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Dipotassium and sodium/potassium crystalline picrate complexes with the crown ether 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydrodibenzo[b,n]-[1,4, 7,10,13,16,19,22]octaoxacyclotetracosin (dibenzo-24-crown-8).

The crystal structures of the dipotassium and the mixed sodium/potassium picrate complexes with the crown ether dibenzo-24-crown-8 (DB24C8) were solved and found to be nearly identical. (I): NaK-pic2(DB24C8), [NaK(C6H2N3O7)2(C24H32O8)]. Mr = 966.8, triclinic, P1, a = 8.164 (2), b = 9.960 (2), c = 13.368 (3) A, alpha = 103.92 (3), beta = 108.03 (2), gamma = 93.23 (2) degrees, V = 993.0 (7) A3, Z = 1, Dm = 1.54 (T = 298 K). Dx = 1.62 (1) g cm-3, lambda = (Mo K alpha) 0.71069 A, mu = 2.37 cm-1, F(000) = 500, T = 103 K, R = 0.086 for 2904 unique reflections. (II): K2pic2(DB24C8), [K2(C6H2N3O7)2(C24H32O8)]. Mr = 982.9, triclinic, P1, a = 8.231 (4), b = 9.850 (2), c = 13.346 (4) A, alpha = 103.91 (2), beta = 106.82 (3), gamma = 93.37 (2) degrees, V = 995.7 (9) A3, Z = 1, Dm = 1.59 (T = 298 K), Dx = 1.638 (8) g cm-3, lambda (Mo K alpha) = 0.71069 A, mu = 3.30 cm-1, F(000) = 508, T = 163 K, R = 0.042 for 4835 unique reflections. Both structures feature eight-coordinated cations between alternating layers of relatively flat crown ligands and paired picrates. In the mixed-metal system the two cations are disordered between two P1-related sites; these metal sites have a coordination environment only slightly different from that in the dipotassium structure. Na+ is able to occupy an environment similar to that of K+ under the conditions of these crystals, a situation not previously observed in the chemistry of crown ethers or macrocylic multidentates.

Chelating Agents↗

A new index for rating aesthetics of implant-supported single crowns and adjacent soft tissues--the Implant Crown Aesthetic Index.

OBJECTIVES: The important item of aesthetics is rarely included in evaluation studies. The aim of this study was to develop and validate an index for rating aesthetics of implant-supported single crowns and adjacent soft tissues. MATERIAL AND METHODS: Nine items were selected, which have an influence on the aesthetic result. The items are based on the anatomic form, colour and surface characteristics of the crown and on the anatomic form, colour and surface characteristics of the peri-implant soft tissues. Two oral-maxillofacial surgeons and two prosthodontists rated 24 implant-supported single-tooth restorations and adjacent soft tissues on a form with the nine items of the rating index. The rating was carried out twice by each of the examiners. Weighted Cohen's kappa was calculated to express the intra- and interobserver agreement. RESULTS: Intraobserver results indicated that the agreement between the first and second rating of both the prosthodontists was good (both 0.7) and that the agreement of the oral-maxillofacial surgeons was moderate (0.49 and 0.56). The best interobserver agreement was found between the two prosthodontists (0.61, good agreement). CONCLUSIONS: The Implant Crown Aesthetic Index is an objective tool in rating aesthetics of implant-supported single crowns and adjacent soft tissues. The rating is best be carried out by one prosthodontist to have the highest reliability.

Crowns↗

Analysis of the crown fractures and crown-root fractures due to dental trauma assisted by the Integrated Clinic from 1992 to 2002.

The purpose of this study was to analyze crown fractures and crown-root fractures due to dentoalveolar trauma, treated in the Integrated Clinic comprehensive dental care at Aracatuba School of Dentistry (UNESP), from January 1992 to July 2002. The data were obtained from files of trauma cases. On the analysis period, 293 patients had crown fractures or crown-root fractures, in 605 teeth. Sixty-nine percent were males and 31% were females. Adolescents between 11 and 18 years old were the most prevalent group (41.6%) and the maxillary arch was the most commonly traumatized (83%). The most commonly affected tooth was the maxillary central incisor (58.3%). The most frequent causes were falls from bicycles (30.8%). It was concluded that the reality of the local service is similar to the published data.

Accidental Falls↗

Multidisciplinary treatment approach for crown fracture and crown-root fracture - a case report.

