Effect of power arm length combined with additional anterior torque on the axial orientation of the maxillary incisors during en-masse retraction: A finite element analysis.

INTRODUCTION: This study aimed to clarify the effect of power arm length combined with additional torque incorporated into the archwire on the controlled movement of the anterior teeth using the finite element method. METHODS: An adult patient requiring medium anchorage after extraction of the maxillary first premolars was selected for this study. The power arms were placed between the lateral incisor and the canine at 3 levels: 3 mm, 6 mm, and 9 mm. A 150 g of retraction force was applied from each height of the anterior hook to the first molar tube, with 0°, 5°, and 10° of applied lingual root torque on the incisors. RESULTS: A 3-mm hook with 10° of applied torque, a 6-mm hook with 5° of applied torque, or a 9-mm hook with no extra torque constituted the best combinations targeted at controlling the inclination of incisors during retraction. Extrusion and distal tipping of the canine were observed. Moreover, mesial tipping and mesiopalatal rotation of the molar were unavoidable. Finally, intercanine and intermolar widths were decreased. CONCLUSIONS: Adding extra torque on the incisors or using high torque brackets is recommended for patients with maxillary first premolar extraction.

Three-dimensional comparison of continuous and segmented arch techniques in the traction of palatally impacted canines using a non-linear finite element analysis.

OBJECTIVE: To compare the three-dimensional (3D) effects of canine traction on the maxillary teeth when using two different traction methods, the continuous and the segmented arch wire techniques; then to test whether adding a transpalatal arch (TPA) would affect their response to traction. DESIGN: Finite element analysis. METHODS: A cone-beam computed tomography (CBCT) scan of a patient with bilateral palatally impacted canines was chosen, from which a 3D model was derived and imported into ABAQUS. Two arch wires were modelled, a continuous round one and a segmented rectangular one. Four models were obtained by adding a TPA to both techniques. A 100° imposed rotation was then applied at the intersection between the vertical loop and the horizontal segment of each wire. Initial displacement of the maxillary tooth in the labio-lingual and in the vertical directions was measured. The absolute maximum principal stress of the periodontal ligament (PDL) was also assessed. RESULTS: Traction using a continuous arch wire led to different movement patterns of all teeth, some of them were tipped in a labial direction while others were lingually tipped. Traction using a segmented arch wire resulted in a retroclination of the posterior teeth and a proclination of the anterior teeth with a high level of stress on the premolars' PDL. Adding the TPA only affected the displacement of the first molars. The right side showed a maximum displacement of the first premolar, while the left side showed it on the lateral. The total displacement on the right side was higher than the left side. CONCLUSION: The segmented technique caused a uniform displacement of all teeth while the continuous one showed a non-uniform displacement. The angulation and position of the vertical loop affected the displacement of the maxillary teeth. The addition of a TPA acted only on the first molars.

Three-dimensional comparison of the effects of sliding mechanics in labial and lingual orthodontics using the finite element method.

INTRODUCTION: The extraction of maxillary first premolars is usually the treatment of choice to resolve crowding, alveolar protrusion, or Class II malocclusion. The demand for a lingual orthodontic treatment is increasing because of its esthetic value; therefore, understanding lingual biomechanics is essential to every clinician. This study compared the 3-dimensional (3D) effects of sliding mechanics in labial and lingual orthodontics using the finite element method. METHODS: Twelve 3D finite element models were created with different power arm heights and miniscrew positions. A 150 g of retraction force was applied from the head of the miniscrew to the power arm. The 3D displacement of the original nodes was measured, and the stress distribution on defined element zones of the periodontal ligament. RESULTS: Different force directions led to different movement patterns and stress distribution. The lingual models showed a more important lingual crown tipping, extrusion, and higher stress values than the labial models. Results were not affected by the vertical position of the miniscrew. CONCLUSIONS: Bodily en-masse retraction was not achieved in all models. Adding extra torque to the archwires is essential to prevent excessive lingual crown tipping. The lingual appliance induced more lingual tipping and extrusion of the anterior teeth. Expanding the archwire is important to minimize the risk of intercanine width reduction. The vertical position of the miniscrew does not affect the results of en-masse retraction.

Increased upconversion performance for thin film solar cells: a trimolecular composition.

