bluuebunny/crossref_metadata_2025 huggingface dataset:
Uncovering the Potential of Boronic Acid and Derivatives as Radical Source in Photo(electro)chemical Reactions
Authors: Pillitteri Serena , Ranjan Prabhat , Van der Eycken Erik V. , Sharma Upendra K.
Published: April 2022

The chemistry of boron compounds has been profoundly investigated in the last decades, leading to ubiquity in many synthetic applications as well as biologically active molecules. Since the advent of photoredox catalysis, an upsurge in the discovery of suitable radical precursors has been witnessed, and boron is becoming a protagonist in this field. Despite many studies focused on trifluoroborates, the use of boronic acids and esters have received much less attention in this regard. Because of their high oxidation potential, the development of methods to enable their involvement in photocatalyzed reactions is only recent. Nonetheless, this review summarizes novel strategies developed to unlock their role as radical precursors in photochemical reactions and discloses the potential that boronic acids and esters own, when their intrinsic chemical properties are exploited.

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Nanoscale Double‐Heterojunctional Electrocatalyst for Hydrogen Evolution
Authors: Feng Yangyang , Guan Yongxin , Zhou Enbo , Zhang Xiang , Wang Yaobing
Published: April 2022

The active sites and charge/mass transfer properties in electrocatalysts play vital roles in kinetics and thermodynamics of electrocatalysis, and impose direct impacts on electrocatalytic performance, which cannot be achieved by a simplex structure. As a prototype, the authors propose a double‐heterojunctional nanostructure of NiS2/Ni3C@C containing NiS2/Ni3C and Ni3C/C heterojunctions as a general model to optimize the above issues and boost electrocatalytic performance. During the thermal reorganization, the in situ reaction between NiS2 nanoparticles and carbon induces the formation of Ni3C between them and constructs tightly contacted two kinds of interfaces among the three components. The TEM and XPS reveal the intimately contacted three components and the as‐constructed interacted dual interfaces, further confirming the formation of a porous double‐heterojunctional nanostructure. Theoretical calculations uncover that the electron density redistribution occurs at Ni3C/C interface by spontaneous electron transfer from defected carbon to Ni3C and lower ΔGH* achieves at NiS2/Ni3C interface by the concentrated interfacial charge density, which favors the simultaneous realization of high catalytic activity and rapid charge/mass transfer. When applied for hydrogen evolution reaction (HER), the porous double‐heterojunctional NiS2/Ni3C@C exhibits excellent HER activity and durability among all pH values. Profoundly, this special double‐heterojunctional structure can provide a new model for high‐performance electrocatalysts and beyond.
Synthesis, spectroscopic, in vitro, in silico, and in vivo studies of binuclear Cu (II), Ni (II), Ru (II), and Zn (II) complexes with tetradentate Schiff base ligand
Authors: Marimuthu Bhuvaneswari , Michael Samuel , Jeyaraman Porkodi , Arulanandam Xavier
Published: April 2022

A novel Schiff base macrocyclic ligand was synthesized by the condensation of 4‐(3,4‐diaminophenyl)benzene‐1,2‐diamine with β‐naphthol‐1‐aldehyde. Binuclear complexes were synthesized from this Schiff base by reaction with Cu (II), Ni (II), Ru (II), and Zn (II) metal salts. Square planar geometrical structures of Cu (II), Ni (II), and Ru (II) complexes were achieved by several physicochemical methods, namely UV–Vis, FT‐IR, NMR, ESI‐Mass, and thermogravimetric analysis, respectively. Density functional theory (DFT) calculations at the B3LYP/6‐31G(d) level were carried out to gain an insight into the thermodynamic stability and biological accessibility of the complexes. Moreover, molecular docking analysis was done against a novel target protein PDB: 6M71 (SARS‐CoV‐2). Both the Schiff base ligand and metal complexes showed excellent interaction with protein receptor. All the metal complexes have the strong tendency to undergo intercalation mode of binding with CT DNA. All the in vivo and in vitro screening studies showed that the complexes exhibit higher activities than the free Schiff base.
Performance of the 2017 European Alliance of Associations for Rheumatology/American College of Rheumatology Classification Criteria in Patients With Idiopathic Inflammatory Myopathy and Anti–Melanoma Differentiation–Associated Protein 5 Positivity
Authors: So Ho , So Jacqueline , Lam Tommy Tsz‐On , Wong Victor Tak‐Lung , Ho Roy , Li Wai Ling , Mok Chi Chiu , Lau Chak Sing , Tam Lai‐Shan
Published: April 2022

Objective

This study aimed to evaluate whether the 2017 European Alliance of Associations for Rheumatology (EULAR)/American College of Rheumatology (ACR) classification criteria for adult and juvenile idiopathic inflammatory myopathies (IIMs) could appropriately classify the diagnosis in adult patients with anti–melanoma differentiation–associated protein 5 (anti–MDA‐5)–positive IIM. In addition, this study sought to determine whether a status of anti–MDA‐5 positivity could be incorporated into the EULAR/ACR IIM classification criteria set and whether the recently modified criteria based on the presence of myositis‐specific autoantibodies (MSAs) could be used to appropriately classify the diagnosis in patients with anti–MDA‐5–positive IIM.

Methods

Consecutive adult patients clinically diagnosed as having anti–MDA‐5–positive IIM from 10 hospitals in Hong Kong were retrospectively recruited; patient characteristics were obtained from electronic medical records. We used a commercial line blot immunoassay to detect MSAs. We also determined a proposed set of phenotypic‐serologic classification criteria specific for anti–MDA‐5.

