bluuebunny/crossref_metadata_2025 huggingface dataset:
Single‐Atom Catalysts on Covalent Triazine Frameworks: at the Crossroad between Homogeneous and Heterogeneous Catalysis
Authors: Iemhoff Andree , Vennewald Maurice , Palkovits Regina
Published: September 2022

Heterogeneous single‐site and single‐atom catalysts potentially enable combining the high catalytic activity and selectivity of molecular catalysts with the easy continuous operation and recycling of solid catalysts. In recent years, covalent triazine frameworks (CTFs) found increasing attention as support materials for particulate and isolated metal species. Bearing a high fraction of nitrogen sites, they allow coordinating molecular metal species and stabilizing particulate metal species, respectively. Dependent on synthesis method and pretreatment of CTFs, materials resembling well‐defined highly crosslinked polymers or materials comparable to structurally ill‐defined nitrogen‐containing carbons result. Accordingly, CTFs serve as model systems elucidating the interaction of single‐site, single‐atom and particulate metal species with such supports. Factors influencing the transition between molecular and particulate systems are discussed to allow deriving tailored catalyst systems.
Ruthenium(II)/Imidazolidine Carboxylic Acid‐Catalyzed C−H Alkylation for Central and Axial Double Enantio‐Induction
Authors: Li Yanjun , Liou Yan‐Cheng , Oliveira João C. A. , Ackermann Lutz
Published: September 2022

Enantioselective C−H activation has surfaced as a transformative toolbox for the efficient assembly of chiral molecules. However, despite of major advances in rhodium and palladium catalysis, ruthenium(II)‐catalyzed enantioselective C−H activation has thus far largely proven elusive. In contrast, we herein report on a ruthenium(II)‐catalyzed highly regio‐, diastereo‐ and enantioselective C−H alkylation. The key to success was represented by the identification of novel C2‐symmetric chiral imidazolidine carboxylic acids (CICAs), which are easily accessible in a one‐pot fashion, as highly effective chiral ligands. This ruthenium/CICA system enabled the efficient installation of central and axial chirality, and featured excellent branched to linear ratios with generally >20 : 1 dr and up to 98 : 2 er. Mechanistic studies by experiment and computation were carried out to understand the catalyst mode of action.
Strengthening low‐NOx combustion with flue gas recirculation in a 600‐MWe down‐fired furnace
Authors: Liu Sheng , Kuang Min , Qi Shengchen , Zhao Xiaojuan
Published: September 2022

For a down‐fired furnace using a cascade‐arch‐firing low‐NOx and high‐burnout configuration (CLHC, which includes flue gas recirculation and is taken as a strengthened low‐NOx combustion solution), the gas/particle flow, coal combustion, and NOx emissions were investigated at various flue gas recirculation (FGR) ratios of 5%, 10%, 15%, and 20% (labeled as settings of FGR = 5%, 10%, 15%, and 20%, respectively). The aim was to disclose the FGR role on the strengthened low‐NOx combustion characteristics and meanwhile obtain an available FGR ratio. With increasing FGR, although the downward flame penetration increased continuously, the large local high‐temperature zone favoring combustion in the furnace shrunk. Increasing FGR lowered gas temperatures and strengthened the reductive atmosphere in the downstream of the reburning zone to restrain combustion and meanwhile weaken the NO‐reduction effect of reburning. Trends of the final performance indexes with the FGR ratio showed that NOx production increased continuously, while burnout loss generally undergone an increase‐to‐decrease trend. In view of the above findings and the gained optimal furnace performance (i.e., NOx emissions of 530 mg/m3 at 6% O2 accompanied by carbon content in fly ash at 5.28%), low FGR levels such as FGR = 5% with a hot‐air dilution in FGR should be preferred for the CLHC furnace where FGR is used to deliver the fine pulverized‐coal particles for reburning. In comparison to an advanced in‐service low‐NOx art, the CLHC reduced further NOx production by 41.4% while remained a high burnout achievement except a limited increase in CO emission.
A likelihood ratio test for completed sampling in population size estimation studies
Authors: Farcomeni Alessio
Published: September 2022

We propose a likelihood ratio test to assess that sampling has been completed in closed population size estimation studies. More precisely, we assess if the expected number of subjects that have never been sampled is below a user‐specified threshold. The likelihood ratio test statistic has a nonstandard distribution under the null hypothesis. Critical values can be easily approximated and tabulated, and they do not depend on model specification. We illustrate in a simulation study and three real data examples, one of which involves ascertainment bias of amyotrophic lateral sclerosis in Gulf War veterans.
Energetically unfavorable protein angles: Exploration of a conserved dihedral angle in triosephosphate isomerase
Authors: Allen Patrick W. , Cook Jordan A. , Colquhoun Anh N. , Sorin Eric J. , Tapavicza Enrico , Schwans Jason P.
Published: September 2022