Photochemical upconversion based on triplet-triplet annihilation (TTA-UC) is employed to enhance the short-circuit currents generated by two varieties of thin-film solar cells, a hydrogenated amorphous silicon (a-Si:H) solar cell and a dye-sensitized solar cell (DSC). TTA-UC is exploited to harvest transmitted sub-bandgap photons, combine their energies and re-radiate upconverted photons back towards the solar cells. In the present study we employ a dual-emitter TTA-UC system which allows for significantly improved UC quantum yields as compared to the previously used single-emitter TTA systems. In doing so we achieve record photo-current enhancement values for both the a-Si:H device and the DSC, surpassing 10-3 mA cm-2 sun-2 for the first time for a TTA-UC system and marking a record for upconversion-enhanced solar cells in general. We discuss pertinent challenges of the TTA-UC technology which need to be addressed in order to achieve its viable device application.

Nanostructuring of self-assembled porphyrin networks at a solid/liquid interface: local manipulation under global control.

Molecules of (5,10,15,20-tetraundecylporphyrinato)-copper(II) [(TUP)Cu] can self-assemble into four different polymorphs at the interface between highly oriented pyrolytic graphite and 1-octanoic acid. Scanning tunneling microscopy (STM) reveals that it is possible to combine the global control over monolayer structure, provided by the composition and concentration of the supernatant solution, with local control, from nanomanipulation by the STM tip. In the initially formed monolayer, with a polymorph composition governed by the concentration of (TUP)Cu in the supernatant solution, the exchange of molecules physisorbed at the solid/liquid interface with those in the liquid is very limited. By using a nanoshaving procedure at the tip, defects are created in the monolayer, and these serve as local manipulation sites to create domains of higher or lower molecular density, and to incorporate a second molecular species, (TUP)Co into the monolayer of (TUP)Cu.

Polymorphism in porphyrin monolayers: the relation between adsorption configuration and molecular conformation.

Self-assembled monolayers of meso-5,10,15,20-tetrakis(undecyl)porphyrin copper(II) on a graphite/1-octanoic acid interface have been studied by Scanning Tunnelling Microscopy. Four distinct polymorphs were observed, varying in their unit cell size. Arrays of unit cells of the various polymorphs seamlessly connect to each other via shared unit cell vectors. The monolayers are not commensurate, but coincident with the underlying graphite substrate. The seamless transition between the polymorphs is proposed to be the result of an adaptation of the molecular conformations in the polymorphs and at the boundaries, which is enabled by the conformational freedom of the alkyl tails of these molecules.

Gold(III) porphyrins containing two, three, or four ß,ß'-fused quinoxalines. Synthesis, electrochemistry, and effect of structure and acidity on electroreduction mechanism.

Gold(III) porphyrins containing two, three, or four ß,ß'-fused quinoxalines were synthesized and examined as to their electrochemical properties in tetrahydrofuran (THF), pyridine, CH2Cl2, and CH2Cl2 containing added acid in the form of trifluoroacetic acid (TFA). The investigated porphyrins are represented as Au(PQ2)PF6, Au(PQ3)PF6, and Au(PQ4)PF6, where P is the dianion of the 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin and Q is a quinoxaline group fused to a ß,ß'-pyrrolic position of the porphyrin macrocycle. In the absence of added acid, all three gold(III) porphyrins undergo a reversible one-electron oxidation and several reductions. The first reduction is characterized as a Au(III)/Au(II) process which is followed by additional porphyrin- and quinoxaline-centered redox reactions at more negative potentials. However, when 3-5 equivalents of acid are added to the CH2Cl2 solution, the initial Au(III)/Au(II) process is followed by a series of internal electron transfers and protonations, leading ultimately to triply reduced and doubly protonated Au(II)(PQ2H2) in the case of Au(III)(PQ2)(+), quadruply reduced and triply protonated Au(II)(PQ3H3) in the case of Au(III)(PQ3)(+), and Au(II)(PQ4H4) after addition of five electrons and four protons in the case of Au(III)(PQ4)(+). Under these solution conditions, the initial Au(PQ2)PF6 compound is shown to undergo a total of three Au(III)/Au(II) processes while Au(PQ3)PF6 and Au(PQ4)PF6 exhibit four and five metal-centered one-electron reductions, respectively, prior to the occurrence of additional reductions at the conjugated macrocycle and fused quinoxaline rings. Each redox reaction was monitored by cyclic voltammetry and thin-layer spectroelectrochemistry, and an overall mechanism for reduction in nonaqueous media with and without added acid is proposed. The effect of the number of Q groups on half-wave potentials for reduction and UV-visible spectra of the electroreduced species are analyzed using linear free energy relationships.

Dye-Sensitized Solar Cell with Integrated Triplet-Triplet Annihilation Upconversion System.

