Coumarin-modified ruthenium complexes: Synthesis, characterization, and antiproliferative activity against human cancer cells.

Among ruthenium complexes studied as anticancer metallodrugs, NKP-1339, NAMI-A, RM175, and RAPTA-C have already entered clinical trials due to their potent antitumor activity demonstrated in preclinical studies and reduced toxicity in comparison with platinum drugs. Considering the advantages of ruthenium-based anticancer drugs and the cytostatic activity of organometallic complexes with triazole- and coumarin-derived ligands, we set out to synthesize Ru(II) complexes of coumarin-1,2,3,-triazole hybrids (L) with the general formula [Ru(L)(p-cymene)(Cl)]ClO4. The molecular structure of the complex [Ru(2a)(p-cymene)(Cl)]ClO4 (2aRu) was determined by single-crystal X-ray diffraction, which confirmed the coordination of the ligand to the central ruthenium(II) cation by bidentate mode of coordination. Coordination with Ru(II) resulted in the enhancement of cytostatic activity in HepG2 hepatocellular carcinoma cells and PANC-1 pancreatic cancer cells. Coumarin derivative 2a positively regulated the expression and activity of c-Myc and NPM1 in RKO colon carcinoma cells, while the Ru(II) half-sandwich complex 2cRu induced downregulation of AKT and ERK signaling in PANC-1 cells concomitant with reduced intracellular levels of reactive oxygen species. Altogether, our findings indicated that coumarin-modified half-sandwich Ru(II) complexes held potential as anticancer agents against gastrointestinal malignancies.

Megalin Expression in Primary Oral Squamous Cell Carcinoma Is Associated with the Presence of Lymph Node Metastases, Vascular Invasion, and Lower Overall Survival.

Megalin (LRP2) is a rapidly recycling multiligand endocytic receptor primarily expressed in polarized epithelial cells. Although megalin might be involved in tumor growth and invasiveness through several mechanisms, its role has been understudied in the field of molecular oncology so far. The present study aimed to evaluate the impact of megalin expression in oral squamous cell carcinoma (OSCC) on disease progression. Megalin expression was evaluated immunohistochemically in 63 OSCC specimens. Data obtained were retrospectively compared with patient clinicopathological features and their survival. The proportion of megalin-expressing cells in the primary OSCC tissue was significantly associated with metastatic spreading to lymph nodes, vascular invasion and lower overall survival rate. Results obtained by the study suggest that megalin can be considered as a novel molecule involved in OSCC pathogenesis, but also useful as a potential biomarker for cancer progression.

Comparison of Nonheme Manganese- and Iron-Containing Flavone Synthase Mimics.

Heme and nonheme-type flavone synthase enzymes, FS I and FS II are responsible for the synthesis of flavones, which play an important role in various biological processes, and have a wide range of biomedicinal properties including antitumor, antimalarial, and antioxidant activities. To get more insight into the mechanism of this curious enzyme reaction, nonheme structural and functional models were carried out by the use of mononuclear iron, [FeII(CDA-BPA*)]2+ (6) [CDA-BPA = N,N,N',N'-tetrakis-(2-pyridylmethyl)-cyclohexanediamine], [FeII(CDA-BQA*)]2+ (5) [CDA-BQA = N,N,N',N'-tetrakis-(2-quinolilmethyl)-cyclohexanediamine], [FeII(Bn-TPEN)(CH3CN)]2+ (3) [Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)-1,2-diaminoethane], [FeIV(O)(Bn-TPEN)]2+ (9), and manganese, [MnII(N4Py*)(CH3CN)]2+ (2) [N4Py* = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine)], [MnII(Bn-TPEN)(CH3CN)]2+ (4) complexes as catalysts, where the possible reactive intermediates, high-valent FeIV(O) and MnIV(O) are known and well characterised. The results of the catalytic and stoichiometric reactions showed that the ligand framework and the nature of the metal cofactor significantly influenced the reactivity of the catalyst and its intermediate. Comparing the reactions of [FeIV(O)(Bn-TPEN)]2+ (9) and [MnIV(O)(Bn-TPEN)]2+ (10) towards flavanone under the same conditions, a 3.5-fold difference in reaction rate was observed in favor of iron, and this value is three orders of magnitude higher than was observed for the previously published [FeIV(O)(N2Py2Q*)]2+ [N,N-bis(2-quinolylmethyl)-1,2-di(2-pyridyl)ethylamine] species.