Over the past 3.5 billion years of evolution, enzymes have adopted a myriad of conformations to suit life on earth. However, torsional angles of proteins have settled into limited zones of energetically favorable dihedrals observed in Ramachandran plots. Areas outside said zones are believed to be disallowed to all amino acids, except glycine, due to steric hindrance. Triosephosphate isomerase (TIM), a homodimer with a catalytic rate approaching the diffusion limit, contains an active site lysine residue (K13) with dihedrals within the fourth quadrant (Φ = +51/Ψ = −143). Both the amino acid and the dihedral angles are conserved across all species of TIM and known crystal structures regardless of ligand. Only crystal structures of the engineered monomeric version (1MSS) show accepted β‐sheet dihedral values of Φ = ‐135/Ψ = +170 but experiments show a 1000‐fold loss in activity. Based on these results, we hypothesized that adopting the unfavorable torsion angle for K13 contributes to catalysis. Using both, computational and experimental approaches, four residues that interact with K13 (N11, M14, E97, and Q64) were mutated to alanine. In silico molecular dynamics (MD) simulations were performed using 2JK2 unliganded human TIM as a starting structure. Ramachandran plots, containing K13 dihedral values reveal full or partial loss of disallowed zone angles. N11A showed no detectable catalytic activity and lost the unfavorable K13 dihedral angles across four separate force fields during simulation while all other mutants plus wild type retained activity and retained the conserved K13 dihedral angles.
Molecular genetic associations between a prominent serotonin transporter gene polymorphism (5‐HTTLPR/rs25531) and individual differences in tendencies toward autistic traits and generalized internet use disorder in China and Germany
Authors: Zhang YingYing , Yao Shuxia , Schmitt Helena , Becker Benjamin , Kendrick Keith M. , Montag Christian
Published: September 2022

Background

The serotonin transporter polymorphism 5‐HTTLPR is an extensively investigated genetic marker of autistic traits or autism spectrum disorder, and recently has also been studied in the realm of internet use disorder (IUD), yet the findings remain controversial. Therefore, the present study aimed to explore associations between 5‐HTTLPR (also including SNP rs25531) and autistic traits/IUD tendencies and to assess whether the relationship between autistic traits and IUD tendencies varies by this genetic marker in participants from China and Germany.

Methods

A total of 540 Chinese and 563 German subjects were genotyped for 5‐HTTLPR/rs25531 and completed the Adult Autism Spectrum Quotient questionnaire and the short version of the Internet Addiction Test.

Results

Carriers of the low expressing S'S’ genotype (S, LG) showed significantly higher levels of autistic traits than the high expressing allele (e.g. LA) carriers in both samples. There was no significant effect of 5‐HTTLPR/rs25531 on IUD either in the Chinese or Germany samples, whereas positive correlations between autistic traits and IUD varied by 5‐HTTLPR/rs25531 genotypes and also differed between Chinese and German samples. In the Chinese sample, positive correlations were mainly driven by S'S’ and S'L' carriers, while they were mainly determined by S'L’ and L'L' carriers in the German sample. Further analyses revealed that the associations between autistic traits and IUD tended in parts to be more strongly pronounced in the complete German sample compared to the complete Chinese sample, and also varied depending on 5‐HTTLPR/rs25531 genotypes (in S'S’ carriers: China > Germany; in S'L’ and L'L’ carriers: China < Germany; both in terms of more positive associations).

Conclusions

Our findings suggest carriers of low expressing alleles (S, LG) are more likely to show higher autistic traits in both Chinese and German samples. Furthermore, the present work shows that both 5‐HTTLPR/rs25531 and cultural differences might be of relevance to understand associations between autistic traits and IUD tendencies, but this needs to be further backed up.
RETRACTED: Enterprise strategic plan: Service business model
Authors: Maldynova Aizhana V. , Osmanov Zhasym D. , Smagulova Nyailya T. , Baigelova Aigul N. , Orazgaliyeva Elmaira B.
Published: September 2022

For the innovative development of the economy of Kazakhstan, marketing strategies for promoting innovative products concentrate scientific research and become a new element in the process of managing the market activities of enterprises. The purpose of the study was to determine the place of servitisation in Kazakhstani business, measure the level of servitisation and study the attitude of participants in the industrial market to the new strategy. To achieve the goal set within the framework of this study, marketing research was carried out. Data analysis was carried out using two programmes for data analysis. Presents the basic modelling principles used to form the structure with hidden variables. The authors tested the relationship between the level of motivation of the client and the level of servitisation. The client's motivation level does not affect the servitisation level. A literature review has shown that the implementation of servitisation is a complex task that depends on previous success. Among innovative enterprises in Kazakhstan, due to the underdevelopment of the market, traditional services dominate, while such trendy services as training, utilisation, integration are rarely offered and have a weak level of prevalence.
Thiotemplated Biosynthesis of Bacterial Polyyne Fatty Acids by a Designated Desaturase Triad
Authors: Kim Hak Joong , Ishida Keishi , Hertweck Christian
Published: September 2022

Various bacterial species are capable of producing highly modified fatty acid derivatives with conjugated triple bonds, which play important ecological roles as antifungals and toxins in mutualistic and pathogenic interactions. Furthermore, the terminal polyyne moiety is of interest as pharmacophore and as tag in bioorthogonal chemistry and live imaging. To gain insight into the assembly of these highly reactive natural products, we investigated tetrayne (caryoynencin and protegencin) biosynthesis genes (cay and pgn) from Trinickia caryophylli and Pseudomonas protegens. Pathway dissection and reconstitution in the heterologous host Burkholderia graminis revealed the genes minimally required for polyyne formation. Mutational analyses and biochemical assays demonstrated that polyyne biosynthesis is thiotemplated, involving a fatty acyl‐AMP ligase, a designated acyl carrier protein, and a thioesterase. Heterologous expression of point‐mutated desaturase genes showed that three desaturases work synergistically to introduce four triple bonds. These findings point to an intricate desaturase complex and provide important information for future bioengineering experiments.
Spontaneous gas gangrene of the lower limb in a patient with rectal cancer: A fatal diagnostic pitfall
Authors: Mahjoubi Mohamed Farès , Rezgui Bochra , Mabrouk Aymen , Essid Nada , Jedidi Laila , Ben Moussa Mounir
Published: September 2022

