Psychromyces glacialis, an Arctic glacier fungus. One isoform was found to be an approximately 25 kDa protein (PsgIBP_S), while the other is a 28 kDa larger protein (PsgIBP_L) that forms an intermolecular dimer. Their TH activities were less than 1 °C at millimolar concentrations, implying that both isoforms are moderately active but not hyperactive IBP species. It further appeared that both isoforms exhibit high IRI activity even at submicromolar concentrations. Furthermore, the isoforms can bind to the whole surface of a hemispherical single ice crystal, although such ice-binding was generally observed for hyperactive IBP species. These results suggest that the binding ability of IBPs to whole ice crystal surfaces is deficient for hyperactivity but is crucial for significant IRI activity.Many psychrophilic microorganisms synthesize ice-binding proteins (IBPs) to survive the cold. The functions of IBPs are evaluated by the effect of the proteins on the nonequilibrium water freezing-point depression, which is called “thermal hysteresis (TH)”, and the inhibitory effect of the proteins on the growth of larger ice crystals, which is called “ice recrystallization inhibition (IRI)”. To obtain mechanical insight into the two activities, we developed a modified method of ice affinity purification and extracted two new IBP isoforms from  Among these creatures, a vast number of microorganisms in glaciers are known to develop survival strategies to adapt to ice-laden environments, and these strategies include adaptation to low availabilities of water and nutrients and preventing ice-induced damage by producing cryoprotective substances. These substances include cations, phosphates, nucleotides, amino acids, polyols (ex. glycerol), sugars , and proteins (ex. ice-binding protein). The cryoprotective substances are now utilized in industrial and medical fields, and how each substance functions to control ice-crystal growth must be clarified3 to develop further advancements in cryo-technology.Glaciers cover 10% of the land surface on Earth and are considered to provide a habitat for various living organisms4. Notably, IBP is sometimes called antifreeze protein (AFP). The IBP-adsorbed ice crystals cannot undergo further growth. IBPs have been identified from various kinds of cold-adapted organisms, such as fish5, insects6, plants7, and microorganisms8. Microorganisms synthesize a β-helical IBP that lacks the structural regularity due to the nonrepetitive nature of the amino acid sequence. Recent studies have demonstrated that many IBP molecules locate some ice-like organized waters on their flat surface10, which may undergo complementary binding to the waters that comprise the basal, prism, and/or pyramidal planes defined for an embryo single ice crystal. Notably, the unit structure of a single ice crystal at an atomic scale is a hexagonal cylinder, which is defined by three equivalent a-axes (a1–a3) that are perpendicular to the c-axis. The basal planes are the two top planes in the hexagonal unit. The c-axis penetrates the center portion of the basal planes of the hexagonal cylinder.Ice-binding protein (IBP) is the most promising cryoprotective substance and uniquely binds to embryonic single ice crystals in a supercooled aqueous solutionTf) of water and does not cause a significant change in the melting point (Tm). The TH value is hence evaluated as a difference between these two points for an IBP solution 11. The known IBPs have been categorized into moderately active and hyperactive groups based on the maximal TH values evaluated for each solution12. Most insect-derived IBPs belong to the hyperactive group, which exhibits 2 − 6 °C of high TH values when evaluated at only micromolar concentrations. In contrast, ordinary fish-derived IBPs are categorized into the moderately active group, which exhibits less than 1.5 °C at millimolar concentrations. In the frozen state of water, larger ice crystals grow at the expense of smaller ones, and this process is called ice-recrystallization. When an IBP exerts strong IRI activity, the IBP maintains an ice crystal size and minimizes freezing damage to the host organism. The fluorescence-based ice plane affinity (FIPA) pattern provides further information about the target ice planes of IBP species13. By submerging a single ice crystal hemisphere of 2–3 cm in diameter into a vessel that contains a solution of fluorescence-labeled IBPs, their adsorptions show specific patterns on the ice hemisphere under UV light. When six equally distant ellipses are illuminated on the equator, it indicates that the IBP binds to six equivalent prism planes of a single ice crystal. Similarly, the illumination of six ellipses on the mid-latitude implies that the IBP is binding to six equivalent pyramidal planes. Entire illumination of the hemisphere implies that the IBP sample binds to the whole ice crystal plane.The ability of microorganism-derived β-helical IBPs to bind ice can be evaluated by two physical quantities, including thermal hysteresis (TH) and ice recrystallization inhibition (IRI). The TH activity is an IBP-induced depression of the nonequilibrium freezing point Psychromyces glacialis, was previously identified17. This microorganism was previously called Rhodotorula svalbardensis, but it was recently changed to the above name to be identified as a member of Glaciozyma species18. P. glacialis has been isolated from a variety of glacial environments, such as cryoconite holes, dark ice, snow, subglaciers, and glacier meltwater in Svalbard, Norway19 and Greenland20. The microorganism was not found in the other near-polar regions, suggesting that P. glacialis is highly endemic to specific areas. A preliminary study showed that the IBP from P. glacialis (PsgIBP) could modify the shape of a single ice crystal, which suggested that IBP production is beneficial for the survival of this fungus in icy environments. Here, we re-evaluated the biochemical properties and ice-binding ability of PsgIBP. We found that the PsgIBP sample is a mixture of two isoforms, a relatively small isoform (PsgIBP_S) and a dimer-forming large isoform (PsgIBP_L), for which moderate TH and significant IRI activities were detected. The FIPA analysis further showed its ability to bind to the whole plane of a single ice crystal hemisphere. The correlation between TH, IRI, and FIPA and its physiological role will be discussed in terms of the cold-survival mechanism of this microorganism.IBP from a cold-adapted dimorphic fungus, Psychromyces glacialis cells were originally isolated from a cryoconite hole in Svalbard and were cultivated in our laboratory. Since a preliminary study showed that P. glacialis secretes IBPs into the extracellular space17, we purified native PsgIBP from the culture supernatant. Ice-affinity purification (IAP), a uniquely developed method to purify IBPs21, was utilized for the initial step of our purification procedure. In the ordinary method, IBP is obtained from the ice phase as the IBP undergoes irreversible adsorption to the growth-induced ice fronts, while the other molecules cannot be incorporated into the ice phase. A merit of the IAP method is that the method can always be used unless the molecular weight (MW), isoelectric point, and/or thermostability of the IBP is unknown. The ordinary IAP method uses a frosty copper probe, which necessitates special instrumental settings  forms a dimer14, we speculate that PsgIBP_L undergoes dimerization similar to LeIBP. To estimate the MW of the two purified isoforms of PsgIBP, SEC was performed using a Superose12 column instead of a Superdex200 column. Figures In the chromatography process with the Superdex200 column, the elution time of PsgIBP_L was much faster than that of PsgIBP_S despite their very similar MWs verified by SDS–PAGE. Since an IBP from the Arctic yeast 8. Here, we measured the TH activity for the purified PsgIBP_S and _L samples by using a homemade photomicroscopic system, in which the stage temperature was manipulated to monitor the crystal growth of a single ice crystal that was generated in the sample solution  despite their structural similarity.0 °C dessee Fig. ” sectionAntarctomyces psychrotrophicus IBP (AnpIBP) and much lower than that of the hyperactive Typhula ishikariensis IBP isoform 8 (TisIBP8). On the basis of the TH activity measurements, it could be said that both PsgIBP isoforms are categorized into the moderately active group of IBPs.It should be noted that the TH activity measurement for PsgIBP isoforms at higher concentrations was extremely difficult to obtain because the size of an ice crystal at higher PsgIBP concentrations becomes very small, which makes it difficult to leave one single ice crystal in the sample solution. Although the TH activity of the PsgIBP_L isoform is slightly higher than that of the PsgIBP_S isoform, the two activities are comparable to that of a previously reported moderately active Tm and Tf,, which is called the “TH gap”, modifies the shape of a single ice crystal into a hexagonal plate, a hexagonal bipyramid, a hexagonal trapezohedron, or a lemon-like morphology. Notably, the two PsgIBP isoforms affected the shape of a single ice crystal differently  activity of the microbial IBPs tends to be high compared with that of fish and insect IBPs, and it was speculated that ice recrystallization is among the main causes of damage to microorganisms due to freezing12 because most of them bind to the basal plane in addition to the prism and pyramidal planes. In the case of microbial IBPs, a species binding to the basal plane does not always exhibit such a significant TH activity. For example, arctic yeast LeIBP binds to the basal and 1st prism planes but exhibits a TH activity of only 0.9 °C at millimolar concentrations14. An IBP derived from perennial ryegrass Lolium perenne is another example that exhibits affinity to the basal plane with weak TH activity29. These observations suggested that the ability of basal-plane binding is not sufficient for hyperactivity. The current study introduces two new IBP species that possess moderate TH activity and whole ice-plane affinity.IBPs have been categorized into hyperactive and moderately active groups based on their TH activities. Many researchers have investigated what kind of factor determines the strength of TH activity and how it correlates with IRI activity. In the case of insect IBPs, which typically show 5 °C or higher TH activity, basal-plane affinity is thought to be the key determinant for hyperactivityTf, the PsgIBP_S-bound ice crystal was changed into a truncated hexagonal bipyramid at lower concentrations, which is typically observed for moderately active IBPs that generally do not bind to the basal plane12. When the PsgIBP_S concentration was higher, the bursting ice growth progressed toward both the a- and c-axis directions, which was similarly observed for hyperactive IBPs. That is, PsgIBP_S exhibits signs of both hyper and moderate activities. Based on these results, we speculated that although PsgIBP_S can bind multiple ice surfaces, including the basal planes, the binding affinity to the basal plane is weak compared with that of ordinary hyperactive IBPs. An IBP from a bacterial symbiont of a psychrophilic ciliate Euplotes focardii was reported to bind weakly to most of the pyramidal planes, while it can bind strongly to limited portions near the basal planes and near the secondary pyramidal planes30. This mechanism uniquely causes a “Saturn-shaped ice burst pattern” below the freezing point. In the case of PsgIBPs, such strong and weak binding was not observed in the FIPA analysis , suggesting that this IBP has a strong basal-plane affinity. Why does PsgIBP_L exhibit moderate TH activity? We speculate that dimerization might help answer this question. The dimerization was identified for the LeIBP from the Arctic yeast Glaciozyma sp. AY3031. In the X-ray crystal structure of the LeIBP dimer, two IBP molecules form a complex in a back-to-back manner through their C-terminal long tails to expose their ice-binding sites at opposite sides. When the C-terminal tail of LeIBP was removed, its dimer formation was destroyed, and its TH activity was increased compared with that of the wild type. Notebly, the present P. glacialis is phylogenetically close to Glaciozyma sp. AY3018. On the basis of these results, it is speculated that in PsgIBP_L, a loss of freely accessible ice-binding sites due to dimerization leads to lower TH activity in a similar manner to that of LeIBP.In the case of PsgIBP_L, the ice crystal burst occurred in six 32, since the IBP binding to multiple ice planes will keep the water molecules away in both water–adsorption and water-desorption processes at the ice-water interface. Thus, it may be assumed that the whole-plane binding of PsgIBPs is crucial for their high IRI activity, unless its basal-plane affinity is weak. Gruneberg et al. recently examined a correlation between TH and the IRI of fifteen diverse IBPs and pointed out that the IRI activity increases proportionately to their molecular weight16. This assumption holds true in our experiment  plate at − 1 °C. We hence examined whether P. glacialis undergoes cell growth on frozen PDA at − 1 °C but found that it did not grow. This result agrees with a previous result17, in which P. glacialis could not grow at − 1 °C even on an unfrozen PDA.8. Our experiments showed that both PsgIBP_S and PsgIBP_L isoforms function as effective IR inhibitors even at nano- to micromolar concentrations  was isolated from cryoconite holes in Svalbard as described previously17 and were cultivated in PDB medium at 4 °C.Psychromyces glacialis was grown in 500 ml of potato dextrose broth (PDB) medium at 10 °C. Then, IBP expression was induced by decreasing the temperature to 4 °C. After 6–12 months, the cells were removed by centrifugation and filtration. The culture supernatant was dialyzed against pure water and subjected to our modified ice-affinity purification method 22, longsnout poacher-derived IBP 38, and barfin plaice-derived AFP 39. Bovine thyroglobulin (660 kDa) from Sigma–Aldrich was used to measure the void volume of the Superose12 