Results

In the patient cohort (n = 120; 31.7% with dermatomyositis, 68.3% with clinically amyopathic dermatomyositis [CADM]), the diagnosis could be classified with the EULAR/ACR criteria in 86 patients (71.7%) and with the Bohan and Peter criteria in 49 patients (40.8%). However, when combined with criteria specifically modified for CADM, the diagnosis could be classified by the Bohan and Peter criteria in 76.7% of patients. We observed that the sensitivity of the EULAR/ACR criteria could be improved to 98.3% if anti–MDA‐5 antibody–positive status was considered as one of the criteria. The MSA‐based criteria had 100% sensitivity. When we applied our proposed specific phenotypic‐serologic criteria for the classification of patients with anti–MDA‐5 antibodies, 97.5% of patients were able to be classified as having IIM.

Conclusion

In this cohort of patients with anti–MDA‐5–positive IIM, the diagnosis could not be classified by the EULAR/ACR criteria in almost 30% of patients. We suggest incorporating anti–MDA‐5 antibody positivity as a criterion into existing criteria sets or developing specific criteria for patients with anti–MDA‐5–positive IIM.
Hg(II)‐Mediated Intramolecular Cyclization of Alkynyl Hydrazones: Towards a New Reaction‐Based Sensing Approach for Hg(II) Ions
Authors: Buse Tütüncü Büşra , Cebeci Miray , Emrullahoğlu Mustafa
Published: April 2022

Drawing upon an intramolecular cyclization/annulation reaction sequence mediated by Hg2+ ions, a BODIPY‐based fluorescent probe decorated with an alkynyl hydrazone motif responds rapidly and selectively to Hg2+ ions, with a detection limit of 29 nM and a fluorescence turn‐on ratio of 15‐fold. With the addition of Hg2+ ions, the BODIPY‐based alkynyl hydrazone transforms into a pyrazole ring to mediate a turn‐on emission response clearly observable to the naked eye under visible light excitation.
“It Felt More like a Revolution.” How Behavioral Ecology Succeeded Ethology, 1970–1990
Authors: Stuhrmann Cora
Published: April 2022

As soon as ethology's status diminished in the early 1970s, it was confronted with two successor disciplines, sociobiology and behavioral ecology. They were able to challenge ethology because it no longer provided markers of strong disciplinarity such as theoretical coherence, leading figures and a clear identity. While behavioral ecology developed organically out of the UK ethological research community into its own disciplinary standing, sociobiology presented itself as a US competitor to the ethological tradition. I will show how behavioral ecology took the role of legitimate heir to ethology by rebuilding a theoretical core and an intellectual sense of community, while sociobiology failed to use its public appeal to reach disciplinary status. Meanwhile, ethology changed its disciplinary identity to encompass all biological studies of animal behavior.
Typologies of Canadian young adults who drive after cannabis use: A two‐step cluster analysis
Authors: Huỳnh Christophe , Beaulieu‐Thibodeau Alexis , Fallu Jean‐Sébastien , Bergeron Jacques , Jacques Alain , Brochu Serge
Published: April 2022

Young adults that drive after cannabis use (DACU) may not share all the same characteristics. This study aimed to identify typologies of Canadians who engage in DACU. About 910 cannabis users with a driver's license (17–35 years old) who have engaged in DACU completed an online questionnaire. Two‐step cluster analysis identified four subgroups, based on driving‐related behaviors, cannabis use and related problems, and psychological distress. Complementary comparative analysis among the identified subgroups was performed as external validation. The identified subgroups were: (1) frequent cannabis users who regularly DACU; (2) individuals with generalized deviance with diverse risky road behaviors and high levels of psychological distress; (3) alcohol and drug‐impaired drivers who were also heavy frequent drinkers; and (4) well‐adjusted youths with mild depressive‐anxious symptoms. Individuals who engaged in DACU were not a homogenous group. When required, prevention and treatment need to be tailored according to the different profiles.
The Structure‐Function Relationship of Human Bleomycin Hydrolase: Mutation of a Cysteine Protease into a Serine Protease
Authors: Zheng Yi‐Zhen , Cui Jingxuan , Wang Yung‐Lin , Huang Szu‐Jo , Lin En‐Chi , Huang Sheng‐Cih , Rudolf Jeffrey D. , Yan Xiaohui , Chang Chin‐Yuan
Published: April 2022

Human bleomycin hydrolase (hBH) catalyzes deamidation of the anticancer drug bleomycins (BLM). This enzyme is involved in BLM detoxification and drug resistance. Herein, we report the putative BLM‐binding site and catalytic mechanism of hBH. The crystal structures and biochemical studies suggest that hBH cleaves its C‐terminal residue without significant preference for the type of amino acid, and therefore can accordingly accommodate the β‐aminoalanine amide moiety of BLM for deamidation. Interestingly, hBH is capable of switching from a cysteine protease to a serine protease that is unable to cleave the secondary amide of hBH C‐terminus but reacts with the primary amide of BLMs.
Catalytic Radical Reactions of Unsaturated Sugars
Authors: Goti Giulio
Published: April 2022

