. Ti2+, Co2+, Cu2+, Ni2+, Ca2+, Zn2+ and Mn2+ ions did not display any notable effect on the peroxidase‐like activity of nGO, MoS2 and WS2 2D‐NPs. However, Fe2+, Ag+, Hg2+ and Pb2+ ions’ effects on the overall ABTS reaction were significant enough to be visualised by partial least square discriminant analysis (PLSDA). We report that, similar to that of many natural enzymes, the nanozyme activity of 2D‐NPs is regulated by a number of metal cations allowing their identification and discrimination by using a statistical analysis tool.
Percutaneous transcatheter occlusion of left atrioventricular valve in a patient with single ventricle and severe atrioventricular valve regurgitation
Authors: al Nasef Mohamed , Oslizlok Paul , Walsh Kevin P.
Published: October 2020

Many patients with single ventricle physiology suffer from atrioventricular valve (AVV) regurgitation which may worsen their cardiac function and cause symptoms. It has been postulated that elimination of the nondominant hypoplastic AVV regurgitation, might improve the clinical status in patients post‐Fontan surgery. We describe a case of hypoplastic left heart variant, post Fontan surgery who had severe left AVV regurgitation and underwent percutaneous transcatheter occlusion of the hypoplastic left AVV, using a VSD occluder device. At 3 months post procedure, the patient is improved. Transcatheter closure of a regurgitant hypoplastic AVV in a patient with single ventricle helps to improve the patient's cardiac function and clinical status.
Bimetal‐organic Framework Encapsulated in Graphene Aerogel‐grafted Ni Foam: An Efficient Electrocatalyst for the Oxygen Evolution Reaction
Authors: Chen Chen , Wang Jianzhi , Li Pan , Tian Qifeng , Xiao Zhuangwei , Li Shuaijie , Cai Ning , Xue Yanan , Chen Weimin , Yu Faquan
Published: October 2020

Metal‐organic frameworks (MOFs) have been considered as promising platforms for preparing the efficient oxygen evolution reaction (OER) catalysts, but few of them are directly employed as active components due to their poor electrical conductivity. Herein, a lamellar bimetallic MFN (MIL‐53(FeNi)) encapsulated in graphene aerogel‐grafted Ni foam has been developed (denoted as MFN@GA/NF). The graphene aerogel (GA) provides abundant space for the in‐situ growth of MFN and functions as a “bridge” to connect nickel foam (NF) with MFN by virtue of good conductivity. Benefitting from its structural integrity, the obtained hierarchical MFN@GA/NF exhibited excellent OER performances in alkaline media with an overpotential of 250 mV (20 mA cm−2) and 326 mV (200 mA cm−2), as well as remarkable stability in continuous electrolysis for over 100 h. This work provides a new channel for engineering MOF‐based functional materials with featured architectures.
Bulky N‐Heterocyclic‐Carbene‐Coordinated Palladium Catalysts for 1,2‐Addition of Arylboron Compounds to Carbonyl Compounds
Authors: Okuda Yuta , Nagaoka Masahiro , Yamamoto Tetsuya
Published: October 2020

The synthesis of primary, secondary, and tertiary alcohols by the 1,2‐addition of arylboronic acids or boronates to carbonyl compounds, including unactivated ketones, using novel bulky yet flexible N‐heterocyclic carbene (NHC)‐coordinated 2,6‐di(pentan‐3‐yl)aniline (IPent)‐based cyclometallated palladium complexes (CYPs) as catalysts is reported. The PhS‐IPent‐CYP‐catalyzed reactions are efficient at low catalyst loadings (0.02–0.3 mol% Pd), and the exceptional catalytic activity for 1,2‐addition is attributed to the steric bulk of the NHC ligand. These reactions can yield a wide range of functionalized benzylic alcohols that are difficult to synthesize by classical protocols using highly active organomagnesium or lithium reagents.
One‐pot Fixation of CO2 into Glycerol Carbonate using Ion‐Exchanged Amberlite Resin Beads as Efficient Metal‐free Heterogeneous Catalysts
Authors: Alassmy Yasser A. , Paalman Patrick J. , Pescarmona Paolo P.
Published: October 2020