column. A calibration line was drawn on the basis of the partition coefficients (K) versus the logarithm of the molecular weight of the proteins14. The coefficient K was calculated with the following equation:Ve is the peak elution volume, Vo is the void volume, and Vt is the total bed volume of the column.The molecular weight was estimated for the PsgIBP_S and PsgIBP_L samples by size-exclusion chromatography using a Superose12 column . This column was equilibrated with 20 mM Tris–HCl (pH 8.0) + 500 mM NaCl at a flow rate of 0.8 ml/min at 4 °C. A 0.5-mL sample containing 1 mg/ml protein was loaded onto the column. The protein samples were bovine serum albumin  from Sigma–Aldrich , green fluorescence protein-labeled notched-fin-eelpout-derived AFP 40. Briefly, 1 μl of the sample solution in a glass capillary was inserted into a copper holder and placed on a photomicroscope system (Leica DMLB100) equipped with a temperature controller (Linkam 10002L). The solution was flash-frozen by decreasing the temperature to − 25 °C at a rate of 55 °C/min and was then warmed up to approximately 0 °C to form a single ice crystal. At that time, the melting point (Tm) of the sample was recorded. After the formation of a single ice crystal, the sample was incubated at Tm − 0.05 °C for 3 min. Then, the temperature was decreased at a rate of 0.1 °C/min. The temperature at which the ice crystal grew was recorded as the freezing point (Tf) of the sample, which enables the calculation of TH (TH =|Tm−Tf |).The thermal hysteresis activity was measured as previously described13. Briefly, a single ice crystal hemisphere (φ = 3 cm) attached to a “cold finger” was immersed and grown in 35 ml of fluorescently labeled IBP solution at a concentration of 25 μg/ml. The temperature of the cold-finger was initially set at − 8 °C and was gradually decreased up to − 12 °C. After growing the hemisphere to φ = 8 cm, it was illuminated under UV light and photographed in a cold room at − 1 °C. 6-(Tetramethylrhodamine-5-(and-6)-carboxamido) hexanoic acid, succinimidyl ester (5(6)-TAMRA-X SE) and rhodamine red-X, succinimidyl ester 5-isomer , both of which react with lysine residues, were used for the fluorescent labeling of RsIBPs and AnpIBPs, respectively.FIPA analysis was performed as previously described22 with slight modifications. In short, morphological changes in the ice crystals that were in 30% sucrose with the presence of IBP were observed under a microscope equipped with a temperature controller (which was the same as that used in the TH measurement). Then, we can compare the size of ice crystals before and after 60 min of incubation at − 6 °C. The average size of the ice crystals was measured with ImageJ software. The concentration threshold was defined as the protein concentration at which IR did not occur. Each measurement was performed in triplicate.IRI activity was measured as previously describedSupplementary Figures.


MYH7 and TPM1, the genetic etiology and pathogenesis of EA/LVNC remain largely unknown.Traditional definitions of Ebstein’s anomaly (EA) and left ventricular noncompaction (LVNC), two rare congenital heart defects (CHDs), confine disease to either the right or left heart, respectively. Around 15–29% of patients with EA, which has a prevalence of 1 in 20,000 live births, commonly manifest with LVNC. While individual EA or LVNC literature is extensive, relatively little discussion is devoted to the joint appearance of EA and LVNC (EA/LVNC), which poses a higher risk of poor clinical outcomes. We queried PubMed, Medline, and Web of Science for all peer-reviewed publications from inception to February 2022 that discuss EA/LVNC and found 58 unique articles written in English. Here, we summarize and extrapolate commonalities in clinical and genetic understanding of EA/LVNC to date. We additionally postulate involvement of shared developmental pathways that may lead to this combined disease. Anatomical variation in EA/LVNC encompasses characteristics of both CHDs, including tricuspid valve displacement, right heart dilatation, and left ventricular trabeculation, and dictates clinical presentation in both age and severity. Disease treatment is non-specific, ranging from symptomatic management to invasive surgery. Apart from a few variant associations, mainly in sarcomeric genes  Congenital heart defects (CHDs) are cardiogenic malformations present at or before birth that account for a high burden of neonatal morbidity and mortality in the developed world. As improvements in cardiac medicine enable patients with CHDs to live longer, there remains an unmet need for tailored medical care and treatment. Here, we provide a brief overview of two rare CHDs—Ebstein’s anomaly (EA) and left ventricular noncompaction (LVNC)—and thoroughly review publications that discuss combined EA/LVNC.Reported EA prevalence ranges from one in 200,000 to, more commonly, one in 20,000 live births, and accounts for less than one percent of CHD cases ,2,3,4. IEA mainly affects the tricuspid valve and right ventricle. Specific EA characteristics include the attachment of posterior and septal leaflets to the ventricular septum, apical displacement of the valve, redundant and fenestrated anterior leaflet, atrialization of the portion of right ventricle above the valve, and dilation of the right ventricle and atrioventricular junction ,5,6.Significant EA pathology originates from the right heart dilation, and consequently, over two-thirds of EA patients display enlargement of the right heart, including the atrialized inlet portion of the right ventricle and often the functional right ventricular apex and outflow tract . PronounClinical heterogeneity of EA patients ranges in anatomic and physiologic severity, and as such, treatment from medication to valve repair is highly individualized ,9. FetalCategorization of EA as mild, moderate, or severe is based on varied classification systems: (1) Carpentier et al.  assess fEA also commonly manifests with left ventricular noncompaction (LVNC), a cardiomyopathy of ventricular myocardium that does not transit from a weak and “spongy” stage to a compacted state during development ,15. MorpCommon LVNC-associated cardiac comorbidities include ventricular septal defect (VSD), ASD, and patent ductus arteriosus (PDA). One pathologic predictor of LVNC is a greater base–apex strain, resulting from longitudinal deformation .Prevalence of LVNC is even more variable than EA, and diagnosis may be missed in patients with asymptomatic clinical presentation or absent imaging. Similar to EA, early LVNC presentation in infancy increases the risk of mortality . Often, x/y < 0.5) on short-axis ECHO ,,24,23,24Dual EA/LVNC patients present with clinical characteristics of both myocardial disorders B 22,76,,76,77. APatients born with both EA and LVNC and diagnosed in infancy have a higher risk of poor outcomes such as heart failure and sudden cardiac death and manifest with anatomical variations that pose an additional surgical challenge ,55,82,83In cases of combined EA/LVNC, typically one of the two conditions is present in the relatively mild state. Some case reports describe patients initially diagnosed by EA and a later diagnosis of LVNC following an ischemic attack or unexplained clinical phenomena that prompted additional imaging ,62,66. EA clinical association of arrhythmia for patients with EA/LVNC originated as early as 1978. Monibi et al. evaluated 17 newborns with EA and found that 13 presented with high normal or elevated hematocrit without cyanosis, and 9 of 13 who had LV catheterization and cineangiocardiography displayed abnormal contraction with unusually elongated and distorted long axis and irregularity of septal and lateral walls . Of the Two decades hence, cineangiography of 26 adults with EA identified that 16 presented with abnormal LV contraction  .Among 106 EA patients studied between 2001 and 2003 at the Mayo Clinic, there were 76 severe cases, 19 (18%) presented with LVNC, and 22 (21%) with WPW syndrome . While nIn a study of 12 survivors among 16 neonates with EA who underwent right ventricular exclusion surgery, shortening fractions were found to be significantly lower prior to follow-up Glenn and Fontan procedures . In our All imaging modalities used for diagnosis and EA/LVNC characterization are noted in EA/LVNC treatment  is nonspAll clinical trial information available for EA or LVNC in the US and EU are described in MYH7 [NKX2.5 [GATA4 [TAZ [TBX20 [The genetic etiology and pathogenesis of EA/LVNC are largely unknown. Studies identified clinically significant variants at a variety of loci in EA and LVNC Z [TBX20  or LVNC-Z [TBX20  genetic MYH7 locus, which encodes the β-myosin heavy chain (βMyHC), is significantly implicated in EA, LVNC, and EA/LVNC [Many of these variants are in sarcomeric or cytoskeletal proteins and have broad implications in cardiac formation, function, and conduction ,103. The EA/LVNC ,88,104. MHY7 (p.R281T) variant. Of the 11 LVNC-affected members, 4 also presented with EA. This MYH7 variant is suspected to prevent salt-bridge formation, destabilizing the myosin head and resulting in altered contractility [Following a genome-wide linkage analysis of a German familial case of LVNC with 11 affected members among 25, Budde et al. discovered the actility .MYH7 locus of 141 unrelated EA patients via mutation screening and detected seven distinct heterozygous mutations, of which five were novel. In total, 6 patients among the 8 who possessed these MYH7 variants and none of the remaining 133 subjects presented with LVNC [Postma et al. examined the ith LVNC .MYH7 mutations with EA/LVNC [MYH7 mutations or possibly other sarcomeric variants that follow a pattern of autosomal dominant inheritance and variable penetrance [TPM1 (p.D159N and p.L131V) [After reviewing this latter publication and a few other EA/LVNC genetic studies, Vermeer et al. concluded the association of at least nine distinct  EA/LVNC . Five ofnetrance . This conetrance  and varip.L131V) ,71.MYH7 [Most recently, in a familial case of LVNC where only the proband presented with EA/LVNC, exome sequencing of the proband and parents and subsequent Sanger sequencing of other family members identified a maternally inherited heterozygous splicing variant in MYH7 .Non-sarcomeric proteins linked to EA/LVNC include SCN5A, a sodium channel, NONO, a nonoctamer-containing POU-domain DNA-binding protein, and KLHL26, a kelch-like protein .SCN5A (p.I230T) variant [Neu et al. described one EA/LVNC-affected member among four related children who presented with early cardiac arrhythmia; all four were heterozygous for the  variant .The NONO protein plays crucial roles in transcriptional regulation and RNA splicing. One frameshift and one deletion variant of NONO were discovered in EA/LVNC patients who also presented with a noncardiac syndrome ,42.TPM1 and MYH7, but showed chromosomal gain bands in 15q11.2 and 1q44 [In a separate case, one EA/LVNC patient tested negative for a panel of 17 genes, including and 1q44 .KLHL26 (p.R237C) variant segregated with disease. The KLHL family of proteins is known to have a role in actin binding, cytoskeletal rearrangement, and ubiquitin-mediated protein degradation.Recently, our group identified 10 EA/LVNC-affected members out of 17 in a familial study with an autosomal dominant pattern of inheritance . From exThe abundance of loci implicated in either EA or LVNC alone and combined EA/LVNC underscores the complexity and genetic uncertainty for these CHDs.The characterization of EA as a distinct right heart defect persisted for nearly 150 years since its discovery in 1866 by Wilhelm Ebstein. Similarly, LVNC is mainly defined as a condition of the left heart. However, in the last 10–15 years, there has been an accumulation of evidence for more than a coincidental occurrence of EA and LVNC. Because of the prevalence of right-hearted lesions in LVNC and left-hearted lesions in EA seen in this review and others ,105, a tThe human heart begins to develop during the third week of human gestation . The heaCardiac fibroblasts within the developing myocardium are largely derived following epicardial-to-mesenchymal transition (EMT) of the epicardium are known, in parallel, to provide signals for development of the atrioventricular valve as well as the compact myocardium ,112. TheThe tricuspid valve is comprised of anterior, septal, and posterior leaflets; delamination of the septal leaflet from the muscular ventricular septum ,117 likeAs these events unfold, myocardial compaction of the trabeculae, which began forming in week 4, occurs in week 8 ,118. As MIB1 (mindbomb homolog 1) variant [TBX20 using induced pluripotent stem cells (iPSCs); they found decreased cellular proliferation in disease lines and showed phenotype reversal following variant correction [Two LVNC investigations offered direct insight into genetic etiology. One described autosomal dominant LVNC associated with a  variant . MIB1 enrrection .While EA/LVNC pathophysiology remains unknown, when we reflect on the considerable overlap of developmental pathways in the formation of the tricuspid valve and compacted myocardium and the genetic variants associated with both CHDs, it is unsurprising that EA commonly manifests with LVNC.Investigating sarcomeric and cytoskeletal variants may provide evidence for arrhythmia stemming from a cellular or tissue-level contractile impediment rather than a global consequence of anatomical alterations. Aberrant contractile ability may further hinder apical constriction, depolarization, and subsequent delamination of cells during EndEMT or EMT processes .Understanding the molecular and cellular events that unfold during the progression of disease-specific variants will provide broader insight into typical vs. aberrant cardiac development. Although clinical approaches have improved, there remains an unmet need for effective EA/LVNC treatment. Nonspecific pharmaceutical and mechanical interventions will likely remain the most common frontline treatment options for EA/LVNC until a deeper understanding of the genetic and molecular underpinnings of both CHDs becomes available.


