Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 53
Filter
1.
Neuroscience ; 292: 129-36, 2015 Apr 30.
Article in English | MEDLINE | ID: mdl-25711941

ABSTRACT

A functional polymorphism (5-HTTLPR) within the serotonin transporter gene (SERT) has been associated with personality dimensions such as neuroticism, with emotional reactivity to negative events, and with an increased risk of affective disorders. More specifically, the short (S) allele of 5-HTTLPR has been linked to increased amygdala activity and has been identified as a risk allele for depressive disorders. Recently, Homberg and Lesch (2011) urged for a conceptual change in the current deficit-oriented connotation of the 5-HTTLPR S-allele and argued that the S-allele could be considered adaptive in certain contexts. They postulated that S-allele carriers show hypervigilant behavior in social situations and should thus show increased social conformity. Therefore, we tested whether 5-HTTLPR modulates the neural correlates of real-life social joint action through functional near-infrared spectroscopy (fNIRS). Thirty participants, homozygote for 5-HTTLPR, were measured and analyzed while they were involved in a previously published joint-action paradigm, which reliably leads to an activation of the left parietal cortex. We found that homozygote S-allele carriers showed increased inferior parietal lobe activation, compared to the LL-allele carriers for the contrast "joint action greater solo action". Therefore, our results provide evidence for beneficial effects of the S-allele on the neural correlates of social interactions.


Subject(s)
Brain/physiology , Motion Perception/physiology , Motor Activity/physiology , Polymorphism, Genetic , Serotonin Plasma Membrane Transport Proteins/genetics , Asperger Syndrome/psychology , Brain Mapping , Female , Homozygote , Humans , Male , Neuropsychological Tests , Personality , Psychiatric Status Rating Scales , Spectroscopy, Near-Infrared , Surveys and Questionnaires , Young Adult
2.
Ophthalmologe ; 111(3): 247-53, 2014 Mar.
Article in German | MEDLINE | ID: mdl-23765372

ABSTRACT

BACKGROUND: Clinical application of a keratoprosthesis (KPRO) is still a challenging task. Recent developments reflect the concepts of nut and bolt, intrastromal implantation or an osteoodontokeratoprosthesis (OOKP). A new concept of a textile KPRO has been evaluated in a limited human study with considerable difficulties which after termination of the study and considerable improvements was restarted using animal experiments. MATERIALS: The ACTO TexKPRO is made from polyvinylidene difluoride (PVDF) fibers and transparent silicone. The first and second developmental stages differed in density and size of fibers and furthermore in surface modifications of the fibers and optics which were improved for the second prototype. METHODS: Implantation of the prosthesis was performed in four patients with corneal blindness and in two cases retinal disease which required surgery. In the later animal experiments surgery was performed on three rabbits. Surgery was performed by redressing the conjunctiva, opening of the eyeball with a central 6.5 mm trephination, removal of the lens and iris and implantation and suturing of the TexKPRO. If required a silicone oil endotamponade was placed. RESULTS: All eyes were stable with the keratoprosthesis. The first prototype showed conjunctival recession on the textile haptics with highly susceptible endopthalmitis risk due to infection of the PVDF so that we decided to remove the prosthesis from all eyes after one case of severe endophthalmitis occurred. The longest time of placement was 40 months and the shortest time 6 months. All eyes were restored by keratoplasty. In animals with the new haptic we found better conjunctivalization and stable implantation of the KPRO. DISCUSSION: The textile KPRO provides a stable implantation procedure and safe connection of fibers to the scleral wound bed. The optical and mechanical implantation is safe and stable. Surface epithelialization is improved with the new surface modifications and different PVDF fiber density but beforel new implantations are planned further conceptual changes will be introduced.