Spontaneous gas gangrene of lower limb is rare. It may complicate digestive cancer or neutropenia. We report a case of spontaneous gas gangrene of the lower limb complicating a rectal cancer, initially diagnosed as deep vein thrombosis. The diagnostic delay was fatal.
Dynamics of the Reversible Inhibition during Methane Oxidation on Bimetallic Pd‐Pt Catalysts Studied by Modulation‐Excitation XAS and DRIFTS
Authors: Boubnov Alexey , Gremminger Andreas , Casapu Maria , Deutschmann Olaf , Grunwaldt Jan‐Dierk
Published: September 2022

Water and NO reversibly inhibit catalytic methane oxidation to CO2 over Pd/Al2O3 and Pd−Pt/Al2O3 at temperatures near 50 % conversion. Modulation‐excitation X‐ray absorption spectroscopy (ME‐XAS) was used to characterize the interaction of the inhibitors with the Pd and Pt components. Simulated X‐ray absorption near‐edge structure (XANES) spectra of Pd and Pt with various surface species were used to verify the findings of ME‐XAS measurements. Diffuse‐reflectance infrared Fourier‐transform spectroscopy (DRIFTS) allowed to correlate methane oxidation with surface formate species. An interaction of water with active Pd sites and water coverage of the Al2O3 support caused a drastic drop in formate production, correlated with the observed inhibition. In a similar manner, nitrite groups formed from gas‐phase NO inhibited the production of formates. At higher temperatures, the inhibition was reversed into a promoting effect by surface nitrates formed from NO that oxidized gas‐phase methane. This approach is not only interesting for emission control but in general for catalysts where dynamic structural changes occur.
Unveiling the Potential of Innovative Gold(I) and Silver(I) Selenourea Complexes as Anticancer Agents Targeting TrxR and Cellular Redox Homeostasis
Authors: De Franco Michele , Saab Marina , Porchia Marina , Marzano Cristina , Nolan Steven P. , Nahra Fady , Van Hecke Kristof , Gandin Valentina
Published: September 2022

A series of NHC‐based selenourea Ag(I) and Au(I) complexes were evaluated for their anticancer potential in vitro, on 2D and 3D human cancer cell systems. All NHC‐based selenourea complexes possess an outstanding cytotoxic potency, which was comparable or even better than that of the reference metallodrug auranofin, and were also able to overcome both platinum‐based and multi‐drug resistances. Intriguingly, their cytotoxic potency did not correlate with solution stability, partition coefficient or cellular uptake. On the other hand, mechanistic studies in cancer cells revealed their ability to strongly and selectively inhibit the redox‐regulating enzyme Thioredoxin Reductase (TrxR), being even more effective than auranofin, a well‐known TrxR inhibitor, without affecting other redox enzymes such as Glutathione Reductase (GR). The inhibition of TrxR in H157 human cancer cells caused, in turn, the disruption of cellular thiol‐redox homeostasis and of mitochondria pathophysiology, ultimately leading to cancer cell death through apoptosis.
Bromine Pentafluoride BrF5, the Formation of [BrF6]− Salts, and the Stereochemical (In)activity of the Bromine Lone Pairs
Authors: Möbs Martin , Graubner Tim , Eklund Kim , Karttunen Antti J. , Kraus Florian
Published: September 2022

BrF5 can be prepared by treating BrF3 with fluorine under UV light in the region of 300 to 400 nm at room temperature. It was analyzed by UV‐Vis, NMR, IR and Raman spectroscopy. Its crystal structure was redetermined by X‐ray diffraction, and its space group was corrected to Pnma. Quantum‐chemical calculations were performed for the band assignment of the vibrational spectra. A monoclinic polymorph of BrF5 was quantum chemically predicted and then observed as its low‐temperature modification in space group P21/c by single crystal X‐ray diffraction. BrF5 reacts with the alkali metal fluorides AF (A=K, Rb) to form alkali metal hexafluoridobromates(V), A[BrF6] the crystal structures of which have been determined. Both compounds crystallize in the K[AsF6] structure type (R
, no. 148, hR24). For the species [BrF6]+, BrF5, [BrF6]−, and [IF6]−, the chemical bonds and lone pairs on the heavy atoms were investigated by means of intrinsic bond orbital analysis.
Oligonucleotides Featuring a Covalently Mercurated 6‐Phenylcarbazole Residue as High‐Affinity Hybridization Probes for Thiopyrimidine‐Containing Sequences
Authors: Kotammagari Tharun K. , Tähtinen Petri , Lönnberg Tuomas
Published: September 2022

Short oligonucleotides incorporating either 1‐mercuri‐6‐phenylcarbazole, 8‐mercuri‐6‐phenylcarbazole, or 1,8‐dimercuri‐6‐phenylcarbazole C‐nucleoside in the middle of the chain have been synthesized and studied for their potential as hybridization probes for sequences containing thiopyrimidine nucleobases. All of these oligonucleotides formed very stable duplexes with complementary sequences pairing the organometallic moiety with either 2‐ or 4‐thiothymine. The isomeric monomercurated oligonucleotides were also able to discriminate between 2‐ and 4‐thiothymine based on the different melting temperatures of the respective duplexes. DFT‐optimized structures of the most stable mononuclear HgII‐mediated base pairs featured a coordinated covalent bond between HgII and either S2 or S4 and a hydrogen bond between the carbazole nitrogen and N3. The dinuclear HgII‐mediated base pairs, in turn, were geometrically very similar to the one previously reported to form between 1,8‐dimercuri‐6‐phenylcarbazole and thymine and had one HgII ion coordinated to a thio and the other one to an oxo substituent.
Interface Engineering of Conjugated Polymer‐Based Composites for Photocatalysis
Authors: Xiao Ziheng , Xiao Jie , Sun Qian , Wang Yifan , Pan Lun , Shi Chengxiang , Zhang Xiangwen , Zou Ji‐Jun
Published: September 2022