The increased incidence of traumatic injuries to anterior teeth is a consequence of leisure activities, where the most common injuries are crown fractures. Treatment of the dental trauma is complex and requires a comprehensive and accurate diagnostic and treatment plan. It is also important to consider the biological, functional, esthetic and economic aspects, as well as the patient's desire. The purpose of this article is to report a case that shows the multidisciplinary approach required to successfully manage the rehabilitation of a maxillary central incisor with a complex crown fracture and a maxillary lateral incisor, that at first presented an oblique crown-root fracture, and after the orthodontic extrusion, suffered a more apical new crown-root fracture.

Adult↗

The use of crown ethers in peptide chemistry-V. Solid-phase synthesis of peptides by the fragment condensation approach using crown ethers as non-covalent protecting groups.

We have previously described the conditions by which peptide synthesis by the solid-phase fragment condensation approach can be carried out using crown ethers as non-covalent protection for the N alpha-amino group. Here we demonstrate that the procedure can be extended to large, partially protected peptide fragments possessing free Lys and/or Arg residues. The first step was to ensure that complex formation on the side chain of amino acids was not detrimental to the methodology and exhibited the same solubility and coupling properties as N alpha-complexed peptides. Thus, a model hexapeptide was synthesized using Fmoc chemistry containing Lys and Arg residues, which, when complexed with 18-Crown-6, was readily soluble in DCM and coupled quantitatively to a resin-bound tetrapeptide. Two tripeptides were then prepared, one containing a free Ser residue, the other free Tyr, to examine the possible occurrence of side reactions. After coupling using standard conditions only the former tripeptide exhibited the formation of the O-acylation by-product (5%). Another model hexapeptide containing Lys, Tyr, Ser and Asp protected with a TFA-stable adamantyl group was complexed with 18-Crown-6 and coupled to the resin-bound tetrapeptide with near quantitative yield. Extending the length of the peptide to 21 and 40 residues, which represent sequences Gly52 to Leu72 (21-mer) and Pro33 to Leu72 (40-mer) from Rattus norvegicus chaperonin 10 protein, respectively, resulted in partially protected fragments that were readily soluble in water, thus enabling purification by RP-HPLC. Complexation with 18-Crown-6 gave two highly soluble products that coupled to resin-board tetramer with 68% and 50% coupling efficiencies for the 21-mer and 40-mer, respectively. Treatment with 1% DIEA solutions followed by acidolytic cleavage and purification of the major product confirmed that the correct product has been formed, when analysed by amino acid analysis and ESI-MS. These results served to extend the methodology of non-covalent protection of large partially protected peptide fragments for the stepwise fragment condensation of polypeptides.

Amino Acids↗

Crown rootless1, which is essential for crown root formation in rice, is a target of an AUXIN RESPONSE FACTOR in auxin signaling.

Although the importance of auxin in root development is well known, the molecular mechanisms involved are still unknown. We characterized a rice (Oryza sativa) mutant defective in crown root formation, crown rootless1 (crl1). The crl1 mutant showed additional auxin-related abnormal phenotypic traits in the roots, such as decreased lateral root number, auxin insensitivity in lateral root formation, and impaired root gravitropism, whereas no abnormal phenotypic traits were observed in aboveground organs. Expression of Crl1, which encodes a member of the plant-specific ASYMMETRIC LEAVES2/LATERAL ORGAN BOUNDARIES protein family, was localized in tissues where crown and lateral roots are initiated and overlapped with beta-glucuronidase staining controlled by the DR5 promoter. Exogenous auxin treatment induced Crl1 expression without de novo protein biosynthesis, and this induction required the degradation of AUXIN/INDOLE-3-ACETIC ACID proteins. Crl1 contains two putative auxin response elements (AuxREs) in its promoter region. The proximal AuxRE specifically interacted with a rice AUXIN RESPONSE FACTOR (ARF) and acted as a cis-motif for Crl1 expression. We conclude that Crl1 encodes a positive regulator for crown and lateral root formation and that its expression is directly regulated by an ARF in the auxin signaling pathway.

Amino Acid Motifs↗

The degree of zinc phosphate cement coverage of complete crown preparations and its effect on crown retention.

This investigation examined the amount of retentive area covered by cement under complete coverage crowns and its effect on retention. Sixty crowns of self-cured acrylic resin were prepared on 60 identical brass dies and were divided into six groups of 10 crowns each according to different cement applications. The results showed that retention was dependent on the amount of retentive area covered by the cement. The amount of cement in the occlusal part of the cementation space did not affect retention.

