bluuebunny/crossref_metadata_2025_split huggingface dataset:
Main anatomical characteristics of the hominin fossil humeri from the Sima de los Huesos Middle Pleistocene site, Sierra de Atapuerca, Burgos, Spain: An update
Authors: Carretero José‐Miguel , García‐González Rebeca , Rodríguez Laura , Arsuaga Juan‐Luis 
Published: March 2023

AbstractSome of the Sima de los Huesos (SH) humeri have been previously studied and described elsewhere. Here we present an updated inventory and a review of the specimens recovered to the present day. The morphological key traits of the adult and subadult specimens are described, discussed, and illustrated. The SH humeri share with Neandertals many traits usually considered to be Neandertal specializations, thus, most of this morphological pattern is not exclusive to them. The variation found within fossil samples stresses the frequential nature of all these traits and in the specific case of the SH humeri, most of the traits considered as phylogenetically relevant are retained by their descendants, the Neandertals. Some traits are plesiomorphic for the entire genus Homo or are present in European hominins since the early Pleistocene. Finally, some other traits display high variability within the SH sample or different hominin samples and are of uncertain phylogenetic value. Altogether, this evidence is consistent with the hypothesis based on the overall cranial and postcranial morphology that the SH hominins are a sister group to the later Neandertals.
Comparative analysis of the two suborders of Thysanoptera and characterization of the complete mitochondrial genome of Thrips parvispinus
Authors: Pakrashi Avas , Patidar Abhishek , Singha Devkant , Kumar Vikas , Tyagi Kaomud 
Published: March 2023

AbstractThrips parvispinus is a serious sucking pest on a number of economically important crops in the oriental region. It has gained importance recently for its drastic range extension distribution as an invasive pest. Here, the complete mitochondrial genome (15,067 bp) of Thrips parvispinus was sequenced and characterized. It possesses 37 genes and the putative noncoding region is duplicated. Comparative analyses of nucleotide diversity, skewness, codon usage bias, and selection pressure in mitochondrial protein‐coding genes of the available 31 thrips mitogenomes (24 Terebrantia + 7 Tubulifera) were performed. Phylogenetic analysis showed a sister relationship of T. parvispinus to the clade (T. florum + T. hawaiiensis). Phylogenetic analyses formed the monophyly of subfamilies Phlaeothripinae and Idolothripinae within the family Phlaeothripidae (Suborder Tubulifera). Low nucleotide diversity was indicative of reversal of strand asymmetry in the Tubulifera. Neutrality analysis showed that directional mutation plays a major role in shaping codon usage bias in both suborders. Principal component analysis indicated distinct codon usage patterns in each suborder. Our data suggested weaker selection constrains on Terebrantia than in the Tubulifera. More tubuliferan mitogenomes are required to resolve previous classification hypotheses and elucidate genome evolution in these two suborders.
Preclinical evaluation of the Versius surgical system: A next‐generation surgical robot for use in minimal access prostate surgery
Authors: Vasdev Nikhil , Charlesworth Philip , Slack Mark , Adshead Jim 
Published: March 2023

AbstractObjectivesTo evaluate the Versius surgical system for robot‐assisted prostatectomy in a preclinical cadaveric model using varying system setups and collect surgeon feedback on the performance of the system and instruments, in line with IDEAL‐D recommendations.Materials and methodsProcedures were performed in cadaveric specimens by consultant urological surgeons to evaluate system performance in completing the surgical steps required for a prostatectomy. Procedures were conducted using either a 3‐arm or 4‐arm bedside unit (BSU) setup. Optimal port placements and BSU layouts were determined and surgeon feedback collected. Procedure success was defined as the satisfactory completion of all steps of the procedure, according to the operating surgeon.ResultsAll four prostatectomies were successfully completed; two were completed with a 3‐arm BSU setup and two using a 4‐arm BSU setup. Small adjustments were made to the port and BSU positioning, according to surgeon preference, in order to complete the surgical steps. The surgeons noted some instrument difficulties with the Monopolar Curved Scissor tip and the Needle Holders, which were subsequently refined between the first and second sessions of the study, in line with surgeon feedback. Three cystectomies were also successfully completed, demonstrating the capability of the system to perform additional urological procedures.ConclusionsThis study provides a preclinical assessment of a next‐generation surgical robot for prostatectomies. All procedures were completed successfully, and port and BSU positions were validated, thus supporting the progression of the system to further clinical development according to the IDEAL‐D framework.
Online practical assessment in biochemistry designed on Bloom's taxonomy to assess the student's competency: Prior exposure of the students to online tools beneficial
Authors: Kempegowda Swetha Nagarahalli , Ramachandra Shobha Chikkavaddaragudi , Arun Brunda , Devaraju Abhijith , Shivashankar Kusuma Kasapura , Raghunathachar Sahana Kabbathy , Bettadapura Anjalidevi Shankarrao , Puttalingaiah Sujatha , Devegowda Devananda , Vishwanath Prashant , Nataraj Suma Maduvanahalli , Prashant Akila 
Published: March 2023