The functionalization of unsaturated carbohydrates is a powerful approach for the synthesis of a variety of glycoside derivatives, sugar mimics, and enantiomerically pure molecules. This Review will discuss recently developed catalytic radical methods for the functionalization of glycals, exo‐glycals, and exo‐enes, highlighting the opportunities they offer for new reaction design. While providing new routes for the synthesis of complex carbohydrates, catalytic radical transformations of unsaturated sugars overcome the limitations that typically affect classical protocols, such as the use of stoichiometric oxidants/reductants and hazardous and toxic reagents. Currently unaddressed challenges will also be discussed, suggesting new directions for future work and fostering new methodological developments and applications in the field.
CeO2 Supported Gold Nanocluster Catalysts for CO Oxidation: Surface Evolution Influenced by the Ligand Shell
Authors: Truttmann Vera , Drexler Hedda , Stöger‐Pollach Michael , Kawawaki Tokuhisa , Negishi Yuichi , Barrabés Noelia , Rupprechter Günther
Published: April 2022

Monolayer protected Au nanocluster catalysts are known to undergo structural changes during catalytic reactions, including dissociation and migration of ligands onto the support, which strongly affects their activity and stability. To better understand how the nature of ligands influences the catalytic activity of such catalysts, three types of ceria supported Au nanoclusters with different kinds of ligands (thiolates, phosphines and a mixture thereof) have been studied, employing CO oxidation as model reaction. The thiolate‐protected Au25/CeO2 showed significantly higher CO conversion after activation at 250 °C than the cluster catalysts possessing phosphine ligands. Temperature programmed oxidation and in situ infrared spectroscopy revealed that while the phosphine ligands seemed to decompose and free Au surface was exposed, temperatures higher than 250 °C are required to efficiently remove them from the whole catalyst system. Moreover, the presence of residues on the support seemed to have much greater influence on the reactivity than the gold particle size.
Nanometric‐Thick Metal‐Free h‐Boron Nitride/Graphene Films as Base Catalyst for the Synthesis of Benzoxazoles
Authors: Rendón‐Patiño Alejandra , Primo Ana , Cojocaru Bogdan , Gabriela Ion Sabina , Popescu Dana G. , Parvulescu Vasile , García Hermenegildo
Published: April 2022

Catalysts are frequently used as pelletized powdered materials, but rarely as thin films. The present work reports the use of 2D h‐boron nitride on few layers defective graphene (h‐BN/fl‐G) films of about 10 nm thickness as base catalyst for the synthesis of benzoxazoles by coupling a 2‐amino‐phenol with p‐substituted benzaldehydes. The synthesis of benzoxazole derivatives has aroused much interest in the last decades due to their application as potent anticancer agents against MCF‐7 and MDA‐MB‐231 breast cancer cells. The results demonstrate that these nanometer‐thick films exhibit three orders of magnitude higher activity than K2CO3 taken as benchmark base catalyst. The activity and selectivity of h‐BN/fl‐G films depend on the nature of substituents on benzaldehyde, the solvent and reaction temperature.
Resources to respond: A career construction theory perspective on demands, adaptability, and career crafting
Authors: Nalis Irina , Kubicek Bettina , Korunka Christian
Published: April 2022

This study tests and extends the career construction theory's model of adaptation and provides valuable insights into the interplay of agency and structure in career self‐management. It studies the interactive effect of career adaptability resources with intensified career demands on career crafting by examination of structural predictors for adapting responses, and the role of career adaptability as a moderator between intensified demands and career crafting responses. Using a representative sample of the German working population (N = 2000), the authors test the model with structural equation modeling. Latent structure analysis showed that each of the four career adaptabilities strengthens the relationship between intensified career demands and the career crafting responses of goal setting/networking and reflection. It suggests to focus strongly on the development of career resources in order to enable career crafting.
Chloride Anion Adsorption from Wastewater Using a Chitosan/β‐Cyclodextrin‐Based Composite
Authors: Zhao Jun , Tang Qilong , Liu Jiaxin , Liu Tong , Liu Duo
Published: April 2022

In order to remove Cl− ions from wastewater, an adsorbent composite with high efficiency for Cl− adsorption was prepared by the crosslinking method, where chitosan (CTS) was used as the matrix to crosslink the β‐cyclodextrin polymer (β‐CDP). The preparation conditions of the composite membrane were optimized based on the chloride adsorption effect. The chloride adsorption performances of the CTS/β‐CDP complex and the CTS/β‐CDP composite membrane were significantly higher than that of the CTS‐only membrane, and the composite membrane showed slightly better performance than the complex. The structure and properties of the chitosan/β‐cyclodextrin‐based composite membrane were characterized by scanning electron microscopy, X‐ray diffraction, and Fourier transform infrared spectroscopy. The prepared composite material can be used for the adsorptive removal of Cl− in water, with further research and development prospects.
Preparation of Porous Carbon from Dichloromethane and p‐Phenylenediamine with Short KOH Activation Depth
Authors: Li Anchang , Wang Jingxian , Zhang Kai , Fu Wenwu , Cheng Lin , Zhang Ming , Shen Zhongrong
Published: April 2022

KOH chemical activation of pores is a very effective method to prepare carbon materials for supercapacitors. In this work, we have explored a facile route to the preparation of porous precursor materials through a solvothermal reaction between p‐phenylenediamine (PDA) and dichloromethane. Their pores provide diffusion paths and spaces for KOH to penetrate into the precursor, resulting in the direct formation of porous carbon materials during the carbonization and activation. This method can effectively avoid the industrial problems such as the large carbon consumption and the low yield in the process of conventional bulk carbon materials by KOH activation from the outside to inside. The resulted porous carbon material achieves a high yield up to 13.0 % with a specific surface area of 3033.5 m2 g−1. A high specific capacitance of 331.5 F g−1 in 1 M H2SO4, 392.3 F g−1 in 6 M KOH and 246.1 F g−1 in 1 M Li2SO4 can be achieved at a scan rate of 2 mV s−1 for the porous carbon. Meanwhile, symmetric capacitors fabricated using this porous carbon can also provide high specific energy density and excellent cycling stability.
Scalable Composites Benefiting from Transition‐Metal Oxides as Cathode Materials for Efficient Lithium‐Sulfur Batteries
Authors: Marangon Vittorio , Scaduti Eugenio , Vinci Viviana Fatima , Hassoun Jusef
Published: April 2022

