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TEMPO radicals showing magnetic interactions. I. 4-(4-Halobenzylideneamino)TEMPO and related compounds.

X-ray crystal structure analyses of the 4-(4-halobenzylideneamino)TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidyl-1-oxyl) radicals 4-(4-fluorobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl, 4-(4-chlorobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl, 4-(4-bromobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl and 4-(4-iodobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl, and other 4-Ar-CH=N-TEMPO [Ar = 4-Ph-Ph, 2,2,6,6-tetramethyl-4-(4-phenylbenzylideneamino)piperidyl-1-oxyl, 4-Py, 2,2,6,6-tetramethyl-4-(4-pyridylmethylideneamino)piperidyl-1-oxyl, and 3,5-diCl-Ph, 4-(3,5-dichlorobenzylideneamino)-2,2,6,6-tetramethylpiperidyl-1-oxyl] radicals have been performed at room temperature. Some of these radicals show intermolecular ferromagnetic interactions at extremely low temperatures. X-ray analysis revealed that crystals of the 4-I-Ph derivative showed two modifications [(a) and (b)]; measurements of the magnetic properties of these crystals showed a ferromagnetic transition at an extremely low temperature for modification (a) and an antiferromagnetic interaction for modification (b). The structural features of these TEMPO radical crystals can be classified into three groups: (i) the crystal structures of the 4-Cl-Ph, 4-I-Ph(a) and 4-Ph-Ph derivatives, which show a ferromagnetic transition; (ii) the structures of the 4-Br-Ph and 4-Py derivatives, which show a ferromagnetic interaction (straight theta > 0); (iii) miscellaneous: the antiferromagnetic 4-F-Ph and 4-I-Ph(b) derivatives (straight theta < 0) and the ferromagnetic 3,5-diCl-Ph (straight theta > 0) derivative. Sheet-like arrangements of O atoms and intra-sheet interactions through the CH(2) or CH(3) groups of the TEMPO rings are related to the mechanisms of the ferromagnetic interactions.

Journal Article↗

2,4-Disila-1-germatricyclo[2.1.0.0(2,5)]pentane: a new type of cage compound of group 14 elements with an extremely long Ge-C bridge bond and an "Umbrella"-type configuration of a Ge atom.

The thermolysis of 1,1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene 1 at 175 degrees C results in the quantitative formation of 1,2,3,4-tetrakis[di-tert-butyl(methyl)silyl]-5-phenyl-2,4-disila-1-germatricyclo[2.1.0. 02,5]pentane 2, representing a new type of cage compound of group 14 elements. The crystal structure of 2 was established by X-ray crystallography, which showed an extremely long Ge-C bridge bond of 2.242(3) A and an "umbrella"-type configuration of the Ge atom. The compound 2 readily reacted with benzaldehyde to produce 1,4,5,7-tetrakis[di-tert-butyl(methyl)silyl]-3,6-diphenyl-2-oxa-1,4-disila-5-germabicyclo[2.2.1]hept-5-ene 3 with an endocyclic Ge=C double bond.

Journal Article↗

[A case of ossified yellow ligaments (ossified ligamenta flava) of the thoraco-lumbar region and magnetic resonance imaging].

A Case of ossified yellow ligaments in thoraco-lumbar region is reported. A 47-year-old-male complained low back pain with suddenness in August, 1984. One month later, he noticed dyesthesia on his right lower extremity and gait disturbance. These symptoms progressed slowly. In June, 1985, he admitted to The Jikei University Hospital. On neurological examinations, he was noticed an intermittent claudication, spastic paraparesis and stocking type sensory loss in his lower extremities. Plain lumbar X-ray films showed ossified yellow ligaments (OYL) in the posterior half of the spinal canal from the level of 10th thoracic to second lumbar vertebrae. Magnetic resonance imaging disclosed marked indentations of the spinal cord at the same level. The wide laminectomy was carried out and OYL were removed totally in gentle manner. Postoperative course was uneventful. His sensory disorders improved remarkably and he gained good muscle strength in his lower extremities, but a considerable spasticity remained still. OYL is closely related to the developmental canal stenosis, the spondylosis and the other degenerative disorders such as ossification of posterior longitudinal ligaments. This allows more complicated neurological signs and symptoms in the case of OYL. When OYL is suggested, it is recommended to performed whole spinal radiological survey. The surgical consideration should be done. From this point of view, MRI would be a most useful weapon.

Adult↗

Traumatic cervical tracheal disruption: report of two cases.

