bluuebunny/crossref_metadata_2025_split huggingface dataset:
Origin of the Rate Acceleration in the C−C Reductive Elimination from Pt(IV)‐complex in a [Ga4L6]12− Supramolecular Metallocage
Authors: Norjmaa Gantulga , Maréchal Jean‐Didier , Ujaque Gregori 
Published: September 2021

AbstractThe reductive elimination on [(Me3P)2Pt(MeOH)(CH3)3]+, 2P, complex performed in MeOH solution and inside a [Ga4L6]12− metallocage are computationally analysed by mean of QM and MD simulations and compared with the mechanism of gold parent systems previously reported [Et3PAu(MeOH)(CH3)2]+, 2Au. The comparative analysis between the encapsulated Au(III) and Pt(IV)‐counterparts shows that there are no additional solvent MeOH molecules inside the cavity of the metallocage for both systems. The Gibbs energy barriers for the 2P reductive elimination calculated at DFT level are in good agreement with the experimental values for both environments. The effect of microsolvation and encapsulation on the rate acceleration are evaluated and shows that the latter is far more relevant, conversely to 2Au. Energy decomposition analysis indicates that the encapsulation is the main responsible for most of the energy barrier reduction. Microsolvation and encapsulation effects are not equally contributing for both metal systems and consequently, the reasons of the rate acceleration are not the same for both metallic systems despite the similarity between them.
Study of the Cycloaddition of CO2 with Styrene Oxide Over Six‐Connected spn Topology MOFs (Zr, Hf) at Room Temperature
Authors: Jin Lijian , Qin Qiuju , Dong Lihui , Liu Shaoqing , Xie Shangzhi , Lu Jinkai , Xu Aihao , Liu Jiaxing , Liu Hao , Yao Yinchao , Hou Xueyan , Fan Minguang 
Published: September 2021

AbstractA series of MOFs with a 6‐connected spn topology were synthesized (MOF‐808‐(Zr, Hf), PCN‐777‐(Zr, Hf), MOF‐818‐(Zr, Hf)). Through the in situ DRIFTS of NH3 adsorption‐desorption, we found that the activated catalyst mainly contains Lewis acid sites. The effects of different organic ligands on the Lewis acid of the Zr6 cluster were analyzed by XPS and NH3‐TPD, and the relative Lewis acidity of the same metal was obtained: PCN‐777>MOF‐808>MOF‐818. In the Py‐FTIR results, we confirmed that MOF‐818 has a higher acid site density. In the activity test, MOFs with mesoporous structure showed better catalytic activity under normal temperature and pressure. Among them, MOF‐818 can still maintain a high degree of crystallinity after catalysis. Finally, we use density functional theory to propose the mechanism of the cycloaddition reaction of carbon dioxide and styrene oxide. The results show that the metal is coordinated with styrene oxide and halogens attack the β carbon of the epoxide.
Diphosphino‐Functionalized 1,8‐Naphthyridines: a Multifaceted Ligand Platform for Boranes and Diboranes
Authors: Cui Jingjing , Dietz Maximilian , Härterich Marcel , Fantuzzi Felipe , Lu Wei , Dewhurst Rian D. , Braunschweig Holger 
Published: September 2021

AbstractA 1,8‐naphthyridine diphosphine (NDP) reacts with boron‐containing Lewis acids to generate complexes featuring a number of different naphthyridine bonding modes. When exposed to diborane B2Br4, NDP underwent self‐deprotonation to afford [NDP‐B2Br3]Br, an unsymmetrical diborane comprised of four fused rings. The reaction of two equivalents of monoborane BBr3 and NDP in a non‐polar solvent provided the simple phosphine‐borane adduct [NDP(BBr3)2], which then underwent intramolecular halide abstraction to furnish the salt [NDP‐BBr2][BBr4], featuring a different coordination mode from that of [NDP‐B2Br3]Br. Direct deprotonation of NDP by KHMDS or PhCH2K generates mono‐ and dipotassium reagents, respectively. The monopotassium reagent reacts with one or half an equivalent of B2(NMe2)2Cl2 to afford NDP‐based diboranes with three or four amino substituents.
Switching the Mechanism of NADH Photooxidation by Supramolecular Interactions
Authors: Mengele Alexander K. , Weixler Dominik , Chettri Avinash , Maurer Maite , Huber Fabian Lukas , Seibold Gerd M. , Dietzek Benjamin , Eikmanns Bernhard J. , Rau Sven 
Published: September 2021