Subject(s)
Corneal Diseases/surgery , Surgical Mesh , Textiles , Animals , Corneal Transplantation/instrumentation , Equipment Failure Analysis , Humans , In Vitro Techniques , Prosthesis Design , Rabbits , Treatment Outcome
3.
Opt Lett ; 38(19): 3704-7, 2013 Oct 01.
Article in English | MEDLINE | ID: mdl-24081031

ABSTRACT

The change in phase of the free space terahertz (THz) electric field as a sample of material introduced into the THz beampath of a CW THz system is measured and used to calculate the index of refraction of materials at 250 GHz.

4.
J Appl Microbiol ; 115(5): 1134-46, 2013 Nov.
Article in English | MEDLINE | ID: mdl-23902582

ABSTRACT

AIMS: Construction of a transgenic Arxula adeninivorans strain that produces a high concentration of adenine deaminase and investigation into the application of the enzyme in the production of food with low purine content. METHODS AND RESULTS: The A. adeninivorans AADA gene, encoding adenine deaminase, was expressed in this yeast under the control of the strong inducible nitrite reductase promoter using the Xplor(®) 2 transformation/expression platform. The recombinant enzyme was biochemically characterized and was found to have a pH range of 5.5-7.5 and temperature range of 34-46 °C with medium thermostability. A beef broth was treated with the purified enzyme resulting in the concentration of adenine decreasing from 70.4 to 0.4 mg l(-1). CONCLUSIONS: It was shown that the production of adenine deaminase by A. adeninivorans can be increased and that the recombinant adenine deaminase can be used to lower the adenine content in the food. SIGNIFICANCE AND IMPACT OF THE STUDY: Adenine deaminase is one component of an enzymatic system that can reduce the production of uric acid from food constituents. This study gives details on the expression, characterization and application of the enzyme and thus provides evidence that supports the further development of the system.


Subject(s)
Aminohydrolases/chemistry , Food Microbiology , Saccharomycetales/enzymology , Adenine/analysis , Aminohydrolases/genetics , Animals , Cattle , Genes, Fungal , Organisms, Genetically Modified , Promoter Regions, Genetic , Recombinant Proteins/chemistry , Recombinant Proteins/genetics , Saccharomycetales/genetics
5.
J Appl Microbiol ; 115(3): 796-807, 2013 Sep.
Article in English | MEDLINE | ID: mdl-23773263

ABSTRACT

AIMS: Isolation and characterization of xanthine oxidoreductase and its application in the production of food with low purine content. METHODS AND RESULTS: The A. adeninivorans xanthine oxidoreductase is an inducible enzyme. The best inducers were identified by enzyme activity tests and real-time PCR and used to produce large amounts of the protein. Xanthine oxidoreductase was partially purified and biochemically characterized, showing pH and temperature optimum of 8·5 and 43°C, respectively. The enzyme decreased xanthine and hypoxanthine concentrations in yeast extract and was active simultaneously with other purine-degrading enzymes so that all of the substrates for uric acid production were reduced in a single step. CONCLUSIONS: It was shown that induced A. adeninivorans can produce sufficient amount of xanthine dehydrogenase and that the enzyme is able to reduce xanthine and hypoxanthine content in food, and when used in conjunction with other enzymes of the pathway, uric acid concentration is significantly reduced. SIGNIFICANCE AND IMPACT OF THE STUDY: Reduction in dietary purines is recommended to people suffering from hyperuricemia. Elimination of most purine-rich foods may affect balanced nutrition. Food with lowered purine concentration will assist in controlling the disease. This study is a continuation of previous studies that characterized and overexpressed other enzymes of the purine degradation pathway.