Photocatalysis can create a green way to produce clean energy resources, degrade pollutants and achieve carbon neutrality, making the construction of efficient photocatalysts significant in solving environmental issues. Conjugated polymers (CPs) with adjustable band structures have superior light‐absorption capacity and flexible morphology that facilitate contact with other components to form advanced heterojunctions. Interface engineering can strengthen the interfacial contact between the components and further enlarge the interfacial contact area, enhance light absorption, accelerate charge transfer and improve the reusability of the composites. In order to throw some new light on heterojunction interface regulation at a molecular level, herein we summarize CP‐based composites with improved photocatalytic performance according to the types of interactions (covalent bonding, hydrogen bonding, electrostatic interactions, π‐π stacking, and other polar interactions) between the components and introduce the corresponding interface building methods, identifying techniques. Then the roles of interfaces in different photocatalytic applications are discussed. Finally, we sum up the existing problems in interface engineering of CP‐based composites and look forward to the possible solutions.
Infusion of Variable Chemical Structure to Tune Stacking among Metal‐Organic Layers in 2D Nano MOFs
Authors: Manna Biplab , Yokoi Hiroyuki , Yamashita Akihiro , Sato Shota , Ohyama Junya , Kunitake Masashi , Ida Shintaro
Published: September 2022

Invited for the cover of this issue is the group of Biplab Manna at the University of Kumamoto. The image depicts various kinds of stacking between the metal–organic layers of MOFs. Read the full text of the article at 10.1002/chem.202201665.
Association between serum cystatin C and early impairment of cardiac function and structure in type 2 diabetes patients with normal renal function
Authors: Huang Zhuoshan , Zhong Junlin , Zhang Shaozhao , Xiong Zhenyu , Huang Yiquan , Liu Menghui , Lin Yifen , Zhong Xiangbin , Ye Xiaomin , Zhuang Xiaodong , Liao Xinxue
Published: September 2022

Background

Type 2 diabetes mellitus (T2DM) patients may have cardiac remodeling and dysfunction from the early stage of disease. This study aimed to determine the association between cystatin C (CysC) and early cardiac functional or structural impairment in T2DM patients without renal dysfunction.

Methods

A total of 1135 T2DM patients without renal dysfunction and known heart diseases were included in our study. Cardiac function and structure were evaluated by echocardiography. Patients were diagnosed as left ventricular hypertrophy (LVH), impaired left ventricular (LV) diastolic function, and categorized into four different LV geometry patterns including normal, concentric remodeling, concentric hypertrophy, and eccentric hypertrophy.

Results

In multivariate linear regression analyses, CysC was positively associated with interventricular septum, LV mass index, left atrial volume index, E/e' ratio, and negatively associated with Tissue Doppler e', E/A ratio (p < .05). As a continuous variable, increasing CysC levels were associated with prevalence of LVH (OR: 1.47, 95% confidence interval [CI]: 1.22–1.77), impaired LV diastolic function (OR: 1.58, 95% CI: 1.33–1.87), concentric hypertrophy (OR: 1.54, 95% CI: 1.23–1.93) and eccentric hypertrophy (OR: 1.34, 95% CI: 1.00–1.80) according to multivariate logistic regression analyses. While as a categorical variable, the highest CysC quartile (CysC > 1.04 mg/L) was associated with LVH (OR: 2.95, 95% CI: 1.74–5.00), impaired LV diastolic function (OR: 4.09, 95% CI: 2.54–6.60), and concentric hypertrophy (OR: 3.26, 95% CI: 2.05–5.18).

Conclusions

CysC was significantly associated with early LV remodeling and cardiac functional impairment in T2DM patients with normal renal function. It could be a reliable and convenient biomarker detecting early impairment of cardiac function and structure in T2DM patients.
7H‐Pyrrolo[2,3‐d]pyrimidine‐4‐amines as Potential Inhibitors of Plasmodium falciparum Calcium‐Dependent Protein Kinases
Authors: Seanego Tswene D. , Chavalala Hlamulo E. , Henning Hendrik H. , de Koning Charles B. , Hoppe Heinrich C. , Ojo Kayode K. , Rousseau Amanda L.
Published: September 2022

A series of pyrrolo[2,3‐d]pyrimidines were designed in silico as potential bumped kinase inhibitors targeting P. falciparum calcium dependent protein kinase 4 (PfCDPK4), with the potential to inhibit PfCDPK1 based on earlier studies of the two kinases. A small series of these compounds were prepared and assessed for inhibitory activity against PfCDPK4 and PfCDPK1 in vitro. Four of the compounds displayed promising inhibitory activity against either PfCDPK4 (IC50=0.210–0.530 μM), or PfCDPK1 (IC50=0.589 μM). These data will enable optimisation of the molecular model to better predict inhibitory activity against PfCDPK4.
Interventions to increase racial and ethnic minority accrual into cancer clinical trials: A systematic review
Authors: Nouvini Rosa , Parker Patricia A. , Malling Charlotte D. , Godwin Kendra , Costas‐Muñiz Rosario
Published: September 2022

Background

Racial and ethnic minorities (REMs) continue to be underrepresented in clinical trials despite the 1993 National Institutes of Health's Revitalization Act mandating the representation of women and underrepresented minority groups in clinical trials. Although Blacks represent 15% and Hispanics 13% of the cancer population, their clinical trial enrollment rates are disproportionately low at 4% to 6% and 3% to 6%, respectively. A systematic review exploring interventions aimed at improving cancer clinical trial (CCT) enrollment for REMs was conducted.