AbstractOnline assessments are needed during the prevailing pandemic situation to continue educational activities while ensuring safety. After conducting the online practical assessment (OPrA) in Biochemistry, we analyzed the students' responses. The blueprint of the OPrA was prepared by the faculty, referring to the various levels and domains of Bloom's taxonomy. Four components were chosen for the online assessment: digital spotters, enumerating the steps of objective structured practical examination, interpretation of quantitative estimation, and case discussion. Each faculty assessed about 12–13 students in separate breakout rooms over 15–20 min on all four components. Feedback on the conduct of the examination was collected from the students and faculty anonymously and analyzed. Out of the 200 students who attended the online assessment, only one scored less than 50%, majority of them scored between 71% and 90%. Under the individual exercises, the average score of students in “Spotters” was 9.8 out of 10; in “OSPE,” 8.7 out of 10; in “Quantitative experiments,” 15.2 out of 20 and in “Case discussion,” 22.4 out of 30. Around 20% had previous experience attending the OPrA. They differed in their opinion from the rest of the students on five aspects; time allotted for the assessment (p value = 0.02, χ2 = 5.07), students using unfair means during the online viva (p value = 0.02, χ2 = 5.57), their computing skills (p value = 0.001, χ2 = 19.82), their performance (p value = 0.001, χ2 = 8.84), and overall conduct of the examination (p value = 0.001, χ2 = 15.55). OPrA tools may be designed referring to Bloom's taxonomy, and prior exposure to the online tools may benefit the students.
Application of QbD‐based approach to the development and validation of an RP‐HPLC method for simultaneous estimation of pregabalin and naringin in dual‐drug loaded liposomes
Authors: Gupta Isha , Adin Syeda Nashvia , Aqil Mohd. , Mujeeb Mohd. , Akhtar Mohd. 
Published: March 2023

AbstractThe current work delineates the development of a novel, rugged and sensitive stability‐indicating risk‐based HPLC method based on an analytical quality‐by‐design (QbD) approach for the concurrent estimation of naringin and pregabalin in dual‐drug‐loaded nanopharmaceuticals. Preliminary screening trials were conducted, along with systemic risk analysis, in order to identify the critical method attributes, namely injection volume, pH and acetonitrile content, that influence critical quality attributes. The Box–Behnken design was used to optimize the tailing factor as a response to pregabalin and naringin in a short run time. The chromatographic conditions were improved by running 17 experimental runs generated by design expert software. After analysing the optimized zone within the confines of the design space, the following chromatographic conditions were chosen: mobile phase water–acetonitrile adjusted to pH 6.9 with phosphate buffer (80:20, %v/v), at flow rate of 1.0 ml/min using a C18 analytical column at an isobestic wavelength of 212 nm. Furthermore, the optimized method was validated in accordance with International Conference on Harmonization guidelines and was found to be within the prescribed limits. The developed RP‐HPLC method has a high degree of practical utility in in vivo and in vitro studies for the synchronous detection of pregabalin and naringin in pharmaceutical nanodosage forms such as protein‐based nanoparticles, nanocrystals, polymeric nanoparticles and metallic nanoparticles.
Incorporating a Polyethyleneglycol Linker to Enhance the Hydrophilicity of Mitochondria‐Targeted Triphenylphosphonium Constructs
Authors: Uno Shinpei , Harkiss Alexander H. , Chowdhury Roy , Caldwell Stuart T. , Prime Tracy A. , James Andrew M. , Gallagher Brendan , Prudent Julien , Hartley Richard C. , Murphy Michael P. 
Published: March 2023