Subject(s)
Purines/metabolism , Saccharomycetales/enzymology , Food Additives , Hypoxanthine/metabolism , Uric Acid/metabolism , Xanthine/metabolism , Xanthine Dehydrogenase/chemistry , Xanthine Dehydrogenase/genetics , Xanthine Dehydrogenase/metabolism
6.
Ophthalmologe ; 108(10): 910-5, 2011 Oct.
Article in German | MEDLINE | ID: mdl-21853219

ABSTRACT

Chemical burns of the eye are becoming rare due to improvements in occupational protection. Effective decontamination is the foundation for good clinical results of this ophthalmological emergency. The toxicological aspect focuses on classifying the specific toxicity of a chemical substance by evaluating the degree of eye irritation and eye burns. Chemical substances are classified into defined risk levels by specific tests. The traditional ophthalmological approach is based on the clinical presentation of eye burns as a result of contact with a specific toxic substance. In an integral approach it is shown that substance-specific characteristics, such as concentration and specific reactivity as well as individual features, such as mode and duration of exposition have an influence on the clinical appearance of the tissue damage. The decontamination is dependent on the mode of action and the effectiveness of the decontamination solution. Amphoteric substances have the best effectiveness for decontamination of the eye due to their specific characteristics.


Subject(s)
Burns, Chemical/drug therapy , Burns, Chemical/etiology , Decontamination/methods , Eye Burns/chemically induced , Eye Burns/drug therapy , Irritants/toxicity , Ophthalmic Solutions/therapeutic use , Humans , Therapeutic Irrigation/methods
7.
Ophthalmologe ; 106(9): 775-82, 2009 Sep.
Article in German | MEDLINE | ID: mdl-19806381

ABSTRACT

INTRODUCTION: Monthly controls are necessary after injections of vascular endothelial growth factor (VEGF) to enable timely recognition of a renewed decrease in vision. However, these monthly control intervals are not realistic for many older patients with age-related macular degeneration (AMD), and outpatient clinics often reach their logistical limits because of inadequate funding for the additional medical work. Against this background, we conceived the ACTO self-test as a novel screening method for patients to discover unnoticed visual changes outside the routinely scheduled ophthalmic examination. MATERIAL AND METHODS: The paper version of the ACTO self-test consists of a reading chart gradated in decimal steps as well as six questions regarding the quality of the Amsler grid. The patient uses a self-screening test to examine each eye separately and then transfers the results to a table. Along with the self-examination, the Action Eyesight Service Center is available to the patient by phone to motivate the patient and schedule a new appointment if improved test results occur. If decreased values or suspected decreased visual function occur, these are verified immediately by the referring physician. RESULTS: There is a good correlation between the steps of the ACTO self-test and standard visual acuity at 4 m (r(2)=0.9). Altogether, 1,444 patients were followed by phone and 745 participated in repeated regular audits, for a total of 3,003 phone contacts. The treating physician was informed about decreased visual acuity or increased Amsler distortion in the ACTO test in 137 cases, and immediate verification was done. We had 699 dropouts; the reasons were decreased visual acuity below the limits of the ACTO test in 39%, additional monthly examinations by the local ophthalmologist in 29%, and a desire for no more telephone follow-up (despite initial written consent) in 32%. Decreased vision when reading or an increased score on the Amsler test within the ACTO screening test was observed in 18% of AMD patients during the maintenance phase. CONCLUSION: Monthly screening by the ACTO screening test in combination with phone audits offers a new way to test visual acuity, with the Amsler score helping to detect changes in visual function. For patients with visual changes, confirmation by the ophthalmic physician can be achieved in time. Self-assessment cannot replace qualified ophthalmologic examination, but monthly self-controls enhance safety, reduce the number of physician contacts, and improve the detection of visual changes, with the option of immediate ophthalmic retreatment.


Subject(s)
Macular Degeneration/diagnosis , Macular Degeneration/drug therapy , Vascular Endothelial Growth Factor A/administration & dosage , Vision Disorders/diagnosis , Vision Disorders/drug therapy , Vision Tests/methods , Visual Acuity/drug effects , Aged , Female , Follow-Up Studies , Humans , Injections, Intralesional , Macular Degeneration/complications , Male , Reproducibility of Results , Self Care/methods , Sensitivity and Specificity , Treatment Outcome , Vision Disorders/etiology , Vitreous Body/drug effects
8.
Z Orthop Unfall ; 145(5): 622-4, 2007.
Article in German | MEDLINE | ID: mdl-17939073

ABSTRACT

Ruptures of the patellar tendon are less often observed compared to those of the Achilles or quadriceps tendon. A bilateral rupture is a rarity. Steroid medications or a variety of systemic diseases are associated with spontaneous tendon ruptures. Less often traumatic rupture is the result of severe overloading of the extensor mechanism of the knee. We report on a 60-year-old female without an obvious trauma, systemic disease or medication who suffered a spontaneous bilateral patellar tendon rupture.