Stereochemistry of Hexacoordinated Zn(II), Cu(II), Ni(II), and Co(II) Complexes with Iminodiacetamide Ligands.

Metal complexes of iminodiacetamide (imda) ligands and metal ions Zn(II), Cu(II), Ni(II), and Co(II) were prepared using eight imda ligands (L1-L8) substituted with groups of different steric and electronic properties on the central amine N atom (H atom, methyl, isopropyl, and benzyl) and the para position of the phenyl rings (nitro and dimethylamino). The effect of these substituents on the stoichiometry (ML and ML2), geometry, and stereochemistry (mer, trans-fac, cis-fac) of the complexes was studied in the solid state, in solution, and by density functional theory calculations. Single-crystal and powder X-ray diffraction, thermogravimetry, and IR spectroscopy showed that in the solid state imda ligands preferentially form trans-fac ML2 complexes, with the exception of the cis-fac complex 7Zn. NMR spectroscopy of diamagnetic Zn(II) and paramagnetic Co(II) complexes revealed the formation of both ML and ML2 complexes in solution, which was also confirmed by UV-vis titrations. Variable-temperature NMR was used to study the effect of the substituent on the central amine N atom on the Zn-N bond strength and nitrogen inversion. The relative stabilities of the isomers were rationalized by computations and the optimized structures used for geometry analysis.

ANGIOMYOMA OF THE UPPER LIP - CASE REPORT AND REVIEW OF THE LITERATURE.

A case is presented of upper lip angiomyoma in a 36-year-old man. The tumor was painless, palpable and clinically visible. The operation was performed under local anesthesia in the Outpatient Department. There were no complications during the postoperative course. Current literature on the subject is listed in the introduction, followed by presentation of the case and histologic characteristics of the tumor. This case is described as one of the differential diagnostic possibilities in the diagnosis of soft tissue tumors of the lip. Also, through review of the literature, different clinical appearances of angiomyoma, histologic variations and immunohistochemical characteristics are discussed that can help identify this tumor.

Myofascial pain of the head and neck among Croatian war veterans treated for depression and posttraumatic stress disorder.

BACKGROUND: During the Croatian War of Independence, 1991-1995, Croatian soldiers were exposed to traumatic and stressful events. Certain number of soldiers who took part in the war, developed depression and posttraumatic stress disorder (PTSD). Stress is one of the etiological factors in the development of myofascial pain (MPS), although the mechanism of these processes is not entirely understood. The aims of this study were to determine the frequency of myofascial pain among Croatian war veterans with depression and PTSD, association between MPS and severity of depression, to describe the most common locations of trigger points in the region of head and neck, and to find out if there is any association in frequency between MPS and endotracheal intubation. SUBJECTS AND METHODS: A total of 101 Croatian war veterans suffering from PTSD and depression participated in the current study. Diagnosis of myofascial pain was based on detailed anamnestic history and careful clinical examination. RESULTS: Our findings showed a high rate of myofascial pain among Croatian war veterans, with occipital region and right temporal region as the most common places of trigger points. Higher severity of depression was accompanied by a higher percentage of subjects with MPS. Finally, there was no significant association between endotracheal intubation and development of MPS among the war veterans. CONCLUSIONS: It can be concluded that the rate of myofascial pain among Croatian war veterans is high and therefore it must be considered in patients with depression and PTSD. Moreover, the severity of depressive symptomatology seems to be related to the presence of myofascial pain.