The FST (fixation index) with the 1000 Bull Genomes Dataset showed 48 non‐overlapping top (0.1%) FST regions of which three overlapped HapFLK regions. We identified 1982 highly differentiated (FST > 0.40) missense mutations in the Yaroslavl genomes. These genes were enriched in the epidermal growth factor and calcium‐binding functional categories. The top FST intervals contained eight genes with allele frequencies quite different between the Yaroslavl and Kholmogory breeds and the rest of the 1000 Bull Genomes Dataset, including KAT6B, which had a nearly Yaroslavl breed‐specific deleterious missense mutation with the highest FST in our dataset (0.99). This gene is a part of a long haplotype containing other genes from FST and hapFLK analyses and with a negative association with weight and carcass traits according to the genotyping of 30 phenotyped Yaroslavl cattle individuals. Our work provides the industry with candidate genetic variants to be focused on in breed improvement efforts.The genomes of local livestock could shed light on their genetic history, mechanisms of adaptations to environments and unique genetics. Herein we look into the genetics and adaptations of the Russian native dairy Yaroslavl cattle breed using 22 resequenced individuals and comparing them with two related breeds (Russian Kholmogory and Holstein), and to the taurine set of the 1000 Bull Genomes Project (Run 9). HapFLK analysis with Kholmogory and Holstein breeds (using Yakut cattle as outgroup) resulted in 22 regions under selection ( Dwelling in harsh climate conditions, Russian cattle breeds have been required to develop adaptations which can now be traced in the genome regions under selection and convergently evolving genes . GVCF files were submitted to the 1000 Bull Genomes Project and included in Run 9. After quality control (QC) and linkage disequilibrium pruning, we calculated the pairwise PI_HAT measure  + 0.5*P(IBD = 1)) of relatedness using plink (−genome) software  Co. Ltd (China) to ~50 Gbp each. Cleaned reads were mapped to the reference cattle genome assembly (bosTau9) using BWA‐MEM and processed using the 1000 Bull Genomes Project pipeline  Z‐score from the Wilcoxon rank sum test of alternative vs. reference read MQs (MQRankSum) <−12.5; and (v) Z‐score from the Wilcoxon rank sum test of alternative vs. reference read position bias (ReadPosRankSum) <−8. The thresholds for these parameters were adopted from gatk Best Practices  < 0.1 for the signatures of selection scan with hapFLK (‐K 30 ‐‐nfit = 30) with the Yakut cattle samples as an outgroup. The p‐values were calculated using the scaling_chi2_hapflk.py script  statistics were calculated for 22 Yaroslavl cattle individuals against 4 779 animals (coverage >6×) of taurine cattle from the 1000 Bull Genomes Project (Run 9) using vcftools v.0.1.13 with the parameters ‐‐fst‐window‐size 50 000 ‐‐fst‐window‐step 25 000 ‐‐max‐missing 0.9 and for individual SNPs omitting the ‐‐fst ‐window‐size, ‐‐fst‐window‐step options. Translation of the cattle genome coordinates between the UMD3.1 and ARS/UCD1.2 builds was performed using the UCSC Genome Browser liftover tool with default parameters. The top 0.1% FST windows were compared with hapFLK intervals. The direction of selection was determined using local phylogenetic trees and haplotype clustering for hapFLK intervals with no FST interval overlaps. Candidate SNPs were annotated with the NGS‐SNP pipeline  on 11 chromosomes assigned to Yaroslavl cattle  contained a single gene, TMEM225, with one missense mutation (Phe73Leu) showing an FST value of 0.76 when Yaroslavl cattle were contrasted against the 1000 Bull Genome Dataset. Transmembrane protein 225B was previously related to hyperactivity of sperm in pigs  and TTC28 contained four (FST range 0.95–0.97). SNX25 is a key gene in the regulation of TGF‐β signalling, and therefore contributes to the immune system , the highest among all of the Yaroslavl cattle missense variants, suggesting that this variant is nearly Yaroslavl cattle specific. Indeed, among 5 074 remaining animals from the taurine set of the 1000 Bull Genomes Project successfully genotyped at this locus, the same mutation was found only in a heterozygous state in two Modern Angler and two Lithuanian Red individuals while the frequency of the derived A allele was 0.64 in the resequenced Yaroslavl cattle population. A 50 kb region with high FST (0.36) in Yaroslavl cattle also contained KAT6B. This interval was 574 kbp away from a strong signature of selection identified by the hapFLK and containing genes VCL and AP3M1. In between them another 200 kbp region with FST = 0.53 was located containing ADP. An additional missense mutation with high FST (0.986) was located upstream of VCL in MSS51. PCR genotyping and association analysis of MSS51 and KAT6B mutations using 30 Yaroslavl cattle individuals revealed the complete linkage of derived alleles and a negative association of the haplotype with weight and carcass traits , of which 6 069 156 were used in the hapFLK analysis. This resulted in 22 regions under selection , epidermal growth factor‐like domain (FDR = 0.0004), EGF‐like calcium‐binding (FDR = 0.001), etc. The epidermal growth factor plays an important role in mammary gland development and epithelial regeneration and contributes to innate immune responses  with SNP ct Table . These Sis Table  revealedOur work provides the first nucleotide‐level genome‐wide assessment of the Russian Yaroslavl cattle genomes in the context of breeds from around the world and points to signatures of selection and specific genetic variants which could contribute to adaptations and phenotypes for further breed improvement.Appendix S1Click here for additional data file.Appendix S2Click here for additional data file.Figure S1Figure S2Click here for additional data file.Table S1Table S2Table S3Table S4Table S5Table S6Table S7Click here for additional data file.