Acrylic Resins↗

Effect of incomplete crown ferrules on load capacity of endodontically treated maxillary incisors restored with fiber posts, composite build-ups, and all-ceramic crowns: an in vitro evaluation after chewing simulation.

OBJECTIVE: The aim of this study was to compare the fracture resistance of endodontically treated maxillary central incisors with incomplete crown ferrules after chewing simulation. MATERIAL AND METHODS: Forty caries-free maxillary central incisors were divided into 4 groups (n = 10). Endodontic treatment was performed. Teeth were decoronated 2 mm above the cemento-enamel junction (CEJ). Group I (control) provided a 360 degrees circumferential 2-mm ferrule. In group II, a 2-mm ferrule was present on the palatal aspect (status after occlusal overload), and in group III on the facial aspect (status after traumatic injury). In group IV, the ferrule was interrupted by bi-proximal cavitations (simulating caries treatment). The teeth received glass fiber reinforced posts and composite core restorations. All-ceramic crowns were adhesively cemented. Specimens were simultaneously exposed to thermal cycling and mechanical loading (1.2 million cycles; 6,000 cycles 5 degrees/55 degrees C) and finally statically loaded until failure in a universal testing machine (crosshead speed = 1 mm/min). For statistical analysis, the Kruskal-Wallis test was applied followed by the Mann-Whitney U-test as post hoc testing. RESULTS: The median fracture load values (min./max.) were: group I = 502 (326/561), group II = 658 (280/827), group III = 899 (396/1176), and group IV = 360 (279/646). Analysis revealed statistically significant differences between test groups, except between groups I and IV and groups II and IV. CONCLUSIONS: The fracture resistance of endodontically and post/core restored teeth is dependent on the degree of tooth conservation. An incomplete crown ferrule is associated with greater variation in load capacity and, despite high fracture values, inclines to fracture.

Composite Resins↗

[Effect of the 3/4 crown and porcelain-fused crown restorations on the tooth displacement and the loading force of the supporting tissues].

A mechanical simulation model of tooth and alveolar bone in the application of 3/4 crown and porcelain-fused crown restorations was made and analyzed using three-dimensional finite element technique. The results obtained were as follows. 1. When the physiological tooth mobility was less than 150 microns, the teeth were sufficiently fixed using the splint and the bridge connected with more than two teeth, in the case of 20 percent absorption of the alveolar bone, and more than three teeth in the case of 40 percent absorption. In the case of 60 percent absorption, the teeth were fixed with the splint of six teeth connections, and were fixed with the bridge of five teeth connections. 2. The periodontium supporting force decreased markedly according to the increase of the number of the abutment teeth. 3. The teeth accompanied with the absorption of the alveolar bone were connected, in order to inhibit the tooth mobility and the periodontium supporting force. In this application, it had the inhibitory action when the replacing ratio of metal and ceramics to a crown of the tooth was less than 35 percent. 4. According to the finite element analysis, the design bases of fixed restorations applied in the teeth accompanied with the absorption of the alveolar bone were preferred.

Alveolar Bone Loss↗

One-appointment composite crown: an alternative to conventional crown and bridge.

When presented with little coronal tooth structure remaining, four options exist: (1) extraction only, (2) extraction and restoration, (3) root canal therapy and a cast restoration (which may involve crown lengthening and/or orthodontic extrusion), or (4) root canal therapy and a composite/amalgam crown. A technique for the composite crown option is described with case presentations.

Adult↗

[Individual differences in the marginal periodontium of crowned and non-crowned topographically identical teeth].

A comparison was made on 191 crowned teeth in 125 patients altogether with removable partial replacements after average wear of 4.8 years with the corresponding number of contralateral uncrowned teeth. It could be shown that there was no significant difference between crowned and uncrowned teeth in respect of periodontal changes (loosening and deepening of pockets of pockets, periodontal diagnosis). Findings in crowned teeth had a frequent tendency to worsen.

Crowns↗

[Retention of crowns as affected by film thickness of zinc phosphate cement and taper angle of crowns (author's transl)].