Botryoid Cyst, a Rare Type of Odontogenic Cyst

Botryoid cyst, a rare type of odontogenic cyst, is usually considered a multilocular variant of lateral periodontal cyst. It was first described in 1973, and up to the present less than a hundred cases have been reported in the literature. Botryoid cysts are characterized by a multilocular histologic finding and a higher risk of recurrence than lateral periodontal cysts. In this article, we present a case of botryoid cyst from our clinical practice, accompanied by literature review of previous cases reported in the literature so far. Study results showed that botryoid cysts mostly affected population in their fifties, with a slight female (53.5%) predominance over males (46.5%). The mandible was the most frequently affected region, accounting for 70 (83.3%) cases. Maxilla was only sporadically affected accounting for 14 (16.7%) cases. Radiographic appearance of botryoid cysts can be multilocular or unilocular. It is concluded that the recurrence rate is relatively high (30.1%), therefore long term follow up is needed.

Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds.

Two hexanuclear niobium halide cluster compounds with a [Nb6X12](2+) (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable Bo field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of (95)Mo nuclei in structurally related compounds containing [Mo6Br8](4+) cluster cores. Experimentally determined δiso((93)Nb) values are in the range from 2,400 to 3,000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (Vzz and δ33) coinciding with the molecular four-fold axis of the [Nb6X12](2+) unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (Vzz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (Vyy) and the largest CS principal axis (δ11) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by (79/81)Br NQR and (35)Cl solid-state NMR measurements.

Trigeminal neuralgia--case and treatment analysis at the Department of Oral Surgery of the University Hospital Dubrava.

The aim of the study was to explore certain risk factors for trigeminal neuralgia (TN), assess the prevalence of misdiagnoses of TN made by primary care dentists, compare the treatment practice for TN at the Department of Oral Surgery with the guidelines, and the importance of interdisciplinary approach in TN treatment. The study included 237 patient records (70 men and 167 women, aged 5-91 years) referred to the Department under the diagnosis of TN. From their medical records, demographic data, referral diagnose, clinical diagnose, additional diagnostic procedures and treatment were analysed. Neuralgia of the trigeminal nerve affects predominantly elderly female population, while the impact of the season on the incidence of the disease has not been determined. The most common therapy used at the Department were blockades, carbamazepine or their combination. 63.3% patients were referred for further diagnostic tests following the first examination. The number of misdiagnosed cases referred by primary care dentists (33.6%) points that better training in diagnosing TN is needed for the dental practitioners. The treatment methods at the Department need to be harmonized with the latest guidelines on neuralgia treatment. Due to the complexity of etiological factors, an interdisciplinary approach is necessary.

Comparison of Tooth Size Measurements in Orthodontics Using Conventional and 3D Digital Study Models.

(1) Background: The objective of this study was to assess which digitization method produces the biggest deviation in the 3D images of tooth size from plaster models made using alginate impressions, which are considered the gold standard in orthodontics. (2) Methods: The sample used in this study included 30 subjects (10 males and 20 females). Measurements were made on four types of models: (1) digital models obtained through intraoral scanning and digitized models of plaster cast made from (2) alginate impressions, (3) silicone impressions, and (4) conventional plaster models. Mesio-distal (MD) and buccal/labial-lingual/palatal (BL) dimensions were measured on the reference teeth of the right side of the jaw (central incisor, canine, first premolar, and first molar). Comparisons of tooth size between the methods were conducted using a repeated measurement analysis of variance and the Friedman test, while the intraclass correlation coefficient was used to determine agreement between the different methods. (3) Results: The results showed a similar level of agreement between the conventional and digital models in both jaws and the anterior, middle, and posterior segments. Better agreement was found for the MD measurements (r = 0.337-0.798; p ≤ 0.05) compared to the BL measurements (r = 0.016-0.542), with a smaller mean difference for MD (0.001-0.50 mm) compared to BL (0.02-1.48 mm) and a smaller measurement error for MD (0.20-0.39) compared to BL (0.38-0.89). There was more frequently a better level of agreement between 3D images than measurements made using a digital caliper on the plaster models with 3D images. (4) Conclusions: The differences in measurements between the digital models and conventional plaster models were small and clinically acceptable.

Ambulatory oral surgery: 1-year experience with 11680 patients from Zagreb district, Croatia.

