aRMSD: A Comprehensive Tool for Structural Analysis.

A new free tool for structural comparison is presented that combines existing and new features into a single software package. aRMSD incorporates the functions of establishing a pairwise correlation between the atoms of two molecular structures and the calculation of the optimal rotation matrix that minimizes the root-mean-square deviation (RMSD) between the molecules. The complexity of the Hungarian assignation problem is reduced by decomposing molecules into different subsets based on different atom or group types allowing for an efficient and robust treatment of large molecules while tolerating different substituents. Various weighting functions can be used for the calculation of RMSD values and similarity descriptors, and the utilization of coordinate uncertainties allows for the calculation of standard deviations for all calculated properties through error propagation. A new three-dimensional (3D) graphical representation that combines multiple aspects of structural information is presented which is useful in the analysis of structural similarity and diversity. The capabilities of aRMSD are demonstrated by selected examples that show how the program can be utilized in the analysis of structural changes and in the correlation of structure and activity in molecules. The source code of the program can be downloaded at https://github.com/armsd/aRMSD .

Dehydrogenative Coupling Reactions with Oxidized Guanidino-Functionalized Aromatic Compounds: Novel Options for σ-Bond Activation.

We present a new option for metal-free σ-bond activation, making use of oxidized, guanidino-functionalized aromatic compounds (GFAs). We demonstrate this new option by the homocoupling reactions of thiols and phosphines. The kinetics and the reaction pathway were studied by a number of experiments (including heterocoupling of thiols and phosphines), supported by quantum-chemical computations. Reaction of the oxidized GFA with p-dihydrobenzoquinone to give p-benzoquinone shows that typical proton-coupled electron-transfer reactions are also possible.

The control of the electronic structure of dinuclear copper complexes of redox-active tetrakisguanidine ligands by the environment.

The electronic structures of dinuclear copper complexes of the general formula [GFA(CuX2)2], where X = Br or Cl and GFA denotes a redox-active bridging Guanidino-Functionalized Aromatic ligand, were analysed and compared. The diamagnetic complexes [GFA(CuBr2)2] can all be described as dinuclear CuI complexes with bridging GFA2+ dicationic ligand units exhibiting a [CuI-GFA2+-CuI] electronic structure. The electronic structure prevails in the solid state and in all applicable organic solvents. The situation changes completely for the [GFA(CuCl2)2] complexes. They are paramagnetic in the solid state, where they are adequately described as dinuclear CuII complexes with neutral bridging GFA ligand units ([CuII-GFA-CuII]). In solution, they exist either as [CuII-GFA-CuII] or as valence-tautomeric [CuI-GFA2+-CuI] complexes, depending on the polarity of the solvent. Only in the case of GFA = 2,3,5,6-tetrakis(tetramethylguanidino)pyridine and in acetone as solvent, the two valence tautomers are in a temperature-dependent equilibrium. Quantum chemical computations show that the structural difference between the two valence tautomeric forms is smaller for this complex than for the others, explaining the low energy barrier for the intramolecular electron transfer in accordance with Marcus theory.

A Valence Tautomeric Dinuclear Copper Tetrakisguanidine Complex.

We report on the first valence tautomeric dinuclear copper complex, featuring 2,3,5,6-tetrakis(tetramethylguanidino)pyridine as a bridging redox-active GFA (guanidino-functionalized aromatic) ligand. The preferred electronic structure of the complex is massively influenced by the environment. In the solid state and in nonpolar solvents a paramagnetic, dinuclear Cu(II) complex with a neutral GFA ligand is present. In polar solvents, the electronic structure changes to a diamagnetic, dinuclear Cu(I) complex with a twofold-oxidized GFA ligand. Using acetone as a solvent, both electronic structures are accessible due to a temperature-dependent equilibrium between the two valence tautomeric complexes. Our results pave the way for a broader use of valence tautomeric transition-metal complexes in catalytic reactions since anionic coligands can now be tolerated owing to the neutral/positively charged GFA ligand.

