Typical Conformation Research Articles

The crystal structure of the N-terminal domain of the backbone pilin LrpA reveals a new closure-and-twist motion for assembling dynamic pili in Ligilactobacillus ruminis.

Sortase-dependent pili are long surface appendages that mediate attachment, colonization and biofilm formation in certain genera and species of Gram-positive bacteria. Ligilactobacillus ruminis is an autochthonous gut commensal that relies on sortase-dependent LrpCBA pili for host adherence and persistence. X-ray crystal structure snapshots of the backbone pilin LrpA were captured in two atypical bent conformations leading to a zigzag morphology in the LrpCBA pilus structure. Small-angle X-ray scattering and structural analysis revealed that LrpA also adopts the typical linear conformation, resulting in an elongated pilus morphology. Various conformational analyses and biophysical experiments helped to demonstrate that a hinge region located at the end of the flexible N-terminal domain of LrpA facilitates a new closure-and-twist motion for assembling dynamic pili during the assembly process and host attachment. Further, the incongruent combination of flexible domain-driven conformational dynamics and rigid isopeptide bond-driven stability observed in the LrpCBA pilus might also extend to the sortase-dependent pili of other bacteria colonizing a host.

Compressible Hydrogels with Stabilized Chirality from Thermoresponsive Helical Dendronized Poly(phenylacetylene)s

AbstractFabrication of chiral hydrogels from thermoresponsive helical dendronized phenylacetylene copolymers (PPAs) carrying three‐fold dendritic oligoethylene glycols (OEGs) is reported. Three different temperatures, i.e. below or above cloud point temperatures (Tcps) of the copolymers, and under freezing condition, were utilized, affording thermoresponsive hydrogels with different morphologies and mechanical properties. At room temperature, transparent hydrogels were obtained through crosslinking among different copolymer chains. Differently, opaque hydrogels with much improved mechanical properties were formed at elevated temperatures through crosslinking from the thermally dehydrated and collapsed copolymer aggregates, leading to heterogeneity for the hydrogels with highly porous morphology. While crosslinking at freezing temperature synergistically through ice templating, these amphiphilic dendronized copolymers formed hydrogels with highly porous lamellar structures, which exhibited remarkable compressible properties as human articular cartilage with excellent fatigue resistance. Amphiphilicity of the dendronized copolymers played a pivotal role in modulating the network formation during the gelation, as well as morphology and mechanical performance of the resulting hydrogels. Through crosslinking, these dendronized copolymers featured with typical dynamic helical conformations were transformed into hydrogels with unprecedently stabilized helicities due to the restrained chain mobilities in the three‐dimensional networks.

Compressible Hydrogels with Stabilized Chirality from Thermoresponsive Helical Dendronized Poly(phenylacetylene)s.

Fabrication of chiral hydrogels from thermoresponsive helical dendronized phenylacetylene copolymers (PPAs) carrying three-fold dendritic oligoethylene glycols (OEGs) is reported. Three different temperatures, i.e. below or above cloud point temperatures (Tcps) of the copolymers, and under freezing condition, were utilized, affording thermoresponsive hydrogels with different morphologies and mechanical properties. At room temperature, transparent hydrogels were obtained through crosslinking among different copolymer chains. Differently, opaque hydrogels with much improved mechanical properties were formed at elevated temperatures through crosslinking from the thermally dehydrated and collapsed copolymer aggregates, leading to heterogeneity for the hydrogels with highly porous morphology. While crosslinking at freezing temperature synergistically through ice templating, these amphiphilic dendronized copolymers formed hydrogels with highly porous lamellar structures, which exhibited remarkable compressible properties as human articular cartilage with excellent fatigue resistance. Amphiphilicity of the dendronized copolymers played a pivotal role in modulating the network formation during the gelation, as well as morphology and mechanical performance of the resulting hydrogels. Through crosslinking, these dendronized copolymers featured with typical dynamic helical conformations were transformed into hydrogels with unprecedently stabilized helicities due to the restrained chain mobilities in the three-dimensional networks.