Photon upconversion (UC) by triplet-triplet annihilation (TTA-UC) is employed in order to enhance the response of solar cells to sub-bandgap light. Here, we present the first report of an integrated photovoltaic device, combining a dye-sensitized solar cell (DSC) and TTA-UC system. The integrated device displays enhanced current under sub-bandgap illumination, resulting in a figure of merit (FoM) under low concentration (3 suns), which is competitive with the best values recorded to date for nonintegrated systems. Thus, we demonstrate both the compatibility of DSC and TTA-UC and a viable method for device integration.

Unusual multi-step sequential Au(III)/Au(II) processes of gold(III) quinoxalinoporphyrins in acidic non-aqueous media.

The electrochemistry of gold(III) mono- and bis-quinoxalinoporphyrins was examined in CH(2)Cl(2) or PhCN containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) before and after the addition of trifluoroacetic acid to solution. The investigated porphyrins are represented as Au(PQ)PF(6) and Au(QPQ)PF(6), where P is the dianion of the 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin and Q is a quinoxaline group fused to a ß,ß'-pyrrolic position of the porphyrin macrocycle; in Au(QPQ)PF(6) there is a linear arrangement where the quinoxalines are fused to pyrrolic positions that are opposite each other. The porphyrin without the fused quinoxaline groups, Au(P)PF(6), was also investigated under the same solution conditions. In the absence of acid, all three gold(III) porphyrins undergo a single reversible Au(III)/Au(II) process leading to the formation of a Au(II) porphyrin which can be further reduced at more negative potentials to give stepwise the Au(II) porphyrin π-anion radical and dianion, respectively. However, in the presence of acid, the initial Au(III)/Au(II) processes of Au(PQ)PF(6) and Au(QPQ)PF(6) are followed by an internal electron transfer and protonation to regenerate new Au(III) porphyrins assigned as Au(III)(PQH)(+) and Au(III)(QPQH)(+). Both protonated gold(III) quinoxalinoporphyrins then undergo a second Au(III)/Au(II) process at more negative potentials. The electrogenerated monoprotonated monoquinoxalinoporphyrin, Au(II)(PQH), is then further reduced to its π-anion radical and dianion forms, but this is not the case for the monoprotonated bis-quinoxalinoporphyrin, Au(II)(QPQH), which accepts a second proton and is rapidly converted to Au(III)(HQPQH)(+) before undergoing a third Au(III)/Au(II) process to produce Au(II)(HQPQH) as a final product. Thus, Au(P)PF(6) undergoes one metal-centered reduction while Au(PQ)PF(6) and Au(QPQ)PF(6) exhibit two and three Au(III)/Au(II) processes, respectively. These unusual multistep sequential Au(III)/Au(II) processes were monitored by thin-layer spectroelectrochemistry and a reduction/oxidation mechanism for Au(PQ)PF(6) and Au(QPQ)PF(6) in acidic media is proposed.

Little exchange at the liquid/solid interface: defect-mediated equilibration of physisorbed porphyrin monolayers.

The transition from low to high density 2D surface structures of copper porphyrins at a liquid/solid interface requires specific defects at which nearly all exchange of physisorbed molecules with those dissolved in the supernatant occurs.

Multiple photosynthetic reaction centres composed of supramolecular assemblies of zinc porphyrin dendrimers with a fullerene acceptor.

Multiple photosynthetic reaction centres have successfully been constructed using supramolecular complexes of zinc porphyrin dendrimers [D(ZnP)(n): n = 4, 8, 16] with fulleropyrrolidine bearing a pyridine ligand (C(60)py). Efficient energy migration occurs completely between the ZnP units of dendrimers prior to the electron transfer with increasing the generation of dendrimers to attain an extremely long charge-separation lifetime.

Controlled templating of porphyrins by a molecular command layer.

The copper porphyrin (5,10,15,20-tetraundecylporphyrinato)copper(II) can be templated in a well-defined arrangement using p-(hexadecyloxycarbonyl)phenylacetylene as a command layer on graphite. The bicomponent system was characterized at the submolecular level at a solid/liquid interface by scanning tunneling microscopy (STM). It is proposed that the layer of copper porphyrins is templated on top of the command layer in a hierarchical fashion, via a combination of intermolecular π-π stacking and van der Waals interactions. A very subtle effect, i.e., a superstructure in the alkyl chain region of the phenylacetylene monolayers, was identified as a decisive factor for the templating process.

Entropically driven photochemical upconversion.