AbstractA series of three Ru(II) polypyridine complexes was investigated for the selective photocatalytic oxidation of NAD(P)H to NAD(P)+ in water. A combination of (time‐resolved) spectroscopic studies and photocatalysis experiments revealed that ligand design can be used to control the mechanism of the photooxidation: For prototypical Ru(II) complexes a 1O2 pathway was found. Rudppz ([(tbbpy)2Ru(dppz)]Cl2, tbbpy=4,4'‐di‐tert‐butyl‐2,2'‐bipyridine, dppz=dipyrido[3,2‐a:2′,3′‐c]phenazine), instead, initiated the cofactor oxidation by electron transfer from NAD(P)H enabled by supramolecular binding between substrate and catalyst. Expulsion of the photoproduct NAD(P)+ from the supramolecular binding site in Rudppz allowed very efficient turnover. Therefore, Rudppz permits repetitive selective assembly and oxidative conversion of reduced naturally occurring nicotinamides by recognizing the redox state of the cofactor under formation of H2O2 as additional product. This photocatalytic process can fuel discontinuous photobiocatalysis.
Humic and Fulvic Acids as Specific Sorbents of Herbicides in Water
Authors: Vrantsi Eleni , Lakka Achillia , Bozinou Eleni , Athanasiadis Vassilis , Papadaki Eirini S. , Dourtoglou Vassilis G. , Lalas Stavros I. 
Published: September 2021

AbstractThe ability of humic and fulvic acids (isolated from lignite with a simple, quick, and inexpensive method) to bind the active ingredients of herbicides contaminating drinking water is evaluated. During this study drinking water samples are contaminated with formulated herbicides (imazamox or a mixture of thifensulfuron methyl and tribenuron methyl), while humic and fulvic acids are used as reducing agents. The maximum reducing ability presented by humic and fulvic acids is 72.72% for thifensulfuron methyl and tribenuron methyl and 37.52% for imazamox. Humic acids’ binding ability is superior to that of fulvic acids.
Drought in Northeast Brazil: A review of agricultural and policy adaptation options for food security
Authors: Marengo Jose A. , Galdos Marcelo V. , Challinor Andrew , Cunha Ana Paula , Marin Fabio R. , Vianna Murilo dos Santos , Alvala Regina C. S. , Alves Lincoln M. , Moraes Osvaldo L. , Bender Fabiani 
Published: September 2021

AbstractThe semiarid lands of Northeast Brazil represent one of the most densely populated regions of the country. Rainfall variability together with land degradation and large‐scale poverty in rural areas makes this region vulnerable to droughts. Most of the agriculture in this region is rainfed and deficient rainfall leads to severe drought impacts. In this review, we examine different short‐ and long‐term strategies directed to cope with possible impacts of droughts proposed by the government, farmers, civil society, and the private sector. These are approaches to adaptation to drought in the Northeast of Brazil, and among them, we have agricultural management and soil conservation and better management of water resources. Other actions include seasonal climate forecasts and funds transfer and credits to affected small‐scale farmers. Although some of these actions are for the short term and may help to survive the drought situation, they may be only postdisaster mitigation options that do not improve adaptive capacity. They favor maladaptation and create dependency of farmers to government actions. Some experiences such as AdaptaSertão show potential benefits for small‐scale farmers. We identify key challenges for moving toward a more holistic risk management approach and highlight the need to integrate actions and tools for adaptation, combining technology‐based solutions with in‐depth knowledge of local and regional social, economic, and cultural aspects, among them seasonal climate forecasts and drought impacts studies, among some other proactive predisaster ways, rather than reactive postdisaster actions. Adaptation strategies must increase long‐term resilience of food production in the Brazilian Northeast, going beyond an individual drought event.
Engineered s‐Triazine‐Based Dendrimer‐Honokiol Conjugates as Targeted MMP‐2/9 Inhibitors for Halting Hepatocellular Carcinoma
Authors: Khalil Hosam H. , Osman Heba A. , Teleb Mohamed , Darwish A. I. , Abu‐Serie Marwa M. , Khattab Sherine N. , Haiba Nesreen S. 
Published: September 2021