Design, synthesis and pharmacological evaluation of novel thiazole derivatives as c-Met kinase inhibitors and anticancer agents

In search of novel anticancer agents, the design and synthesis of novel sixteen thiazole derivatives (7a-p) have been reported along with their characterization using 1H NMR, 13C NMR, FT-IR, MS, and HPLC. All the synthesized compounds were evaluated against c-Met kinase, followed by anticancer evaluation of the most promising compounds using the MTT assay. The results of these studies identified compound 7a with an IC50 value of 0.4 nM against c-Met kinase along with good anticancer activity against HT29 (IC50 = 7.79 µM, SI of 6.33) and MDA-MB-231 (IC50 = 5.78 µM, SI of 8.65) cancer cell lines. In order to study the in-depth binding interactions of all the synthesized compounds at the active site of c-Met kinase using molecular docking, the typical U-shaped bent conformation of the identified compounds was predicted for all synthesized compounds. Compounds 7a and 7j were found with the best binding energy of −7.98 and −8.26 kcal/mol, respectively. The present work has led to the start-point in the design and discovery of thiazole derivatives as novel c-Met kinase inhibitors and potential anticancer agents.

Signaling Commitment via Insincere Conformity: A New Take on the Persistence of Unpopular Norms

I develop and test a theory to address instances of “visibly unpopular” norms—norms that are widely seen as neither collectively optimal nor enjoyable to conform with. Based on 76 interviews with Korean professionals engaging with a norm pertaining to excessive drinking at after-hours business gatherings ( hoesik)—widely recognized as undesirable and disapproved of by both individuals and groups—I find that conformity serves as an effective signal of commitment to exchange partners not despite of but precisely because of the conformist’s visible aversion. Insofar as typical conformity with visibly unpopular norms appears “insincere” as such, conformity may continue. Vignette experiments further validate such insincere conformity’s signaling value. The implication is that despite the prevailing notion that norms persist because they promote collectively optimal solutions or are perceived as such, norms widely acknowledged as individually and collectively suboptimal may still endure.

Metalloid-Organic Intermolecular Complexes with Charge State-Controlled Conformations.

Shape alterations of molecular systems, induced by their (electric) charging/discharging, could facilitate useful electronic and/or mechanical functions in molecular-scale devices and machines. The present study reports structures, stabilities, charge distributions, and IR spectra for a group of complexes of a main-group metalloid (boron) atom with hydrocarbon molecules. The considered systems include the smallest species demonstrating the basic principle of operation, as well as their size-extended analogues, generalizing it to larger counterparts based on such units. The system geometries vary considerably between neutral and ionic counterparts and exhibit two-three typical conformations related to twisting by up to about 90 degrees. The predicted structures correlate with specific infrared spectra, which can enable their experimental identification and transformation tracking. The above-mentioned characteristics suggest the potential utility of such systems for intermolecular switches, with the possible spectral monitoring of their functioning.

Exploring biased activation characteristics by molecular dynamics simulation and machine learning for the μ-opioid receptor.

Biased ligands selectively activating specific downstream signaling pathways (termed as biased activation) exhibit significant therapeutic potential. However, the conformational characteristics revealed are very limited for the biased activation, which is not conducive to biased drug development. Motivated by the issue, we combine extensive accelerated molecular dynamics simulations and an interpretable deep learning model to probe the biased activation features for two complex systems constructed by the inactive μOR and two different biased agonists (G-protein-biased agonist TRV130 and β-arrestin-biased agonist endomorphin2). The results indicate that TRV130 binds deeper into the receptor core compared to endomorphin2, located between W2936.48 and D1142.50, and forms hydrogen bonding with D1142.50, while endomorphin2 binds above W2936.48. The G protein-biased agonist induces greater outward movements of the TM6 intracellular end, forming a typical active conformation, while the β-arrestin-biased agonist leads to a smaller extent of outward movements of TM6. Compared with TRV130, endomorphin2 causes more pronounced inward movements of the TM7 intracellular end and more complex conformational changes of H8 and ICL1. In addition, important residues determining the two different biased activation states were further identified by using an interpretable deep learning classification model, including some common biased activation residues across Class A GPCRs like some key residues on the TM2 extracellular end, ECL2, TM5 intracellular end, TM6 intracellular end, and TM7 intracellular end, and some specific important residues of ICL3 for μOR. The observations will provide valuable information for understanding the biased activation mechanism for GPCRs.

