Bicyclische Oxalamidine – Bausteine für hochsubstituierte 2,2′-Bipyridine und Benzolderivate

Bicyclic Oxalic Amidines as Building Blocks for Highly Substituted 2,2′-Bipyridines and Benzene Derivatives The bis-imidoylchlorides 1 derived from oxalic acid exhibit a high regio- and chemoselectivity. As in the case of 2-picolylamine 2 the acylation with oxalyl chloride furnished the expected open chained oxalic diamides 3a while the imidoylchlorides 1 yield exclusively the new pyrido[1,2-a]-pyrazines 4 . These heterocycles represent readily crystallisable and orange-red coloured compounds with a mesomeric dipolar aromatic substructure. The synthetic value of 4 is based on their easy transformation into highly substituted arenes and hetarenes. Thus, electron deficient dienophiles as dimethyl acetylenedicarboxylate lead to the bipyridines 6 via Hetero-Diels-Alder-Reaction and subsequent 1,5-hydrogen shift. In a complex reaction the derivatives of maleic acid 7a – c yield the bipyridines of type 9 while the new hexasubstituted arenes 10 can be isolated under anaerobic conditions and with an excess of dienophilic component. A x-ray structural determination of 10b shows an alternation of bond lenghts in the benzene ring. This can be considered as a distinct disturbance of aromaticity caused by the arrangement of substituents.     

Structural diversity and solution behavior of low-valent iridium complexes bearing 1,4-diazabutadiene ligands

Three types of 1,4-diazabutadiene stabilized low-valent iridium complexes, namely [IrCl(cod)(MesDAB)] (1), [IrCl(coe)(MesDAB)] (2) and [IrCl(MesDAB)₂] (3), have been prepared from 1,4-bis(2,4,6-trimethylphenyl)-1,4-diaza-1,3-butadiene (MesDAB) and [IrCl(cod)]₂ or [IrCl(coe)₂]₂, respectively. The complexes have been investigated by NMR spectroscopy and X-ray diffraction experiments. While tetra-coordinated 2 and penta-coordinated 3 maintain their solid state structure in solution, penta-coordinated 1 shows fluxional behavior. The crystal structures determined indicate strong π-backbonding towards the MesDAB ligand in all cases.     

A fully automated calibration method for an optical see-through head-mounted operating microscope with variable zoom and focus

Ever since the development of the first applications in image-guided therapy (IGT), the use of head-mounted displays (HMDs) was considered an important extension of existing IGT technologies. Several approaches to utilizing HMDs and modified medical devices for augmented reality (AR) visualization were implemented. These approaches include video-see through systems, semitransparent mirrors, modified endoscopes, and modified operating microscopes. Common to all these devices is the fact that a precise calibration between the display and three-dimensional coordinates in the patient's frame of reference is compulsory. In optical see-through devices based on complex optical systems such as operating microscopes or operating binoculars-as in the case of the system presented in this paper-this procedure can become increasingly difficult since precise camera calibration for every focus and zoom position is required. We present a method for fully automatic calibration of the operating binocular Varioscope M5 AR for the full range of zoom and focus settings available. Our method uses a special calibration pattern, a linear guide driven by a stepping motor, and special calibration software. The overlay error in the calibration plane was found to be 0.14-0.91 mm, which is less than 1% of the field of view. Using the motorized calibration rig as presented in the paper, we were also able to assess the dynamic latency when viewing augmentation graphics on a mobile target; spatial displacement due to latency was found to be in the range of 1.1-2.8 mm maximum, the disparity between the true object and its computed overlay represented latency of 0.1 s. We conclude that the automatic calibration method presented in this paper is sufficient in terms of accuracy and time requirements for standard uses of optical see-through systems in a clinical environment.     

Photonic Side-Channel Analysis of Arbiter PUFs

As intended by its name, physically unclonable functions (PUFs) are considered as an ultimate solution to deal with insecure storage, hardware counterfeiting, and many other security problems. However, many different successful attacks have already revealed vulnerabilities of certain digital intrinsic PUFs. This paper demonstrates that legacy arbiter PUF and its popular extended versions (i.e., feed-forward and XOR-enhanced) can be completely and linearly characterized by means of photonic emission analysis. Our experimental setup is capable of measuring every PUF internal delay with a resolution of 6 ps. Due to this resolution, we indeed require only the theoretical minimum number of linear independent equations (i.e., physical measurements) to directly solve the underlying inhomogeneous linear system. Moreover, it is not required to know the actual PUF responses for our physical delay extraction. We present our practical results for an arbiter PUF implementation on a complex programmable logic device manufactured with a 180 nm process. Finally, we give an insight into photonic emission analysis of arbiter PUF on smaller chip architectures by performing experiments on a field programmable gate array manufactured with a 60 nm process.     