We report herein the cases of two patients who suffered tracheal disruption, both of whom underwent successful surgical treatment. The first patient was a 48-year-old truck driver who suffered severe dyspnea after jamming his neck in a truck door. An endotracheal tube was unable to be inserted due to bleeding and thus, an emergency tracheostomy was performed. On admission massive subcutaneous emphysema was noted in the neck and anterior chest, and tracheal disruption was confirmed by a lateral neck X-ray, computed tomography (CT), and fiberscopy. An emergency end-to-end anastomosis of the trachea with insertion of a T-type silicon tube into the lower trachea was performed. The second patient was a 36-year-old man who suffered severe dyspnea after having his neck caught in a chain while driving a motorcycle. On admission, marked subcutaneous emphysema in the neck and paradoxical movement of the trachea were noted. Tracheal disruption was confirmed by a lateral neck X-ray and CT, and a similar operation to that of the first patient was performed. This type of injury is rare; however, lateral neck X-ray, CT, and fiberscopy proved extremely useful for making an accurate diagnosis following which successful emergency surgery was able to be performed, achieving good long-term results.

Adult↗

A quantitative cryo-scanning X-ray microanalysis protocol for the examination of the eye.

Analysis of elements present in fluids contained in small, poorly accessible sections of biological tissue is challenging. The choroid of the eye, which is a vascular tissue approximately 100 microm thick, surrounds the retina for the purposes of nutrient supply and metabolite removal, and which in the chick shows dramatic volumetric change in response to visual experiences. Because fluid homeostasis is critical to good vision, a complete understanding of the ionic changes driving large shifts in ocular fluids is required. However, the structure of the choroid and retina make extraction of pure fluids for analysis extremely difficult. Elemental x-ray analysis on a transverse chorioretinal specimen was performed after rapid freezing of a whole chick eye in liquid nitrogen, and mechanically fracturing the frozen globe. Using a Polaron Cryotrans System on a Cambridge S-360 scanning electron microscope and a Kevex Quantum detector, spectra were obtained for blood vessels, lymphatic vessels and vitreous that were readily visible at 265x. Analysis was performed on a frozen control solution of the elements found in the vessels. The elements and their concentrations found in blood vessels by x-ray analysis compared well with those from whole blood as established by conventional means. The analysis for lymph yielded results compatible with expectations; no other published data for small lymphatics enable a direct comparison. In conclusion, x-ray analysis can be used to acquire information that is otherwise unobtainable from tissue in situ. The same bulk-frozen elemental microanalysis protocol would have application to other organs and tissues when access to the site would destroy the integrity of the tissue under investigation.

Animals↗

[A case of cerebral cysticercosis: cyst growth is confirmed by CT scan during 6 years of follow-up].

A rare case of a 40-year-old woman with cerebral cysticercosis is reported. She has lived on the Island of Tokunoshima and has never travelled overseas. She was hospitalized in the hospital of Kagoshima University in 1980. A small cyst in the right temporal lobe, and a calcified area in the left parietal lobe was noticed on CT scan. When she was admitted to our hospital in December 1986, the cyst in the right temporal lobe was larger than it was 6 years before. An operation was performed for the cyst in the right temporal lobe. The cyst was pathologically confirmed as cysticercosis. Postoperatively, immunological reaction of cysticercosis was positive, but X-rays and CT scan of extremities showed no abnormal findings. Cerebral cysticercosis is a rare disease in Japan. CT scan is very useful in the diagnosis of this disease. Multiple cysts and calcified area in the parenchymal region are specific findings on CT scan.

Adult↗

A rapid and precise method for the determination of vitamin D3 in rat skin by high-performance liquid chromatography.

In order to develop the investigations into photobiogenesis of vitamin D3, a rapid and precise method for the determination of the vitamin in rat skin was established by using high-performance liquid chromatography (HPLC). The proposed method included saponification of small pieces of rat skin, extraction of the unsaponifiable matter and application to HPLC using "Zorbax SIL" (straight-phase) as an adsorbent and 0.5% isopropanol in n-hexane as a mobile phase. The applicable lower limit of the method was 2ng of vitamin D3/cm2 of subcutaneous tissue-removed skin and it was possible to assay a concentration higher than 2 ng/cm2. The proposed method was applied to determine the content of vitamin D3 in rat skin obtained from in vivo and in vitro irradiation experiments. In the in vitro experiment, the yield of vitamin D3 increased in proportion to the irradiation time. On the other hand, the yield in the in vivo experiment showed a proportional increase similar to the in vitro experiment until 60 min irradiation, while a nearly constant value was obtained by irradiation for longer than 60 min. When the rat skin obtained from the in vitro experiment was irradiated with monochromatic UV rays in the range s60-350 nm, the most effective wavelength for the formation of vitamin D3 was confirmed to be 303 nm, which differs from the result obtained from the experiment in a test tube (295 nm). Moreover, the yield of vitamin D3 by irradiation with UV rays below 288 nm was extremely low, which again differed from the results of a test tube experiment. These differences were thought to be due to the filter effect of the malpighian layer in the epidermis of rat skin.