The size and shape of snowflake-shaped polymers in dilute solution: Analytical and numerical approaches

We investigate the conformational properties of a hyper-branched polymer structure with a dendrimer-like topology, known as a snowflake polymer. This polymer is characterized by two parameters: fs, which represents the functionality of the central star-like core, and f, which represents the functionality of the side branching points. To analyze the conformational properties, we have employed various approaches, including analytical methods based on direct polymer renormalization and the Wei's approach as well as numerical molecular dynamics simulations. These methods have allowed us to estimate a size and shape characteristics of the snowflake polymer as functions of f and fs. Our results consistently illustrate that as the number of branching points increases, the typical polymer conformation becomes more effectively compact compared to a linear polymer. Overall, our study provides valuable insights into the conformational behavior of the snowflake polymer and highlights the impact of branching parameters on its overall compactness.

Characterization of a novel LTA/LPS-binding antimicrobial and anti-inflammatory temporin peptide from the skin of Fejervary limnocharis (Anura: Ranidae)

Septic shock caused by Gram-positive bacteria continues to be a major cause of morbidity and mortality in intensive care units globally. Most Temporins are excellent growth inhibitors of gram-positive bacteria and candidates for developing antimicrobial treatments due to their biological action and small molecular weight. In this study, a novel Temporin peptide from the skin of Fejervarya limnocharis frog, named as Temporin-FL, was characterized. Temporin-FL was found to adopt typical α-helical conformation in SDS solution and to exhibit selective antibacterial activity against Gram-positive bacteria through a membrane destruction mechanism. Accordingly, Temporin-FL showed protective effects against Staphylococcus aureus-induced sepsis in mice. Finally, Temporin-FL was demonstrated to exert anti-inflammatory effects by neutralizing the action of LPS/LTA and by inhibiting MAPK pathway activation. Therefore, Temporin-FL represents a novel candidate for moleculartherapy of Gram-positive bacterial sepsis.

Selectivity Rule of Cryptands for Anions: Molecular Rigidity and Bonding Site.

Cryptands utilize inside CH or NH groups as hydrogen bond (H-bond) donors to capture anions such as halides. In this work, the nature and selectivity of confined hydrogen bonds inside cryptands were computationally analyzed with the energy decomposition scheme based on the block-localized wavefunction method (BLW-ED), aiming at an elucidation of governing factors in the binding between cryptands and anions. It was revealed that the intrinsic strengths of inward hydrogen bonds are dominated by the electrostatic attraction, while the anion preferences (selectivity) of inner CH and NH hydrogen bonds are governed by the Pauli exchange repulsion and electrostatic interaction, respectively. Typical conformers of cages are classified into two groups, including the C3(h) -symmetrical conformers, in which all halide anions are located near the centroids of cages, and the "semi-open" conformers, which exhibit shifted bonding sites for different halide anions. Accordingly, the difference in governing factors of selectivity is attributed to either the rigidity of cages or the binding site of anions for these two groups. In details, the C3 conformers of NH cryptands can be enlarged more remarkably than the C3(h) -symmetrical conformers of CH cryptands as the size of anion (ionic radius) increases, resulting in the relaxation of the Pauli repulsion and a dramatic reduction in electrostatic attraction, which eventually rules the selectivity of NH cryptands for halide anions. By contrary, the CH cryptands are more rigid and cannot effectively reduce the Pauli repulsion, which subsequently governs the anion preference. Unlike C3 conformers whose rigidity determines the selectivity, semi-open conformers exhibit different binding sites for different anions. From F- to I- , the bonding site shifts toward the outside end of the pocket inside the semi-open NH cryptand, leading to the significant reduction of the electrostatic interaction that dominates the anion preference. Differently, binding sites are much less affected by the size of anion inside the semi-open CH cryptand, in which the Pauli exchange repulsion remains the key factor for the selectivity of inner hydrogen bonds.

Molecular Cloning and Characterization of a Novel Antimicrobial Peptide from the Skin of Kaloula pulchra.