AbstractDespite the advances in developing MMP‐2/9 inhibitors, off‐target side effects and pharmacokinetics problems remain major challenges hindering their clinical success in cancer therapy. However, recent targeting strategies have clearly revitalized MMP research. Herein, we introduce new s‐triazine‐based dendrimers endowed with intrinsic MMP‐2/9 inhibitory potential and tetherable to hepatocellular carcinoma‐specific targeting ligands and anticancer agents via biodegradable linkages for targeted therapy. The designed dendrimeric platform was built with potential zinc‐binding branching linkers (hydrazides) and termini (carboxylic acids and hydrazides) to confer potency against MMP‐2/9. Preliminary cytotoxicity screening and MMP‐2/9 inhibition assay of the free dendrimers revealed promising potency (MMP‐9; IC50=0.35–0.57 μM, MMP‐2; IC50=0.39–0.77 μM) within their safe doses (EC100=94.15–42.75 μM). The hydrazide dendrimer was comparable to NNGH and superior to the carboxylic acid analogue. MTT assay showed that the free dendrimers were superior to the reference anticancer agent honokiol. Their anticancer potency was enhanced by HK conjugation, targeting ligands installation and PEGylation as exemplified by the hydrazide dendrimer conjugate (TPG3−NH2)‐SuHK‐FA‐SuPEG (Huh‐7; IC50=5.54 μM, HepG‐2; IC50=10.07 μM) being 4 folds more active than HK, followed by the carboxylic acid conjugate (TPG3−OH)‐HK‐LA‐PEG (Huh‐7; IC50=14.97, HepG‐2; IC50=21.29 μM). This was consistent with apoptosis studies.
Analysis of Islet‐1, Nkx2.1, Pax6, and Orthopedia in the forebrain of the sturgeon Acipenser ruthenus identifies conserved prosomeric characteristics
Authors: López Jesús M. , Jiménez Sara , Morona Ruth , Lozano Daniel , Moreno Nerea 
Published: September 2021

AbstractThe distribution patterns of a set of conserved brain developmental regulatory transcription factors were analyzed in the forebrain of the basal actinopterygian fish Acipenser ruthenus, consistent with the prosomeric model. In the telencephalon, the pallium was characterized by ventricular expression of Pax6. In the subpallium, the combined expression of Nkx2.1/Islet‐1 (Isl1) allowed to propose ventral and dorsal areas, as the septo‐pallidal (Nkx2.1/Isl1+) and striatal derivatives (Isl1+), respectively, and a dorsal portion of the striatal derivatives, ventricularly rich in Pax6 and devoid of Isl1 expression. Dispersed Orthopedia (Otp) cells were found in the supracommissural and posterior nuclei of the ventral telencephalon, related to the medial portion of the amygdaloid complex. The preoptic area was identified by the Nkx2.1/Isl1 expression. In the alar hypothalamus, an Otp‐expressing territory, lacking Nkx2.1/Isl1, was identified as the paraventricular domain. The adjacent subparaventricular domain (Spa) was subdivided in a rostral territory expressing Nkx2.1 and an Isl1+ caudal one. In the basal hypothalamus, the tuberal region was defined by the Nkx2.1/Isl1 expression and a rostral Otp‐expressing domain was identified. Moreover, the Otp/Nkx2.1 combination showed an additional zone lacking Isl1, tentatively identified as the mamillary area. In the diencephalon, both Pax6 and Isl1 defined the prethalamic domain, and within the basal prosomere 3, scattered Pax6‐ and Isl1‐expressing cells were observed in the posterior tubercle. Finally, a small group of Pax6 cells was observed in the pretectal area. These results improve the understanding of the forebrain evolution and demonstrate that its basic bauplan is present very early in the vertebrate lineage.
An optimum security enabled System‐on‐Chip selection for Internet of Things applications using genetic algorithm modeling
Authors: Krishnamoorthy Ramesh , Krishnan Kalimuthu 
Published: September 2021

SummaryThe System‐on‐Chip (SoC) is the core component in embedded systems that push toward the evolution of the Internet of Things. The quick growth of embedded SoC devices has a substantial influence to overcome security issues in embedded system design. Since microcontroller‐based systems are security and safety‐critical, this article focuses on security aspects of state‐of‐the‐art microcontrollers through performing design space analysis of several crypto‐core algorithms. These crypto functions are analyzed and compared to identify and implement the appropriate algorithm for on‐chip security. The genetic algorithm (GA) optimization model is utilized for the optimal selection of secured SoC from the commercial devices that are stored in the database. In this work, the fitness function is proposed with various levels such as performance‐centric, security enabled, low operating power, and application‐specific SoC selection. We also validate the GA results by implementing the security benchmarks on resultant devices by analyzing the execution time and performance. The accuracy of the GA‐based optimum SoC selection is estimated using confusion matrix method that produces the accuracy of .
Coherent Evolution of Signal Amplification by Reversible Exchange in Two Alternating Fields (alt‐SABRE)
Authors: Pravdivtsev Andrey N. , Kempf Nicolas , Plaumann Markus , Bernarding Johannes , Scheffler Klaus , Hövener Jan‐Bernd , Buckenmaier Kai 
Published: September 2021