Splenectomy is one crucial solution for hypersplenism with portal hypertension. However, portal vein system thrombosis (PVST) caused by hemodynamic changes affects the prognosis of patients. We analyze the changes in portal vein hemodynamics following splenectomy for Wilson’s disease combined with portal hypertension and the influencing factors that lead to PVST.P was calculated according to the logistic regression prediction model, and the ROC curve for each independent factor was plotted.A retrospective cohort study was conducted, in which 237 Wilson’s disease patients with hypersplenism underwent splenectomy. The hemodynamic indices of the portal vein were monitored before surgery and on the 1st, 7th, and 14th days around surgery. The patients were divided into PVST and non-PVST groups. The clinical factors were identified by univariate and multivariate logistic regression. The Logit P < 0.01). The PVST incidence rate was 55.7%. Univariate analysis revealed that the platelet (PLT) levels on the postoperative 3rd and 7th days , D-dimer (D-D) on the postoperative 7th and 14th days , preoperative portal vein velocity, flow, diameter (P < 0.001), and splenic vein diameter (P < 0.001) were all statistically and significantly different between the two groups. Multivariate logistic regression revealed a significant increase in PLT on the postoperative 7th day  and D-D on the postoperative 14th day . Preoperative portal and splenic vein diameters  were the risk factors for PVST. However, preoperative portal vein velocity and flow  were protective factors for PVST. Logit P was calculated using a logistic regression prediction model with a cut-off value of −0.32 and an area under receiver operating characteristic curve of 0.952 with 88.61% accuracy.The portal vein velocity, flow, and inner diameter showed a downward trend around surgery, with statistically significant differences between each time point (Splenectomy relieves portal hypertension by reducing the hemodynamics index. PVST is linked to multiple factors, including preoperative portal vein diameter, velocity, flow, and splenic vein diameter, especially PLT on the postoperative 7th day and D-D on the postoperative 14th day. The predictive model is accurate in predicting PVST. ATP7B on chromosome 13. The disturbance of ATP enzyme synthesis of copper and ceruloplasmin is caused by its mutation during biliary tract excretion, resulting in copper accumulation in the liver, which leads to mitochondrial damage and lipid oxidation in liver cells, accelerating liver cirrhosis progression (Wilson’s disease (WD) is a recessive genetic disease caused by mutations in the copper transport gene gression . Liver cSplenectomy, as a spleen hypersplenism treatment secondary to WD cirrhosis and gastric fundus esophageal varices, is the current mainstream therapeutic schedule. However, following splenectomy, forming portal vein system thrombosis (PVST) is the most common and serious complication. With the improvement of clinical examination methods such as Doppler ultrasound and spiral computed tomography (CT), as well as a deeper understanding of thrombosis, the harm caused by PVST and its prognostic influence have garnered considerable attention .Yilmaz et al. reported that PVST incidence was 5.0%–8.0% in the natural course of cirrhosis, reaching 20% after splenectomy , 7.According to relevant reports, the portal dynamic indicators of patients are changed accordingly during the perioperative period of similar surgery, which may have guiding significance for evaluating patients’ PVST formation and surgery efficacy . Current9/L, platelets (PLT) <60 × 109/L. (4) Bone marrow hyperplasia was suggested by bone marrow puncture. (5) The score of preoperative liver function was less than 8 points in Child-Pugh with normal coagulation function and complete clinical data. The exclusion criteria were as follows: (1) Splenic artery embolization or transjugular intrahepatic portosystemic shunt (TIP) was performed before. (2) A combination of serious blood system diseases and immune system diseases such as idiopathic thrombotic purpura and Hodgkin’s lymphoma. (3) Liver cirrhosis caused by hepatitis B virus, alcohol, schistosomiasis, and autoimmune hepatitis. (4) Patients with preoperative PVST and severe extraspinal symptoms that cannot be operated on. The diagnostic criteria were as follows: (1) Diagnostic criteria of WD  Diaia of WD .All patients underwent splenectomy by the same group of chief physicians with senior professional titles. Specialized statistical analysts collected data from the hospital’s case database and classified patients into PVST and non-PVST groups based on their postoperative conditions.During perioperative treatment, Patients received symptomatic treatments such as liver protection and enzyme reduction before the operation. Vitamin K1 was administered to patients with abnormal blood coagulation 1 week before the operation, and patients with Child-Pugh C should be adjusted to Child-Pugh B or A before the operation. Prothrombin complex and antibiotics should be taken prophylactically during operation if it lasts longer than 3 h. All patients underwent splenectomy or splenectomy combined with peripheral vascular devascularization. The enlarged spleen was compressed and dragged out when the exposed splenic artery was ligated, and split-cutting of the upper and lower poles of the spleen vessels was completed following laparotomy separation of the gastrocolonic and gastrosplenic ligaments. If pericardial devascularization is performed, the high esophageal branch, collateral paraesophageal branch, inferior phrenic branch, and peripheral blood vessels within the range of 6–8 cm in the lower esophagus should be dissected. Finally, wound hemostasis and serosal suture were performed. Drainage tubes were placed, and the abdomen was closed layer by layer.The ACUSON Antares 5.0 MHz widescreen convex array probe was used to dynamically monitor the hemodynamic characteristics of the portal vein before and after operation, including the portal vein diameter, maximum velocity, maximum flow, and the formation range of postoperative PVST. Simultaneously, clinical data on patients were collected, including sex, age, Child-Pugh grade, mode of operation, anatomical splenectomy, body mass index, diabetes mellitus, hypertension, and ascites. In addition, the levels of albumin, aspartate aminotransferase, alanine aminotransferase, and total bilirubin, which indicate the liver function, were detected before the operation. The routine blood tests performed before surgery include WBC and hemoglobin. Partially activated prothrombin time, prothrombin time, international standardized ratio, and fibrinogen were recorded to assess coagulation function before the operation. Perioperative platelet count (PLT), D-D and operation time, and intraoperative blood loss during the operation were documented.t-test or Mann–Whitney U rank-sum test. Enumeration data were represented by rate (%) and tested by using χ2 or Fisher’s exact test. Simple linear regression was adopted for single-factor analysis with measurement data as the dependent variable. The factors of the clinical data were gradually incorporated into a multifactor binomial logistic regression model. According to multivariate analysis results, a logistic regression prediction model was established, a receiver operating characteristic (ROC) curve was drawn, and the area under curve including 95% confidence interval was calculated. Simultaneously, the best demarcation point corresponding to the maximum Youden index (sensitivity + specificity − 1) was taken as the boundary value . All tests were bilateral, and P < 0.05 was considered statistically significant.The data were analyzed using SPSS26.0  statistical software, and GraphPad Prism 5.0 was used to draw statistical plots. The normal distribution of measurement data was represented by n = 132) and non-PVST groups (n = 105) according to PVST occurrence after the operation, as displayed in PVST occurrence was determined by color Doppler ultrasound or abdominal CT before and 2 weeks after the operation. We screened 237 patients for eligibility and divided them into PVST . Velocity, flow, and diameter maximum values were 22.67 ± 1.46 cm/s, 907.32 ± 37.25 mL/min, and 14.97 ± 2.05 mm, respectively, on the day before surgery, with minimum values of 21.11 ± 1.22 cm/s, 886.28 ± 16.64 mL/min, and 12.83 ± 1.37 mm on the 14th day following surgery  patients from our observation and the distribution of thrombus, as depicted in t = 3.369, P = 0.001; t = −10.567,P < 0.001), a plasma level of D-D on the 7th and 14th days after surgery , and portal vein velocity, flow, diameter, and splenic vein diameter before splenectomy . Univariate analysis revealed that the influencing factors of PVST formation included a plasma count of PLT on the 3rd and 7th days after surgery (9/L vs. (218.64 ± 11.45) × 109/L, P = 0.001; day 7: (487.17 ± 35.40) × 109/L vs. (441.07 ± 30.61 × 109/L), P < 0.001], and D-D significantly increased on the 7th and 14th days   × 10ctively) , 4.P < 0.05 was included in multivariate regression analysis and the results indicated that the plasma levels of PLT and D-D on the 7th and 14th days after the operation  and portal vein diameter, velocity, flow, and splenic vein diameter before splenectomy were significantly correlated with postoperative PVST , which significantly predict PVST formation (The single factor ormation .P = (−16.953 + 0.042POD7PLT + 0.613POD14D-D + 0.448PVD − 0.548PVV − 0.013PVF + 0.513SVD) . The fact that larger the area under the receiver operating characteristic curve (AUROC) of Logit P, the higher the risk of PVST formation after surgery was primarily demonstrated by the ROC curve of Logit P and the factors that constitute the model to predict postoperative PVST formation . It demonstrated a statistical difference between platelets and D-D , implying an increase in the plasma of PLT for every unit (1 × 109/L) along with a parallel increase in D-D by 0.017 units . This result implies that surgery could cut off the blood flowing back through the splenic vein to reduce portal vein blood flow and relieve portal hypertension for gastrointestinal bleeding and hypersplenism. In addition, it could increase the portal vein blood flow into the liver for patients undergoing pericardial devascularization, as decreased portal vein collateral circulation reduces the rate of hepatic encephalopathy to some extent , and the mode of operation –26. Acco9 L) along with a parallel increase in D-D substance by 0.017 units. However, P-sel is highly expressed before surgery as a specific indicator of platelet activation function (PVST formation is mainly restricted by three factors: (1) hemodynamic alterations. Increased portal venous pressure in cirrhosis was linked to an increased risk of PVST incidents based on the theory of markedly slowing down portal vein blood flow, obstructing liver blood return, aggravating hepatic congestion, and causing compensatory portal vein widening . The posfunction . Injuriefunction , 41. How9/L or the partial thromboplastin time exceeds two times the normal value after surgery.In long-term clinical practice, we have found that PVST formation can be effectively prevented by careful preparation in the perioperative period, while the above risk factors occur. The routine method of Doppler ultrasound examination is performed before the operation. Following this, the appropriate intervention should be actively taken aiming at 2–3 high-risk factors of portal vein diameter >14 mm, flow velocity <23.2 cm/s, flow <888 ml/min, and splenic vein diameter >10 mm. Intraoperative maneuvers should be gentle, avoiding excessive traction of the splenic vein, while also reducing intima damage. When the splenic vein is ligated during surgery, it should be as close as possible for inferior mesenteric vein and bifurcation of vein to shorten the remaining vein of spleen and alleviate hemodynamic changes. According to our clinical experience, it is highly suggested that 4000 iu of low-molecular-weight heparin should be injected subcutaneously for q12 h in the early stage combined with urokinase 200,000 units when the platelet count exceeds 476 × 109/L, D-D at 15.99 mg/L, portal vein diameter at 14 mm, velocity at 23.2 cm/s, flow at 888 mL/min, and splenic vein diameter at 10 mm, which can be used as a clinical reference. Logit P more sensitively reflects PVST incidence based on the logistic regression prediction model with a cut-off value of −0.32 and an AUROC and an accuracy of 0.952% and 88.61%, respectively. However, it is crucial to construct an individual nomogram model to facilitate discrimination and calibration, whereas clinical validity with larger sample sizes is ensured to confirm these findings. Simultaneously, animal experiments are required to confirm the molecular mechanism underlying thrombosis.In summary, splenectomy for WD can reduce portal vein velocity, flow, and inner diameter to relieve portal hypertension. Our work revealed that the PVST group had the highest level of PLT on the 7th day and D-D on the 14th day after surgery, which constituted the influencing factor of PVST formation combined with portal vein velocity, flow, inner diameter, and splenic vein inner diameter. The constructed ROC curve indicated the cut-off points of PLT at 476 × 10