AIM: To examine the types and frequencies of oral surgery diagnoses and ambulatory oral surgical treatments during one year period at the Department of Oral Surgery, University Hospital Dubrava in Zagreb, Croatia. METHODS: Sociodemographic and clinical data on 11680 ambulatory patients, treated between January 1 and of December 31, 2011 were retrieved from the hospital database using a specific protocol. The obtained data were subsequently analyzed in order to assess the frequency of diagnoses and differences in sex and age. RESULTS: The most common ambulatory procedure was tooth extraction (37.67%) and the most common procedure in ambulatory operating room was alveolectomy (57.25%). The test of proportions showed that significantly more extractions (P<0.001) and intraoral incisions (P<0.001) were performed among male patients, whereas significantly more alveolectomies and apicoectomies were performed among female patients (P<0.001). A greater prevalence of periodontal disease was found in patients residing in Zagreb than in patients residing in rural areas. CONCLUSION: The data from this study may be useful for planning of ambulatory oral surgery services, budgeting, and sustaining quality improvement, enhancing oral surgical curricula, training and education of primary health care doctors and oral surgery specialists, and promoting patients' awareness of the importance of oral health.

Synthesis, characterisation and biological evaluation of monometallic Re(I) and heterobimetallic Re(I)/Fe(II) complexes with a 1,2,3-triazolyl pyridine chelating moiety.

Bioorganometallic complexes have attracted considerable interest and have shown promise for potential application in the treatment and diagnosis of cancer, as well as bioimaging agents, some acting as theranostic agents. The series of novel ferrocene, benzimidazo[1,2-a]quinoline and fluorescein derivatives with bidentate pyridyl-1,2,3-triazole and 2,2'-dipyridylamine and their tricarbonylrhenium(I) complexes was prepared and fully characterised by NMR, single-crystal X-ray diffraction, UV-Vis and fluorescence spectroscopy in biorelevant conditions. The fluorescein and benzimidazo[1,2-a]quinoline ligands and their complexes with Re(I) showed interactions with ds-DNA/RNA and HSA, characterised by thermal denaturation measurements, fluorimetric and circular dichroism titrations. The binding constants revealed that addition of Re(I) increases the affinity of fluorescein but decreases the affinity of benzimidazo[1,2-a]quinoline. The complexation of Re(I) had the opposite effect on fluorescein and benzimidazo[1,2-a]quinoline ligands' fluorimetric sensitivity upon biomacromolecule binding, Re(I) fluorescein complex emission being strongly quenched by DNA/RNA or HSA, while emission of Re(I) benzimidazo[1,2-a]quinolone complex was enhanced, particularly for HSA, making it a promising fluorescent probe. Some mono- and heterobimetallic complexes showed considerable antiproliferative activity on colon cancer cells (CT26 and HT29), with ferrocene dipyridylamine complexes exhibiting the best inhibitory activity, comparable to cisplatin. The correlation of the cytotoxicity data with the linker type between the ferrocene and the 1,2,3-triazole ring suggests that direct binding of the metallocene to the 1,2,3-triazole is favourable for antitumor activity. The Re(I) benzimidazo[1,2-a]quinolone complex showed moderate antiproliferative activity, in contrast to the Re(I) fluorescein complex, which exhibited weak activity on CT26 cells and no activity on HT29 cells. The accumulation of the Re(I) benzimidazo[1,2-a]quinolone complex in the lysosomes of CT26 cells indicates the site of its bioactivity, thus making this complex a potential theranostic agent.

Oligomicrodontia in a Pediatric Cancer Survivor after Chemotherapy: A Case Report.

Chemotherapy used on pediatric patients especially those below 3 years of age causes disturbances in dental development. The aim of this case report was to present the late dental effects of chemotherapy in a patient treated for anaplastic ependymoma (WHO III) at an early age. Radiographic findings at the age of 9 years showed oligomicrodontia of six teeth, maxillary lateral incisors, and maxillary and mandibular first premolars. Pediatric cancer survivors after chemotherapy have an increased risk of one or more dental development disorders. To ensure proper dental care and to assess the long-term effects on oral health, tooth development, and occlusion, the involvement of a dentist is crucial. Adequate diagnosis and well-planned treatment of the dental defect can significantly improve patient oral health-related quality of life.