Synthesis of β‐Aminonitrones by Regioselective Oxidation of 4H‐Imidazoles

A new regioselective synthesis for aminonitrones of type 4 via oxidative modification of 4H‐imidazoles 1 has been developed. An X‐ray structural analysis revealed an unexpected tautomeric fixation of the hydrogen atom in 4 . NMR investigations of the ¹⁵N‐labelled derivative 4b showed that this fixation is also present in solution. All new synthesized aminonitrones reported here are unusually stable which can be explained by contribution of anionic as well as cationic delocalized mesomeric structures. Treatment of 4 with acetic anhydride leads to formation of the O‐acylated hydroxylamine derivatives 5 .     

Komplexbildung und selektive Cyclisierung substituierter Oxalamidine

Crystallographic data for the acyclic benzylic substituted oxalamidine 3 and the alkyl substituted oxalamidine 4 reveal different structures for compound 3 (s‐trans(E/E) configuration and intramolecular hydrogen bridges) and compound 4 (s‐cis(E/E) configuration without hydrogen bridges). On the basis of the different configurations of these isomeric oxalamidines, the complexation on a (CO)₄Mo‐fragment varies remarkably: Complex formation of ligand 3 takes place at the sp²‐hybridized nitrogen atoms by rotation of the central C–C‐axis, isomerisation of the C N bonds, and by breaking of the hydrogen bridges. Because of the steric hindrance in 4 , the initiating coordination should occur on the sp³‐nitrogen atoms, followed by a intramolecular proton transfer and rehybridization. This complexation is favoured in the cases of cyclic oxalamidines. The molecular structures of the oxalamidines 3 and 4 , their (CO)₄Mo‐complexes 5 , 6 , and of the coordination compound of the cyclic 2,3‐bis(phenyl‐amino)chinoxaline 8 were unambiguously clarified by X‐ray analysis. The cyclization of the different substituted oxalamidines 3 and 4 by phosgene or thiophosgene in the presence of NaN[Si(CH₃)₃]₂ in THF proceeds regioselectively to the asymmetric 2‐imidazolidinones and ‐thiones 11 and 14 , respectively. In contrast to 3 , 4 cyclizes in toluene selectively to the isomeric symmetric 2‐imidazolidinthione 13 . Furthermore, the cyclization on the coordinated oxalamidines with oxalyl chloride provides exclusively the coordinated 2‐imidazolidinones 12 and 15 , which retain the substituent pattern of the starting complexes 5 and 6 – the (CO)₄Mo‐fragment acts as a protecting group.     

Novel building blocks for oligonuclear copper complexes derived from β‐ketoenamines of histidine

Condensation products of L‐histidine with the 3‐oxoenolethers diethyl‐ethoxymethylene‐malonate ( 1 ) and ethyl‐ethoxymethylene‐cyanoacetate ( 2 ) react with copper(II) as di‐anionic ligands to give neutral 1:1 complexes Cu‐ His1 and Cu‐ His2 . Both complexes crystallize as oligonuclear units, even from strongly donating solvents like N‐methylimidazole (Meim) (Cu‐ His1 ) and pyridine (Cu‐ His2 ). X‐ray structure analyses show supramolecular structures, formed of two (Cu‐ His1 ) or four (Cu‐ His2 ) formula units of the complex, which arrange to macrocycles by means of intermolecular coordination of the imidazole‐N. Strong H‐bridges result in a face‐to‐face orientation of the hydrophilic sites of two great rings. ESI‐MS investigations in pyridine solution give evidence for the existence of dimeric, tetrameric and – in case of Cu‐ His2 – trimeric units, besides the monomeric adducts with one pyridine. In contrast to the dimeric or tetrameric (“cubane‐like”) copper(II) complexes of amino alcohols and their β‐ketoenamines, the complexes Cu‐ His1 and Cu‐ His2 show no significant spin coupling from room temperature down to 4 K. The complexes Cu‐ His1 and Cu‐ His2 give no electrochemically reversible Cu^II/I reduction in pyridine. However, the isolation of a stable diamagnetic copper(I) complex of the methylester derivative, Cu^I‐ HisMe1 , supports the assumption, that similar histidine‐derived copper complexes should display reversible redox behaviour and catalytic activity in reactions with O₂.