Conventional photochemical upconversion (UC) through homo-geneous triplet-triplet annihilation (TTA) is subject to several enthalpic losses that limit the UC margin. Here, we address one of these losses: the triplet energy transfer (TET) from the sensitizer to the emitter molecules. Usually, the triplet energy level of the emitter is set below that of the sensitizer. In our system, the triplet energy level of the emitter exceeds that of the sensitizer by ∼600 cm(-1). Choosing suitable concentrations for the sensitizer and emitter molecules, we can exploit entropy as a driving force for the migration of triplet excitation from the sensitizer to the emitter manifolds. Thereby we obtain a new record for the peak-to-peak TTA-UC energy margin of 0.94 eV. A modified Stern-Volmer analysis yields a TET rate constant of 2.0 × 10(7) M(-1) s(-1). Despite being relatively inefficient, the upconverted fluorescence is easily visible to the naked eye with irradiation intensities as low as 2 W cm(-2).

Three-metal coordination by novel bisporphyrin architectures.

The synthesis and characterization of a new type of bisporphyrin system is reported where the two macrocycles are linked in a cofacial arrangement by a substituted carbazole bridge. The three nitrogen atoms of the carbazole bridge in the compounds may complex a metal ion and thus provide a new parameter for varying the physical properties and flexibility of the dyad after formation of a three-metal system. In the present study, four bis-metalloporphyrin complexes were synthesized and examined by electrochemistry and thin-layer spectroelectrochemistry in CH(2)Cl(2) and PhCN. Two of the examined compounds contain Cu(II) or Zn(II) porphyrins and a carbazole linker with a bound Cu(II) ion, giving a three metal system, while the other two examined compounds contained the same porphyrins but with a carbazole bridge which lacks the Cu(II) component. Since carbazoles and Cu(II) ions are both electroactive, redox properties of several unlinked carbazoles with and without bound Cu(II) ions were also examined as to their electrochemical behavior under the same solution conditions as the dyads to better understand the redox reactions which may occur at the carbazole group linking the two porphyrin macrocycles. Several mononuclear porphyrins with structures related to macrocycles in the dyads were also investigated.

Oxygen reduction catalyzed by a fluorinated tetraphenylporphyrin free base at liquid/liquid interfaces.

The diprotonated form of a fluorinated free base porphyrin, namely 5-(p-aminophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (H(2)FAP), can catalyze the reduction of oxygen by a weak electron donor, namely ferrocene (Fc). At a water/1,2-dichloroethane interface, the interfacial formation of H(4)FAP(2+) is observed by UV-vis spectroscopy and ion-transfer voltammetry, due to the double protonation of H(2)FAP at the imino nitrogen atoms in the tetrapyrrole ring. H(4)FAP(2+) is shown to bind oxygen, and the complex in the organic phase can easily be reduced by Fc to produce hydrogen peroxide as studied by two-phase reactions with the Galvani potential difference between the two phases being controlled by the partition of a common ion. Spectrophotometric measurements performed in 1,2-dichloroethane solutions clearly evidence that reduction of oxygen by Fc catalyzed by H(4)FAP(2+) only occurs in the presence of the tetrakis(pentafluorophenyl)borate (TB(-)) counteranion in the organic phase. Finally, ab initio computations support the catalytic activation of H(4)FAP(2+) on oxygen.

Evaluation of optical fiber microcell reactor for use in remote acid sensing.

An optical fiber acid-sensor based on protonation of a porphyrin solution within a single-hole structured optical fiber is proposed and demonstrated. The liquid-core fiber acts as a microcell reactor, and changes in the spectral signature with acidification are detected. Challenges and limitations in the practical deployment of such sensors are evaluated. An effective chemical sensor is demonstrated, but issues such as diffusion limit its full utilization. Some solutions are discussed.

Molecular electrocatalysis for oxygen reduction by cobalt porphyrins adsorbed at liquid/liquid interfaces.

Molecular electrocatalysis for oxygen reduction at a polarized water/1,2-dichloroethane (DCE) interface was studied, involving aqueous protons, ferrocene (Fc) in DCE and amphiphilic cobalt porphyrin catalysts adsorbed at the interface. The catalyst, (2,8,13,17-tetraethyl-3,7,12,18-tetramethyl-5-p-amino-phenylporphyrin) cobalt(II) (CoAP), functions like conventional cobalt porphyrins, activating O(2) via coordination by the formation of a superoxide structure. Furthermore, due to the hydrophilic nature of the aminophenyl group, CoAP has a strong affinity for the water/DCE interface as evidenced by lipophilicity mapping calculations and surface tension measurements, facilitating the protonation of the CoAP-O(2) complex and its reduction by ferrocene. The reaction is electrocatalytic as its rate depends on the applied Galvani potential difference between the two phases.