Bacterial resistance to all currently available conventional antibiotics has caused a global public health crisis and led to an imperative search for new agents. Antimicrobial peptides (AMPs) are essential components of host innate immune defense against microbial invasions. The objective of this study was to report a novel AMP, brevinin-2KP, from the skin of the black Kaloula pulchra frog and describe its structural and biological characterization. The physical and chemical parameters of brevinin-2KP were predicted with the ExPASy Bioinformatics Resource Portal. The assembled sequences were aligned with ClustalW, and the phylogenetic tree was constructed using Mega. Circular dichroism (CD) experiments were carried out to identify the secondary structure and the stability of peptide in different solvent environments. The cytotoxicity of brevinin-2KP was evaluated by the MTT test. To determine antibacterial activity of brevinin- 2KP, a standard two-fold broth dilution method was used. SEM was carried out to observe the morphological change in the bacterial treated by brevinin-2KP. The live/dead bacterial viability was measured with a LIVE/DEAD® BacLight kit. Histamine release and mast cell degranulation assays were performed. The precursor of brevinin-2KP contains 72 amino acid residues, including a conserved signal peptide, acidic propeptide with KR residues, and mature peptide with a sequence of GVITDALKGAAKTVAAELLKKAHCKLTNSC. Phylogenetic analysis based on the amino acid sequences of 34 brevinin-2 peptides from 30 anuran species demonstrates that K. pulchra is genetically closely related to the genus Hylarana. The CD spectra analysis indicates that brevinin-2KP adopts random coil in the water and an organized α-helical conformation in SDS solution. Further, this secondary structure is stable under high salt and high-temperature conditions. Brevinin-2KP is weakly active towards the tested Gram-positive and Gram-negative bacteria as well as fungi due to its membranolytic action. Moreover, brevinin-2KP inhibits the proliferation of several mammal cells with IC50 values ranging from 3.27 to 59.75 μM. In addition, brevinin-2KP promotes degranulation and histamine release of mast cells, indicating that it is involved in the inflammatory response. This is the first report on AMP identified from the skin of K. pulchra. Brevinin-2KP adopts a typical amphipathic α-helix conformation in membrane mimic environment and shows antimicrobial and antitumor activities by potential membranolytic mechanism. In addition, brevinin-2KP can promote degranulation and histamine release of mast cells. Brevinin-2KP is expected to become a good drug temple molecule.

Skin Byproducts of Reinhardtius hippoglossoides (Greenland Halibut) as Ecosustainable Source of Marine Collagen

Collagen is a ubiquitous protein present in the extracellular matrix of all major metazoan animals, with approximately 28 different human collagen types described in the literature, each with unique physicochemical properties. Collagens found broad application in the cosmeceutical, pharmaceutical, and biomedical fields and can be isolated from environmentally sustainable sources such as marine byproducts, which are abundant in the fish processing industry and are highly appealing low-cost sources. In this study, marine collagen was isolated from the skins of Greenland halibut (Reinhardtius hippoglossoides), an unexplored byproduct from fish processing plants, using three different collagen extraction methods, due to the use of distinct salting-out methods using a solution of 2.6 M NaCl + 0.05 M Tris-HCl pH = 7.5, (method I); a combination of 0.7 M NaCl followed by a solution of 2.3 M NaCl + 0.05 M Tris-HCl pH = 7.5 (method II); and one method using only 0.9 M NaCl (method III), yielding COLRp_I, COLRp_II, and COLRp_III collagens. These extracted type I collagens were produced with a yield of around 2 and 4% and characterized regarding the physicochemical properties, considering possible biotechnological applications. This work evidenced that the typical triple helix structure conformation was preserved in all extraction methods, but influenced the thermal behavior, intrinsic morphology, and moisture capacity of the collagens, with interest for biotechnological application, as the incorporation as an ingredient in cosmetic formulation. Furthermore, the use of collagen isolated from skin byproducts represents a high economic value with decreasing collagen cost for industrial purposes and is also an environmentally sustainable source for industrial uses.

Nanoreactor Based on Cyclodextrin for Direct Electrocatalyzed Ammonia Synthesis.