AbstractParahydrogen (pH2) is a convenient and cost‐efficient source of spin order to enhance the magnetic resonance signal. Previous work showed that transient interaction of pH2 with a metal organic complex in a signal amplification by reversible exchange (SABRE) experiment enabled more than 10 % polarization for some 15N molecules. Here, we analyzed a variant of SABRE, consisting of a magnetic field alternating between a low field of ∼1 μT, where polarization transfer is expected to take place, and a higher field >50 μT (alt‐SABRE). These magnetic fields affected the amplitude and frequency of polarization transfer. Deviation of a lower magnetic field from a “perfect” condition of level anti‐crossing increases the frequency of polarization transfer that can be exploited for polarization of short‐lived transient SABRE complexes. Moreover, the coherences responsible for polarization transfer at a lower field persisted during magnetic field variation and continued their spin evolution at higher field with a frequency of 2.5 kHz at 54 μT. The latter should be taken into consideration for an efficient alt‐SABRE. Theoretical and experimental findings were exemplified with Iridium N‐heterocyclic carbene SABRE complex and 15N‐acetonitrole, where a 30 % higher 15N polarization with alt‐SABRE compared to common SABRE was reached.
The impact of prenatal maternal stress due to potentially traumatic events on child temperament: A systematic review
Authors: Rodríguez‐Soto Nayra C. , Buxó Carmen J. , Morou‐Bermudez Evangelia , Pérez‐Edgar Koraly , Ocasio‐Quiñones Idanara T. , Surillo‐González Marta Beatriz , Martinez Karen G. 
Published: September 2021

AbstractThe objective of the current study was to complete a systematic review of the relationship between prenatal maternal stress due to potentially traumatic events (PTEs) and child temperament. Eligible studies through June 2020 were identified utilizing a search strategy in PubMed and PsycInfo. Included studies examined associations between prenatal maternal stress due to PTE and child temperament. Two independent coders extracted study characteristics and three coders assessed study quality. Of the 1969 identified studies, 20 met full inclusion criteria. Studies were classified on two dimensions: (1) disaster‐related stress and (2) intimate partner violence during pregnancy. For disaster‐related prenatal maternal stress, 75% (nine out of 12) of published reports found associations with increased child negative affectivity, 50% (five out of 10) also noted associations with lower effortful control/regulation, and 38% (three out of eight) found associations with lower positive affectivity. When considering prenatal intimate partner violence stress, 80% (four out of five) of published reports found associations with higher child negative affectivity, 67% (four out of six) found associations with lower effortful control/regulation, and 33% (one out of three) found associations with lower positive affectivity. Prenatal maternal stress due to PTEs may impact the offspring's temperament, especially negative affectivity. Mitigating the effects of maternal stress in pregnancy is needed in order to prevent adverse outcomes on the infant's socioemotional development.
Impact of renin‐angiotensin system inhibitors on long‐term clinical outcomes of patients with rheumatic heart disease
Authors: Liu Cheng , Lai Yanxian , Wu Deping , Fu Ruibin , Li Yanfang , Li Hu , Guan Tianwang , Shen Yan 
Published: September 2021