Dependence of the retention of crowns at their axial wall on the film thickness of zinc phosphate cement and the taper angle was investigated. Stainless steel dies, composed of a preparation and an occlusally perforated crown the taper angle of which was 2.9, 5.7, 8.5 and 11.3 degrees respectively (Fig. 1, (a) and (b)), were cemented within three min. after the start of mix with a Shofu Micro Cement having a powder-liquid ratio of 1.5 g/0.5 cc. The thickness of the cement layer at the axial wall was regulated to a given value between 9 and 55 mu through the use of a discrepancy measurer. A Shimazu Autograph tensile test machine was employed to measure 48-hr retention (kg/cm2). The retention of the crowns was strongly dependent on the cement film thickness and the taper angle when the film thickness was below a critical value (15 mu in this experiment), but not when the film thickness was above this value (Fig. 3). This may be explained by the term of mechanical interlocking of either of the unreacted powder grains and the matrix phase in the luting cement, as schematically drawn in Fig. 6. The same findings were more evidently appeared on the semilogarythmic diagram in Fig. 4. In this diagram, the critical value was shown as intersection of two straight lines which could be drawn through all the measurements for four taper angles, using the least squares.

Crowns↗

Tetraaza analogues of lithium and sodium alums: synthesis and X-ray structures of the single strand polymer [Li(THF)2(Al[SO2(NtBu)2]2)] infinity and the contact ion pairs [Na(15-crown-5)][Al(SO2(NtBu)2)2] and ([Na(15-crown-5)][O2S(mu-NBn)2Al(mu-NBnSO2NBn)])2.

The reaction of an alkali metal aluminohydride MAlH4 (M = Li, Na) with N,N'-bis-(tert-butyl)sulfamide or N,N'-bis-(benzyl)sulfamide in THF produces the complex ions (Al[SO2(NR)2]2)- (R = tBu, Bn). The X-ray structures of [Li(THF)2(Al[SO2(NtBu)2]2)] infinity (1), [Na(15-crown-5)][Al(SO2(NtBu)2)2], (2) and ([Na(15-crown-5)][O2S(mu-NBn)2Al(mu-NBnSO2NBn)])2 (3.3THF) are reported. The two diazasulfate ligands [SO2(NtBu)2]2- are N,N' chelated to Al3+ in both 1 and 2. In the lithium derivative 1 the spirocyclic (Al[SO2(NtBu)2]2)- anions are bridged by the bis-solvated cations Li(THF)2+ to give a polymeric strand. In the sodium salt 2 the complex anion is O,O' chelated to Na+, which is further encapsulated by a 15-crown-5 ligand to give a monomeric ion-pair complex. By contrast, the benzyl derivative 3 forms a dimer in which the terminal [SO2(NBn)2]2- ligands are (N,N'),(O,O') bis-chelated to Al3+ and Na+, respectively, and the bridging ligands adopt a novel N,O-chelate, N'-monodentate bonding mode. The central core of 3 consists of two four-membered AlOSN rings bridged by two NtBu groups. Crystal data: 1, orthorhombic, Pna2(1), a = 20.159(5) degrees, b = 10.354(3) degrees, c = 15.833(4) degrees, alpha = beta = gamma = 90 degrees, V = 3304.7(15) A3, Z = 4; 2, monoclinic, P2(1)/n, a = 16.031(2) A, b = 9.907(2) A, c = 23.963(4) A, beta = 103.326(2) degrees, Z = 4; 3, triclinic, P1, a = 12.7237(11) A, b = 14.0108(13) A, c = 16.2050(14) A, alpha = 110.351(2) degrees, beta = 111.538(2) degrees, gamma = 97.350(2) degrees, Z = 1.

Journal Article↗

Formation of Separated versus Contact Ion Triplets in Magnesium Thiolates. Synthesis and Characterization of [Mg(15-crown-5)(SCPh(3))(2)] and [Mg(15-crown-5)(THF)(2)][S-2,4,6-tBu(3)C(6)H(2))](2).