The Rietveld refinement analysis of XRD and Raman data revealed that all of the prepared samples were single phase with a cubic spinel-type structure. With the substitution of Re, the lattice parameters were slightly increased, and Raman spectra peak positions corresponding to the movement of the tetrahedral sublattice shifted to a higher energy position. Furthermore, Raman spectra showed the splitting of T2g mode into branches, indicating the presence of different cations at crystallographic A- and B-sites. The SEM micrograph confirms that surface Re exchange changes the coordination environment of metals and induces Fe-site structure distortion, thereby revealing more active sites for reactions and indicating the bulk sample’s porous and agglomerated morphology. The vibrating sample magnetometer (VSM) results demonstrated that the synthesized nanoparticles of all samples were ferromagnetic across the entire temperature range of 300–4 K. The estimated magnetic parameters, such as the saturation magnetization, remanent magnetization, coercivity, blocking temperature (BT), and magnetic anisotropy, were found to reduce for the Co-site doping with the increasing doping ratio of Re, while in the Fe site, they enhanced with the increasing doping ratio. The ZFC-FC magnetization curve revealed the presence of spin-glass-like behavior due to the strong dipole–dipole interactions in these ferrite nanoparticles over the whole temperature range. Finally, the dielectric constant (r′ε) and dielectric loss (tanδ) were sharply enhanced at low frequencies, while the AC conductivity increased at high frequencies. The sharp increases at high temperatures are explained by enhancing the barrier for charge mobility at grain boundaries, suggesting that samples were highly resistive. Interestingly, these parameters  were found to be higher for the Fe-site doping with the increasing Re doping ratio compared with the Co site.In this work, nanoparticles of Co Ms) [K) [cH) [cT) [2O4, where A represents divalent and Fe3+ represents trivalent metal elements. The unit cell of AFe2O4 consists of 32 closely packed oxygen atoms with 64 divalent tetrahedral A-sites and 32 trivalent octahedral B-sites. Only 8 of the available 64 A-sites are occupied by cations, and only 16 of the 32 B-sites are occupied by cations. Furthermore, spinel ferrites have received significant attention because of metal ion substitution and anion exchange phenomena attributes to the enormous electronic and geometric structure, which usually leads to charge separation, carrier migration, and variation in the energy bands. The metal ion-dependent physical properties are mostly inspired by the synthesis approach and the cation distribution between the tetrahedral and octahedral sites. Recently, it has been extensively reported that the structural defect, particle size, shape, composition, and arrangement of A2+ and Fe3+ cations can strongly affect the crystal structure and interactions between ions, altering spinel ferrites’ magnetic, electrical, and optical properties [Spinel ferrite has wide applications in electronic devices, environmental protection, and biomedical technology ,2,3,4. IMs) , high anMs) [K) ,7, high [K) [Hc) , high CuHc) [Tc) , thermalHc) [Tc) ,11, and operties ,13,14,15operties .2O4) are used in various applications because of their good electrical insulation, high coercivity, and easy synthesis method [2+ with zinc and discovered an increasing coercivity behavior as a result of anisotropy change [3 transition metal, which has been reported as a superior dopant of some semiconductors and oxides to change the properties of the hosting materials. Teli et al. discussed the potential spintronic and optoelectronic application of Rhenium-doped alkaline earth oxides through density functional theory (DFT) calculation [2O4 occupies an unconventional ferrimagnetic state with potential application in spintronics [Among spinel ferrite materials, cobalt ferrites  were synthesized by the sol-gel method. Both series of nanoparticles undergo the same procedure with different stoichiometric ratios. During the synthesis, rhenium powder , Co(NO3)2·6H2O , and Fe(NO3)3·9H2O  were used as oxidizing agents. The ingredients were weighed in desired stoichiometric proportions, and the metal nitrates were mixed and dissolved in 150 mL of distilled water using a magnetic stirrer at room temperature. Rhenium was dissolved in deionized (DI) water and placed in an ultrasonic bath at 40 °C for 30 min. The base solution of metal nitrates and rhenium solution were mixed and stirred for 1 h at 30 °C. Then, 50 mL 0.1 M HNO3 was added to the mixture and stirred for 30 min. Afterwards, 80 mmol ethylene glycol  was added to foster the formation of sol and prevent agglomeration. The precursor’s mixture was heated to 80 °C and stirred steadily on a hot plate until a puffy dark brown gel appeared. The gel was then transferred into a dish for combustion and maintained at the same temperature. This study investigates the effects of Rhenium substitution for Co and Fe on the structural and physical properties of inverse-spinel CoFe2O4.The nanoparticles of CoThe viscous gel began to froth until a dried gel was achieved. Finally, the dry gel was calcinated at 800 °C for 3 h to obtain crystalline cobalt ferrite nanoparticles. The targeted nanoparticle sample was obtained by grinding the bulk with a mortar and pestle for 40 min. For further clarification, the synthesized process of the required rhenium-doped cobalt ferrite is illustrated in Phase identification and impurity detection were carried out with an X-ray diffraction (XRD) method using an Aeris model  with Cu kα radiation with 2θ from 10° to 80°. SEM  was used to investigate the morphology of the samples. A vibrating sample magnetometer  was used to obtain magnetic hysteresis loops and ZFC-FC curves at room and low temperatures. Moreover, Raman spectra were measured by confocal Raman microscope . Dielectric constant and dielectric loss were obtained by a broadband dielectric/impedance analyzer .1−xRexFe2O4 and CoFe2−xRexO4) nanoparticles. All samples were tested in continuous mode from 10° to 80°, indicating the successful formation of the single phase without any distortion. 1−xRexFe2O4 and CoFe2−xRexO4  prepared samples. After further refinement by the software Fullprof, all XRD peaks were well-indexed. It can be seen that all samples have prominent peaks that correspond to (111), (220), (311), (400), (422), and (440) planes, which all belong to the Fd3m cubic spinel structure, indicating that Re does not change the structure of the hosting material and maintains a pure single phase of cobalt ferrite nanoparticles. Furthermore, the experimental XRD data were used with the software JANA 2006 to estimate the lattice parameters, surface-to-volume ratio, and reliability factors. The average crystallite size was calculated from the linewidth of (311) broadening of the XRD pattern with the Scherer formula [D shows the crystallite size in nm, θ represents the diffracted Braggs angle, β defines the full width of half maximum of the diffraction peaks, and We performed the X-ray diffraction (XRD) tests of the sol-gel prepared samples to investigate the phase purity and crystal structure of the acquired (Co formula :(1)D=0.9wp), and reliability factor (Rp) of Rietveld refinement were also evaluated.h, k, and l are Miller indices, and d is the interplanar spacing. The values of the lattice constant (a = b = c(Å)) increased slightly with the doping ratio, indicating the strong presence of Re ion in our samples. The refined structural parameters of pure and Re-doped cobalt ferrite nanoparticles are presented in 4+ radius in the octahedral site is 0.63 Å, which is rather close to the replaced Fe3+ radius (0.65 Å) and is not expected to be a substantial driver of the structural transformation [4+ will change the Fe ions from trivalent to divalent [Firstly, the grain size decreases slightly with the increasing amount of doping, possibly resulting from the strain effect of Co and Re ions. The structural strain prevents the growth of crystallites by the substituting elements. With the small amount of doping, the doping of Re induced a lattice shrinkage of the neighbor lattices, causing a reduction in the grain size. Secondly, the Reormation . The insdivalent . Many otdivalent .1−xRexFe2O4 and CoFe2−xRexO4 (0 ≤ x ≤ 0.05) nanoparticles was inspected by scanning electron microscopy (SEM). The pure and Re-doped cobalt ferrite SEM images were taken at a 5 μm scale, as shown in 1−xRexFe2O4, which increases with the content of Re in the Co site. In the literature, many previous works have reported the agglomerations. For example, Mritunjoy et al. observed similar agglomeration behavior when doping the cobalt ferrite with Cu, asserting that Van der Waals force and dipole–dipole interaction mainly contributed to this enhancement in the interparticle interactions [The surface morphology information of the synthesized Coractions . Shakil ractions . When doractions .Furthermore, it is noted that, with the increase in the Re doping ratio, the Co-site doped sample particles agglomerate faster than the Fe-site doped samples, which may be due to the dipole–dipole interactions between each grain. The agglomeration is severely reduced by adding Re to the Fe site, as seen in 1−xRexFe2O4 and CoFe2−xRexO4 samples calculated from the XRD and SEM result. It can be seen that the particle size measured from the SEM image is more than 10 times larger than the grain size calculated by XRD spectra, further indicating an agglomeration behavior of the particles, which has also been reported by other studies [ studies ,33.2O4, (c) Co0.98Re0.02Fe2O4, (d) Co0.95Re0.05Fe2O4, (e) CoFe1.98Re0.02O4, and (f) CoFe1.95Re0.05O4 nanoparticles are presented in Raman spectroscopy is a powerful technique to investigate the structure of nanoparticles, especially for tracing the spinel’s structural evolution and cation distribution ,35,36. T1g: 648–680 cm−1; Eg: 278–293 cm−1; and 3T2g: 539–565, 449–471, and 163–177 cm−1), predicted from the group theory analysis [−1, which correspond to the five predicted Raman active modes (A1g + Eg + 3T2g), confirming the formation of spinel phases. Besides, two bands at ~621 cm−1 and ~356 cm−1 also appear as a result of the quantum size effect and the inverse and mixed-type spinel ferrite reported in the literature [1g(2) and A1g(1) peaks at 621 and 685 cm−1, respectively, can be attributed to the Fe3+-O and Re2+-O bonds at tetrahedral voids (AO4) [2g(2) and T2g(1) at 460 and 567 cm−1, respectively, are attributed to the asymmetry bending motions of the oxygen in Fe3+-O and Re2+-O bonds at tetrahedral voids, and T2g(3) at 195 cm−1 is derived from the vibration of cations in octahedral voids [g peaks at 300 cm−1 correspond to the symmetric oxygen bending in AO4 units [According to the XRD analysis, Re-doped cobalt ferrite belongs to the cubic space group Fd3m, which has five Raman active modes  ,43. The