AbstractAimsRheumatic heart disease (RHD) remains a major global health problem. Renin–angiotensin–aldosterone system inhibitors (RAASi) are commonly administered in the treatment of cardiovascular disease, but its role in RHD patients is still limited. We performed a retrospective study to determine the effect of RAASi on long‐term outcomes for RHD patients.Methods and resultsA 1:1 propensity score matching was implemented to balance baseline characteristics between groups RAASi and non‐RAASi. Cox proportional hazards regression model was used to investigate the associations of RAASi with the risks of all‐cause mortality, cardiovascular death (CVD), and cerebrovascular death. Binary logistic regression analysis was used to evaluate the associations of RAASi with the risks of 1, 3, and 5 year heart failure (HF) rehospitalization, new‐onset atrial fibrillation (AF), and new‐onset stroke. A total of 734 RHD patients were enrolled as study participants; nearly half of these participants had combined valve damage (54.4%), worse New York Heart Association functional class status (III and IV, 55.2%), surgical treatment (54.2%), and AF (65.0%). After propensity score matching, 514 RHD patients were finally analysed. RAASi treatment was associated with decreased risks of all‐cause mortality [adjusted hazard ratio (HR) = 0.52, 95% confidence interval (CI): 0.37–0.73, P < 0.001], CVD (adjusted HR = 0.48, 95% CI: 0.30–0.76, P = 0.002), and cerebrovascular death (adjusted HR = 0.22, 95% CI: 0.08–0.60, P = 0.003). Further subgroup analysis showed that RAASi treatment was associated with decreased risks of all‐cause mortality (adjusted HR = 0.50, 95% CI: 0.31–0.79, P = 0.004), CVD (adjusted HR = 0.48, 95% CI: 0.25–0.91, P = 0.025), and cerebrovascular death (adjusted HR = 0.19, 95% CI: 0.05–0.65, P = 0.008) in RHD patients without surgical treatment, and better effect was observed in RHD patients with surgical treatment on the risks of all‐cause mortality (adjusted HR = 0.47, 95% CI: 0.26–0.85, P = 0.012) and CVD (adjusted HR = 0.43, 95% CI: 0.21–0.90, P = 0.024) except cerebrovascular death (adjusted HR = 0.52, 95% CI: 0.08–3.36, P = 0.491). RAASi treatment was associated with decreased HF rehospitalization risk of 1 year [adjusted odds ratio (OR) = 0.38, 95% CI: 0.23–0.61, P < 0.001], 3 year (adjusted OR = 0.43, 95% CI: 0.28–0.68, P < 0.001), and 5 year (adjusted OR = 0.48, 95% CI: 0.30–0.77, P = 0.002) as well as new‐onset AF risk (adjusted OR = 0.38, 95% CI: 0.21–0.68, P = 0.001). RAASi treatment had nothing to do with new‐onset stroke risk (adjusted OR = 0.80, 95% CI: 0.47–1.38, P = 0.428).ConclusionRenin–angiotensin–aldosterone system inhibitor treatment was significantly associated with decreased risks of mortality, HF rehospitalization, and new‐onset AF in RHD patients in median 5.9 year follow‐up.
Effect of Oxygen on Ammonothermal Synthesis: Example of Na2[Zn(NH2)4] ⋅ (NH3)x and Na2[Zn(NH2)4] ⋅ (H2O)x
Authors: Kunkel Sebastian , Nasir Jamal , Schmedt auf der Günne Jörn , Niewa Rainer 
Published: September 2021

AbstractPolycrystalline powder and single crystals of Na2[Zn(NH2)4] ⋅ (NH3)0.24 and Na2[Zn(NH2)4] ⋅ (H2O)0.37 were obtained under ammonobasic conditions at 823 K and 200 MPa. Upon substituting the constituent ammonia by water, the space group (C2/c) and crystal structure remain generally unchanged. Nevertheless, the presence of water during the ammonothermal synthesis has a fundamental impact on the transport direction, changing from exothermic for the pure ammonia system to an endothermic material transport for the hydrate formation under essentially the same experimental conditions. That indicates that even a small amount of oxygen can have a fundamental influence on the solubility and its temperature dependence of dissolved species during ammonobasic synthesis. Chemical analysis, Raman spectroscopy and thermal analysis consistently support the composition assignment. Solid‐state NMR measurements back up the exchange of exclusively ammonia by water, rather than introduction of hydroxide ions. A minor enhancement of the thermal stability of the hydrate compared to the ammoniate is observed.
Self‐connection and well‐being: Development and validation of a self‐connection scale
Authors: Klussman Kristine , Nichols Austin Lee , Curtin Nicola , Langer Julia , Orehek Edward 
Published: September 2021

AbstractSelf‐connection is defined as an (1) awareness of oneself, (2) acceptance of oneself based on this awareness, and (3) alignment of one's behavior with this awareness. Although some promising results suggest that self‐connection uniquely contributes to well‐being, they have relied on an untested, single‐item measure. To advance empirical examination of self‐connection and its role in well‐being, the current research developed and validated a 12‐item Self‐Connection Scale (SCS). We recruited a total of 1,469 participants across three studies to examine the SCS and its three underlying components. Using both exploratory and confirmatory factor analyses, we found evidence supporting the factor structure and inter‐item reliability as well as evidence of construct, concurrent, and incremental validity. Importantly, results from three studies suggest that the SCS is associated with multiple important indicators of health and well‐being. The scale also demonstrated incremental validity beyond mindfulness, authenticity, self‐concept clarity, self‐compassion, and self‐acceptance in its association with various mental health and well‐being indicators. Thus, the SCS provides a valuable tool to measure and examine self‐connection and its relationship to well‐being and other important psychological outcomes.