AbstractThe targeting of bioactive molecules and probes to mitochondria can be achieved by coupling to the lipophilic triphenyl phosphonium (TPP) cation, which accumulates several hundred‐fold within mitochondria in response to the mitochondrial membrane potential (Δψm). Typically, a simple alkane links the TPP to its “cargo”, increasing overall hydrophobicity. As it would be beneficial to enhance the water solubility of mitochondria‐targeted compounds we explored the effects of replacing the alkyl linker with a polyethylene glycol (PEG). We found that the use of PEG led to compounds that were readily taken up by isolated mitochondria and by mitochondria inside cells. Within mitochondria the PEG linker greatly decreased adsorption of the TPP constructs to the matrix‐facing face of the mitochondrial inner membrane. These findings will allow the distribution of mitochondria‐targeted TPP compounds within mitochondria to be fine‐tuned.
Computationally Supported Inversion of Ketoreductase Stereoselectivity
Authors: Delgado‐Arciniega Estela , Wijma Hein J. , Hummel Chantal , Janssen Dick B. 
Published: March 2023

AbstractWhereas directed evolution and rational design by structural inspection are established tools for enzyme redesign, computational methods are less mature but have the potential to predict small sets of mutants with desired properties without laboratory screening of large libraries. We have explored the use of computational enzyme redesign to change the enantioselectivity of a highly thermostable alcohol dehydrogenase from Thermus thermophilus in the asymmetric reduction of ketones. The enzyme reduces acetophenone to (S)‐1‐phenylethanol. To invert the enantioselectivity, we used an adapted CASCO workflow which included Rosetta for enzyme design and molecular dynamics simulations for ranking. To correct for unrealistic binding modes, we used Boltzmann weighing of binding energies computed by a linear interaction energy approach. This computationally cheap method predicted four variants with inverted enantioselectivity, each with 6–8 mutations around the substrate‐binding site, causing only modest reduction (2‐ to 7‐fold) of kcat/KM values. Laboratory testing showed that three variants indeed had inverted enantioselectivity, producing (R)‐alcohols with up to 99 % enantiomeric excess. The broad substrate range allowed reduction of acetophenone derivatives with full conversion to highly enantioenriched alcohols. The results demonstrate the use of computational methods to control ketoreductase stereoselectivity in asymmetric transformations with minimal experimental screening.
Micro/nano‐wrinkled elastomeric electrodes enabling high energy storage performance and various form factors
Authors: Yoo Changeun , Lee Seokmin , Song Yongkwon , Chang Woojae , Park Moon Kyu , Ko Younji , Cho Jinhan 
Published: March 2023

AbstractStretchable elastomer‐based electrodes are considered promising energy storage electrodes for next‐generation wearable/flexible electronics requiring various shape designs. However, these elastomeric electrodes suffer from the limited electrical conductivity of current collectors, low charge storage capacities, poor interfacial interactions between elastomers and conductive/active materials, and lack of shape controllability. In this study, we report hierarchically micro/nano‐wrinkle‐structured elastomeric electrodes with notably high energy storage performance and good mechanical/electrochemical stabilities, simultaneously allowing various form factors. For this study, a swelling/deswelling‐involved metal nanoparticle (NP) assembly is first performed on thiol‐functionalized polydimethylsiloxane (PDMS) elastomers, generating a micro‐wrinkled structure and a conductive seed layer for subsequent electrodeposition. After the assembly of metal NPs, the conformal electrodeposition of Ni and NiCo layered double hydroxides layers with a homogeneous nanostructure on the micro‐wrinkled PDMS induces the formation of a micro/nano‐wrinkled surface morphology with a large active surface area and high electrical conductivity. Based on this unique approach, the formed elastomeric electrodes show higher areal capacity and superior rate capability than conventional elastomeric electrodes while maintaining their electrical/electrochemical properties under external mechanical deformation. This notable mechanical/electrochemical performance can be further enhanced by using spiral‐structured PDMS (stretchability of ~500%) and porous‐structured PDMS (areal capacity of ~280 μAh cm−2).
Synergistic interactions between the charge‐transport and mechanical properties of the ionic‐liquid‐based solid polymer electrolytes for solid‐state lithium batteries
Authors: Agrawal Ashutosh , Yari Saeed , Hamed Hamid , Gouveia Tom , Lin Rongying , Safari Mohammadhosein 
Published: March 2023