O4 units ,46.1g (685 cm−1), T2g(2) (460 cm−1), and Eg (300 cm−1) modes increase. According to the literature, these three peaks originate from the movement of the tetrahedral voids, which indicates that the inclusion of Re mainly influences the structure of the tetrahedral sites, i.e., increasing the vibrational energy of Fe3+–O and Re2+–O bonds by varying the bond length [2g(3) (195 cm−1) mode, the peak position increases with the Fe-site doping ratio, while its fluctuates slightly for Co-site doping samples. This implies that the substitution of iron to Re also influences the structure of octahedral sites, leading to a more distorted structure compared with Co-site doping. Other modes’ peak positions are altered slightly with the increase in the doping ratio. The shift in Raman peaks indicates that Re substitution imposes a distortion of the tetrahedral sublattice and influences the octahedral sublattice for Fe-site doping.d length . RegardisM), coercivity (Hc), magnetic anisotropy (K), remanence magnetization (rM), squareness ratio (Mr/Ms), and magnetic moment (Bn in Bohr magneton), are listed in Hc is the coercivity, Ms is the saturation magnetization (emu/g), and CoFeM2O4 is the molecular weight of the ferrite. For the Co-site doping, the saturation magnetization and remanence magnetization decreases with the increasing doping ratio, while in the Fe-site, they are enhanced with the increasing doping ratio. For the Co-site doping, the saturation magnetization decreases with the increase in the doping ratio from 0 to 0.05 , while for the Fe-site doping, the saturation magnetization increases . The variation in saturation magnetization is closely related to the size and shape of the nanoparticles. From SEM, it is observed that the particles agglomerate with the increase in substitution of Re to Co as a result of an increase in dipole interactions, changing the surface properties of the particles. It is likely that, because of agglomeration resulting from Re doping, the surface-to-volume ratio of the particle decreases, reducing the surface effect, and the orientation of the magnetic moment can also be influenced by the neighboring particles. However, the particle size decreases slightly with the increase in doping of Re to Fe, increasing the saturation magnetization. Additionally, the coercivity measured at 4 K decreases with the increase in the Re–Co substitution ratio, while it increases with the increase in doping of Re to Fe. This can be explained by the change in anisotropy with the inclusion of Re. Moreover, the magnetic moment increases with the decrease in the Co-site doping ratio, which can be explained by the change in magnetic anisotropy. The magnetic anisotropy decreases for Co-site doping, leading to a more random orientation of the moment and a decrease in the net magnetic moment. Similarly, the anisotropy of Fe-site doping increases, resulting in an increase in the total magnetic moment with an increase in the doping ratio. Compared with other dopants, Re-doped cobalt ferrite maintains a higher total magnetic moment [The magnetic hysteresis loop (M-H) tests of the pure and Re-doped cobalt ferrite at 300 and 4 K are illustrated in c moment ,49, indisM and cH in Co-site doping and increase in sM and cH in Fe-site doping are closely related to the change in magnetocrystalline anisotropy resulting from Re doping. As shown in When comparing Co-site doping and Fe-site doping, the decrease in 2+ ions at the octahedral sites. This decreasing and increasing behavior mainly results from the surface effects generated from the grain size variation. Moreover, it is observed that, at a low temperature (4 K), the remanence magnetization, coercivity field, and squareness of all samples are higher than those at 300 K. 1−xRexFe2O4 and CoFe2−xRexO4 nanoparticles, showing an irreversible behavior. It can be seen from the figure that the blocking temperature of all of the nanoparticles is about 250 K, with a slight increase in Fe-site doping and a decrease in Co-site doping, which reflects the variation trend of anisotropy at 4 K.When Re is doped in the Co site, Re mainly occupies octahedral sites with opposite spin alignment with iron in both the octahedral and tetrahedral sites. This structure appears to be at the lowest energy state and results in a decrease in anisotropy. When doping Re in the Fe site, the structure occupies a higher energy state, increasing anisotropy as a result of replacing heavy Re ions with smaller Co2O4, Co0.98Re0.02Fe2O4, and CoFe1.98Re0.02O4 nanoparticles were obtained in various temperature and frequency ranges of 1 Hz to 1 MHz with an applied AC electric field. The obtained results of the dielectric constant, tangent loss, and AC conductivity are shown in The dielectric properties of the spinel ferrite are strongly determined by the chemical composition and site occupancy of metal cations . To furtr’ε) of the dielectric constant versus frequency at various temperatures for CoFe2O4, Co0.98Re0.02Fe2O4, and CoFe1.98Re0.02O4 nanoparticles. The insets of 2O4, Co0.98Re0.02Fe2O4, and CoFe1.98Re0.02O4), representing the typical behavior of spinel ferrite nanoparticles. The real part undergoes a sharp decrease with frequency up to 1 kHz and remains constant at a high frequency. Such behavior could be described by considering many sources of dielectric polarization, such as ionic or interfacial polarization. At lower frequencies, the main contribution to the polarization is ionic, which is thus responsible for the high value of the real part. In comparison, at higher frequencies, only electronic polarization remains active because of the inability of electric dipoles to follow the fast variation in the alternating electric field. The contribution of net ionic and orientation polarizability becomes slow at higher frequencies, which causes a decrease in the real part and finally remains almost constant. The decrease in ionic polarizability or initial loss can be attributed to orientation.2O4, Co0.98Re0.02Fe2O4, and CoFe1.98Re0.02O4 nanoparticles are shown in tanδ in the low-frequency region can be attributed to the high resistivity of grain boundaries, which are more effective at lower frequencies. The energy loss may be attributed to collision, vibration, and other charge particle interaction phenomena. The AC conductivity versus frequency at various temperatures of CoFe2O4, Co0.98Re0.02Fe2O4, and CoFe1.98Re0.02O4 nanoparticles is shown in 2+ and Fe3+ ions and hole hopping between Co3+ and Co2+ ions [3+ by Re4+ induces electron hopping, which supports the formation of polarons. Moreover, Rahman et al. reported that the formation of polaron derives from the increase in structure distortion, which means that Fe-site doping increases the structure distortion, while Co-site doping decreases the distortion [The tangent loss factor , and magnetic anisotropy, decreased in the Co-site doping with the increasing doping ratio of Re, while in the Fe site, they were enhanced with the increasing doping ratio. The variation in saturation magnetization is closely related to the size and shape of the nanoparticles. From SEM, it is observed that the particles agglomerate with the increase in the substitution of Re to Co owing to an increase in dipole interactions, changing the surface properties of the particles. It is likely that, because of agglomeration resulting from Re doping, the surface-to-volume ratio of the particle decreases, reducing the surface effect, and the neighboring particles can also influence the orientation of the magnetic moment. Finally, the dielectric measurement revealed that the real part (r’ε) and tangent loss (tanδ) show a response at low frequencies. The sharp increase at high temperatures enhances the barrier for charge mobility at grain boundaries, suggesting that samples were highly resistive. The real part and the tangent loss were found to be higher in the Fe-site doping with the increasing Re doping ratio as compared with the Co site, which was attributed to interfacial or space charge polarization.In summary, the effect of Rhenium Co-site and Fe-site doping on the structural, microstructural, magnetic, Raman, and dielectric properties of CoFe


In addition, Ba4Al7Li28.08O26.92N1.08 doped with the activator ion Eu2+, exhibits a broad bandemission with a maximum at λmax = 524 nm (2.34 eV)with a fwhm of 112 nm (4373 cm–1/0.54 eV), whichcan be described by a superposition of two adjusted emission bandsat λmax = 515 nm (2.41 eV) with a fwhm of 70 nm (2704cm–1/0.34 eV), and at λmax = 574nm (2.18 eV) with a fwhm of 127 nm (4127 cm–1/0.51eV).Thenew compound Ba 4Al7Li28.08O26.92N1.08:Eu2+ was synthesizedby a high-temperature solid-state reaction. The anionic network inthe structure consists of AlO3N/AlO4 and highlycondensed edge- and corner-sharing LiO4 tetrahedra resultingin a degree of condensation of ∼1.25. The 10-fold coordinatedBa2+ cations are incorporated between seven-membered ringsof the anionic framework and form endless chains along the crystallographic b-axis. The new compound could be successfully doped withthe activator ion Eu2+ exhibiting interesting luminescenceproperties.The compound Ba The best-known representativesinclude compounds such as Sr[Li2Al2O2N2]:Eu2+1 and Sr[Li2.5Al1.5O3N]:Eu2+,2 where mainly Sr2+ cations are incorporatedin the vierer ring3 channels.Up to now, no compound is known in which Ba2+ cations fillthe channels formed by the anionic framework structure. Extendingthe field to include the substance classes of pure oxide and nitridevariants, the first and only barium lithoaluminate with the sum formulaBa3Li7Al3O11 was publishedby Nishita and Yamane in 2021.4 In thelast years, variants with other alkaline earth cations such as Ca[LiAl3N4]:Eu2+,5 Ca[LiAlN2],6 Ca18.75[Li10.5Al39N55],7 Sr4[LiAl11N14]:Eu2+,8 Sr[LiAl3N4]:Eu2+,9 Sr2LiAlO4:Eu2+,11 and Sr0.833Al1.167Li2.833O4:Eu2+12 could be synthesized and characterized.Additionally, most of these phases could successfully be doped withthe activator ion Eu2+ showing interesting luminescenceproperties in the yellow to red spectral region. These compounds forma highly condensed anionic framework, which is discussed to be favorablefor phosphors in relation to a small Stokes shift, less electron-phononcoupling, and a favorable thermal-quenching behavior.14Becausethe field of oxonitridolithoaluminatesis still a fairlynew substance class, there are not yet many known compounds in whichexclusively LiT and coordinating anions N/O [κ = n(T)/n]. In relationto binary nitrides and oxides of elements such as Si, Al, Be, andLi, the degree of condensation increases with the formal substitutionof O by N and with the decrease in oxidation number of the tetrahedralcenter κ(Si3N4) = 0.75, κ(SiO2) = 0.5, κ(AlN) = 1, κ(β-Be3N2) = 1.34, κ(BeO) = 1, and κ(Li2O) =2. Although for most silicate and aluminate compounds, there is noknown degree of condensation greater than 1 due to the fact that theAl4 and Si4 tetrahedra are exclusivelyedge- and corner-shared among each other. In the case of beryllates,there are some representatives such as Sr[Be6ON4]:Eu2+ (κ = 1.2),15MBe20N14:Eu2+  (κ = 1.42),16 and Eu3Be22N16O (κ = 1.29)17 exhibiting a degree of condensation greaterthan 1. The structure of the mentioned beryllates is characterizedby Be4 tetrahedra, which are connected over severaledges and corners, and in the compound Eu3Be22N16O additionally by trigonal planar BeN3 units.The lower oxidation state of beryllium enforces an increase of tetrahedralcenters, which leads necessarily to a higher degree of condensation.In the field of (oxonitrido)lithoaluminates, KLi4AlO4 (κ = 1.25)18 is the onlyknown representative with a degree of condensation greater than 1.The anionic framework in KLi4AlO4 is built upby “isolated” AlO4 tetrahedra, which frequentlyshare common corners and edges with LiO4 tetrahedra.The degree of condensation κ is defined by the ratioof tetrahedralcenters 4Al7Li28.08O26.92N1.08 and with a highly condensed LiO4 tetrahedra frameworkresulting in a degree of condensation of ∼1.25.Here, we present the crystal structure and luminescence propertiesof a new oxonitridolithoaluminate possessing the composition Ba4Al7Li28.08O26.92N1.08 crystallizesin