Thermochromism of Cu(I) Tetrakisguanidine Complexes: Reversible Activation of Metal-to-Ligand Charge-Transfer Bands.

Tetranuclear, intensely blue-coloured Cu(I) complexes were synthesised in which two Cu2 X3 (-) units (X=Br or I) are bridged by a dicationic GFA (guanidino-functionalised aromatic) ligand. The UV/Vis spectra show a large metal-to-ligand charge-transfer (MLCT) band around 638 nm. The tetranuclear "low-temperature" complexes are in a temperature-dependent equilibrium with dinuclear Cu(I) "high-temperature" complexes, which result from the reversible elimination of two CuX groups. A massive thermochromism effect results from the extinction of the strong MLCT band upon CuX elimination with increasing temperature. For all complexes, quantum chemical calculations predict a small and method-dependent energy difference between the possible electronic structures, namely Cu(I) and dicationic GFA ligand (closed-shell singlet) versus Cu(II) and neutral GFA ligand (triplet or broken-symmetry state). The closed-shell singlet state is disfavoured by hybrid-DFT functionals, which mix in exact Hartree-Fock exchange, and is favoured by larger basis sets and consideration of a polar medium.

Chemistry of guanidinate-stabilised diboranes: transition-metal-catalysed dehydrocoupling and hydride abstraction.

Herein, we analyse the catalytic boron-boron dehydrocoupling reaction that leads from the base-stabilised diborane(6) [H2 B(hpp)]2 (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate) to the base-stabilised diborane(4) [H2 B(hpp)]2 . A number of potential transition-metal precatalysts was studied, including transition-metal complexes of the product diborane(4). The synthesis and structural characterisation of two further examples of such complexes is presented. The best results for the dehydrocoupling reactions were obtained with precatalysts of Group 9 metals in the oxidation state of +I. The active catalyst is formed in situ through a multistep process that involves reduction of the precatalyst by the substrate [H2 B(hpp)]2 , and mechanistic investigations indicate that both heterogeneous and (slower) homogeneous reaction pathways play a role in the dehydrocoupling reaction. In addition, hydride abstraction from [H2 B(hpp)]2 and related diboranes is analysed and the possibility for subsequent deprotonation is discussed by probing the protic character of the cationic boron-hydrogen compounds with NMR spectroscopic analysis.

Bonding in diborane-metal complexes: a quantum-chemical and experimental study of complexes featuring early and late transition metals.

The coordination chemistry of the doubly base-stabilised diborane(4), [HB(hpp)]2 (hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a]pyrimidinate), was extended by the synthesis of new late transition-metal complexes containing Cu(I) and Rh(I) fragments. A detailed experimental study was conducted and quantum-chemical calculations on the metal-ligand bonding interactions for [HB(hpp)]2 complexes of Group 6, 9, 11 and 12 metals revealed the dominant B-H-M interactions in the case of early transition-metal fragments, whereas the B-B-M bonding prevails in the case of the late d-block compounds. These findings support the experimental results as reflected by the IR and NMR spectroscopic parameters of the investigated compounds. DFT calculations on [MeB(hpp)]2 and model reactions between [B2H4⋅2NMe3] and [Rh(µ-Cl)(C2H4)2] showed that the bicyclic guanidinate allows in principle for an oxidative addition of the B-B bond. However, the formation of σ-complexes is thermodynamically favoured. The results point to the selective B-H or B-B bond-activation of diborane compounds by complexation, depending on the chosen transition-metal fragment.

Diborane(4)-metal bonding: between hydrogen bridges and frustrated oxidative addition.

The metal complexes [M{HB(hpp)}(2)(CO)(4)] (M = Cr, Mo or W) and [M(cod){HB(hpp)}(2)Cl] (M = Rh or Ir) of the doubly-base stabilized diborane(4) ligand [HB(hpp)](2) were fully characterized and their bonding nature was investigated in detail. While bonding in the group 6 complexes predominantly occurs through the hydrogen atoms, the metal-ligand interaction in the group 9 complexes can be regarded as an early stage oxidative addition of the boron-boron bond leading to diboryl compounds.