The one‐pot synthesis of glycerol carbonate from carbon dioxide and glycerol was achieved using ion‐exchanged Amberlite resin beads as metal‐free heterogeneous catalysts. Two commercially available Amberlite resin beads consisting of polystyrene cross‐linked with divinylbenzene and functionalized with either trimethyl ammonium chloride (IRA‐900) or dimethyl ethanol ammonium chloride (IRA‐910) groups were used as starting materials to prepare the catalysts. These polymeric beads were transformed into their iodide (Amb‐900‐I, Amb‐OH‐910‐I) or hydroxide (Amb‐900‐OH and Amb‐OH‐910‐OH) counterparts through straightforward ion‐exchange reactions. First, the two resin bead catalysts in hydroxide form were tested in the base‐catalyzed transcarbonation reaction of glycerol with propylene carbonate. Both resin bead catalysts were more active compared to benchmark basic catalysts as hydrotalcites and attained 80 % yield of glycerol carbonate over Amb‐OH‐910‐OH after 2 h at 115 °C, employing a 4 : 1 ratio between propylene carbonate and glycerol. Then, the one‐pot reaction of CO2, glycerol and propylene oxide to produce propylene carbonate, glycerol carbonate and propylene glycol was investigated as the main target of this study. The reaction involves two steps: the reaction of propylene oxide with CO2 yielding propylene carbonate, and the transcarbonation of the formed cyclic carbonate with glycerol. Amb‐900‐I, Amb‐OH‐910‐I, Amb‐OH‐910‐OH and combinations of the latter two were employed as catalysts. Although Amb‐OH‐910‐I alone is poorly active in the transcarbonation reaction, it showed the highest catalytic activity in the one‐pot cascade reaction, surprisingly surpassing the performance of the Amb‐OH‐910‐I/Amb‐OH‐910‐OH mixtures and reaching high yields of glycerol carbonate (81 %, 115 °C, 4 h). These findings led to proposing a mechanism for the one‐pot reaction using the Amb‐OH‐910‐I catalyst. The bead format led to easy recovery of the catalyst, which displayed good reusability in consecutive runs.
Synthesis of Unprecedented 4d/4f‐Polypnictogens
Authors: Reinfandt Niklas , Schoo Christoph , Dütsch Luis , Köppe Ralf , Konchenko Sergey N. , Scheer Manfred , Roesky Peter W.
Published: October 2020

A series of 4d/4f‐polyarsenides, ‐polyarsines and ‐polystibines was obtained by reduction of the Mo‐pnictide precursor complexes [{CptMo(CO)2}2(μ,η2:2‐E2)] (E=As, Sb; Cpt=tBu substituted cyclopentadienyl) with two different divalent samarocenes [Cp*2Sm] and [(CpMe4nPr)2Sm]. For the reductive conversion of the Mo‐stibide only one product was isolated, featuring a planar tetrastibacyclobutadiene moiety as an unprecedented ligand for organometallic compounds. For the corresponding Mo‐arsenide a tetraarsacyclobutadiene and a second species with a side‐on coordinated As22− anion was isolated. The latter can be considered as reaction intermediate for the formation of the tetraarsacyclobutadiene.
Untersuchungen zur Bildung von Benzol aus Benzaldehyd
Authors: Frank Stephanie , Schieberle Peter
Published: October 2020