the monoclinic space group P21/m (no. 11) with the lattice parameters a = 1052.41(3), b = 615.93(2), c = 1088.45(4) pm, β = 98.86(1)°, and a volume of V = 0.69712(4) nm3. Details on the crystal structurerefinement and atomic coordinates are given in Supporting Information.The compound Ba4Al7Li28.08O26.92N1.08 is built up bytwo crystallographically distinguishable barium sites, which are coordinatedtenfold by O2– and N3– anions,respectively. Based on the high-quality single-crystal data set, thereare indications to distinguish between N and O on the anion positions.The O2 to O11 sites are fully occupied by O and show minimal deviationfrom the occupancy of 1 by setting them free in the refinement. Byrefining N on these sites, this leads to a significant overoccupation.In comparison, the mixed occupied N1/O1 site exhibits a significantunder- or overoccupation, respectively, in the case of a pure occupationof O and N. The resulting anionic displacement parameters of thissite show a relatively large deviation in relation to the other fullyoccupied O2–O11 sites, indicating a mixed occupied site ofN and O. In addition, a better R-value was also observedwhen this site is mixed occupied. Furthermore, the connectivity ofthe different sites as well as the resulting bond lengths comparedwith compounds known from literature confirms the assignment. Becausethe N1/O1 site is mixed occupied by 54% N and 46% O, three differentcoordination spheres result for the Ba1 site. The first possibilityis that the Ba1 site is coordinated by 10 O2– anions.In the second case, the Ba1 site would be coordinated by nine O2– and one N3– anions, and the thirdpossibility would be that the Ba1 site forms a coordination sphereto eight O2– and two N3– anions.The Ba1–O distances range from 286.07(2) to 310.9(2) pm andthe Ba1–O1/N1 distance is 310.07(4) pm. The Ba2 site is exclusivelycoordinated by 10 O2– anions and their Ba2–Odistances vary between 277.9(2) and 320.71(5) pm. Due to the highdisplacement of the Ba2+ cations of the Ba2 site and therelatively high residual electron density around this position, splitpositions were introduced in the single-crystal refinement and areadditionally described by the Ba3 and Ba4 site. Due to the spatialproximity and to avoid a strong correlation between the Ba2, Ba3,and Ba4 sites, only an isotropic refinement of the displacement parameterswas applied. Considering the Ba3 and Ba4 site, the Ba3–O distancesare between 279.1(2) and 322.4(2) pm, while the Ba4–O distancesrange from 275.1(2) to 324.5(2) pm. The Ba–O/N distances ofthe Ba1 and Ba2 site, including the split position Ba3 and Ba4 site,correspond well with the sum of the ionic radii and are in good accordancewith Ba–O/N distances known from literature.23 The described split positions above are then referredto as the Ba2 site in the following. The polyhedra of the Ba1 andBa2 sites could be described as distorted single-capped triangularcupola, which polyhedron shape could also be observed in compoundssuch as Eu3Be22N16O.17 The program VESTA 3 as well as from theLi4/Al4 site, where the latter is occupied by about 53% with Al and47% with Li. Mixed occupied sites of Al and Li have also been observedin other compounds known from literature such as Sr4[LiAl11N14]:Eu2+.8 Depending on the occupation of the Li4/Al4 site and the resultingoccupation of the N1/O1 site, this unit is arranged in such a waythat a planar triple-unit of AlO3N tetrahedra or of twoAlO4 plus one LiO4 tetrahedra is formed, whichare corner-shared via the N3– and via the O2– anion, respectively. The Al1–O and Al2–Odistances range from 176.9(2) to 181.9(3) pm and from 175.4(2) to177.7(2) pm, while the Al1–O1/N1 distance is 179.8(2) pm andthe Al2–O1/N1 distance is 182.2(3) pm, which are in good accordancewith the sum of ionic radii and Al–O/N distances known fromliterature.10 With respectto the mixed occupation of the Li4/Al4 site, the Li4/Al4–Odistances range from 185.6(2) to 186.74(5) pm and the Li4/Al4–O1/N1distance is 192.6(2) pm corresponding to the average Al–O/Nand Li–O/N distances of a pure Al and Li site (average Al2–Odistances of 176.9 pm and average Li1–O distances of 195.8pm). These triple-units are then sandwiched between the Ba1 polyhedraof the Ba polyhedra chains in such a way that each AlO3N/AlO4 or LiO4 tetrahedron is connected tothe Ba1 polyhedra by a common edge, and in addition, the AlO3N/AlO4 tetrahedra of the Al1 site are face-shared to theBa2 polyhedra and those of the Al2 site are edge-shared to the Ba2polyhedra. The planar triple-units among themselves are corner-sharedvia the LiO4/AlO3N tetrahedron, each via twoO2– anions, and arrange along the crystallographic b-axis in the form of a 21 screw axis /n is ∼1.25,resulting in a highly condensed anionic framework. This is due tothe fact that the proportion of Li+ cations in the structureis much higher than that of the Al3+ cations and, comparedto (oxo)nitridosilicates or -aluminates, the Li+ cationsin the form of LiO4 tetrahedra can be connected over severaledges due to the lower formal charge of Li+ compared toAl3+ and Si4+. Due to the high electrostaticrepulsion of the Al3+ and Si4+ cations resultingfrom the high formal charge, the tetrahedra are connected to eachother only via common corners and edges because the tetrahedral centerswould come too close to each other in case of face-sharing. A degreeof condensation greater than 1 can already be observed in (oxo)nitridoberyllatessuch as Eu3Be22N16O17 because the formal charge of Be2+ is also smallerthan that of Al3+ and Si4+ here. The highlycondensed LiO4 framework in the structure of the titlecompound is built up by eight crystallographically distinguishableLi sites and two sites mixed occupied by Al and Li. Along the crystallographic b-axis, a channel within the seven-membered ring is formed,where the seven-membered ring is exclusively built up by corner- andedge-sharing LiO4 tetrahedra of the Li1, Li2, Li6, Li7,and Li9 sites. On the one hand, the seven-membered rings are identicallyarranged and are corner-shared to each other via the O2– anions except for the LiO4 tetrahedra of the Li9 site,which are edge-shared via two O2– anions, but onthe other hand, two seven-membered rings share the LiO4 tetrahedron of the Li6 site. The single-crystal refinement showsthat the Li9 site is only occupied by about 80% (occ. = 0.82) andalthough every fifth LiO4 tetrahedron of the Li9 site isabsent in the structure, the structure of the seven-membered ringsis maintained due to the high interconnection of the LiO4 tetrahedra of the Li9 site. A unit of two seven-membered rings,sharing the LiO4 tetrahedron of the Li6 site, arrange themselvesin the structure so that they enclose the planar triple-unit consistingof three AlO3N tetrahedra or two AlO4 plus oneLiO4 tetrahedra, respectively, by sharing common cornersand edges. In addition, the LiO4 tetrahedra of the seven-memberedring are also edge-shared to the polyhedra of the Ba1 and Ba2 sites and by two sites, which are mixedoccupied by Al and Li. According to the single-crystal refinement,the Li3/Al3 site is Al-rich and is occupied by 94% Al and only 6%Li, while the Li5/Al5 forms a Li-rich site and is occupied by 97%Li and only 3% Al. Indications for a mixed occupation are the largeanisotropic displacement parameters for pure Li or Al sites and theaverage Li3/Al3–O distances of 178.8 pm and Li5/Al5–Odistances of 193.6 pm, which are between those of a pure Al (averageAl2–O distances of 176.9 pm) and Li site (average Li1–Odistances of 195.8 pm), for example. Additionally, the Li11 site isonly 90% occupied by Li and hence every 10th LiO4 tetrahedronof this site is consequently not present in the structure. The cross-linkedframework is formed by corner- and edge-shared LiO4 andAlO4 tetrahedra  were examined on a single-crystal. Ba4Al7Li28.08O26.92N1.08:Eu2+ can be excited by near-UV to blue light and exhibitsan emission in the green to yellow spectral region with a maximumat λmax = 524 nm (2.34 eV) and a fwhm of 112 nm (4373cm–1/0.54 eV). The measured emission profile canbe described by a superposition of two adjusted emission bands atλmax = 515 nm (2.41 eV) with a fwhm of 70 nm (2704cm–1/0.34 eV), and at λmax = 574nm (2.18 eV) with a fwhm of 127 nm (4127 cm–1/0.51eV). In the CIE-xy color space, this correspondsto the value x = 0.337(1) and y =0.523(1)  see 7.2+. In the structureof Ba4Al7Li28.08O26.92N1.08, the Ba1 site on the one hand and the sum of splitpositions  in the other hand could be suitableto host the activator ion Eu2+. In the case of the Ba1site, the Ba2+ cation is coordinated by 10 anions. Whichcoordination sphere is formed around this Ba2+ cation dependson the occupation of the O1/N1 site, which is occupied by 53% N and47% O. Consequently, this coordination sphere can vary between 10O2– anions and 8 O2– plus 2 N3– anions, which has an effect on the position of theemission band and the fwhm. The Ba1–O distances range from286.07(2) to 310.9(2) pm, whereby the Ba1–O1/N1 distance is310.07(4) pm, resulting in a polyhedron size of 56.46 Å3. The split position of the Ba2 site exclusively forms a coordinationsphere to 10 O2– anions resulting in a polyhedronsize of 54.27 Å3. Considering the Ba3 and Ba4 site,additionally describing the split position, the Ba–O distancesvary only minimally, which could also have an effect on the emissionband. The Ba2–O distances vary between 277.9(2) and 320.71(2)pm, whereby the Ba3–O distance ranges from 279.1(2) to 322.4(2)pm and the Ba4–O distances range from 275.1(2) to 324.5(2)pm. Because the average Ba–O/N distances (300.5 pm) and thepolyhedron size (56.46 Å3) for the Ba1 site is similarcompared to the Ba2 split position with average Ba–O distancesof 300.0–300.3 pm and a polyhedron size of 54.27 Å3, the difference in the emission bands may be dominated bythe nephelauxetic effect.30 The 5d electron-level lowering for the activator ion Eu2+ isstronger when it is coordinated by N3– anions thanby O2– anions due to the higher formal charge ofN3– compared with O2–. Consequently,it leads to a red shift of the emission band, for example, regardingthe Ba1 site. In the case of the Ba1 site, the relatively large fwhmis caused by the fact that the coordination sphere varies dependingon the occupation of the N1/O1 site (inhomogeneous line broadening).However, because the coordination sphere of the Ba2 split positionis exclusively built up by O2– anions, the nephelauxeticeffect is smaller resulting in a blue shift of the emission band dueto a less energetic lowering of the 5d levels. Basedon the nephelauxetic effect and considering the different coordinationsphere of the Ba1 site and the split position Ba2 site, it would indicatethat the Ba1 site seems reasonable for the emission band at λmax = 574 nm (2.18 eV) with a fwhm of 127 nm and the Ba2 site,including the Ba3 and Ba4 site, can attribute to the emission bandat λmax = 515 nm (2.41 eV) with a fwhm of 70 nm.Because especially the fwhm of Eu2+-based emission aretemperature-dependent, the values of the luminescence properties ofthe title compound as well as the following values of the compoundsknown from literature are related to room temperature.The observed double band emissionin 2+ as central cation, such as Sr[Li2Al2O2N2]1 and Sr[Li2.5Al1.5O3N]2 for instance.In addition, the pure nitride and oxide variants such as Sr[LiAl3N4],9 SrxLix2+Alx2–O4,31 and Sr2LiAlO410 could alsobe synthesized, and all these compounds could be successfully dopedwith the activator ion Eu2+. The variant Sr[Li2Al2O2N2]:Eu2+ crystallizesin the tetragonal space group P42/m and has one Sr site, which is coordinated by four O2– and four N3– anions with Sr–Odistances of 265.9(4) pm and Sr–N distances of 276.5(5) pm,resulting in a narrow band emission at 614 nm with a fwhm of 48 nm(1286 cm–1/0.1549 eV). The compound Sr[Li2.5Al1.5O3N]:Eu2+ crystallizes in thetetragonal space group I4/m andhas one Sr site, which is coordinated by eight equidistant O/N siteswith Sr–O/N distances of 267.4(4) pm, resulting in an emissionmaximum at 578 nm with a fwhm of 80 nm (2380 cm–1). In relation to the pure nitride variant Sr[LiAl3N4]:Eu2+, which crystallizes in the triclinic spacegroup P1̅, there are two