AbstractThe performance sensitivity of the solid‐state lithium cells to the synergistic interactions of the charge‐transport and mechanical properties of the electrolyte is well acknowledged in the literature, but the quantitative insights therein are very limited. Here, the charge‐transport and mechanical properties of a polymerized ionic‐liquid‐based solid electrolyte are reported. The transference number and diffusion coefficient of lithium in the concentrated solid electrolyte are measured as a function of concentration and stack pressure. The elastoplastic behavior of the electrolyte is quantified under compression, within a home‐made setup, to substantiate the impact of stack pressure on the stability of the Li/electrolyte interface in the symmetric lithium cells. The results spotlight the interaction between the concentration and thickness of the solid electrolyte and the stack pressure in determining the polarization and stability of the solid‐state lithium batteries during extended cycling.
De‐Risking S‐F Bond Formation: A Gas Cylinder‐Free Strategy to Access S(IV) and S(VI) Fluorinated Compounds**
Authors: Kordnezhadian Reza , Zogu Armir , Borgarelli Carlotta , Van Lommel Ruben , Demaerel Joachim , De Borggraeve Wim M. , Ismalaj Ermal 
Published: March 2023

AbstractThe sulfur‐fluorine partnership occupies a privileged position in fluorine chemistry given the functional versatility that it imparts to organic structures. Despite this, available methodologies to forge S−F bonds are limited compared to C−F bond formation. Here, we describe a synthetic protocol that selectively enables the oxidative halogenation of aliphatic, aromatic, and heteroaromatic thiols to their corresponding SF4Cl, SO2F and SF3 derivatives. Selective oxidation of thiols to either S(IV)‐F or S(VI)‐F compounds is achieved by employing bench‐stable calcium hypochlorite as chlorine surrogate (CLOgen), in the presence of KF as fluoride source. Density functional theory (DFT) calculations provided insight into the mechanistic aspects of the transformation and rationalized the observed isomeric preference towards the SF4Cl derivatives. Ultimately, this glovebox‐free method selectively dispatches three classes of compounds upon reaction condition fine‐tuning. Furthermore, first‐in‐class transformations are reported, including the preparation of aliphatic SF4Cl intermediates, their transformation into aliphatic sulfur pentafluoride analogs, and post‐functionalizations that allow accessing highly complex SF4‐bridged scaffolds.
Adsorption‐Induced In‐Situ Construction of TiO2 Hollow Sphere/UiO‐66‐NH2 Heterostructures with Boosted Photocatalytic Activity toward Cr(VI) Reduction
Authors: Xu Qiankun , Li Yaru , Ji Wen , Mei Jun , Wang Xianbiao 
Published: March 2023

AbstractWater contamination caused by highly toxic Cr(VI) should be resolved imminently with a more efficient photocatalytic approach. The interaction between photocatalyst heterostructure is critical for charge separation which largely affects the photocatalytic efficiency. Herein, TiO2 hollow sphere/UiO‐66‐NH2 (TiO2/UiO‐66‐NH2) heterostructures were successfully synthesized by an adsorption‐induced in‐situ solvothermal growth strategy. The UiO‐66‐NH2 particles were well dispersed on TiO2 hollow spheres by solvothermal treatment of Zr4+ adsorbed TiO2 hollow spheres with NH2‐BDC ligand. The photocatalytic activities of TiO2/UiO‐66‐NH2 heterostructures were investigated by reduction of Cr(VI) with visible light irradiation. With the introduction of UiO‐66‐NH2, the reduction efficiency toward Cr(VI) by TiO2/UiO‐66‐NH2 heterostructures reached 89% after 180 min of irradiation, which is much higher than those of TiO2 hollow spheres (10%) and UiO‐66‐NH2 crystals (29%). Moreover, the TiO2/UiO‐66‐NH2 heterostructures display good regeneration ability and can still maintain 70% of Cr(VI) removal ability after four cycles. The integration of TiO2 and UiO‐66‐NH2 could construct a type‐II heterojunction to broaden the absorption range of light and suppress the recombination of photoproduced electrons and holes. As a result, such unique composite structure significantly enhance the photocatalytic performance towards Cr(VI) reduction. This work not only inspires a new approach for in‐situ solvothermal synthesis of semiconductor@MOFs composites, but provides a novel photocatalyst for highly efficient removal of Cr(VI) from wastewater.
Indirect Nuclear Spin‐Spin Exchange Coupling through Solvated Electron in Small Sizes of Cyclic and Cage‐Shaped Perfluoroalkanes
Authors: Chen Xiao , Bu Yuxiang 
Published: March 2023