Subject(s)
Athletic Injuries/surgery , Dancing/injuries , Patellar Ligament/injuries , Tendon Injuries/surgery , Anastomosis, Surgical , Athletic Injuries/diagnostic imaging , Athletic Injuries/pathology , Bone Wires , Diagnosis, Differential , Female , Humans , Middle Aged , Ossification, Heterotopic/pathology , Patellar Ligament/diagnostic imaging , Patellar Ligament/pathology , Patellar Ligament/surgery , Postoperative Care , Radiography , Reoperation , Rupture, Spontaneous , Sutures , Tendon Injuries/diagnostic imaging , Tendon Injuries/pathology
9.
Article in German | MEDLINE | ID: mdl-17440269

ABSTRACT

OBJECTIVE: In this prospective study using the Munich II nomenclature for cervical cytology. Pap smear results obtained by the ThinPrep monolayer technique and those obtained by the conventional method were compared. METHODS: Pap smears were obtained from 1,000 women using an Ayre spatula/endocervical brush combination. Following transfer of the cell sample onto a slide, the same collection devices were rinsed in a liquid medium and processed using ThinPrep-2000 processor (split-sample technique). RESULTS: Specimen inadequacies due to drying artefacts, cell overlap or low number of epithelial cells were rare with both methods without any significant differences. However, ThinPrep slides were significantly less often compromised by red or white blood cells or by cytolysis. In contrast, endocervical cells were missing in 11.6% of slides compared to only 2.3% in conventional Pap smears. ThinPrep yielded results of unknown significance (Pap III) significantly less often (4.2 vs 6.3%). CONCLUSIONS: ThinPrep slides are less frequently compromised by blood components or cytolysis. Inconclusive results of Pap III are slightly less frequent when using ThinPrep. However, there is a significant percentage of slides lacking the endocervical component. Using a combination of spatula and cytobrush, this may not necessarily be due to non-representative cell sampling.


Subject(s)
Papanicolaou Test , Terminology as Topic , Uterine Cervical Dysplasia/pathology , Uterine Cervical Neoplasms/pathology , Vaginal Smears/methods , Adolescent , Adult , Aged , Aged, 80 and over , Artifacts , Cervix Uteri/pathology , Female , Germany , Humans , Middle Aged , Predictive Value of Tests , Prospective Studies
11.
J Am Chem Soc ; 126(5): 1478-84, 2004 Feb 11.
Article in English | MEDLINE | ID: mdl-14759205

ABSTRACT

We report the preparation, crystallization, and solid-state characterization of a benzyl-substituted spirobiphenalenyl radical. The crystal structure shows that the radical is monomeric in the solid state, with the molecules packed in an unusual one-dimensional (1-D) fashion that we refer to as a pi-step stack. This particular mode of 1-D stacking is forced on the lattice arrangement by the presence of the orthogonal phenalenyl units that were specifically incorporated to prevent the crystallization of low-dimensional structures. The structure shows that this strategy is effective, and neighboring molecules in the stack can only interact via the overlap of one pair of active (spin-bearing) carbon atoms per phenalenyl unit, leading to the pi-step structure in which the remaining four active carbon atoms per phenalenyl unit do not interact with nearest neighbor molecules. The magnetic susceptibility data in the temperature range 4-360 K may be fit to an antiferromagnetic Heisenberg S = 1/2 linear chain model with intrachain spin coupling J = -52.3 cm(-1). Despite the uniform stacking, the material has a room temperature conductivity of 1.4 x 10(-3) S/cm and is best described as a Mott insulator.