Animals↗

PSO4: a novel gene involved in error-prone repair in Saccharomyces cerevisiae.

The haploid xs9 mutant, originally selected for on the basis of a slight sensitivity to the lethal effect of X-rays, was found to be extremely sensitive to inactivation by 8-methoxypsoralen (8MOP) photoaddition, especially when cells are treated in the G2 phase of the cell cycle. As the xs9 mutation showed no allelism with any of the 3 known pso mutations, it was now given the name of pso4-1. Regarding inactivation, the pso4-1 mutant is also sensitive to mono- (HN1) or bi-functional (HN2) nitrogen mustards, it is slightly sensitive to 254 nm UV radiation (UV), and shows nearly normal sensitivity to 3-carbethoxypsoralen (3-CPs) photoaddition or methyl methanesulfonate (MMS). Regarding mutagenesis, the pso4-1 mutation completely blocks reverse and forward mutations induced by either 8MOP or 3CPs photoaddition, or by gamma-rays. In the cases of UV, HN1, HN2 or MMS treatments, while reversion induction is still completely abolished, forward mutagenesis is only partially inhibited for UV, HN1, or MMS, and it is unaffected for HN2. Besides severely inhibiting induced mutagenesis, the pso4-1 mutation was found to be semi-dominant, to block sporulation, to abolish the diploid resistance effect, and to block induced mitotic recombination, which indicates that the PSO4 gene is involved in a recombinational pathway of error-prone repair, comparable to the E. coli SOS repair pathway.

DNA Repair↗

[HTLV-I associated encephalo-myelopathy resembling ALS with concurrence of acute promyelocytic leukemia in a member of the relatives].

A 36 year-old woman beginning with spastic paraparesis at her age of 11 visited us for evaluation of progressive muscular weakness of the distal portions of the upper extremities and difficulty in speaking at her age of 33. The neurological features at the present are as follows; fine horizontal gaze-nystagmus, impaired smooth pursuit ocular movement, highly spastic paraplegia with pes equino-varus necessitating canes and the wheel-chair, highly accentuated PTRs and ATRs associated with positive Babinski's sign, diminished or absent deep reflexes in the upper extremities, moderate muscular wasting with fasciculation on the tongue and distal portions of the upper extremities (rt less than lt). Sensory or cerebellar functions remain normal. No autonomic finding has been manifested. The HTLV-I antibody titers of serum (eg. PA method: x8192 ) and cerebrospinal fluid are highly positive in various methods. That of her mother (no blood-transfusion history) is positive. The provirus genome analysis on peripheral lymphocytes using the Southern blotting method by the cleaving enzyme Psi I was unable to discriminate that of an ATL patient. MRI of the central nervous system revealed higher signal area (short SE) at the C5/6 region and atrophy of C7/8 region. Neither a definite lesion in the lower brain stem, cerebellum nor cerebral hemispheres was identified. The skeletal muscle X-ray CT on the lower extremities revealed the atrophic flexor thighs and the anterior tibial and peroneal muscles. Needle EMG showed the prominent neurogenic changes in the atrophic muscles. Oral prednisolone therapy for four months relieved nystagmus and difficulty in walking, slightly. She, however, discontinued because of its side effect.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗

[Case of dermatomyositis complicated with massive pleural effusion that preceded the myopathy].

A 36-year-old man was admitted to a hospital with complaints of fever, polyarthralgia and dyspnea. Erythema was observed on his face, extensor surface of the fingers and extremities, and a chest X-ray revealed massive bilateral pleural effusion. He had no sign of myopathy at this point. Pleural fluid was proved to be exudative and contained extremely high levels of hyaluronic acid. He was also complicated with interstitial pneumonitis and was given a pulse therapy with methyl prednisolone followed by daily administration of 55 mg prednisolone (PSL). Twenty days after the commencement of the therapy, pleural effusion decreased but muscle weakness gradually appeared, accompanied by elevation of myogenic enzymes. Myogenic changes on electromyogram, and irregularity of the muscle fibers with slight inflammatory cell infiltrates in a biopsy specimen were demonstrated. He was transferred to our hospital, and a diagnosis of dermatomyositis was made. Later, pleural effusion waxed and waned depending on the dosage of PSL, but no other causative disorder was demonstrated by extensive examinations. This case indicates that the pleuritis could be one of the vasculitic manifestations of dermatomyositis.

Adult↗

[X-ray study of the loaded portions of the skeleton of the upper extremities in athletes engaged in karate].