The high-efficiency transition metal-free electrocatalytic nitrate reduction reaction (NO3-RR) for ammonia synthesis has received more attention because of its green and environmentally friendly characteristics. Here, we report an efficient electrochemical NH3 synthesis directly from purely organic macrocyclic compounds α-, β-, and γ-cyclodextrins (CDs)-catalyzed transition metal-free electroreduction of nitrate under ambient conditions. In comparison with α-, and β-CDs, parent γ-CD presented uncommon catalytic performance with a relatively higher NH3 yield that can reach up to 2.28 mg h-1 cm-2 with a Faradaic efficiency (FE) of 63.2% at -0.9 V versus a reversible hydrogen electrode in alkaline medium, and the potassium ion-coordinated γ-CD complex can achieve a maximum NH3 production rate up to 4.66 mg h-1 cm-2 with an NH3 FE of 79.3%. Further comparison with permethyl-γ-CD, d-glucose, and poly(vinyl alcohol) for the NO3-RR indicated that the typical torus-shaped cyclic conformation and edge hydroxyl groups of parent CDs play important roles in the electrocatalytic process. The K+-mediated 3D γ-CD-K+ frameworks containing six CDs as nanoreactors greatly strengthen the enrichment effect of nitrate through hydrogen-bonding interaction and electrostatic interaction and promote the mass transfer, thus leading to the efficient NO3-RR in an alkaline electrolyte. This work provides a convenient, green, and economic method for high-performance NO3-RR, which has potential applications in the fields of environment, energy, and industry.

Orthogonal conformation regulation enables highly efficient phosphorescence emission in BODIPY-fluorene derivatives without heavy atoms

The BODIPY-Fluorene derivatives with an orthogonal conformation were prepared for the emission of efficient phosphorescence. The derivatives show visible light absorption (497–513 nm), high phosphorescence quantum efficiency (36.2%) and realize control of luminescence color from green to orange-red. Typical orthogonal conformation and smaller excited state (S1 and T4) energy gap (0.05 eV) are favorable for intersystem crossing (ISC) process. The calculation are carried out for rationalization between the photophysical properties and conformation of the BODIPY-Fluorene derivatives. We demonstrate that the conformational substitution positions and the distance between D-A are promising strategy to regulate the emission lifetime and quantum efficiency for BODIPY derivatives. Moreover, the ability to generate singlet oxygen was measured by photooxidation of 1,3-diphenylisobenzofuran (DPBF) by singlet oxygen (1O2) photosensitization. At the same time, the LED device displays bright orange-red emission. This work paves the way for further research into the design and application of such materials in advanced optics.

Cryo-EM structures of wild-type and E138K/M184I mutant HIV-1 RT/DNA complexed with inhibitors doravirine and rilpivirine

Structures trapping a variety of functional and conformational states of HIV-1 reverse transcriptase (RT) have been determined by X-ray crystallography. These structures have played important roles in explaining the mechanisms of catalysis, inhibition, and drug resistance and in driving drug design. However, structures of several desired complexes of RT could not be obtained even after many crystallization or crystal soaking experiments. The ternary complexes of doravirine and rilpivirine with RT/DNA are such examples. Structural study of HIV-1 RT by single-particle cryo-electron microscopy (cryo-EM) has been challenging due to the enzyme's relatively smaller size and higher flexibility. We optimized a protocol for rapid structure determination of RT complexes by cryo-EM and determined six structures of wild-type and E138K/M184I mutant RT/DNA in complexes with the nonnucleoside inhibitors rilpivirine, doravirine, and nevirapine. RT/DNA/rilpivirine and RT/DNA/doravirine complexes have structural differences between them and differ from the typical conformation of nonnucleoside RT inhibitor (NNRTI)-bound RT/double-stranded DNA (dsDNA), RT/RNA-DNA, and RT/dsRNA complexes; the primer grip in RT/DNA/doravirine and the YMDD motif in RT/DNA/rilpivirine have large shifts. The DNA primer 3'-end in the doravirine-bound structure is positioned at the active site, but the complex is in a nonproductive state. In the mutant RT/DNA/rilpivirine structure, I184 is stacked with the DNA such that their relative positioning can influence rilpivirine in the pocket. Simultaneously, E138K mutation opens the NNRTI-binding pocket entrance, potentially contributing to a faster rate of rilpivirine dissociation by E138K/M184I mutant RT, as reported by an earlier kinetic study. These structural differences have implications for understanding molecular mechanisms of drug resistance and for drug design.