Die menschliche Aufnahme von Benzol soll aufgrund dessen gesundheitsgefährdenden Potentials minimiert werden. Benzol gelangt hauptsächlich über die Atemluft in den menschlichen Körper; hingegen ist die Aufnahme über die Nahrung eher gering. In Getränken mit Kirschgeschmack wurde jedoch Benzol gefunden, und es wurde vermutet, dass der Geruchsstoff Benzaldehyd die Ursache für die beobachteten Benzolverunreinigungen war. Benzaldehyd wird beispielsweise zur Aromatisierung von Getränken mit Kirschgeschmack eingesetzt. Es zeigte sich, dass nur Licht die Bildung von Benzol aus Benzaldehyd förderte. Es wurde vermutet, dass die Benzolgehalte in kommerziellen Kirschsaft‐Erfrischungsgetränken auf das zugesetzte, bereits mit Benzol verunreinigte Aroma zurückzuführen sind. Daher scheint es nötig, die Benzolbildung in benzaldehydhaltigen Aromen zu unterbinden, indem man diese Produkte vor Licht schützt, beispielsweise durch den Gebrauch von getönten Glasgefäßen bei Produktion, Lagerung und Verkauf.
A comparison of cell density and serotonergic innervation of the amygdala among four macaque species
Authors: Jones Danielle N. , Erwin Joseph M. , Sherwood Chet C. , Hof Patrick R. , Raghanti Mary Ann
Published: October 2020

The genus Macaca is an ideal model for investigating the biological basis of primate social behavior from an evolutionary perspective. A significant amount of behavioral diversity has been reported among the macaque species, but little is known about the neural substrates that support this variation. The present study compared neural cell density and serotonergic innervation of the amygdala among four macaque species using histological and immunohistochemical methods. The species examined included rhesus (Macaca mulatta), Japanese (M. fuscata), pigtailed (M. nemestrina), and moor macaques (M. maura). We anticipated that the more aggressive rhesus and Japanese macaques would have lower serotonergic innervation within the amygdala compared to the more affiliative pigtailed and moor macaques. In contrast to our prediction, pigtailed macaques had higher serotonergic innervation than Japanese and moor macaques in the basal and central amygdala nuclei when controlling for neuron density. Our analysis of neural cell populations revealed that Japanese macaques possess significantly higher neuron and glia densities relative to the other three species, however we observed no glia‐to‐neuron ratio differences among species. The results of this study revealed serotonergic innervation and cell density differences among closely related macaque species, which may play a role in modulating subtle differences in emotional processing and species‐typical social styles.
Uniqueness and Nonuniqueness of Steady States of Aggregation‐Diffusion Equations
Authors: Delgadino Matias G. , Yan Xukai , Yao Yao
Published: October 2020

We consider a nonlocal aggregation equation with degenerate diffusion, which describes the mean‐field limit of interacting particles driven by nonlocal interactions and localized repulsion. When the interaction potential is attractive, it is previously known that all steady states must be radially decreasing up to a translation, but uniqueness (for a given mass) within the radial class was open, except for some special interaction potentials. For general attractive potentials, we show that the uniqueness/nonuniqueness criteria are determined by the power of the degenerate diffusion, with the critical power being m = 2. In the case m ≥ 2, we show that for any attractive potential the steady state is unique for a fixed mass. In the case 1 < m < 2, we construct examples of smooth attractive potentials such that there are infinitely many radially decreasing steady states of the same mass. For the uniqueness proof, we develop a novel interpolation curve between two radially decreasing densities, and the key step is to show that the interaction energy is convex along this curve for any attractive interaction potential, which is of independent interest. © 2020 Wiley Periodicals LLC.
Targeting the Rich Conformational Landscape of N‐Allylmethylamine Using Rotational Spectroscopy and Quantum Mechanical Calculations
Authors: Silva Weslley G. D. P. , Poonia Tamanna , van Wijngaarden Jennifer
Published: October 2020

The highly variable conformational landscape of N‐allylmethylamine (AMA) was investigated using Fourier transform microwave spectroscopy aided by high‐level theoretical calculations to understand the energy relationship governing the interconversion between nine stable conformers. Spectroscopically, transitions belonging to four low energy conformers were identified and their hyperfine patterns owing to the 14N quadrupolar nucleus were unambiguously resolved. The rotational spectrum of the global minimum geometry, conformer I, shows an additional splitting associated with a tunneling motion through an energy barrier interconnecting its enantiomeric forms. A two‐step tunneling trajectory is proposed by finding transition state structures corresponding to the allyl torsion and NH inversion. Natural bond orbital and non‐covalent interaction analyses reveal that an interplay between steric and hyperconjugative effects rules the conformational preferences of AMA.