12.
J Am Chem Soc ; 125(47): 14394-403, 2003 Nov 26.
Article in English | MEDLINE | ID: mdl-14624587

ABSTRACT

New synthetic routes to 1,2,3-dithiazolo-1,2,3-dithiazolylium salts, based on double Herz condensations of N-alkylated 2,6-diaminopyridinium salts with sulfur monochloride, have been developed. The two prototypal 1,2,3-dithiazolo-1,2,3-dithiazolyl radicals HBPMe and HBPEt have been prepared and characterized in solution by cyclic voltammetry and EPR spectroscopy. Measured electrochemical cell potentials and computed (B3LYP/6-31G) gas-phase disproportionation enthalpies favor a low on-site Coulombic repulsion energy U in the solid state. The crystal structures of HBPR (R = Me, Et) have been determined by X-ray crystallography (at 293 K). Both consist of slipped pi-stacks of undimerized radicals, with many close intermolecular S- - -S contacts. Magnetic, conductivity, and optical measurements have been performed and the results interpreted in light of extended Hückel band calculations. The crystalline materials are paramagnetic above 100 K, with room-temperature conductivities sigma(RT) of 10(-5)-10(-6) S cm(-1); the slightly greater conductivity of the R = Et compound can be associated with a more well developed band structure. We suggest a Mott-Hubbard insulator ground state for these materials, with an on-site Coulomb repulsion energy U of about 1.0 eV.

13.
Inorg Chem ; 42(24): 7945-50, 2003 Dec 01.
Article in English | MEDLINE | ID: mdl-14632512

ABSTRACT

A stable discrete nickel borohydride complex (Tp*NiBH(4) or Tp*NiBD(4)) was prepared using the nitrogen-donor ligand hydrotris(3,5-dimethylpyrazolyl)borate (Tp*-). This complex represents one of the best characterized nickel(II) borohydrides to date. Tp*NiBH(4) and Tp*NiBD(4) are stable toward air, boiling water, and high temperatures (mp > 230 degrees C dec). X-ray crystallographic measurements for Tp*NiBH(4) showed a six-coordinate geometry for the complex, with the nickel(II) center facially coordinated by three bridging hydrogen atoms from borohydride and a tridentate Tp(-) ligand. For Tp*NiBH(4), the empirical formula is C(15)H(26)B(2)N(6)Ni, a = 13.469(9) A, b = 7.740(1) A, c = 18.851(2) A, beta = 107.605(9) degrees, the space group is monoclinic P2(1)/c, and Z = 4. Infrared measurements confirmed the presence of bridging hydrogen atoms; both nu(B[bond]H)(terminal) and nu(B[bond]H)(bridging) are assignable and shifted relative to nu(B-D) of Tp*NiBD(4) by amounts in agreement with theory. Despite their hydrolytic stability, Tp*NiBH(4) and Tp*NiBD(4) readily reduce halocarbon substrates, leading to the complete series of Tp*NiX complexes (X = Cl, Br, I). These reactions showed a pronounced hydrogen/deuterium rate dependence (k(H)/k(D) approximately 3) and sharp isosbestic points in progressive electronic spectra. Nickel K-edge X-ray absorption spectroscopy (XAS) measurements of a hydride-rich nickel center were obtained for Tp*NiBH(4), Tp*NiBD(4), and Tp*NiCl. X-ray absorption near-edge spectroscopy results confirmed the similar six-coordinate geometries for Tp*NiBH(4) and Tp*NiBD(4). These contrasted with XAS results for the crystallographically characterized pseudotetrahedral Tp*NiCl complex. The stability of Tp*Ni-coordinated borohydride is significant given this ion's accelerated decomposition and hydrolysis in the presence of transition metals and simple metal salts.