Pseudodynamic MRI differs from natural opening of the temporomandibular joint.

OBJECTIVE: One step toward motion analysis of the temporomandibular joint is pseudodynamic magnetic resonance imaging (i.e., with stepwise mouth opening controlled by a Burnett device). This study intends to clarify whether and how pseudodynamic motion differs from natural motion. Furthermore, the fixing efficiency (i.e., the reliability of the mechanical connection to the jaw) of the Burnett device was tested. STUDY DESIGN: In 10 patients we recorded pseudodynamic opening motions by means of MRI and optical tracking technology (as known from image-guided surgery) synchronously; natural opening motions by spatiotemporal tracking only. The MRI was used to allow for interpretation of the pseudodynamic motion as recorded by means of optoelectronic tracking. RESULTS: In 3 subjects the pseudodynamic differed from the natural opening in occurrence of a loop (i.e., a short backward motion of the condyle during the opening process that results from the application of the Burnett device and does not correspond to a natural jaw movement). Fifty percent of the opening steps showed unintended motion and thus did not keep the mandible still during the MRI scan. CONCLUSION: A method was provided to detect motion during MRI scan using optoelectronic tracking. Pseudodynamic motion may differ from natural motion.

Clinical evaluation of mechanically optimized plates for the treatment of condylar process fractures.

OBJECTIVE: In this study we report on finite element calculation to verify the mechanical stability induced by the new geometry of a novel condylar process plate. We report our clinical experiences in the treatment of condylar process fractures using the novel plate. The plate has been designed according to finite element calculations in order to optimize mechanical stability and stiffness. The potential influence of this plate on the postoperative complication rate was assessed. STUDY DESIGN: Thirty-five mandibular condylar process fractures in 30 patients (20 male, 10 female, age: 34.3 +/- 11.5 years) were treated with the Modus condylar process plates (Medartis, Basle, Switzerland) and are included in this study. The time periods for postoperative follow-ups were 6 weeks and 6 months. RESULTS: No plate fractures occurred and there was no injury to the facial nerve. In one patient a screw loosening was observed. Two patients showed inadequate reduction without functional impairment. CONCLUSION: The newly developed condylar process plate proved to provide sufficient mechanical stiffness to avoid plate fractures. The postoperative complication rate can be reduced significantly. Statistical comparison to other osteosynthesis methods of the condylar process was performed and showed significant differences (single miniplates: P = .006 and minidynamic compression plates: P = .055). We conclude that a single Modus condylar process plate shows results comparable to 2 miniplates.

Surface area analysis of dental implants using micro-computed tomography.

OBJECTIVES: In this study, we present and evaluate a micro-computed tomography (micro-CT)-based method for the calculation of the potential bone/implant contact area (p-BICA) on the surface of dental implants. MATERIAL AND METHODS: For seven commercially available implants (Ankylos implant, Brånemark System, Frialit CELLplus, Replace((R)) Select Tapered, Straumann Solid screw, XiVE S CELLplus, 3i Osseotite XP Threaded Miniplant, the p-BICA surface is determined by means of three-dimensional X-ray computed-tomography and computer-based data processing. Measurements were repeated two times, and the stability and repeatability of the measurement method were evaluated. RESULTS: Our analysis revealed a p-BICA of 118 mm(2) for the XiVE S CELLplus implant, 134 mm(2) for the Ankylos, 136 mm(2) for the Frialit CELLplus, 138 mm(2) for the Brånemark System, 139 mm(2) for the Replace((R)), 159 mm(2) for the 3i Osseotite XP and 199 mm(2) for the Straumann Solid screw implant. The measurement method proved to be stable and led to reproducible results. CONCLUSIONS: The micro- and macrostructure of dental implants define the surface and the p-BICA. Precise determination of this parameter can be achieved by means of the micro-CT-based method as presented in this study. The value of p-BICA lies in the predictability of industrial design before preclinical and clinical testing. Based on this method, dental implant properties become comparable even if geometrical details are not disclosed by the manufacturer.