Methods

A systematic search of PubMed, Cochrane CENTRAL, and Ovid PsycINFO was conducted for English‐language studies since 1993. Inclusion criteria included peer‐reviewed, US‐based studies with interventions aimed to recruit underrepresented minority adult patients into cancer clinical trials. REM groups were defined as Black, Hispanic, Asian, American Indian, and Native Hawaiian/other Pacific Islander.

Results

The systematic search identified 3123 studies, of which nine met inclusion criteria. Interventions included patient navigation/coaching (n = 4), a clinical trial educational video (n = 2), institutional research infrastructure changes (n = 1), a relationship building and social marketing recruitment model (n = 1), and cultural competency training for providers (n = 1). A statistically significant improvement in accrual was shown in three of the patient navigation interventions, one of the clinical trial educational videos and an institutional research infrastructure change.

Conclusions

This systematic review illustrates several potential mechanisms by which to increase CCT recruitment for patients of REM backgrounds in various clinical settings. More randomized controlled trials are needed to further explore the benefits of these interventions for REMs.
Oncological and functional outcomes of men undergoing primary whole gland cryoablation of the prostate: A 20‐year experience
Authors: Tan Wei Phin , Kotamarti Srinath , Chen Emily , Mahle Rachael , Arcot Rohith , Chang Andrew , Ayala Alexandria , Michael Zoe , Seguier Denis , Polascik Thomas J.
Published: September 2022

Background

This study reports the oncological and functional outcomes in men with localized prostate cancer (Pca) who were treated with primary whole gland cryoablation (WGC) of the prostate.

Methods

The authors retrospectively reviewed their prospectively collected cryosurgery database between January 2002 and September 2019 for men who were treated with WGC of the prostate at a tertiary referral center. Primary outcome includes biochemical recurrence‐free survival (BRFS). Secondary outcomes include failure‐free survival (FFS), metastasis‐free survival (MFS) and adverse events.

Results

A total of 260 men were included in the study. Men having had prior treatment for Pca were excluded. Median follow‐up was 107 months (interquartile range [IQR], 68.3–132.5 months). BRFS, FFS, and MFS at 10 years were 84%, 66%, and 96%, respectively. High risk D'Amico classification was associated with a lower BRFS and FFS on multivariable analysis. No patient had any Pca‐related death during follow‐up. American Urological Association symptoms score and bother index were unchanged following cryoablation. Median International Index of Erectile Function score precryoablation and post‐cryoablation was 7 (IQR, 3–11) and 1 (IQR, 1–5), respectively. Stress urinary incontinence, defined as requiring any protective pads only occurred in five patients (2%). No patient developed a fistula. Grade > 2 Clavien‐Dindo adverse events occurred in six (2.3%) patients.

Conclusion

WGC of the prostate can achieve excellent oncological and functional outcomes in men with localized Pca at the 10‐year mark. Primary WGC may be a good option for men who desire to preserve urinary continence and have an excellent oncologic outcome.

Lay summary

Primary whole gland cryoablation is an alternative treatment option to radical prostatectomy and radiotherapy for men with organ‐confined prostate cancer.

Patients had excellent cancer outcomes 1 years after whole gland cryoablation, and patients with PSA nadir 0.1 ng/ml or lower after treatment were less likely to have disease recurrence.
Blockchain‐based security enhancement mechanism for employee performance assessment system
Authors: Vignesh Ramamoorthi , Prasad Kulasekaran Mohana
Published: September 2022

In the proposed approach, the blockchain based employee performance assessment system is introduced to enhance the security and privacy of employee data. The proposed three phases are used to enhance the security mechanism in the employee performance assessment system: authentication, encryption, and data retrieval phase. The authentication process is performed in the first phase by utilizing Lamport Merkle digital signature (LMDS) algorithm. The LMDS algorithm generates and verifies a digital ID for each employee. In the next phase blockchain based encryption is carried on employee data using the new light weight cryptography algorithm (NLCA), which uses a 16 bytes (128 bit) block cipher and needs 16 bytes (128‐bit) key to encrypt the data. At last, the data retrieval phase allows users to access the data through the secret key. Proposing a modified Diffie‐Hellman (ReDH) algorithm to exchange the secret key to ensure security. The proposed approach is implemented in the Python platform, and the performance of the proposed approach is compared with existing methods in terms of encryption time, throughput, decryption time, storage efficiency, and search time. Using a blockchain‐based employee performance assessment system enhances system trust level, transparency, accountability, and security efficiency.
Understanding the Surprising Oxidation Chemistry of Au−OH Complexes
Authors: Engbers Silène , Klein Johannes E. M. N.
Published: September 2022