crystallographicallydistinguishable Sr sites in the structure and both are eightfold coordinatedby N3– anions. Because their polyhedron sizes onlydiffer minimally with V = 34.26 Å3 for the Sr1 site and V = 34.00 Å3 for the Sr2 site, the compound exhibits only one narrow band emissionat 650 nm with a fwhm of 50 nm (1180 cm–1/0.1463eV). The compound SrxLix2+Alx2–O4:Eu2+ crystallizes, depending on the x value, in the tetragonal space group P4/n or in the superspace group I4/m(00γ)00. Because the Sr2+ cations aresubject to a statistical disorder in the location of Sr2+ ions in the structure, a modulated structure model was applied.The Sr2+ cations are distributed at seven sites, some ofwhich are partially occupied. All different Sr sites are coordinatedby eight O2– anions forming a slightly distortedcuboid with Sr–O distances varying between 254.4 and 296.4pm regarding space group P4/n. Theluminescence properties were investigated for the composition SrLi3AlO4:Eu2+ resulting in an emission maximumat 570 nm with a fwhm of ∼46 nm (∼1540 cm–1/∼0.19 eV).32 Due to the comparablestructure of the four Sr variants, they show that a (partly) substitutionof N by O and longer Sr–O/N distances leads to a blue shiftin the emission profile.Althoughno barium oxonitridolithoaluminate is known so far, thereare some representatives known in the literature with Sr2LiAlO4:Eu2+ crystallizes not only in the monoclinicspace group P21/m butalso in the orthorhombicspace group Cmcm. The latter shows one emission maximumat 565 nm with a fwhm of 58 nm (2230 cm–1/0.28 eV)due to one Sr site in the structure with Sr–O distances of266.8(5) pm. The former has two crystallographically distinguishableSr sites with Sr2–O distances of 266.7(6) pm and Sr1–Odistances of 269.4(5) pm resulting in a double band emission at 507nm and 562 nm. The Sr1 site in Sr2LiAlO4:Eu2+ could be partly substituted by Ba2+ cations andhas an effect on the luminescence properties. The compound Sr1.85Ba0.15LiAlO4:Eu2+ crystallizesin the orthorhombic space group Pnma with Sr1/Ba1–Odistances of 272.1(9) pm and Sr2–O distances of 265.8(5) pm,which is in comparison to the Sr1–O distances and Sr2–Odistances in the pure Sr variant larger and smaller, respectively.Because the compound shows no split emission band and exhibits onlyone emission maximum at 588 nm with a fwhm of 77 nm (2250 cm–1/0.28 eV), it can be assumed that only the Sr2 site is substitutedby the activator ion Eu2+ due to the smaller Sr–Odistances resulting in a red shift caused by a larger crystal fieldsplitting. Due to the larger ionic radii of Ba2+ in contrastto Sr2+ cations {r[Ba2+ (CN= 8)] = 1.56 pm, r[Sr2+ (CN = 8)] = 1.40pm},33 the M–O/N distances of the Ba2+ cationsare larger on average and thus a blue shift in the emission will beexpected when Ba instead of Sr is incorporated into the structure.The polymorphic compound Sr2+ as the central cation, such as Ba3Si6O12N2:Eu2+,34 Ba3Si6O9N4:Eu2+,36 BaSi2O2N2:Eu2+,38 BaAlSi4O3N5:Eu2+,39 BaAl2Si3O4N4:Eu2+,40 BaAlSi5N7O2:Eu2+,42 and BaSi3Al3O4N5:Eu2+.43 In the aforementioned compounds, the different Ba sites are possiblepositions to host the activator ion Eu2+ and their coordinationspheres are presented in more detail below. The structure of Ba3Si6O12N2:Eu2+ isdescribed by two crystallographically distinguishable Ba sites, whichhave different coordination spheres. The Ba1 site is coordinated bysix O2– anions with Ba–O distances of 277.4(3)pm, while the Ba2 site forms a coordination sphere to six O2– anions and two N3– anions with Ba–O distancesbetween 281.9(3) and 290.2(3) pm and Ba–N distances rangingfrom 299.7(6) to 347.1(6) pm. Because this compound exhibits onlyone emission maximum at 527 nm (fwhm = 65 nm), only one of the twoBa sites is preferred for the incorporation of the activator ion Eu2+, which could be assigned to the Ba2 site. The effect ofN3– and O2– anions on the emissionmaximum could be shown in the compound Ba3Si6O9N4:Eu2+ exhibiting one strongemission maximum at 520 nm (fwhm = 78 nm) and two weak emission maximaat λmax = 370 nm, and 405 nm. According to Wei etal.,35 the strong emission maximum couldbe assigned to the Ba3 site building a coordination sphere to sixO2– anions and three N3– anions,where the Ba–O distances range from 266.8(5) to 287.0(4) pmand the Ba–N distances are 341.2(1) pm. The Ba2 site, responsiblefor the emission maximum at λmax = 450 nm, is coordinatedby six O2– anions, where the Ba–O distancesranging from 263.2(2) to 285.3(1) pm, and to two N3– anions with Ba–N distances between 318.0(2) and 360.2(6)pm. The Ba1 site forms a coordination sphere to nine O2– anions with Ba–O distances between 270.85(1) and 322.1(3)pm and is correlated to the emission maximum at λmax = 370 nm. In this compound, a blue shift in the emission profilecould be observed by the partial substitution of N3– by O2– anions. Furthermore, it could also be possiblethat the two minor emission bands in Ba3Si6O9N4:Eu2+ originate from, for example,defect luminescence, which could be clarified by decay time measurements.In the literature, there are some known oxonitride phosphors thathave Ba4O3N5:Eu2+ and BaAl2Si3O4N4:Eu2+ in the field of barium oxonitridoalumosilicates.Because they have comparable structures, a red shift in the emissionband can be observed with the increase in number of N3– anions in the coordination sphere of the Ba2+ cations.Both compounds crystallizes in the orthorhombic space group A21am having one Ba site. TheBa site in the compound BaAl2Si3O4N4:Eu2+ builds up a coordination sphere tothree N3– and five O2– anionswith Ba–O distances between 275.9 and 322.0 pm and Ba–Ndistances ranging from 306.7 to 333.0 pm. The compound exhibits anobserved emission maximum at 458 nm (fwhm = ∼100 nm). The Basite in the variant BaAlSi4O3N5:Eu2+ is coordinated by four O2– and five N3– anions with Ba–O distances varying between285.6(7) and 286.1(7) pm and Ba–N distances ranging from 312.5(8)and 321.1(4) pm. This oxonitride variant exhibits an emission maximumat 475 nm (fwhm = ∼100 nm).The nephelauxetic effect on the emission bands can also be seenwith the representatives BaAlSi5N7O2:Eu2+ and BaSi3Al3O4N5:Eu2+. The representative with the composition BaSi3Al3O4N5:Eu2+ crystallizesin the monoclinic space group P21/m with one Ba site, which is coordinated by four O2– and four N3– anions with Ba–O distancesin a range of 261.8(7) and 272.0(4) pm and Ba–N distances between274.8(7) and 331.2(8) pm resulting in an emission maximum at 470 nm(fwhm = ∼75 nm). In the structure of BaAlSi5N7O2:Eu2+, which crystallizes in the orthorhombicspace group Imm2, there is one Ba site coordinatedby four O2– and six N3– anionswith Ba–O distances between 285.1(7) and 335.0(7) pm and Ba–Ndistances ranging from 319.7(7) to 336.7(5) pm, resulting in an observedbroad band emission maximum at 515 nm (fwhm = ∼100 nm).Different structures to theaforementioned barium oxonitridoalumosilicatesshow the compounds BaAlSi2O2N2:Eu2+ features a layered structure, which can crystallizein two different orthorhombic space groups Cmcm and Pbcn. In both structure models is one Ba site, which iscuboid-like coordinated by eight O2– anions. Theresulting cuboid is additionally capped by two N3– anions with Ba–O distances between 273(1) and 308.8(9) pmand Ba–N distances ranging from 329.8(6) to 334.3(6) pm resultingin an observed emission maximum at 490–500 nm (fwhm = ∼40nm). In comparison to the phosphors with Ba2+ as the centralcation, the Ba–O/N distances in the compound Ba4Al7Li28.08O26.92N1.08 are in a similar range. Furthermore, the nephelauxetic effect canbe observed for comparable structures or in structures with more thanone Ba site, which forms different coordination spheres to O2– and N3– anions, implying the assignment of theemission bands to the different Ba sites seems consistent in the herepresented compound. An overview of all aforementioned compounds arerepresented in Table S3 in the Supporting Information.Furthermore, the compound BaSi4Al7Li28.08O26.92N1.08. The anionic part of the structure is built up by AlO3N/AlO4 tetrahedra and highly condensed edge- andcorner-sharing LiO4 tetrahedra forming seven-membered ringsand a cross-linked framework. The 10-fold coordinated Ba2+ cations are incorporated between the seven-membered rings and formpolyhedra chains along the crystallographic b-axis.The connection pattern in the anionic framework of LiO4 and AlO4 tetrahedra could not be observed in any knowncompound yet resulting in a new structure type. Due to the high proportionof Li+ cations in the title compound, this results in adegree of condensation of ∼1.25 and represents the first bariumoxonitridolithoaluminate with such a characteristic. In addition,Ba4Al7Li28.08O26.92N1.08 could successfully be doped with the activator ion Eu2+ and shows a broad band emission in the green to yellow spectralregion at λmax = 524 nm (2.34 eV) with a fwhm of112 nm (4373 cm–1/0.54 eV), which can be describedby a superposition of two adjusted emission bands at λmax = 515 nm (2.41 eV) with a fwhm of 70 nm (2704 cm–1/0.34 eV), and at λmax = 574 nm (2.18 eV) with afwhm of 127 nm (4127 cm−1/0.51 eV). By comparingthe Ba–O/N distances and the different coordination spheresof the two crystallographically distinguishable Ba sites with alreadyknown compounds from the literature, it was possible to assign theobserved emission bands to the respective Ba sites. In comparisonto the known luminescent barium oxonitridosilicates and garnets suchas Lu3Al5O12:Ce3+,44 the emission band is in a similar spectral region,but the title compound can be synthesized at much lower temperatures.Due to the lower stability and longer synthesis time in relation tothe aforementioned compounds, further optimization of the compoundBa4Al7Li28.08O26.92N1.08:Eu2+ regarding synthesis and stability haveto be done for any industrial application. Because the LiO4 tetrahedra form a similar highly condensed framework as comparativelythe beryllates; for instance, this could lead to the discovery ofnew phosphors in the field of (oxonitrido)lithoaluminates and also-silicates, which could result in interesting luminescence properties.This work contains a detailed discussionof the crystal structureand luminescence properties of the first barium oxonitridolithoaluminateBa4Al7Li28.08O26.92N1.08 could be synthesizedby a mixture of BaO , Li2CO3 , Al2O3 , Li3N , Eu2O3 , and lithium metal  in a molar ratio of 4:2:2:3:0.04:7.5. The starting materialswere ground in an agate mortar until a homogenous mixture was obtained,filled in a tantalum ampoule  and sealed via arc-welding under a pressure of 400mbar. During the arc-welding, the crucible holder was cooled withwater to avoid chemical reactions. All preparation steps were carriedout using an inert gas -filled glovebox dueto the moisture sensitivity of the starting material (Li and Li3N). The tantalum ampoule was placed into a silica-glass tube,which was filled with 400 mbar argon, heated to 830 °C within7 h, maintained at that temperature for 200 h, and cooled down toroom temperature by a cooling rate of 0.1 °C/min. The yieldedinhomogeneous white powder sample contained a few crystals, from whichone of them was identified as the title compound . Experimentsto obtain the compound as the main phase have not been successfulso far and the single-crystals decompose within a few days.Single-crystals of the compound BaKα radiation, λ= 0.7107 Å) equipped with a Photon 100 CMOS detector. Data processingand multi-scan absorption correction were carried out with the programsSADABAS45 and SAINT.46 For structure solution and refinement, the SHELXS/L48 software implemented in the program WINGX49 was applied. Further details of the crystal structure investigationon a single-crystal of Ba4Al7Li28.08O26.92N1.08 may be obtained from The CambridgeCrystallographic Data Centre via www.ccdc.cam.ac.uk/structures/ under the deposition number 2205834.The reaction productwas analyzed with a polarization contrast microscope to identify suitablesingle-crystals, which were isolated for X-ray measurements on a BrukerD8 Quest diffractometer .A setup of a blue laserdiode  in combination with a CCD Detector was used to recordthe emission spectra of the green-yellow luminescent Ba