The synthesis and structural characterization of two magnesium thiolate complexes are described. Both compounds were prepared by analogous reactions routes, namely, alkane elimination and transamination, but using differently sized ligands. Utilization of the smaller HSCPh(3), resulted in the formation of [Mg(15-crown-5)(SCPh(3))(2)], 1, displaying a seven-coordinate magnesium center with two magnesium-sulfur bonds. Employment of the sterically more encumbered HS-2,4,6-tBu(3)C(6)H(2) yielded a separated cation and anions as displayed in [Mg(15-crown-5)(THF)(2)][S-2,4,6-tBu(3)C(6)H(2)](2), 2. Compound 2 exhibits a seven-coordinate cation, completing its coordination environment with five metal-crown-ether interactions in addition to two tetrahydrofuran (THF) contacts. The compounds were characterized by IR and NMR spectroscopy in addition to X-ray crystallography. Crystal data with Mo Kalpha (lambda = 0.710 73 Å) are as follows: 1, C(48)H(50)MgO(5)S(2), a = 8.4785(4) Å, b = 9.3595(5) Å, c = 13.8306(6) Å, alpha = 87.332(1) degrees, beta = 85.929(1) degrees, gamma = 68.733(1) degrees, Z = 1, triclinic; 2, C(54)H(94)MgO(7)S(2), a = 13.6755(2) Å, b = 12.8045(6) Å, c = 32.7127(12) Å, beta = 97.87(1) degrees, Z = 4, monoclinic.

Journal Article↗

Molecular design of crown ethers. 21.(1,2) synthesis of novel double-armed benzo-15-crown-5 lariats and their complexation thermodynamics with light lanthanoid nitrates in acetonitrile

Three new disubstituted benzo-15-crown-5 derivatives (3-5) have been synthesized from 4',5'-bis(bromomethyl)benzo-15-crown-5 (2) and the corresponding alkanols in the presence of Na(2)S(2), and their complexation thermodynamics with light lanthanoid(III) nitrates (La-Gd) have been studied in anhydrous acetonitrile at 25 degrees C. Plots of K(S) against the reciprocal ionic diameter of lanthanoid exhibited monotonically declining pattern for the parent benzo-15-crown-5 (1) and 3 but showed a characteristic peak at Ce(3+) for 4 and 5. It is interesting to note that the simple extension of the alkyl side chains in 4 and 5 can alter the cation selectivity profiles of 1 and 3. Possessing two 2-oxapropyl groups, 3 gave a comparable K(S) for La(3+) but a significantly decreased K(S) for Ce(3+) compared with the corresponding values for 1, thus exhibiting an exceptionally high La(3+)/Ce(3+) selectivity of 11. Thermodynamically, the complexation of lanthanoid perchlorates with 1 is absolutely entropy-driven in acetonitrile, while the complexation of lanthanoid nitrates with 3-5 is primarily driven by exothermic enthalpy changes with accompanying moderate entropic gain or small entropic loss.

Journal Article↗

Bis-8-hydroxyquinoline-armed diazatrithia-15-crown-5 and diazatrithia-16-crown-5 ligands: possible fluorophoric metal ion sensors.

The synthesis and preliminary photophysical properties of a series of diazatrithia-15-crown-5 and diazatrithia-16-crown-5 ligands containing two 8-hydroxyquinoline sidearms are reported. The ligands were prepared by a two-step process. First, diazatrithiacrown ethers 11 and 12 were prepared by treating bis(alpha-chloroamide) 5 with various dimercaptans followed by reduction using a boron-THF complex. Hydroxymethyl-substituted macrocycle 12 was rearranged to hydroxy-substituted diazatrithia-16-crown-5 in refluxing aqueous HCl. Macrocyclic diamines 11-13 were converted to either 5-chloro-8-hydroxyquinolin-7-ylmethyl-substituted diazatrithiacrown ethers 14-16 by a Mannich aminomethylation reaction or to 8-hydroxyquinolin-2-ylmethyl-substituted diazatrithiacrown ethers 17-19 by reductive amination using 8-hydroxyquinoline-2-carboxaldehyde. Preliminary photophysical studies show that ligands 16 and 19 exhibit increased fluorescence in the presence of Zn(2+), indicating that these ligands could be chemical sensors for Zn(2+).

Journal Article↗

Effects of complexation with 18-crown-6 on the hypernucleofugality of phenyl-lambda3-iodanyl groups. Synthesis of vinyl-lambda3-iodane.18-crown-6 complex.

[structure: see text] 4-tert-Butyl-1-cyclohexenyl(phenyl)(tetrafluoroborato)-lambda(3)-iodane forms a discrete supramolecular complex by the reaction with 18-crown-6. Solvolysis of the cyclohexenyl-lambda(3)-iodane in the presence of 18-crown-6 indicates that the complexation with 18-crown-6 tends to decrease the leaving group ability of hypervalent phenyl-lambda(3)-iodanyl groups.

Journal Article↗