Au is known to be fairly redox inactive (in catalysis) and bind oxygen adducts only quite weakly. It is thus rather surprising that stable Au−OH complexes can be synthesized and used as oxidants for both one‐ and two‐electron oxidations. A charged AuIII−OH complex has been shown to cleave C−H and O−H bonds homolytically, resulting in a one‐electron reduction of the metal center. Contrasting this, a neutral AuIII−OH complex performs oxygen atom transfer to phosphines, resulting in a two‐electron reduction of the hydroxide proton to form a AuIII−H rather than causing a change in oxidation state of the metal. We explore the details of these two examples and draw comparisons to the more conventional reactivity exhibited by AuI−OH. Although the current scope of known Au−OH oxidation chemistry is still in its infancy, the current literature exemplifies the unique properties of Au chemistry and shows promise for future findings in the field.
Metabolic Tumor Imaging with Rapidly Signal‐Enhanced 1‐13C‐Pyruvate‐d3
Authors: Hune Theresa , Mamone Salvatore , Schroeder Henning , Jagtap Anil P. , Sternkopf Sonja , Stevanato Gabriele , Korchak Sergey , Fokken Claudia , Müller Christoph A. , Schmidt Andreas B. , Becker Dorothea , Glöggler Stefan
Published: September 2022

The metabolism of malignant cells differs significantly from that of healthy cells and thus, it is possible to perform metabolic imaging to reveal not only the exact location of a tumor, but also intratumoral areas of high metabolic activity. Herein, we demonstrate the feasibility of metabolic tumor imaging using signal‐enhanced 1‐13C‐pyruvate‐d3, which is rapidly enhanced via para‐hydrogen, and thus, the signal is amplified by several orders of magnitudes in less than a minute. Using as a model, human melanoma xenografts injected with signal‐enhanced 1‐13C‐pyruvate‐d3, we show that the conversion of pyruvate into lactate can be monitored along with its kinetics, which could pave the way for rapidly detecting and monitoring changes in tumor metabolism.
The contribution of Indigenous stewardship to an historical mixed‐severity fire regime in British Columbia, Canada
Authors: Copes‐Gerbitz Kelsey , Daniels Lori D. , Hagerman Shannon M.
Published: September 2022

Indigenous land stewardship and mixed‐severity fire regimes both promote landscape heterogeneity, and the relationship between them is an emerging area of research. In our study, we reconstructed the historical fire regime of Ne Sextsine, a 5900‐ha dry, Douglas fir–dominated forest in the traditional territory of the T'exelc (Williams Lake First Nation) in British Columbia, Canada. Between 1550 and 1982 CE, we found median fire intervals of 18 years at the plot level and 4 years at the study‐site level. Ne Sextsine was characterized by an historical mixed‐severity fire regime, dominated by frequent, low‐severity fires as indicated by fire scars, with infrequent, mixed‐severity fires indicated by cohorts. Differentiating low‐ from mixed‐severity plots over time was key to understanding the drivers of the fire regime at Ne Sextsine. Low‐severity plots were coincident with areas of highest use by the T'exelc, including winter village sites, summer fishing camps, and travel corridors. The high fire frequency in low‐severity plots ceased in the 1870s, following the smallpox epidemic, the forced relocation of Indigenous peoples into small reserves, and the prohibition of Indigenous burning. In contrast, the mixed‐severity plots were coincident with areas where forest resources, such as deer or certain berry species, were important. The high fire frequency in the mixed‐severity plots continued until the 1920s when industrial‐scale grazing and logging began, facilitated by the establishment of a nearby railway. T'exelc oral histories and archeological evidence at Ne Sextsine speak to varied land stewardship, reflected in the spatiotemporal complexity of low‐ and mixed‐severity fire plots. Across Ne Sextsine, 63% of cohorts established and persisted in the absence of fire after colonial impacts beginning in the 1860s, resulting in a dense, homogeneous landscape that no longer supports T'exelc values and is more likely to burn at uncharacteristic high severities. This nuanced understanding of the Indigenous contribution to a mixed‐severity fire regime is critical for advancing proactive fire mitigation that is ecoculturally relevant and guided by Indigenous expertise.
Opposite effects of nutrient enrichment and an invasive snail on the growth of invasive and native macrophytes
Authors: Yan Yimin , Oduor Ayub M. O. , Li Feng , Xie Yonghong , Liu Yanjie
Published: September 2022

Many ecosystems are now co‐invaded by alien plant and herbivore species. The evolutionary naivety of native plants to alien herbivores can make the plants more susceptible to the detrimental effects of herbivory than co‐occurring invasive plants, in accordance with the apparent competition hypothesis. Moreover, the invasional meltdown hypothesis predicts that in multiply invaded ecosystems, invasive species can facilitate each other's impacts on native communities. Although there is growing empirical support for these hypotheses, facilitative interactions between invasive plants and herbivores remain underexplored in aquatic ecosystems. Many freshwater ecosystems are co‐invaded by aquatic macrophytes and mollusks and simultaneously experience nutrient enrichment. However, the interactive effects of these ecological processes on native macrophyte communities remain an underexplored area. To test these effects, we performed a freshwater mesocosm experiment in which we grew a synthetic native community of three macrophyte species under two levels of invasion by an alien macrophyte Myriophyllum aquaticum (invasion vs. no invasion) and fully crossed with two levels of nutrient enrichment (enrichment vs. no enrichment) and herbivory by an invasive snail Pomacea canaliculata (herbivory vs. no herbivory). In line with the invasional meltdown and apparent competition hypotheses, we found that the proportional aboveground biomass yield of the invasive macrophyte, relative to that of the native macrophyte community, was significantly greater in the presence of the invasive herbivore. Evidence of a reciprocal facilitative effect of the invasive macrophyte on the invasive herbivore is provided by results showing that the herbivore produced greater egg biomass in the presence versus in the absence of M. aquaticum. However, nutrient enrichment reduced the mean proportional aboveground biomass yield of the invasive macrophyte. Our results suggested that herbivory by invader P. canaliculata may enhance the invasiveness of M. aquaticum. However, nutrient enrichment of habitats that already harbor M. aquaticum may slow down the invasive spread of the macrophyte. Broadly, our study underscores the significance of considering several factors and their interactions when assessing the impact of invasive species, especially considering that many habitats experience co‐invasion by plants and herbivores and simultaneously undergo various other disturbances, including nutrient enrichment.
Enhanced mutualism: A promotional effect driven by bacteria during the early invasion of Phytolacca americana
Authors: Meng Yunhao , Geng Xinze , Zhu Ping , Bai Xinfu , Zhang Ping , Ni Guangyan , Hou Yuping
Published: September 2022