Composite materials achieved by including transition‐metal oxides with different structures and morphologies in sulfur are suggested as scalable cathodes for high‐energy lithium‐sulfur (Li−S) batteries. The composites contain 80 wt.% sulfur and 20 wt.% of either MnO2 or TiO2, leading to a sulfur content in the electrode of 64 wt.% and revealing a reversible, fast, and lowly polarized conversion process in the cell with limited interphase resistance. The S−TiO2 composite exhibits an excellent rate capability between C/10 and 2C, and a cycle life extended over 400 cycles at 2C, owing to the effects of the nanometric TiO2 additive in boosting the reaction kinetics. Instead, the micrometric sized particles of MnO2 partially limit the electrochemical activity of S−MnO2 to the current rate of 1C. Nevertheless, both S−MnO2 and S−TiO2 withstand a sulfur loading up to values approaching 6 mg cm−2, and deliver an areal capacity ranging from about 4.5 to 5.5 mAh cm−2 at C/5. The excellent performances of the metal oxide‐sulfur electrodes, even at high active material loading, and the possible scalability of the synthetic pathway adopted in the work suggest that the composites are viable cathodes for next‐generation Li−S batteries with high energy density and efficient electrochemical process.
Discovery and Optimization of Piperazine Urea Derivatives as Soluble Epoxide Hydrolase (sEH) Inhibitors
Authors: Çapan İrfan , Jordan Paul M. , Olğaç Abdurrahman , Çalışkan Burcu , Kretzer Christian , Werz Oliver , Banoglu Erden
Published: April 2022

Soluble epoxide hydrolase (sEH) is implicated as a potential therapeutic target for inflammation‐related pathologies in the context of cardiovascular, central nervous system and metabolic diseases. In our search for novel sEH inhibitors, we designed and synthesized novel analogs of the piperazine urea derivative4, a previously discovered dual microsomal prostaglandin E2synthase‐1 (mPGES‐1)/soluble epoxide hydrolase (sEH) inhibitor, to evaluate their potential as sEH inhibitors. We identified two 1,3,4‐oxadiazol‐5‐one and ‐thione congeners (compounds19and20), which demonstrated selective sEH inhibition with IC50values in the two‐digit nanomolar range (42 and 56 nM, respectively). These results suggest that the installation of terminal 1,3,4‐oxadiazol‐5‐one/thione functions to the benzyl end can be regarded as a promising secondary pharmacophore in addition to the urea group for sEH inhibition, and compound19can be regarded as novel lead structure for further optimization of improved sEH inhibitors.
VLCC‐Q: Very low computational complexity optical interconnect architecture with queueing for reducing delay and back pressure probability in data center networks
Authors: Fayyaz Mohsin , Shah Yasir Ali , Fayyaz Ahmed , Mujtaba Ghulam
Published: April 2022

An architecture which promised very low computational complexity for optical interconnects in DCN was previously proposed, the very low computational complexity (VLCC) architecture. In this article, we present enhancement over VLCC architecture called very low computational complexity optical interconnect architecture with queueing (VLCC‐Q) architecture which represents M/D/64 output queue. Contention occurs at the destination if the source nodes which access the same destination node exceeds 64. The performance analysis is carried out through mathematical analysis, TCP simulation in NS2 and eye diagram of optical signal. The mathematical analysis gives theoretical bounds of optical switch, whereas TCP analysis gives practical situation results and eye diagram shows that optical signal is practically recoverable after the optical signal passes through various optical components of the optical interconnect. Results clearly show that VLCC‐Q outperforms VLCC architecture in terms of throughput increase, delay reduction and back pressure probability reduction.
Analysis of illicit drugs in purchased and seized electronic cigarette liquids from the United Kingdom 2014–2021
Authors: Frinculescu Anca , Coombes Gemma , Shine Trevor , Ramsey John , Johnston Atholl , Couchman Lewis
Published: April 2022

Increasing popularity and known shortfalls in the regulation of electronic cigarettes (ECs) emphasises the urgent need for closer content monitoring and for comprehensible information on their possible health effects. This study investigated components of EC liquids in samples submitted from 2014 to 2021 and discussed the trends driven by legislation changes. Samples originating from prisoners, teenagers and ‘test purchases’ of commercially available ECs were analysed by gas chromatography‐mass spectrometry (GC‐MS). For those containing delta‐9‐tetrahydrocannabinol (THC) and/or cannabidiol (CBD), the content of these components was quantified by liquid chromatography with quadrupole time‐of‐flight mass spectrometry (LC‐QTOF‐MS) to show variation of these compounds in EC liquids; 112 EC liquids were included in this study. Nicotine was detected in 87 (78%) of the EC liquids analysed. Twenty‐two, including samples from before and after introduction of the UK Psychoactive Substances Act (2016), contained one or more synthetic cannabinoid receptor agonist (SCRA). THC was detected in only 11 samples, whereas a single sample was found to contain CBD only. Six samples contained a mixture of THC and CBD. In all cases where information was available, the THC/CBD content was less than that stated on the product label. The data collected showed great variation in EC liquid content. Therefore, it is important that users are educated regarding risks associated with EC use. Additionally, substances now controlled under both the UK Misuse of Drugs Act and Psychoactive Substances Act were present. These substances each carry a potential risk to health, which is possibly exacerbated if multiple compounds are inhaled concomitantly.
A mechanistic model of functional response provides new insights into indirect interactions among arctic tundra prey
Authors: Beardsell Andréanne , Gravel Dominique , Clermont Jeanne , Berteaux Dominique , Gauthier Gilles , Bêty Joël
Published: April 2022