Tuning the coordination properties of chiral pseudopeptide bis(2-picolyl)amine and iminodiacetamide ligands in Zn(II) and Cu(II) complexes.

Seven bis(2-picolyl)amine (bpa) and five iminodiacetamide (imda) ligands were prepared with different modifications in their side chain structure. The coordination properties of the ligands (L) were influenced by changes in the aliphatic linker length (C1, C2, or C3), amide group isomers and type of chiral terminal group. Complexation with Cu(II) afforded two polymorphs of a ML complex which features tetradentate coordination of a ligand with C2 linkers, while crystal structures of three trans-fac ML2 complexes with Cu(II) and Ni(II) show tridentate coordination of ligands with a C3 linker. The stoichiometry and stereochemistry of Zn(II) and Cu(II) complexes was further studied in solution by NMR and UV-Vis spectroscopy. DFT calculations gave an insight into the relative stability of isomers, as well as potential hydrogen bonding between two ligands in a ML2 complex. Furthermore, ML complexes of Cu(II) exhibited DNA cleavage activity.

High-temperature experimental and theoretical study of magnetic interactions in diamond and pseudo-diamond frameworks built up from hexanuclear tantalum clusters.

Magnetic interactions in solid-state tantalum cluster compounds have been evidenced by using magnetic susceptibility measurements and corroborated by broken-symmetry DFT calculations. The three selected compounds are based on [Ta(6)X(12)(H(2)O)(6)](3+) (X=Cl or/and Br) units with edge-bridged Ta(6) octahedral clusters. Although two of them crystallise in the tetragonal space group I4(1)/a, all compounds exhibit a similar arrangement of paramagnetic clusters related to the diamond structural framework (Fd ̅3m space group). Magnetic parameters were fitted by using the [5,4] Padé approximant of high-temperature series expansion of susceptibility for the Heisenberg model (S=1/2) in the diamond framework, assuming only nearest-neighbouring interactions. Such a model appropriately describes magnetic-susceptibility measurements at temperatures T>0.7|J|/k. The magnetic interaction parameter J between two [Ta(6)Cl(12)(H(2)O)(6)](3+) clusters is estimated to be -64.28(7) cm(-1) ; it has been enhanced by replacing several chlorine inner ligands with bromine ones (J=-123(3) cm(-1) for two [Ta(6)Br(7.7(1))Cl(4.3(1))(H(2)O)(6)](3+) clusters) and is strongest between two bromine [Ta(6)Br(12)(H(2)O)(6)](3+) clusters with a value of -155(1) cm(-1) . Broken-symmetry DFT calculations within spin-dimer analysis confirmed this trend. Those interactions can be explained on the basis of the overlap between singly occupied a(2u) orbitals localised on neighbouring clusters.

Displacement of a mandibular incisor--an infrequent complication of mandibular fracture.

A case of a mandibular fracture with an unusual complication is reported. A 13-year-old boy was admitted four years after conservative treatment of a symphyseal fracture. He complained of recurrent swelling. A radiographic evaluation showed a horizontally laid permanent mandibular left lateral incisor (PMLLI) that had probably slid into the fracture line and provoked repetitive infection episodes. After a surgery, a clinical and radiological analysis showed satisfactory healing.

Symptomatic capillary telangiectasia of the pons and intracerebral developmental venous anomaly - A rare association.