14.
Dtsch Med Wochenschr ; 128(37): 1884-6, 2003 Sep 12.
Article in German | MEDLINE | ID: mdl-12970822

ABSTRACT

HISTORY: A 61-year-old woman was referred because of painless jaundice, laboratory tests having indicated hepatitis with impaired liver functions. For the past two years she had been taking phenprocoumon because she had atrial fibrillation. INVESTIGATIONS: Serological tests largely excluded infectious, autoimmune or metabolic etiology, so that the diagnosis of drug-induced hepatic disease was made. Liver biopsy showed necrotic liver cells and mild inflammatory reaction. TREATMENT AND COURSE: A perforating duodenal ulcer required urgent surgical intervention, after which liver functions further deteriorated. The patient having refused liver transplantation she was treated symptomatically (oral vitamin K. lactulose, diuretics), phenprocoumon was discontinued and her condition slowly improved. She was discharged after two months. At subsequent examination she was symptom-free, the INR was 1.41, transaminases were normal and ultrasound merely showed a slightly inhomogeneous internal structure. CONCLUSION: Phenprocoumon can cause liver damage even when the drug has been taken for prolonged periods without any problems. A careful history about previously administered drugs should be taken in any case of hepatitis of uncertain etiology.


Subject(s)
Anticoagulants/adverse effects , Chemical and Drug Induced Liver Injury/diagnosis , Liver Failure/chemically induced , Phenprocoumon/adverse effects , Anticoagulants/therapeutic use , Atrial Fibrillation/drug therapy , Chemical and Drug Induced Liver Injury/etiology , Female , Humans , Liver/pathology , Liver Function Tests , Middle Aged , Phenprocoumon/therapeutic use
16.
Dtsch Med Wochenschr ; 128(12): 611-4, 2003 Mar 21.
Article in German | MEDLINE | ID: mdl-12649798

ABSTRACT

HISTORY: A 46-year-old woman presented for an emergency admission because of colic-like upper abdominal pain and markedly impaired general condition. Eight days before admission she had started and continued to take pantoprazole because of symptoms of gastroesophageal reflux. INVESTIGATIONS: Clinical examination and laboratory tests indicated abnormal liver functions suggesting hepatitis. Serology largely excluded an infectious, autoimmunological or metabolic cause. Duplex sonography gave no evidence of bile obstruction or Budd-Chiari syndrome. DIAGNOSIS AND COURSE: The patient's condition and laboratory tests after the drug had been discontinued gradually improved on symptomatic treatment, indicating pantoprazole-induced hepatitis. CONCLUSION: Intake of proton pump inhibitors is a rare cause but should be considered in the differential diagnosis of hepatitis of uncertain etiology.


Subject(s)
Anti-Ulcer Agents/adverse effects , Benzimidazoles/adverse effects , Chemical and Drug Induced Liver Injury/etiology , Enzyme Inhibitors/adverse effects , Proton Pump Inhibitors , Sulfoxides/adverse effects , 2-Pyridinylmethylsulfinylbenzimidazoles , Abdomen/diagnostic imaging , Abdominal Pain/chemically induced , Anti-Ulcer Agents/therapeutic use , Benzimidazoles/therapeutic use , Chemical and Drug Induced Liver Injury/diagnosis , Chemical and Drug Induced Liver Injury/therapy , Diagnosis, Differential , Enzyme Inhibitors/therapeutic use , Female , Gastroesophageal Reflux/drug therapy , Humans , Liver/blood supply , Liver/diagnostic imaging , Liver/drug effects , Middle Aged , Omeprazole/analogs & derivatives , Pantoprazole , Sulfoxides/therapeutic use , Ultrasonography, Doppler, Duplex
17.
Chem Commun (Camb) ; (17): 1872-3, 2002 Sep 07.
Article in English | MEDLINE | ID: mdl-12271651

ABSTRACT

Crystals of (Cl2C3NS)(ClC2NS2), an isothiazolyl-substituted 1,2,3-dithiazolyl radical, consist of evenly spaced, slipped pi-stacks; magnetic and conductivity measurements indicate the material is a Mott insulator with sigma RT = 2 x 10(-7) S cm-1.