Recognition and Binding of RsmE to an AGGAC Motif of RsmZ: Insights from Molecular Dynamics Simulations.

CsrA/RsmE is a post-transcriptional regulator protein widely distributed in bacteria. It impedes the expression of target mRNAs by attaching their 5' untranslated region. The translation is restored by small, noncoding RNAs that sequester CsrA/RsmE acting as sponges. In both cases, the protein recognizes and attaches to specific AGGAX and AXGGAX motifs, where X refers to any nucleotide. RsmZ of Pseudomonas protegens is one of these small RNAs. The structures of some of its complexes with RsmE were disclosed a few years ago. We have used umbrella sampling simulations to force the unbinding of RsmE from the AGGAC motif located in the single-stranded region sited between stem loops 2 and 3 of RsmZ. The calculations unveiled the identity of the main residues and nucleotides involved in the process. They also showed that the region adopts a hairpin-like conformation during the initial stages of the binding. The ability to acquire this conformation requires that the region has a length of at least nine nucleotides. Besides, we performed standard molecular dynamics simulations of the isolated fragments, analyzed their typical conformations, and characterized their movements. This analysis revealed that the free molecules oscillate along specific collective coordinates that facilitate the initial stages of the binding. The results strongly suggest that the flexibility of the single-stranded region of RsmZ crucially affects the ability of its binding motif to catch RsmE.

Different drives of herding: An exploratory study of motivations underlying social conformity.

We often align our behaviors, attitudes, and opinions in line with a majority of others, a phenomenon known as "social conformity." A seminal framework has proposed that conformity behaviors are mainly driven by three fundamental motives: a desire to gain more information to be accurate, to obtain social approval from others, and to maintain a favorable self-concept. However, previous studies usually have interpreted conformity behaviors as driven by one motive or another, largely ignoring the fact that human behaviors could be concurrently induced by multiple and even conflicting motivations. Adopting a typical conformity paradigm widely used in previous studies, we explored distinct and concurrent motives underlying the same conformity behavior, combining personality and individual differences with more nuanced analyses of observed conformity behaviors. Our findings provide novel evidence to show that three motivations exist within a single conformity behavior, suggesting that multiple motivations drive the conformity concurrently. These findings provide a potential solution for the extensive debate about what drives human social conformity and help to better understand the conformity behavior in daily life.

French Bulldogs differ to other dogs in the UK in propensity for many common disorders: a VetCompass study

BackgroundThe French Bulldog is a highly popular dog breed but is linked with many serious health issues. A holistic view of breed health in French Bulldogs would assist efforts to appreciate the overall health strengths and weaknesses in the French Bulldog and to take appropriate steps to mitigate these.Based on random sampling of French Bulldogs and non-French Bulldogs under primary veterinary care during 2016 within the VetCompass Programme, a cohort study design was used to estimate the one-year (2016) period prevalence of the most commonly diagnosed disorders in each group. Risk factor analysis used multivariable logistic regression modelling methods.ResultsThe analysis included 2,781 French Bulldogs and 21,850 non-French Bulldogs. French Bulldogs were younger (1.51 years, IQR 0.86 – 2.77 vs. 4.48 years, IQR 1.94 – 8.14) (p < 0.001) and lighter (12.45 kg, IQR 11.00 – 14.03 versus 13.80 kg, IQR 8.10 – 25.12) (p < 0.001) than non-French Bulldogs. Of 43 common specific-level disorders across both groups, French Bulldogs had significantly increased adjusted odds of 20/43 (46.5 %) disorders and significantly reduced adjusted odds of 11/43 (25.6 %) disorders compared to non-French Bulldogs. Highly predisposed disorders in French Bulldogs included stenotic nares (OR 42.14; 95 % CI 18.50 to 95.99; p < 0.001), Brachycephalic Obstructive Airway Syndrome (OR 30.89; 95 % CI 20.91 to 45.64; p < 0.001), aural discharge (OR 14.40; 95 % CI 9.08 to 22.86; p < 0.001), skin fold dermatitis (OR 11.18; 95 % CI 7.19 to 17.40; p < 0.001) and dystocia (OR 9.13; 95 % CI 5.17 to 16.13; p < 0.001). At a grouped-level of diagnostic precision, French Bulldogs had increased adjusted odds of 12/32 (37.5 %) disorders and reduced adjusted odds of 6/32 (18.8 %) disorders compared to non-French Bulldogs.ConclusionsThese results identified ultra-predispositions with worryingly higher odds in French Bulldogs for several disorders, suggesting that the health of French Bulldogs has diverged substantially from, and may be lower than, the health of the wider non-French Bulldog population. Many of these predispositions are closely associated with the conformational extremes that define the French Bulldog breed. Shifting the typical conformation of the French Bulldog population towards a more moderate phenotype is proposed as a logical opportunity to reduce the serious health issues endemic in the French Bulldog breed.