Prey handling processes are considered a dominant mechanism leading to short‐term positive indirect effects between prey that share a predator. However, a growing body of research indicates that predators are not necessarily limited by such processes in the wild. Density‐dependent changes in predator foraging behavior can also generate positive indirect effects but they are rarely included as explicit functions of prey densities in functional response models. With the aim of untangling proximate mechanisms of species interactions in natural communities and improving our ability to quantify interaction strength, we extended the multi‐prey version of the Holling disk equation by including density‐dependent changes in predator foraging behavior. Our model, based on species traits and behavior, was inspired by the vertebrate community of the arctic tundra, where the main predator (the arctic fox) is an active forager feeding primarily on cyclic small rodent (lemming) and eggs of various tundra‐nesting bird species. Short‐term positive indirect effects of lemmings on birds have been documented over the circumpolar Arctic but the underlying mechanisms remain poorly understood. We used a unique data set, containing high‐frequency GPS tracking, accelerometer, behavioral, and experimental data to parameterize the multi‐prey model, and a 15‐year time series of prey densities and bird nesting success to evaluate interaction strength between species. We found that (1) prey handling processes play a minor role in our system and (2) changes in arctic fox daily activity budget and distance traveled can partly explain the predation release on birds observed during lemming peaks. These adjustments in predator foraging behavior with respect to the main prey density thus appear as the dominant mechanism leading to positive indirect effects commonly reported among arctic tundra prey. Density‐dependent changes in functional response components have been little studied in natural vertebrate communities and deserve more attention to improve our ability to quantify the strength of species interactions.
Heterometallic Iridium, Rhodium and Ruthenium Nitrido Complexes Supported by Oxygen and Sulfur Donor Ligands
Authors: Ng Rain , Chong Man‐Chun , Cheung Wai‐Man , Sung Herman H.‐Y. , Williams Ian D. , Leung Wa‐Hung
Published: April 2022

Heterometallic μ‐nitrido complexes have been synthesized from organometallic complexes containing O/S‐donor ligands and a ruthenium(VI) nitride. The treatment of [Ir(tpip)(L)2] (tpip−=[N(Ph2PO)2]−; L=cyclooctene (coe) or 2,6‐dimethylphenylisocyanide (xylNC)) and [Ir{N(iPr2PS)2}(coe)] with [Ru(LOEt)(N)Cl2] (LOEt−=[Co(η5‐C5H5){P(O)(OEt)2}3]−) (1) afforded [(L)(tpip)Ir(μ‐N)Ru(LOEt)Cl2] (L=coe (2) or xylNC (3)) and [(coe){N(iPr2PS)2}Ir(μ‐N)Ru(LOEt)Cl2] (4), respectively, in which the Ir−N(nitride) bonds show double bond character. The bonding in 2–4 can be described by two resonance forms: Ir(I)−N≡Ru(VI) and Ir(III)=N=Ru(IV). The treatment of [Ph4P][Ir(CO)2Cl2] with 1 afforded (PPh4)[(CO)Cl2Ir(μ‐N)Ru(LOEt)Cl2] (5) that reacted with [Tl(SR)] to give (PPh4)[(CO)(RS)2Ir(μ‐N)Ru(LOEt)Cl2] (R=xyl (6), C6F4H (7)). The reaction of [M(acac)(CO)2)] or [Ru(acac)2(coe)2] (acac−=acetylacetonate) with 1 gave [(CO)(acac)M(μ‐N)Ru(LOEt)Cl2] [M=Ir (8), Rh (9)] or [(H2O)(acac)2Ru(μ‐N)Ru(LOEt)Cl2] (10), whereas the treatment of [Ru(acac)2(MeCN)2] with 1‐azidoadamantane (AdN3) yielded a Ru(II) tetrazene complex, [Ru(acac)2(N4Ad2)] (11).
Long‐term observational studies with cannabis‐based medicines for chronic non‐cancer pain: A systematic review and meta‐analysis of effectiveness and safety
Authors: Bialas Patric , Fitzcharles Mary‐Ann , Klose Petra , Häuser Winfried
Published: April 2022

Background and Objective

This systematic review evaluated the effectiveness, tolerability and safety of cannabis‐based medicines (CbMs) for chronic non‐cancer pain (CNCP) in long‐term observational studies.

Databases and Data Treatment

CENTRAL, EMBASE and MEDLINE were searched until December 2021. We included prospective observational studies with a study duration ≥26 weeks. Pooled estimates of event rates of categorical data and standardized mean differences (SMD) of continuous variables were calculated using a random effects model.

Results

Six studies were included with 2686 participants, with study duration ranging between 26 and 52 weeks. Pain conditions included nociceptive, nociplastic, neuropathic and mixed pain mechanisms. The certainty of evidence for every outcome was very low. The weighted mean difference of mean pain reduction was 1.75 (95% confidence interval [CI] 0.72 to 2.78) on a 0–10 scale. 20.8% (95% CI 10.2% to 34.0%) of patients reported pain relief of 50% or greater. The effect size for sleep problems was moderate and for depression and anxiety was low. Study completions was reported for 53.3% (95% CI 26.8% to 79.9%) of patients, with dropouts of 6.8% (95% CI 4.3% to 9.7%) due to adverse events. Serious adverse events occurred in 3.0% (95 CI 0.02% to 12.8%) and 0.3% (95% CI 0.1% to 0.6%) of patients died.