AbstractSmall perfluorocycloalkanes (hexafluorocyclopropane (c‐C3F6), octafluorocyclobutane (c‐C4F8) and decafluorocyclopentane (c‐C5F10) and cage‐shaped perfluoroalkanes (perfluoro tetrahedral alkane (C4F4), perfluoro prismane (C6F6) and perfluoro cubane (C8F8)) are better electron scavengers. The captured excess electrons are weakly bound inside their backbone voids or over their backbones, forming the solvated electron (
) systems (e@c‐CnF2ns (n=3, 4, 5) and e@CnFn (n=4, 6, 8)). There have been many studies on the structures and properties of such
systems. However, the effect of
on the indirect nuclear spin‐spin coupling (J‐coupling) is unknown. In this work, we explore how
affects NeJ‐coupling between two coupled F nuclei (NeJFF‐coupling) in perfluoroalkane
systems through density functional theory calculations. We find unusual trans‐NeJFF‐couplings (two coupled F nuclei in trans‐position) in e@c‐CnF2n (n=3, 4, 5) and NeJFF‐couplings in e@CnFn (n=4, 6, 8). One excess electron not only changes the molecular structures, but also enforces unique distributions and properties, depending on the structural characteristics. We also confirm that such unusual NeJFF‐couplings are realized by through‐
(T‐SE) transmission mechanism, rather than the conventional through‐bonds (T−B)/through‐space (T−S) ones. The novel transmission mechanism consists of the T‐SE coupling path (path 1) and
‐enhanced T−B
T−S coupling path (path 2), and the two paths jointly control NeJFF through cooperation and competition. Interestingly, the former plays a dominant role for long‐range NeJFF‐coupling (N=5), while the latter plays a role in the short‐range NeJFF‐coupling (N=3, 4). Path bending angle mainly influences path 1, while path 2 is mainly influenced by the path length. This work not only provides novel insights into the mediating role of
in the coupling information exchange, but also proposes a new
‐based coupling mechanism, possibly opening up potential applications for the
‐based indirect nuclear spin couplings.
Influence of the Thiophene Ring on the Molecular Order of Structurally Simple π‐Conjugated Smectogens: 13C NMR Study
Authors: Veeraprakash Bathini , Pratap Gallelli , Lobo Nitin P. , Ramanathan Krishna V. , Narasimhaswamy Tanneru 
Published: March 2023

AbstractStructurally simple rod‐like π‐conjugated mesogens with thiophene directly connected to phenyl, biphenyl, and fluorenone rings with terminal chains are synthesized respectively. The occurrence of smectic A/smectic C phases is concurred by a hot‐stage optical polarising microscope (HOPM), differential scanning calorimetry (DSC), and X‐ray diffraction (XRD). The static 1D and 2D 13C nuclear magnetic resonance (NMR) studies in the liquid crystalline phase are carried out to find the alignment‐induced chemical shifts (AIS) and 13C−1H dipolar couplings. The orientational order parameters of the mesogens determined from 13C−1H dipolar couplings disclose that the long axis is not only collinear to the C3−C4 bond of the thiophene ring but also for the local axes of phenyl and biphenyl rings. For fluorenone‐based mesogen, the molecular biaxiality is found to be high owing to the increased breadth of the molecule. The study unveils that the orientation of thiophene and the phenyl rings is similar in the current mesogens in stark contrast to mesogens, where thiophene is connected to phenyl rings through linking groups.
Intrinsically Chiral Twist‐Bend Nematogens: Interplay of Molecular and Structural Chirality in the NTB Phase
Authors: Walker Rebecca , Pociecha Damian , Salamonczyk Miroslaw , Storey John M. D. , Gorecka Ewa , Imrie Corrie T. 
Published: March 2023

AbstractThe front cover artwork is provided by Dr Rebecca Walker of the Liquid Crystals Group at the University of Aberdeen. The image is a cartoon depiction of the formation of the heliconical chiral twist‐bend nematic phase (N*TB) from its constituent bent molecules. The presence of a single enantiomer of the chiral, lactate‐based liquid crystal dimers biases the formation of helices with only one handedness, unlike in the conventional NTB phase, observed for achiral molecules, for which the left‐ and right‐handed helices are doubly degenerate. Read the full text of the Research Article at 10.1002/cphc.202200807.