Preliminary Analysis of the 3-Dimensional Morphology of the Upper Lip Configuration at the Completion of Facial Expressions in Healthy Japanese Young Adults and Patients With Cleft Lip.

PURPOSE: To develop criteria for the analysis of upper lip configuration of patients with cleft lip while they produce various facial expressions by comparing the 3-dimensional (3D) facial morphology of healthy Japanese adults and patients with cleft lip. PATIENTS AND METHODS: Twenty healthy adult Japanese volunteers (10 men, 10 women, controls) without any observed facial abnormalities and 8 patients (4 men, 4 women) with unilateral cleft lip and palate who had undergone secondary lip and nose repair were recruited for this study. Facial expressions (resting, smiling, and blowing out a candle) were recorded with 2 Artec MHT 3D scanners, and images were superimposed by aligning the T-zone of the faces. The positions of 14 specific points were set on each face, and the positional changes of specific points and symmetry of the upper lip cross-section were analyzed. Furthermore, the configuration observed in healthy controls was compared with that in patients with cleft lip before and after surgery. RESULTS: The mean absolute values for T-zone overlap ranged from 0.04 to 0.15 mm. Positional changes of specific points in the controls showed that the nose and lip moved backward and laterally upward when smiling and the lips moved forward and downward medially when blowing out a candle; these movements were bilaterally symmetrical in men and women. In patients with cleft lip, the positional changes of the specific points were minor compared with those of the controls while smiling and blowing out a candle. The left-versus-right symmetry of the upper lip cross-section exceeded 1.0 mm in patients with cleft lip, which was markedly higher than that in the controls (0.17 to 0.91 mm). These left-versus-right differences during facial expressions were decreased after surgery. CONCLUSION: By comparing healthy individuals with patients with cleft lip, this study has laid the basis for determining control values for facial expressions.

Clinical and 3-Dimensional Analyses of Nasal Forms After Secondary Correction of Cleft Lip-Nose Deformities Using Extended Spreader Cartilage Graft With a Cross-Lap Joint Technique.

PURPOSE: A surgical strategy for definitive cleft lip-nasal correction that stably provides symmetric and natural nasal forms has not been established to date. The purpose of this study was to describe our surgical techniques and 3-dimensional (3D) assessment results after the definitive correction of cleft lip-nose deformity using an extended spreader cartilage graft with a cross-lap joint technique to achieve a rigid strut for lower lateral cartilage repositioning to obtain a desirable nasal tip projection. PATIENTS AND METHODS: This study enrolled 14 patients with unilateral cleft lip (UCL) with or without cleft palate and 8 patients with bilateral cleft lip (BCL) with or without cleft palate who underwent definitive nose correction and were followed for 1 to 3 years. All patients were treated by open rhinoplasty, repositioning of the lower lateral cartilage, use of an extended spreader cartilage graft with a cross-lap joint technique for nasal tip support, and medial-upward advancement of nasolabial components with vestibular expansion by a free mucosal graft. For the BCL nose, pedicle flaps from rim skin were used for columella lengthening. Preoperative and postoperative nasal forms were 3-dimensionally analyzed by use of 3D images serially obtained in 12 patients. RESULTS: The postoperative nasal forms were satisfactorily improved in all patients, without any serious postoperative complications. Preoperative and postoperative 3D analyses showed a significantly projected nasal tip in the postoperative noses of patients in both the UCL group and the BCL group (P < .01 and P < .05, respectively) and a sharper nasal tip angle in the BCL group (P < .05). Lateral deviation of the nasal tip was significantly improved in the center of the face in patients in the UCL group (P < .01). CONCLUSIONS: The results of this study suggest that the extended spreader cartilage graft using the cross-lap joint graft technique is useful to provide a desirable projection of the nasal tip in the center of the face on definitive correction of both UCL and BCL nose deformities.

Crystal structure of tetra-kis-(1-oxidopyridin-2-yl)methane methanol tetra-solvate.