18.
Eur J Neurosci ; 16(4): 652-8, 2002 Aug.
Article in English | MEDLINE | ID: mdl-12270040

ABSTRACT

A characteristic feature of the kinetics of nicotinic acetylcholine receptor (nAChR) channels is fast and nearly complete desensitization with a time course between 10 and 100 ms and recovery from desensitization in the range of some hundred ms. In the present study we used a piezo-driven system for ultra-fast solution exchange, analysed the recovery from the fast desensitized state of mouse recombinant adult-type nAChR channels and found no difference to that of embryonic-type channels. By double pulse experiments with application of pulses with a saturating concentration of 1 mm acetylcholine (ACh) with increasing duration of the first pulse and a constant interval between pulses we detected a second slow desensitized state which was entered with a time constant of 2835 ms. Recovery from the slow desensitized state proceeded with a single exponential with a time constant of 16134 ms. The experimental data were interpreted by the addition of a transition from the desensitized state with two bound ACh molecules to a slow desensitized state to the well known circular kinetic scheme of activation and desensitization of nAChR channels. This slow desensitized state might play a role in muscle fatigue or in pathological states like myasthenic syndromes.


Subject(s)
Action Potentials/physiology , Receptors, Nicotinic/physiology , Acetylcholine/pharmacology , Animals , Cell Line , Humans , Mice , Receptors, Nicotinic/analysis , Receptors, Nicotinic/genetics , Recombinant Proteins/analysis , Recombinant Proteins/genetics
19.
J Am Chem Soc ; 124(32): 9498-509, 2002 Aug 14.
Article in English | MEDLINE | ID: mdl-12167046

ABSTRACT

Alkylation of the zwitterionic heterocycle 8-chloro-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridine (ClBP) with alkyl triflates affords 8-chloro-4-alkyl-4H-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridin-2-ium triflates [ClBPR][OTf] (R = Me, Et, Pr). Reduction of these salts with decamethylferrocene affords the corresponding ClBPR radicals as thermally stable crystalline solids. The radicals have been characterized in solution by cyclic voltammetry and EPR spectroscopy. Measured electrochemical cell potentials and computed (B3LYP/6-31G) gas-phase disproportionation enthalpies are consistent with a low on-site Coulombic barrier U to charge transfer in the solid state. The crystal structures of ClBPR (R = Me, Et, Pr) have been determined by X-ray crystallography (at 293 K). All three structures consist of slipped pi-stacks of undimerized radicals, with many close intermolecular S.S contacts. ClBPMe undergoes a phase transition at 93 K to a slightly modified slipped pi-stack arrangement, the structure of which has also been established crystallographically (at 25 K). Variable-temperature magnetic and conductivity measurements have been performed, and the results interpreted in light of extended Hückel band calculations. The room-temperature conductivities of ClBPR systems (sigma(RT) approximately 10(-)(5) to 10(-)(6) S cm(-)(1)), as well as the weak 1D ferromagnetism exhibited by ClBPMe, are interpreted in terms of weak intermolecular overlap along the pi-stacks. The latter is caused by slippage of the molecular plates, a feature necessitated by the steric size of the R and Cl groups on the pyridine ring.

20.
Science ; 296(5572): 1443-5, 2002 May 24.
Article in English | MEDLINE | ID: mdl-12029128

ABSTRACT

A new organic molecular conductor, based on a spiro-biphenalenyl neutral radical, simultaneously exhibits bistability in three physical channels: electrical, optical, and magnetic. In the paramagnetic state, the unpaired electrons are located in the exterior phenalenyl units of the dimer, whereas in the diamagnetic state the electrons migrate to the interior phenalenyl units and spin pair as a pi-dimer. Against all expectations, the conductivity increases by two orders of magnitude in the diamagnetic state, and the band gap decreases. This type of multifunctional material has the potential to be used as the basis for new types of electronic devices, where multiple physical channels are used for writing, reading, and transferring information.

SELECTION OF CITATIONS
SEARCH DETAIL
...