The enhanced mutualism hypothesis postulates that invasive plants promote self‐growth by enriching beneficial microbes to establish a positive soil feedback. However, the roles of soil microorganisms may vary with increasing time for plant growth. Research on changes in soil microbial communities over time has important implications for understanding the mechanisms underlying plant invasion. Due to the difficulty in evaluating the duration of plant growth, few studies have quantified the changes in soil microorganisms with increasing plant age. This study focuses on the invasive weed Phytolacca americana L., which has growth rings in the main root. We conducted a two‐stage experiment in the field and greenhouse to explore the soil feedback changes with duration of plant growth. We determined the effects of P. americana at different ages on the soil microbial community and soil properties and performed a soil inoculation experiment to quantify the influence of soil microbes on seed germination and seedling performance. We found that the content of some soil nutrients, namely total nitrogen, total phosphorus, nitrate‐N, and available phosphorus, significantly decreased with increasing growth age of P. americana, whereas the available potassium showed an opposite increasing trend. The P. americana growth age also significantly influenced the soil bacterial community structure. However, this phenomenon did not occur in the fungal community. In the bacterial community, the relative abundance of plant growth‐promoting bacteria showed an increasing trend. The soil inoculation experiment had high seed germination rates and biomass accumulation when the plants were grown in conditioned soil from P. americana growth within 5 years, suggesting a positive plant–soil feedback. However, the promoting effect disappeared in conditioned soil from 10 years of age. Our findings demonstrate that plant growth‐promoting bacteria significantly accumulated in the soil during the early stages of P. americana invasion, and that the strength of enhanced positive feedback may play a crucial role in facilitating P. americana invasion. This study highlights the changing nature of plant–microbe interactions during biological invasion and illustrates how bacteria could contribute to the initial success of P. americana, providing new insights into the underlying mechanisms of plant invasion.
Are experiment sample sizes adequate to detect biologically important interactions between multiple stressors?
Authors: Burgess Benjamin J. , Jackson Michelle C. , Murrell David J.
Published: September 2022

As most ecosystems are being challenged by multiple, co‐occurring stressors, an important challenge is to understand and predict how stressors interact to affect biological responses. A popular approach is to design factorial experiments that measure biological responses to pairs of stressors and compare the observed response to a null model expectation. Unfortunately, we believe experiment sample sizes are inadequate to detect most non‐null stressor interaction responses, greatly hindering progress. Using both real and simulated data, we show sample sizes typical of many experiments (<6) can (i) only detect very large deviations from the additive null model, implying many important non‐null stressor‐pair interactions are being missed, and (ii) potentially lead to mostly statistical outliers being reported. Computer code that simulates data under either additive or multiplicative null models is provided to estimate statistical power for user‐defined responses and sample sizes, and we recommend this is used to aid experimental design and interpretation of results. We suspect that most experiments may require 20 or more replicates per treatment to have adequate power to detect nonadditive. However, estimates of power need to be made while considering the smallest interaction of interest, i.e., the lower limit for a biologically important interaction, which is likely to be system‐specific, meaning a general guide is unavailable. We discuss ways in which the smallest interaction of interest can be chosen, and how sample sizes can be increased. Our main analyses relate to the additive null model, but we show similar problems occur for the multiplicative null model, and we encourage similar investigations into the statistical power of other null models and inference methods. Without knowledge of the detection abilities of the statistical tools at hand or the definition of the smallest meaningful interaction, we will undoubtedly continue to miss important ecosystem stressor interactions.
The influence of sugarcane pre‐harvest fire on hantavirus prevalence in Neotropical small mammals
Authors: Gheler‐Costa Carla , Sabino‐Santos Gilberto , Rosalino Luís Miguel , Amorim Luana Santos , Maia Felipe Gonçalves M. , de Andrade Moral Rafael , Ferreira Iuri E. P. , Figueiredo Luiz‐Thadeu M. , Piña Carlos I. , Verdade Luciano M.
Published: September 2022