The asymmetric unit of the title compound, C21H16N4O4·4CH3OH, consists of a quarter mol-ecule of tetra-kis-(1-oxidopyridin-2-yl)methane and one methanol solvent mol-ecule. In the crystal, the pyridine N-oxide derivative is located about a fourfold rotoinversion axis and exhibits S 4 symmetry along the c axis. An inter-molecular O-H⋯O hydrogen bond is observed between the O atom of the pyridine N-oxide and the OH group of the methanol. An inter-molecular C-H⋯O bond is also observed between adjacent pyridine N-oxide rings.

Synthesis of sexithiophene-bridged cage compound: a new class of three-dimensionally expanded oligothiophenes.

A bicyclo-type cage-shaped compound consisting of three sexithiophenes was successfully synthesized and characterized by NMR, HRMS, and X-ray crystallographic analysis. The strained cage architecture was reflected in the blue-shifted absorption spectrum relative to its linear analogue. Intramolecular interaction between three-dimensionally fixed sexithiophenes was suggested by electrochemical analysis.

Bis[tetra-kis-(pyridin-2-yl)methane-κ(3) N,N',N'']cobalt(II) tetra-kis-(thio-cyanato-κN)cobaltate(II) methanol monosolvate.

The title complex, [Co(C21H16N4)2][Co(NCS)4]·CH3OH, consists of one [Co{C(py)4}2](2+) complex cation [C(py)4 = tetra-kis-(pyridin-2-yl)methane], one [Co(NCS)4](2-) complex anion and a methanol solvent mol-ecule. In the cation, the Co(II) atom is coordinated by six N atoms of two C(py)4 ligands in a distorted octa-hedral geometry. In the anion, the Co(II) atom is coordinated by the N atoms of four NCS(-) ligands in a distorted tetra-hedral geometry. The methanol mol-ecule is disordered and was modelled over three orientations (occupancies 0.8:0.1:0.1). There are two weak hydrogen-bond-like inter-actions between the methanol solvent mol-ecule and NCS(-) ligands of the anion [O⋯S = 3.283 (3) and 3.170 (2) Å].

Crystal structure of a second polymorph of tetra-kis-(pyridin-2-yl)methane.

A second polymorph of the title compound, C21H16N4, is reported. The original polymorph was solved by our group [Matsumoto et al. (2003 ▶). Tetra-hedron Lett. 44, 2861-2864] in the monoclinic space group C2/c and refined to R = 0.050. Now the crystal structure of a tetra-gonal polymorph (space group P-421 c) has been solved and refined to R = 0.036. In the crystal, there are no strong inter-molecular inter-actions. Reflecting the high symmetry of the mol-ecular structure, the asymmetric unit is a quarter of the mol-ecule, and the mol-ecule exhibits S4 symmetry along the c axis in the crystal.

Synthesis and characterization of quarteranthene: elucidating the characteristics of the edge state of graphene nanoribbons at the molecular level.

The characteristics of the edge state, which is a peculiar magnetic state in zigzag-edged graphene nanoribbons (ZGNRs) that originates from electron-electron correlation in an edge-localized π-state, are investigated by preparing and characterizing quarteranthene molecules. The molecular geometry that was determined from the X-ray analysis is consistent with a zigzag-edge-localized structure of unpaired electrons. The localized electrons are responsible for the peculiar magnetic (room-temperature ferromagnetic correlation), optical (the lowest-lying doubly excited state), and chemical (peroxide bond formation) behaviors. On the basis of these distinguishing properties and a careful consideration of the valence bonding, insight into the edge state of ZGNRs can be gained.

Aromaticity and π-bond covalency: prominent intermolecular covalent bonding interaction of a Kekulé hydrocarbon with very significant singlet biradical character.

An anthracene-linked bisphenalenyl Kekulé molecule with very significant singlet biradical character has shown a prominent covalent bonding interaction between molecules in a molecular aggregate. High aromatic stabilization energy in the anthracene linker is responsible for the significant singlet biradical character.

Synthesis, electronic, and morphological properties of tetrahedral oligothiophenes with n-hexyl terminal groups.