Synthesis, crystallographic structure, DFT computational studies and Hirschfeld surface analysis of a new tetranuclear anionic bromobismuthate(III): [C12H20N2]2Bi4Br16•2H2O

• A new tetranuclear anionic bromobismuthate [C12H20N2]2Bi4Br16•2H2O was synthesized and characterized. • The X-ray crystal structure of this new complex was elucidated. • Intermolecular interactions were analyzed by Hirshfeld surface analysis. • The electrostatic potentials of the equilibrium geometry and the molecular HOMO-LUMO have been investigated. • Proton affinities, relative stabilities and the relative energies have been studied using the density functional theory (DFT). This present research makes in attention the synthesis of an organic inorganic hybrid compound with new tetranuclear anionic bromobismuthates with formula: [C 12 H 20 N 2 ] 2 Bi 4 Br 16 •2H 2 O by slow evaporation at room temperature. It is characterized by X-ray diffraction. Indeed, this compound crystallizes in the monoclinic space group; P2 1 /c with the following parameters: a = 12.3534(6), b = 24.0296(9), c = 17.8715(8) Å, β= 92.302(5)°, V = 5300.8(4) Å 3 and Z = 4. The crystal structure consists of discrete [Bi 4 Br 16 ] 4− cluster and two kinds of the 2-phenylethylpiperazinium cations. The crystal structure is stabilized through intermolecular N H…Br, C H…Br and N H…O hydrogen bonds and Br…Br interactions. The vibrational absorption bands were identified by infrared spectroscopy. Moreover, computational studies are also performed using DFT calculations at B3LYP/6311++ G (2df,2p) level of theory to understand the typical conformers of 2-phenylethylpiperazine and their proton affinities. Indeed, the molecular orbital calculations such as HOMO-LUMO and molecular electrostatic potential (MEP) surfaces have been calculated. Crystal structure analysis was supported with the Hirshfeld surface (HS) analysis and fingerprint plots enabled the identification of the significant intermolecular interactions. The Hirshfeld surface analysis of intermolecular interactions confirmed that the contacts: Br…H/H…Br and H…H make the largest contribution to the HS and play a dominant role in the crystal structure of the investigated compound.

A Structured Phase Change Material with Controllable Thermoconductive Highways Enables Unparalleled Electricity via Solar‐Thermal‐Electric Conversion

AbstractA solar thermoelectric generator (STEG) that harvests solar energy and converts it into electricity based on the fundamentals of the Seebeck effect is a promising alternative to photovoltaic technologies. The combination of a phase change material (PCM) with STEG further enables stable and durable energy output despite the variations of solar radiation flux. However, the widespread promotion of STEG is still impeded by its restricted output electricity (&lt;50 W m−2), attributed to the undesirable thermal management in PCMs. Herein, an ingenious phase change composite, with the typical conformation of circular truncated cone and embedded with the actinomorphic arrangement of polybenzobisoxazole fibers, is tailored by a mold processing strategy. The fibrous crystals in organic fibers offer temperature‐resistance thermal highways during the charging/discharging processes, while their actinomorphic configuration facilitates a controllable thermo‐conductive behavior. These structural features render concentrated thermal energy to be efficiently stored in the PCM and maximally discharged into the thermoelectric system. A record‐breaking power density as high as 198.70 W m−2 can be achieved in this powerful STEG via real‐environment solar‐thermal‐electric conversion, a value comparable to that of some commercial photovoltaic devices. This work opens up opportunities for durable and giant electricity supply from clean solar energy during real‐time STEG applications.