Comparison of laser surface scanning and fiducial marker-based registration in frameless stereotaxy. Technical note.

The authors compared the accuracy of laser surface scanning patient registration using the commercially available Fazer (Medtronic, Inc.) with the conventional registration procedure based on fiducial markers (FMs) in computer-assisted surgery. Four anatomical head specimens were prepared with 10 titanium microscrews placed at defined locations and scanned with a 16-slice spiral computed tomography unit. To compare the two registration methods, each method was applied five times for each cadaveric specimen; thus data were obtained from 40 registrations. Five microscrews (selected following a randomization protocol) were used for each FM-based registration; the other five FMs were selected for coordinate measurements by touching with a point measurement stylus. Coordinates of these points were also measured manually on the screen of the navigation computer. Coordinates were measured in the same manner after laser surface registration. The root mean square error as calculated by the navigation system ranged from 1.3 to 3.2 mm (mean 1.8 mm) with the Fazer and from 0.3 to 1.8 mm (mean 1.0 mm) with FM-based registration. The overall mean deviations (the arithmetic mean of the mean deviations of measurements on the four specimens) were 3.0 mm (standard deviation [SD] range 1.4-2.6 mm) with the Fazer and 1.4 mm (SD range 0.4-0.9 mm) with the FMs. The Fazer registration scans 300 surface points. Statistical tests showed the difference in the accuracy of these methods to be highly significant. In accordance with the findings of other groups, the authors concluded that the inclusion of a larger number of registration points might improve the accuracy of Fazer registration.

Computer-guided flapless placement and immediate loading of four conical screw-type implants in the edentulous mandible.

AIM: The aim of this prospective study was to evaluate the outcome of computer-guided flapless placement and immediate loading of four conical screw-type implants in the interforaminal region. PATIENTS AND METHODS: From May to August 2003, 25 consecutive patients (m : f=16 : 9) with edentulous mandibles were included in the study. After transmucosal drilling with computer-assisted navigation, four implants were placed in the interforaminal region. The lower dentures were converted and implants immediately loaded. RESULTS: One-hundred implants were successfully placed. In two patients, all implants had to be submerged because of insufficient primary stability of one of the implants; another patient declined to receive immediate loading of implants after surgery and was lost to follow-up. During follow-up of the remaining 22 patients with 88 immediately loaded implants, loosening of four implants (4.5%) was seen in three patients. In these cases, immediate loading was terminated and all implants submerged; subsequently, two implants were lost in one patient, while the other two implants re-osseointegrated. The cumulative survival and success rates of immediately loaded implants were 97.7% after 2 years. Prosthetic success was 100%. CONCLUSION: Transmucosal computer-assisted placement and immediate loading of mandibular implants is a high-end approach to edentulism that provides excellent results while being minimally invasive.

Accuracy of treatment planning based on stereolithography in computer assisted surgery.

Three-dimensional stereolithographic models (SL models), made of solid acrylic resin derived from computed-tomography (CT) data, are an established tool for preoperative treatment planning in numerous fields of medicine. An innovative approach, combining stereolithography with computer-assisted point-to-point navigation, can support the precise surgical realization of a plan that has been defined on an SL model preoperatively. The essential prerequisites for the application of such an approach are: (1) The accuracy of the SL models (including accuracy of the CT scan and correspondence of the model with the patient's anatomy) and (2) the registration method used for the transfer of the plan from the SL model to the patient (i.e., whether the applied registration markers can be added to the SL model corresponding to the markers at the patient with an accuracy that keeps the "cumulative error" at the end of the chain of errors, in the order of the accuracy of contemporary navigation systems). In this study, we focus on these two topics: By applying image-matching techniques, we fuse the original CT data of the patient with the corresponding CT data of the scanned SL model, and measure the deviations of defined parameter (e.g., distances between anatomical points). To evaluate the registration method used for the planning transfer, we apply a point-merge algorithm, using four marker points that should be located at exactly corresponding positions at the patient and at connective bars that are added to the surface of the SL model. Again, deviations at defined anatomical structures are measured and analyzed statistically. Our results prove sufficient correspondence of the two data sets and accuracy of the registration method for routine clinical application. The evaluation of the SL model accuracy revealed an arithmetic mean of the relative deviations from 0.8% to 5.4%, with an overall mean deviation of 2.2%. Mean deviations of the investigated anatomical structures ranged from 0.8 mm to 3.2 mm. An overall mean (comprising all structures) of 2.5 mm was found. The fiducial registration error of the point-merge algorithm ranged from 1.0 mm to 1.4 mm. The evaluated chain of errors showed a mean deviation of 2.5 mm. This study verifies that preoperative planning on SL models and intraoperative transfer of this plan with computer assisted navigation is a suitable and sufficiently reliable method for clinical applications.