A series of tetrahedral oligothiophenes bearing n-hexyl groups at the α-positions of the terminal thiophene rings, (n-C(6)H(13)(C(4)H(2)S)(n))(4)C (Hex-TnTM; n=1-4), has been synthesized by Kosugi-Migita-Stille coupling as a key reaction. Thanks to the improved solubility afforded by the terminal n-hexyl groups, the largest homologue (n=4) was successfully obtained. Whereas the smaller derivatives (n=1, 2) were obtained as liquid substances, the larger derivatives (n=3, 4) were obtained as solids. Hex-T3 TM partially adopts syn conformations between the adjacent thiophene rings in the crystal, probably owing to the packing force. Hex-T3 TM not only appeared in the crystalline state but also the amorphous state, which was stable to up to 80 °C. Regardless of the terminal groups, the derivatives of n=2 exhibited a broad fluorescence with large Stokes shifts compared to the corresponding linear analogues, thereby suggesting the presence of intramolecular interactions between the bithiophene moieties. Interactions between terthiophene branches was also suggested in the radical cations of Hex-T3 TM by cyclic voltammetry measurements.

"Marking" the nitrogen atoms of phenyl-(2-pyridyl)-(3-pyridyl)-(4-pyridyl)-methane. Synthesis and absolute configuration of the corresponding tris(pyridine N-oxide).

To "mark" the nitrogen atoms in phenyl-(2-pyridyl)-(3-pyridyl)-(4-pyridyl)methane (1), we have synthesized the corresponding tris(pyridine N-oxide) 2 by oxidation of 1 with m-chloroperbenzoic acid. The nitrogen atoms of 2 are unequivocally determined by the X-ray crystal analysis of a single crystal of rac-2 whereas the nitrogen atoms cannot be assigned at all in the case of rac-1. N-Oxide 2 can be resolved by chiral high-performance liquid chromatography under similar conditions to those used for the resolution of 1. The calculated circular dichroism (CD) curve for (R)-2 on the basis of time-dependent density functional theory reproduces the experimental spectra very well to suggest that the second-eluted fraction ([CD(+)283]-2) is the R isomer, namely (R)-[CD(+)283]-2. The independent absolute configuration determinations for 1 and 2 are in keeping with the chemical correlation between the two compounds by oxidation of (R)-1 into (R)-2.

Alternating covalent bonding interactions in a one-dimensional chain of a phenalenyl-based singlet biradical molecule having Kekulé structures.

A novel naphthoquinoid singlet biradical (2a) stabilized by phenalenyl rings is prepared by a multistep procedure and is investigated in terms of covalent bonding interactions. The molecule 2a gives single crystals, in which a 1D chain is formed with a very short π-π contact at the overlapping phenalenyl rings. The unpaired electrons in 2a are involved in covalent bonding interactions not only within the molecule but also between the molecules in the 1D chain, and a linear conjugation is made of the alternating intra- and intermolecular covalent bonding interactions through conventional π-conjugation and multicenter bonding, respectively. The linear conjugation causes a lower-energy shift of the optical transition band in the crystal, but the transition energy is higher than that of the benzoquinoid singlet biradical (1a). This optical behavior and the magnetic susceptibility measurements reveal that the intermolecular covalent bonding interaction in the 1D chain of 2a is greater in strength than the intramolecular one, despite the fact that a fully conjugated Kekulé structure can be drawn for 2a.

Synthesis and characterization of teranthene: a singlet biradical polycyclic aromatic hydrocarbon having Kekulé structures.

A teranthene derivative has been successfully isolated in a crystalline form for the first time. Geometrical considerations and physical property investigations indicate that the molecule possesses prominent biradical character in the ground state.

Synthesis and identification of a trimethylenemethane derivative pi-extended with three pyridinyl radicals.

A trimethylenemethane (TMM) derivative 1(2*), in which the parent TMM is pi-extended by the symmetric insertion of three pyridine rings into the C-C bonds of TMM, has been synthesized by the alkali metal reduction of the isolated corresponding dication. Although the frozen-glass X-band cw-ESR spectrum of 1(2*) gave unresolved fine structures due to the small ZFS parameters, pulsed ESR two-dimensional electron spin transient nutation (2D-ESTN) spectroscopy unambiguously can afford to identify diradical 1(2*) as a triplet species.

An extremely simple dibenzopentalene synthesis from 2-bromo-1-ethynylbenzenes using nickel(0) complexes: construction of its derivatives with various functionalities.