Roentgenogrammetric analysis demonstrated a more intensive development in the II and III metacarpal hand bones, as well as in the forearm bones in karatists comparing to those in boxers and football players. The transversal diameter of the medullary cavity was less in the karatists. Visual analysis of the roentgenograms demonstrated presence of sesamoid bones in the area of the proximal interphalangeal joints II and III in the fingers of the karatists, waist thickening on the medial surface of the proximal and middle digital phalanges, a sharp thickening of the compact substance layer in the area of the inferior third of the medial surface of the ulnar bone.

Adaptation, Physiological↗

Practical application of a scan-rotate equalization geometry to mammography.

The presence of dense fibroglandular tissue within the breast is the most significant cause of failure to detect breast cancer with mammography. The dense tissue often produces a range of exposure which exceeds the useful dynamic range of film-screen mammography. It has been shown that equalization radiography overcomes the latitude limitations of film-screen imaging. Equalization compensates for regional variations in x-ray transmission within the patient through spatial modulation of the entrance exposure. We have proposed rotary scanning equalization radiography (RSER), a scan-rotate geometry for efficient equalization radiography. In RSER the image receptor is exposed by repeated scans of a source-modulated fan beam. The fan beam is rotated with respect to the patient between scans. Numerical simulations and theoretical analysis have shown that the superposition of exposure from appropriately modulated fan beams at a variety of angles is an entrance exposure that effectively equalizes the film exposure. The design and characteristics of a prototype RSER imaging system are described. Anthropomorphic breast phantom images are used to determine the improvement in image contrast obtained with RSER, the expected tube loading, and the presence of artifacts. RSER increases the fraction of the breast imaged with high contrast (at least 90% of peak gradient) from 46% (conventional mammography) to 80%. Subjective examination of the phantom images show that RSER achieves image quality very similar to that of much less efficient equalization geometries with only 2.7 times greater tube loading than conventional mammography. As predicted by theoretical analysis of exposure artifacts in RSER, the prototype RSER system is relatively immune to artifacts. Exposure artifacts were demonstrated for extreme variations in x-ray transmission within the patient. These results show that RSER is an efficient, practical means of overcoming the latitude limitations of film-screen mammography, and improving the detection of breast cancer.

Biophysical Phenomena↗

A dosimetric quality audit of photon beams by the Belgian Hospital Physicist Association.

Since 1987, a dosimetric standardization process has been started by the Belgian Hospital Physicist Association (BHPA). As part of this project, on-site visits were performed by a voluntary team, by request of the local physicist. They included mechanical checks on treatment machines and simulators and a dosimetric intercomparison of photon beams, following the EORTC methodology. Until now 16 centres have participated. Dose measurements were performed in order to evaluate the uniformity in dosimetry after the adoption by the BHPA members of the Nederlandse Commissie voor Stralingsdosimetrie (NCS) code of practice for photon beams. Doses were measured with an ionization chamber in water under NCS reference conditions and under other conditions in 13 cobalt beams and 24 high energy X-ray beams from 4 to 25 MV. Under reference conditions, the mean ratio of measured to stated dose is 0.999 (+/- 0.010) and 1.006 (+/- 0.23) for cobalt and X-ray beams, respectively, with a difference between the extreme values (delta) of 0.042 for cobalt beams and 0.084 for X-ray beams. In other conditions, the spread is a little larger for all beams. The results are comparable, but with a smaller dispersion, with those of other national and international similar dose intercomparisons and show the importance of applying a common protocol. The results of mechanical checks show some large deviations in digital displays and indicate the need for a systematic mechanical and beam alignment quality assurance programme.

Belgium↗

[Chest X ray: routine indication in the follow-up of differentiated thyroid cancer?].

AIM: This retrospective study sought to elucidate whether routine chest x-ray is still useful for detection of pulmonary metastases in low risk patients despite the high sensitivity of the tumor marker thyroglobulin. METHOD: The hospital files of 609 patients with well-differentiated thyroid cancer were analysed. Pulmonary formation of metastases was diagnosed in 50 patients. The thyroglobulin value at the time of diagnosis was compared with the chest x-ray findings and, if present, additional diagnostic information such as Iodine-131 whole body scintigraphy (WBS) and thorax CT. RESULTS: The sensitivity of the chest x-ray to detect pulmonary metastases was at 52% lower than that of WBS (64%), thorax CT (82%) and thyroglobulin during suppression therapy (86%). Among the patients with papillary carcinoma stage I and II (UICC 1987), only 1 patient developed pulmonary metastases during follow up. In this low risk group of patients, detection of lung metastases exclusively by chest x-ray, without elevation of thyroglobulin level is extremely rare (calculated probability 1/4000) and associated with considerable costs. CONCLUSION: Routine, life long chest x-ray in low risk patients without a suspected recurrence (e.g. positive thyroglobulin) needs to be reconsidered.

Carcinoma, Papillary↗