Conclusions

Information included in observational studies should be regarded with caution. Within the context of observational studies. CbMs had positive effects on multiple symptoms for some CNCP patients and were generally well tolerated and safe.

Significance

There is very low quality evidence for the long‐term effectiveness (pain, sleep, mood, health‐related quality of life), tolerability and safety of medical cannabis for chronic non‐cancer pain (CNCP) according to reports of prospective observational studies. Predefined criteria of a large magnitude of effect size in these types of studies were not met. Nevertheless, long‐term medical cannabis therapy can be considered in some carefully selected and monitored patients with CNCP.
Influence of diapir structure on formation and distribution of overpressure in the Yinggehai Basin, South China Sea
Authors: Huang Honglin , Li Jun , Yang Hongwei , Zhang Geng , Gao Reyu , An Jintao , Luo Ming , Li Wentuo
Published: April 2022

The Yinggehai Basin (YGH) in the South China Sea is a Cenozoic, high‐temperature, and high‐pressure basin. Exploration and development of natural gas resources in the YGH show that owing to the diapir structures make the formation pressure system is complex, overpressure characteristics are obvious, prediction is difficult, and spatial distribution is irregular, which severely restricts the development of natural gas. To evaluate the influence of diapir structures on the formation and distribution of overpressure, we compared and analyzed the ancient and modern geothermal temperatures, organic matter maturity, clay mineral evolution, burial depth, and pressure coefficient in the diapir and nondiapir zones of the YGH. The results showed that of the diapir structures in the YGH occurred in the following order: Uplift–spiking–piercing–depositing. The Dongfang area is dominated by low‐amplitude turtle‐back diapir structures with weak energy, whereas the Ledong area is dominated by high‐amplitude spiked diapir structures with strong energy, both of which pressurize the upper formation. The Changnan area is dominated by high‐amplitude pierced/depositing diapirs with strong energy, which can relieve pressure. The influence of the diapir and its associated structures on the formation of overpressure can be attributed to the transport of the diapir body and the associated fault‐fracture system and the local thermal effect caused by the upwelling of hot fluids. Under the influence of the diapir structure, the overpressure top surface of the basin was shallower. According to the degree of influence and intensity of the diapir structure, variations in formation pressure coefficient with depth can be divided into four evolution modes: constant pressure, slow pressurization, “Z” pressurization, and “S” pressurization types. This study provides some guidance and references for the identification and accurate prediction of the overpressure formation mechanism in basins containing diapirs, and helps in formulating efficient drilling and production plans.
Pore structure and fractal analysis of coal subjected to multiple treatments based on nuclear magnetic resonance
Authors: Yang Zairong , Zhao Yu , Wang Chaolin , Bi Jing
Published: April 2022

Microwave heating (MW) and freeze fracturing (FF) have been widely used for enhancing the permeability of coal reservoirs. In this paper, the effects of combined MW–FF treatments on coals are experimentally investigated through nuclear magnetic resonance. T2 distributions and fractal dimensions of coals under MW, FF, and the combined MW–FF treatments are compared and analyzed. The results show that the T2 area, porosity, and fractal dimensions of coals increase to varying degrees after MW, FF, and MW–FF treatment. The T2 spectrum peaks increase from 2 to 3 and macrofractures can be observed after the coal was treated with the combined MW–FF treatments. However, these phenomena are not observed under MW or FF treatment. The combined MW–FF treatments can effectively fracture coals with less microwave energy and less liquid nitrogen freezing cycle owing to its intensive thermal shock fracturing. Therefore, the combined MW–FF treatment is favorable for fracturing the coals and hence favorable for the CBM production.
Effectiveness of a third dose of BNT162b2 anti‐SARS‐CoV‐2 mRNA vaccine over a 6‐month follow‐up period in allogenic hematopoietic stem cells recipients
Authors: Chevallier Patrice , Jullien Maxime , Peterlin Pierre , Garnier Alice , Le Bourgeois Amandine , Coste‐Burel Marianne , Béné Marie C. , Guillaume Thierry
Published: April 2022

This study reports the effectiveness of three injections of BNT162b2 anti‐SARS‐CoV‐2 mRNA vaccine in 141 Allo‐HSCT recipients with a median follow‐up of 6 months post‐third shot. We demonstrate a long‐term high protection of Allo‐HSCT recipients since only 2 infections and one death related to COVID‐19 occurred.
Promotive effects of four herbal medicine ARCC on wound healing in mice and human
Authors: Zhong Lingzhi , Shi Cuijuan , Hou Qian , Yang Rungong , Li Meirong , Fu Xiaobing
Published: April 2022

Background

Traditional Chinese medicine (TCM) had been extensively used in China for wound management and had shown great potential in wound treatment while its mechanism is still needed to be addressed.

Objective

The present study sought to investigate the therapuetic effect of the TCM ARCC on acute and chronic wounds.

Methods

Here, using the ultra‐low temperature preparation method, the mixed ultramicro powder prepared with Angelica (A), Angelica (R), Calcined Gypsum (C) and Caleramide (C) named as ARCC. The effects of ARCC on wound healing in adult and aged mice were comparatively evaluated through a full‐thickness skin defect model. In addition, we randomly selected 10 patients aged 55 to 70 years from a cohort of 500 patients with diabetic feet to assess their prognosis.