The use of pre‐harvest fire in sugarcane fields surprisingly results in an increase in the abundance of Neotropical Sigmodontinae rodents, which might carry hantavirus. By contrast, fire suspension induces a decline in rodents in the first 5 years. The present study aimed to evaluate the effect of sugarcane harvest regimes on hantavirus prevalence in wild rodents. Field collections were carried out on a sugarcane production area in Northeast São Paulo, which is responsible for 30% of the ethanol production in Brazil. A few years after pre‐harvest fire suspension, a high prevalence of hantavirus was found in small rodents at lower population density, but apparently higher population growth rate. Differences in life cycle between the rodents and their predators may explain such density patterns, as small rodents can breed twice or even three times each year, whereas their predators usually breed only once a year. Similarly, the temporal dynamics of the predator–prey relationship suggests that hantavirus prevalence is related to small rodent's population growth and not density. Only Akodon montensis, Calomys tener, and Necromys lasiurus contained immunoglobulin G antibodies against the recombinant nucleoprotein of Araraquara orthohantavirus, a genotype of Andes orthohantavirus, with no interspecific variation in seroprevalence among these species. However, males presented higher prevalence rate than females, possibly due to a male‐biased dispersal pattern and a higher frequency of antagonistic interactions. Governance measures to mitigate the role of small wild rodents on the emergence of hantavirus in agricultural landscapes dominated by sugarcane plantations should include the use of wildlife‐friendly management techniques (e.g., to mitigate the mortality of the predators of small rodents), human capacity building concerning wildlife‐related conflicts, and multifunctionality of agricultural landscapes. Future studies should prioritize the possible relationship between microhabitat structure and hantavirus prevalence in small rodents in agricultural landscapes dominated by sugarcane fields.
Synthesis of Monodisperse Colloidal ZnS Spheres by an Acid‐Free Two‐Step Approach
Authors: Fang Qianyao , Wei Wuke , Wu Chengcai , Su Xin , Wu Suli
Published: September 2022

In this work, we demonstrate a new two‐step method for preparing monodisperse ZnS colloidal spheres. The method contains a hot‐injection step for making primary particles as seeds and a heating‐up step for aggregation growth of secondary colloidal spheres. Instead of the most commonly used thioacetamide in previous studies, thiourea (TU) was selected as the sulfur source. The temperature‐dependent thermal decomposition rate of TU makes the releasing of S2− and nucleation of ZnS under proper kinetic control, meanwhile making the reaction a mild and acid‐free process. By separating the two steps and using a milder sulfur precursor, monodisperse ZnS colloidal spheres have been prepared. Their diameters can be delicately tuned in the range from 54 to 172 nm through simply changing the amount of Zn and S precursor. The optical properties of the obtained ZnS spheres were studied by extinction and PL measurements, and they exhibit size‐dependent optical behavior.
Ultra‐stable calcium ion batteries with Prussian blue nanodisks
Authors: Vo Thuan Ngoc , Kang Ji Eun , Lee Hyocheol , Lee Sang‐Wha , Ahn Suk‐kyun , Hur Jaehyun , Kim Il Tae
Published: September 2022

Calcium ion batteries, though more sustainable than lithium‐ion batteries, still face significant challenges, including the lack of highly rechargeable electrodes. Prepared Prussian blue nanodisk electrodes can significantly extend the longevity of Ca‐based cells. The method involves precipitating 20‐nm‐thick nanodisks of Prussian green from Fe(NO3)3 and K3Fe(CN)6, followed by sodiation with NaI. The Prussian‐blue‐based cathode with polyacrylic acid/polyaniline binder delivers an initial discharging capacity of 77.6 mAh g−1 at 0.1 A g−1 and retains 91.0% capacity after 700 cycles. Polyvinyl fluoride is detrimental to the Ca‐based cell, as its coulombic efficiency decreases from 94.8% (120th cycle) to 86.4% (400th cycle). With the same cathode, the Ca‐based cell is much less sensitive to high current densities than the Na‐based cell. This can be because only half the amount of cations is required to move in Ca‐based systems compared to Na‐based systems; thus, the charge‐transfer resistance is noticeably reduced in Ca‐based systems.

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Application of a Screening-Level Pollinator Risk Assessment Framework to Trisiloxane Polyether Surfactants
Authors: Collins Jennifer K. , Jackson Jennifer M.
Published: September 2022

Regulatory requirements exist to assess the potential impacts of pesticides on insect pollinators, but “inert,” coformulants to pesticide formulations are not included in standard regulatory risk assessments. Some publications in the open literature have suggested that the agricultural uses of “inert” ingredients, including trisiloxane polyether surfactants, may result in adverse effects on pollinators. We conducted a screening-level risk assessment to evaluate the potential risk to insect pollinators, using honey bees (Apis mellifera) as a surrogate, from exposure to three trisiloxane polyether surfactants based on agricultural application scenarios following the current US Environmental Protection Agency (USEPA) guidance. The exposure assessment included data from two sources: (1) use data reported in California's (USA) Pesticide Use Registry (PUR) database for all crops, and (2) an almond orchard residue study conducted using the three trisiloxane polyether surfactants. Honey bee laboratory studies with each of the trisiloxane polyether surfactants reported 50% lethal doses (LD50s) or no adverse effect levels, which were used as the effects inputs to BeeREX. The exposure and toxicity data were combined to estimate potential honey bee risk based on the determination of acute and chronic risk quotients (RQs) for larval and adult life stages. The RQs calculated using both the PUR use rates as well as the application rates and peak measured residues from the almond orchard residue study were below the USEPA acute and chronic levels of concern (acute, 0.4; chronic, 1.0). Based on these results, the use of these three trisiloxane polyether surfactants in agricultural use settings can be considered minimal risk to insect pollinators, and higher tier assessment is unnecessary for the characterization of risk. Environ Toxicol Chem 2022;41:3084–3094. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.