Nice and easy: A very simple synthesis for dibenzopentalenes, which starts from 1-bromo-2-ethynylbenzenes, has been developed. It uses Ni(0) complexes (see scheme), from which a relatively stable Ni(II) complex as an important intermediate has been isolated. Dibenzopentalenes with various functional groups can be prepared by the procedure, and their electronic properties are consistent with theoretical calculations.An extremely simple dibenzopentalene synthesis from readily available 2-bromo-1-ethynylbenzenes using a nickel(0) complex is described. Although the yields are moderate, the formation of three C-C bonds in a single process and the high availability of the starting materials are important advantages of this reaction. The corresponding aryl-nickel(II) complex as an important intermediate was isolated as relatively stable crystals, and the structure was confirmed by X-ray crystallographic analysis. The high stability of this complex should play a key role in this reaction. The reaction is applicable to the preparation of dibenzopentalenes bearing various functional groups. Their electronic properties are consistent with theoretical calculations. The cyclic voltammograms of these compounds reveal highly amphoteric redox properties. In particular, the electron-donating property of a tetramethoxy derivative is greater than that of oligothiophenes and dibenzodithiophenes and almost comparable to that of pentacene.

Tetrahedral oligothiophenes; synthesis, X-ray analysis, and optoelectronic properties of highly symmetrical, 3D-branched oligothiophenes.

Tetrakis(bithienyl)methane and tetrakis(terthienyl)methane have been synthesized from tetrakis(2-thienyl)methane by use of Suzuki-Miyaura coupling as a key reaction. Their trimethylsilyl (TMS) derivatives are also synthesized. X-ray analysis reveals that each oligothiophene moiety tends to adopt anti-conformations and show relatively small torsion angles between the adjacent thiophene rings. While the longest absorption maxima of these tetrakis(oligothienyl)methanes exhibit only a slight bathochromic shift compared to the corresponding linear oligothiophene derivative, tetrakis(bithienyl)methane and its TMS derivative exhibit an appreciable red-shift in their fluorescence spectra. The intramolecular interaction between thienyl groups of tetrakis(2-thienyl)methane is supported by DFT calculation.

Synthesis and functionalization of 3,3'-bis(spirodienone)-bridged 2,2'-bithiophene: a new building block for redox-active molecular switching materials.

Bithiophene derivatives bridged with a bis(spirodienone) unit were synthesized and characterized. Lithiation of the thiophene rings of an unsubstituted derivative proceeded without decomposition of the bis(spirodienone) skeleton. Palladium-catalyzed cross-coupling reactions (Suzuki-Miyaura, Sonogashira) with bromides afforded a variety of pi-extended derivatives. Bond breaking and formation under redox conditions were observed by cyclic voltammetry.

8,14,30,36-Tetramethoxy[2.0.2.0](1,6)naphthalenophane-1,19-diyne: a double-helically twisted cyclophane by diastereoselective dimerization.

The title compound and its corresponding etheno- and ethano-bridged compounds were successfully synthesized in enantiomerically pure form by McMurry coupling of 2,2'-dimethoxy-(R)- or -(S)-1,1'-binaphthyl-6,6'-dicarbaldehydes as the key reaction. The reaction proceeded in a highly diastereoselective manner; the reaction of the racemic dialdehyde did not afford the meso coupling product but gave only the racemic one in poor yield. The diyne crystallized in the chiral monoclinic space group P2(1) from toluene/hexane. Structural analysis reveals that it has a considerably twisted double-helical structure in crystal form. The spectral properties (NMR, UV/Vis, and CD) clearly indicate the highly strained nature of the molecule. In particular, its UV/Vis and CD spectra exhibit a bathochromic shift of about 20 nm for the naphthyl pi-pi* transitions.

Tetrakis(4-pyridyl)methane: synthesis, properties, and a diamondoid network structure of its silver(I) complex.

The title compound, which has the highest symmetry among tetrapyridylmethane isomers, has been synthesized from tris(4-pyridyl)methane and 4-chloropyridine. The silver(I) complex of the title compound forms a three-dimensional, non-interpenetrated diamondoid network in a crystal.