Results

As the results showed that the healing rate had delayed in aged mice compared to adult mice, while ARCC prominently augmented the healing process in aged mice. Moreover, ARCC treatment wounds in aged mice showed accelerated re‐epithelization, enhanced granulation tissue formation, and increased vascularization, which was similar to that of adult mice. Furthermore, ARCC also achieved therapeutic effects in diabetic foot patients, accelerating wound healing. The results found that foot ulcers improved significantly 7 days after the ARCC administration, and 80% of patients were healed within 1 month.

Discussion

In the present study, ARCC was found to have therapeutic effects on both acute and chronic wounds in animal models. ARCC also demonstrated therapeutic effects in diabetic feet, which promoted wound healing, prevented wound infection, and avoided the risk of further surgery or amputation. All these evidences suggested ARCC was a promising approach for wound treatment.

Conclusions

ARCC might be recommended as a promising therapeutic medication in diabetic and chronic refractory wounds.
School climate‐related determinants of physical activity among high school girls and boys
Authors: Rajbhandari‐Thapa Janani , Metzger Isha , Ingels Justin , Thapa Kiran , Chiang Kathryn
Published: April 2022

Introduction

In the United States, physical activity (PA) among adolescents is declining; 75% of high school students do not meet daily PA guidelines. Low rates of PA are more prevalent among high school girls. Schools provide an optimal environment to target and promote PA. However, school climate has not yet been studied for its importance in promoting PA among high school students, particularly girls.

Methods

A cross‐sectional analysis was conducted using the Georgia Student Health Survey (GSHS) 2.0 data on perceptions of different school climate measures and self‐reported weekly PA levels to study gender differences in the association of PA with school climate.

Results

Data from a total of 362,926 students (48% males and 52% females) were analyzed. For both genders, the odds of being physically active increased with a more positive report of supportive school environments, school connectedness, peer social support, school physical environments, cultural acceptance, school safety, and adult social support. Peer victimization was associated with increased odds of PA among females but lower odds for males.

Conclusion

Results suggest that improving school climate can increase PA among adolescents. As new or existing school‐based interventions and policies are considered by states and local governments, improving the school climate should be part of the overall strategy. Future research is needed on peer victimization among physically active females.

Implications and Contributions

This study evaluated gender differences in the association between measures of school climate and PA among high school students. School climate or policies fostering positive environments including feelings of safety, connectedness, and peer support may increase adolescent PA; addressing peer victimization and fights may reduce gender disparities in PA.
Spirituality and relational health among Black Americans
Authors: Balkin Richard S. , Neal Sheerah A. , Stewart Keon D. , Hendricks Lavelle , Litam Stacey Diane Arañez
Published: April 2022

Black Americans may be less likely to seek conventional mental health services, often preferring to seek assistance within their social support networks, including spiritual and religious communities. Research related to relational health as a marker of spirituality among Black Americans is limited, especially in counseling literature. Relational health and spirituality preserve wellness particularly among Black Americans. Thus, we have illuminated new pathways for exploring Black American well‐being. A multiple regression analysis of 233 adult participants (68 men and 165 women), who identified as Black American or African American (n = 221) or Bi‐/Multi‐racial (n = 12), indicated a significant relationship between spirituality and relational health. The mentor and community subscales on the Relational Health Indices (RHI) made a significant contribution to the model, indicating that quality relationships impact levels of spirituality. Religious affiliation moderated the relationship between relational health domains and spirituality.
Polarization energies in the fragment molecular orbital method
Authors: Fedorov Dmitri G.
Published: April 2022

Using isolated and polarized states of fragments, a method for computing the polarization energies in density functional theory (DFT) and density‐functional tight‐binding (DFTB) is developed in the framework of the fragment molecular orbital method. For DFTB, the method is extended into the use of periodic boundary conditions (PBC), for which a new component, a periodic self‐polarization energy, is derived. The couplings of the polarization to other components in the pair interaction energy analysis (PIEDA) are derived for DFT and DFTB, and compared to Hartree–Fock and second‐order Møller‐Plesset perturbation theory (MP2). The effect of the self‐consistent (DFT) and perturbative (MP2) treatment of the electron correlation on the polarization is discussed. The difference in the polarization in the bulk (PBC) and micro (cluster) solvation is elucidated.
4‐triphenylmethylaniline substituted cyclotriphosphazene derivatives assisted by multiple phenyl rings
Authors: Mutlu Balcı Ceylan , Palabıyık Duygu
Published: April 2022

In the present study, nucleophilic substitution reactions of hexachlorocyclotriphosphazene (1) and 4‐triphenylmethylaniline (2) were carried out under different mole ratios. As a result of the reactions, mono (3), bis geminal (4), tetrakis geminal (5), and hexakis substituted (6) cyclotriphosphazene derivatives formed. The product diversity and yields of new cyclotriphosphazene derivatives (3–6) were comprehensively investigated by using the proton‐decoupled 31P Nuclear Magnetic Resonance (NMR) spectra of the reaction mixtures. Pure cyclotriphosphazene derivatives (3–5) have been characterized by 1H, 13C and 31P NMR, MALDI‐TOF mass and elemental analyses. The structure of compound 4 was also elucidated by single crystal X‐ray diffraction technique. Along with the spectroscopic techniques, the thermal stabilities of 4‐triphenylmethylaniline substituted cyclotriphosphazene derivatives (4 and 5) were determined by thermogravimetric analysis (TGA) technique.
SLC2A3 variants in familial and sporadic congenital heart diseases in a Chinese Yunnan population
Authors: Ma Lijing , Xu Jiaxin , Tang Qisheng , Cao Yu , Kong Ruize , Li Kunlin , Liu Jie , Jiang Lihong
Published: April 2022

Background

Solute carrier family 2 member 3 (SLC2A3), is a member of a superfamily of transport protein genes. SLC2A3 played an important role in embryonic development. Previous research reported SLC2A3 duplication was reportedly associated with congenital syndromic heart defects. However, it is not clear whether the gene is associated with non‐syndromic congenital heart disease. Our study aimed to elucidate the relationship between its variation and congenital heart disease.