Measurement of volume changes after sinus floor augmentation with a phycogenic hydroxyapatite.

PURPOSE: The purpose of this study was the determination of time-dependent volumetric changes of particulate sinus inlay grafts. A mixture of phycogenic hydroxyapatite (Algipore/C-Graft) and autologous bone collected from the surgical access area was used as the grafting material. MATERIALS AND METHODS: Thirty-three sinus floor augmentations using phycogenic hydroxyapatite combined with autologous bone collected at the augmentation site and venous blood were performed on 18 patients aged 57.4 +/- 12.5 years (mean +/- SD) with severe atrophy of the posterior maxilla. Graft volume was measured 1 to 14 days postoperatively and before the placement of dental implants 6.1 +/- 2.1 months later (mean +/- SD; range, 4 to 11 months) to evaluate the amount of time-dependent resorption of the implanted material on computerized tomographic (CT) images of the augmented region. The images were put into Digital Imaging and Communications in Medicine (DICOM) format and evaluated using the software library Analyze. The implanted bone replacement material was plotted manually on each CT slice, and the volume of the implanted material was calculated. RESULTS: The average volume loss of the bone replacement material during the observation period was 13.9% +/- 1.9% (mean +/- SEM). All sinus floor augmentations healed without complications except for delayed membrane exposure in 2 cases. DISCUSSION: The results indicate that the graft material, a mixture of Algipore, bone chips from the access area, and venous blood, exhibited a small volume loss over a period of approximately 6 months, thus providing predictable height for second-stage implant surgery. CONCLUSION: Further investigations are needed to evaluate long-term stability and implant success.

Point-to-point computer-assisted navigation for precise transfer of planned zygoma osteotomies from the stereolithographic model into reality.

PURPOSE: To evaluate the feasibility and accuracy of a new method for planning and realizing zygomatic osteotomies in cases of established post-traumatic deformities using stereolithographic (SL) models and computer assisted navigation. PATIENTS AND METHODS: In 5 patients, osteotomy and repositioning of the zygomatic complex was planned using SL models. The desired position of the zygoma in the patient was determined by fixing individualized osteosynthesis plates to predefined screw positions. The SL model and the patient were registered to the same 3-dimensional computed tomography data set via an occlusal reference frame on the patient and corresponding reference markers on the model. Prebent osteosynthesis plates from the surgical simulation on the model were fixed to corresponding screw positions on the patient, which were located by computer-assisted navigation. Evaluation of accuracy was performed by image fusion of postoperative computed tomography scans of the model and the patient. RESULTS: Clinical outcome was satisfactory in all cases. The evaluation by image fusion showed alignment of the patient's and the model's zygoma in 4 of 5 cases. Mean measured distance between screw positions in the models and the patients were 1.1 +/- 0.3 mm for 44 screws. In 1 patient the treatment plan was changed intraoperatively because of unforeseen soft tissue limitations. CONCLUSION: Point-to-point navigation is an accurate method to transfer the planning of a complex osteotomy from the SL model to the actual surgical procedure. Surgery is facilitated considerably because repositioning and osteosynthesis are achieved in 1 step.

Seven years of clinical experience with teleconsultation in craniomaxillofacial surgery.