Various combinations of vascular malformations of the brain in one lesion have been reported, while others seem to be very rare. In this report, the authors discuss the case of a coexistence of an capillary telangiectasia of the pons and intracerebral venous anomaly. To our knowledge, this is the first report of coexistence of a capillary telangiectasia of the pons and intracerebral venous anomaly apparted from each other. These discrete vascular malformations of the brain raise attention on possible interrelations in the pathogenesis of these entities. We report a case of pontine capillary telangiectasia and intracerebral venous anomaly in a 42-year-old woman with a right side facial palsy. Hight field magnetic resonance imaging suggested presence of a capillary telangiectasia of the pons. Another lesion in the left frontal gyrus was attributable to the venous anomaly. Along with neuroradiological findings, results of the somatosensor evoked potentials, brain stem auditory potentials, laboratory analysis including blood, cerebrospinal fluid and urine investigation are demonstrated. Awareness of the magnetic resonance imaging finding of the capillary telangiectasias and of the venous anomalies may help in defining clinical correlates of this vascular malformations, while the follow up of these malformations might help to asses risk of vascular rupture. We and others previously selects capillary telangiectasia and venous anomaly in two discrete entities. Coexistence of these malformations in the brain apparted from each other appear to be very rare and raise attention on possible interactions in their natural history and pathogenesis.

Induction of Λ-helicity in a zinc complex with an alanine-appended aminopyridine ligand.

The crystal structure of tris[dimethyl 5-({1-[(pyridin-2-yl-κN)carbamoyl-κO]ethyl}carbamoyl)benzene-1,3-dicarboxylate]zinc(II) dinitrate acetonitrile trisolvate, [Zn(C19H19N3O6)3](NO3)2·3CH3CN or [Zn(L)3](NO3)2·3CH3CN, (1), has been determined by single-crystal X-ray diffraction. The neutral ligand L coordinates to the Zn2+ cation in a bidentate fashion via the pyridine N atom and an amide O atom, forming a six-membered chelate ring. The Λ-helical chirality of the Zn2+ coordination sphere is induced by pendant L-alanine residues through stacking interactions between the arene groups of two coordinated ligands, assisted by a hydrogen bond between amide groups bonded to the stacked arene rings. The third ligand is coordinated to the Zn2+ cation by the same six-membered chelate ring, but in the opposite direction with respect to the analogous chelate rings of the first two coordinated ligands. Besides ionic interactions between [ZnL3]2+ complexes and NO3- anions, several types of hydrogen bonds and intermolecular stacking interactions contribute to the stability of the solid-state phase.

Comparison of different surgical procedures on the stability of dental implants in posterior maxilla: A randomized clinical study.

BACKGROUND: Stability of a dental implant is very important when planning immediate loading and design of a final restoration. The aim of this study was to compare the primary and the secondary stability of dental implants inserted by three different surgical techniques: conventional (standard) technique using a sequence of drills for implant bed preparation, osteotome technique using tapered hand instruments for creating implant sites by condensing the bone and guided flapless implant surgery with surgical templates. MATERIAL AND METHODS: The study included 150 patients (80 males and 70 females), 46-71 years old, who required implant supported fixed partial dentures in the posterior maxilla of D3 or D4 bone density. Patients were randomly assigned into one of the three surgical insertion technique groups. All patients received tapered implants of the same manufacturer of the same length and two different widths (3.3 × 11.5 mm or 4.2 × 11.5 mm). Primary and secondary implant stability were measured by means of resonance frequency analysis (RFA) at the time of implant placement and 5 months after surgery using the Ostell ISQ device (Osstell AB, Sampgatan, Goteborg, Sweden). Statistical analysis included one-sample Kolmogorov Smirnov test, descriptive statistics, multivariate analysis (Bonferoni post-hoc tests) and paired t-tests. RESULTS: Patients in the osteotome group exhibited higher primary stability (P < 0.01) than in the conventional and surgically guided flapless groups. There were no significant differences in the secondary stability (p > 0.05). Wider implants presented higher ISQ values (P<0.01). CONCLUSION: The osteotome technique led to the highest implant primary stability, therefore it can be recommended when immediate loading is planned or for one-piece implant insertion.

A ferrocene-based pseudopeptide chiroptical switch.

We present a double-stranded ferrocene pseudopeptide 2b which exhibits stimuli responsive chirality inversion triggered by solvent exchange or acid addition. Compound 2b exists as a mixture of self-assembled fast exchanging oligomers which macroscopically behave as a chiroptical switch with two stable states. The ferrocene group inversion results in a distinct CD signal in the visible part of the spectrum. The inversion is accomplished through a conformational change due to a rearrangement of hydrogen bonding forcing the rotation of ferrocene rings.