Methods

Genomic DNA extracted from the peripheral blood leukocytes of two families with CHD were sequenced with whole‐exome sequencing to identify variations, used Sanger sequencing to investigate SLC2A3 variants in 494 Chinese patients with CHD and 576 healthy unrelated individuals.

Results

In members from the two families, three with CHD had the SLC2A3 (rs3931701) C > T variant. Of the 494 patients with CHD, 394 had gene variants (86 had the TT type and 308 had the CT type). Of the 576 healthy controls, 272 participants had gene variants (36 had the TT type and 236 had the CT type). The TT type [p < 0.0001, odds ratio (OR) =7.262, 95% confidence interval (CI) =4.631–11.388] and CT type (p < 0.0001, OR =3.967, 95% CI =2.991–5.263) of SLC2A3 (rs3931701) significantly increased the risk of sporadic ASD in a Chinese Yunnan population.

Conclusions

Single nucleotide variations of SLC2A3, particularly, the SLC2A3 (rs3931701) C > T variant increased the risk of CHD among the studied population.
Disclosure of suicidal thoughts and behaviors: The impact of suicide event type
Authors: Ammerman Brooke A. , Park Yeonsoo , O'Loughlin Caitlin M.
Published: April 2022

Objectives

Despite its importance, limited work has investigated the nuances of suicidal thoughts and behavior self‐disclosure. The present study aimed to examine potential differences in self‐disclosure based on whether an individual has disclosed suicidal thinking versus behavior.

Methods

Two hundred and four participants having disclosed their suicidal thoughts or behaviors completed a battery of online questionnaires assessing several key aspects of disclosure (i.e., disclosure recipient, perceived helpfulness of disclosure, impact on treatment seeking), as it pertained to both one's first and overall disclosure experiences.

Results

Individuals who disclosed a suicide attempt, versus ideation, were more likely to have disclosed to a formal support (i.e., health professional) and to seek professional help following disclosure. No significant group differences in perceived helpfulness of experiences were found.

Conclusion

It may be beneficial to increase opportunities for disclosure of suicidal thinking. Overall, disclosures were perceived as helpful and may not impede future help‐seeking behavior.
New reactions of 3,4‐dihydro‐6,7‐dimethoxyisoquinoline ylide with nitrile derivatives
Authors: Molnár Márk , Treuerne Balázs Krisztina E. , Madarász Zoltán , Nyerges Miklós
Published: April 2022

Novel examples for dipolar cycloaddition of isoquinolinium ylides to nitriles leading to new imidazo[2,1‐a]isoquinolines were described and the potential of this reaction in synthetic chemistry was explored. As a by‐product of this research, a number of N‐substituted, 3,4‐dihydro‐1H‐isoquinoline‐1‐carbonitriles were synthesized by a simple, efficient reaction of a series of isoquinolinium bromides and ethyl cyanoformate in the presence of triethylamine.
Automated radiochemical synthesis of pharmaceutical grade [18F]FLT using 3‐N‐Boc‐5′‐O‐dimethoxytrityl‐3′‐O‐nosyl‐thymidine precursor and its Sep‐Pak® purification employing selective elution from reversed phase
Authors: Mitra Arpit , Chakraborty Avik , Upadhye Trupti , Tawate Megha , Lad Sangita , Sahu Sudeep , Rajesh Chinagandham , Bagul Swati , Pawar Yogita , Ray Mukti Kant , Banerjee Sharmila
Published: April 2022

Pharmaceutical grade 3′‐deoxy‐3′‐[18F]fluorothymidine [18F]FLT was synthesized using 3‐N‐Boc‐5′‐O‐dimethoxytrityl‐3′‐O‐nosyl‐thymidine (BOC‐Nosyl) precursor, in the general purpose TRACERlab FX modules. Purification of [18F]FLT, via solid phase extraction (SPE) after radiosynthesis, using a combination of different SPE cartridges, yielded satisfactory results, with radiochemical and chemical purity >99%. While the non‐decay corrected radiochemical yield (RCY) with 20 mg (24 μmole) of BOC‐Nosyl precursor was found to be 6.80 ± 0.16%, the decay corrected radiochemical yield (RCY) was 9.95 ± 0.24%. Residual acetone, acetonitrile, and ethanol levels were found to be 22.97 ± 0.76, 109.08 ± 0.93, and 7,666.45 ± 3.7 ppm, respectively. A simplified method for solid‐phase purification of [18F]FLT was developed, circumventing the need for HPLC purification. Biodistribution in C57BL/6 mice with B16F10 cell line‐induced melanoma showed tumor to blood ratio of ~3.8 at 90 min. PET/CT imaging of normal rabbit injected with [18F]FLT shows selective uptake in the bone marrow and small intestine. [18F]FLT was found to be excreted through the kidneys and get collected in the urinary bladder, 120 min post injection. PET/CT imaging performed in rabbit model at 30, 60, 90, and 120 min post [18F]FLT injections showed concordance with tissue distribution kinetics of mice tumor model.