PURPOSE: In this work the experiences from 50 telemedically supported treatments in craniomaxillofacial surgery are summarized and different setups for their technical realization are described. Furthermore, for the first time the innovative UMTS (universal mobile telecommunication system) is applied for the transmission of arthroscopic videos of the temporomandibular joint and other craniomaxillofacial structures. MATERIALS AND METHODS: The combination of computer-assisted navigation technology in augmented reality environments with telecommunication is used for execution of interactive stereotaxic teleconsultation. Furthermore, treatments without navigation are telemedically supported. This study is composed of 4 technical system configurations: 1) integrated services digital network (ISDN)-based videoconferencing without remote control of the navigation computer; 2) transmission control protocol/internet protocol (TCP/IP)-based interactive teleconsultation via bundled ISDN lines (including remote control of the navigation computer); 3) TCP/IP-based interactive teleconsultation via network; 4) combination of TCP/IP-connection and ISDN-based videoconferencing. The telemedically supported treatments are: orbitozygomatic osteotomies, positioning of the mandibular condyle in orthognathic surgery, insertion of implants, positioning of the maxilla in orthognathic surgery, distraction osteogenesis, arthroscopies of the temporomandibular joint, and operation simulations on stereolithographic models. The surgical interventions are evaluated on a 5-level system performance scale from the technical point of view. In a separate trial 20 videosequences of arthroscopies of the temporomandibular joint are transmitted via UMTS cellular phones and independently evaluated by 3 experts (ie, a total of 60 streamings) to investigate feasibility of this technology in the field of craniomaxillofacial surgery. RESULTS: In the years from 1996 to 2002 a total of 50 treatments were telemedically supported. All intraoperative applications were successfully finished; 48 of 60 UMTS transmissions were finished without any interruptions in constant quality, slight interruptions were observed in 8 tests, and a complete breakdown was observed during 4 streamings that required a restart of the transmission. Resolution was sufficient to diagnose even tiny anatomic structures inside the temporomandibular joint, but orientation was hardly recognizable. CONCLUSION: In many applications telecommunication technology can contribute to a quality improvement in cranio- and maxillofacial surgery because of the global availability of specialized knowledge. The required technical expenditure for teleconsultation crucially depends on the infrastructure that is already available at the clinic and the remote site. UMTS is a promising technology with the potential to be valuable in numerous craniomaxillofacial applications.

Influence of three currently used bone replacing materials on the in vitro proliferation of human peripheral blood mononuclear cells.

OBJECTIVES: A cell culture system for biocompatibility testing of bone grafting materials is described. We investigated the in vitro viability and proliferative response of peripheral blood mononuclear cells (PBMC) from 10 healthy donors in the presence of three materials currently used for bone grafting: Algipore, Bio-Oss and Bone Source, for immunologic biocompatibility testing. MATERIAL AND METHODS: PBMC isolated from venous blood from 10 healthy donors were incubated for 4 days with each bone replacing material, in the presence and absence of interleukin-2 (IL-2). After 4 days, H3-thymidine was added for 18 h and the incorporated radioactivity was measured with a beta-plate counter. RESULTS: Basal PBMC counts were 152.9+/-66.2 counts per minute (c.p.m.) (mean+/-SD), in the presence of 0.4 U IL-2/well 206.5+/-83 c.p.m. were measured. With Algipore and Bio-Oss, which are deproteinized bone replacing materials, the proliferation rate of PBMC with IL-2 was not significantly modified: for Algipore 151+/-51 c.p.m./+IL-2 188.8+/-62 c.p.m., for Bio-Oss 144.5+/-64.9 c.p.m./+IL-2 176.3+/-71.23 c.p.m. For Bone Source 164.2+/-80.4/+IL-2 188.3+/-81 c.p.m. were measured. CONCLUSION: This in vitro experiment indicates, that the investigated bone replacing materials are not acting as specific antigens/haptens and are not generating increased proliferative responses of human PBMC from healthy donors. Even with IL-2, that induces proliferation of T lymphocytes, which encountered their specific antigen, the proliferation rate of PBMC from healthy donors was not increased after incubation with this bone grafting materials.