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Occupational allergic rhinitis and contact urticaria caused by bishop's weed (Ammi majus).

Bishop's weed (Ammi majus) has been known to induce toxic phytophotodermatitis. We now describe IgE-mediated rhinitis and contact urticaria caused by exposure to bishop's weed in a 31-year-old atopic female florist. A skin prick-prick test with bishop's weed flowers gave an 8-mm wheal, and the bishop's weed-specific IgE level in the patient's serum was 9.7 PRU/ml (RAST class 3). In an immunoblotting experiment with the patient's serum, nine IgE-binding protein bands with the molecular weights 19, 34, 39-41 (doublet), 52-61 (doublet), and >67 (triplet) kDa were detected in bishop's weed extract. The patient became symptomless after she had ceased to work as a florist.

Adult↗

IGF binding protein-1 (IGFBP-1) is preferentially associated with the fetal-facing basal surface of the syncytiotrophoblast in the human placenta.

IGF receptors are expressed in a spatially polarized manner on the syncytiotrophoblast cell membrane. We therefore examined the hypothesis that IGFBPs expressed at the maternal-fetal interface interact with distinct surfaces of the syncytiotrophoblast membrane to modulate IGF function. Membrane vesicles were prepared specifically from the maternal-facing, microvillous membrane (MVM) and the fetal-facing, basal membrane (BM) surfaces of the syncytiotrophoblast. The association of IGFBPs with each membrane preparation was determined by ligand blot analysis. A doublet migrating at 38/42 kD was detected in both MVM and BM preparations. Selective immunoprecipitation followed by ligand blot analysis identified this IGF binding species as IGFBP-3. Additionally, a protein migrating at approximately 29 kD was associated primarily with the BM. This protein was identified as IGFBP-1 by both immunoprecipitation and ligandblotting techniques. Non-denaturing PAGE revealed five distinct bands corresponding to different degrees of phosphorylation. The phosphorylation pattern of BM-associated IGFBP-1 was identical to that of native IGFBP-1 in amniotic fluid. Immunohistological analysis of term placenta revealed IGFBP-1-specific staining of the syncytiotrophoblast and the fetal capillary/pericapillary bed. The localization of IGFBP-1 to a distinct compartment within the fetal placenta, not in proximity to the syncytiotrophoblast type I IGF receptor, suggests it may play a role in regulating/targeting IGF activity within the stromal compartment or by exerting IGF-independent effects on the basal surface of the syncytiotrophoblast. The nature of its binding to the BM has not been determined.

Female↗

Membrane proteins PmpG and PmpH are major constituents of Chlamydia trachomatis L2 outer membrane complex.

The outer membrane complex of Chlamydia is involved in the initial adherence and ingestion of Chlamydia by the host cell. In order to identify novel proteins in the outer membrane of Chlamydia trachomatis L2, proteins were separated by sodium dodecyl sulfate polyacrylamide gel electrophoresis. By silver staining of the protein profile, a major protein doublet of 100-110 kDa was detected. In-gel tryptic digestion and matrix-assisted laser desorption/ionization mass spectrometry identified these proteins as the putative outer membrane proteins PmpG and PmpH.

Amino Acid Sequence↗

Monoclonal antibody CI-panHu defines a pan-human cell-surface antigen unique to higher primates.

The murine monoclonal antibody CI-panHu reacts strongly with the cell surface of all human cells, including erythrocytes, tumour cells and HLA-A,B,C-negative cell lines. As such, this antibody defines the first pan-human cell-surface antigen reported. The antigenic determinant detected is associated with a protein doublet of 16,000 MW whose expression is restricted to cells from humans, apes and some species of Old World monkeys. Antibody reactivity is not diminished by routine fixation procedures, nor by paraffin-embedding, and the antigenic determinant is relatively protease-resistant. The use of this antibody as a positive control in immunoassays of human cells is discussed.

Animals↗

pp60src is an endogenous substrate for calpain in human blood platelets.

Calpain is distributed ubiquitously in virtually every tissue (Croall, D. E., and DeMartino, G. N. (1991) Physiol. Rev. 71, 813-846), but its physiological role remains to be determined. The identification of its natural endogenous substrates would be of great interest. Since pp60src, a major tyrosine kinase in platelets, is known to be easily cleaved during purification from cells (Feder, D., and Bishop, J. M. (1990) J. Biol. Chem. 265, 8205-8211), we examined the possibility that it is an endogenous substrate of calpain. In the whole cell lysate from resting platelets, which was analyzed by Western blotting with monoclonal antibody 327, we found pp60src almost exclusively in a 60-kDa form, with a trace of 52-kDa form. Addition of A23187 (a calcium ionophore) or dibucaine, which are known to be activators of platelet calpain (Croall and DeMartino, 1991; Fox, J. E., Reynolds, C., Morrow, J. S., and Phillips, D. R. (1987) Blood 76, 2510-2519; Fox, J. E., Austin, C. D., Boyles, J. K., and Steffen, P. K. (1990b) J. Cell Biol. 111, 483-493), caused dose- and time-dependent cleavage of actin-binding protein and p235 protein (talin). At the same time, loss of the 60-kDa species of pp60src and generation of the 52-kDa (occasionally seen as doublets) and 47-kDa species were detected by the Western blotting. In platelets aggregated by 1 unit/ml thrombin, apparently identical cleavage products were found. The cleavage of pp60src was inhibited by calpeptin (20 microM), an inhibitor of calpain (Tsujinaka, T., Kajiwara, Y., Kambayashi, J., Sakon, M., Higuchi, N., Tanaka, T., and Mori, T. (1988) Biochem. Biophys. Res. Commun. 153, 1201-1208; Tsujinaka, T., Ariyoshi, H., Uemura, Y., Sakon, M., Kambayashi, J., and Mori, T. (1990) Life Sci. 46, 1059-1066; Fox, J. E., Clifford, C. C., and Austin, C. D. (1990) Blood 76, 2510-2519; Fox, J. E., Austin, C. D., Boyles, J. K., and Steffen, P. K. (1990) J. Cell. Biol. 111, 483-493; Fox, J. E., Austin, C. D., Clifford, C. C., and Steffen, P. K. (1991) J. Biol. Chem. 266, 13289-13295). Addition of EGTA (3 mM) to the extracellular media completely inhibited the cleavage of actin-binding protein, talin, and pp60src in response to A23187 (1 microM). Intact pp60src was distributed in both cytosolic and particulate (membrane) fractions. Cleaved species were found exclusively in the cytosolic fraction. pp60src-associated enolase kinase activity was reduced. Thus, pp60src is an endogenous substrate for calpain, the cleavage of which may have regulatory effects on the kinase.

Antibodies, Monoclonal↗

Characterization of the cystic fibrosis transmembrane conductance regulator in a colonocyte cell line.

An anti-peptide antibody raised to the C-terminal sequence of the cystic fibrosis transmembrane conductance regulator (CFTR) was used to examine CFTR immunoreactivity in the T84 colonocyte cell line. Immunoblots of T84 cell lysates detected CFTR as a 170-kDa protein that appeared as a broad band or doublet in SDS/PAGE. This protein comigrated with the predominant immunoblot signal detected in human pancreas and colon. An equivalent protein was detected as a prominent substrate for protein kinase A and for protein kinase C in T84 cell immunoprecipitates with this antibody. The immunoprecipitated protein resembled the protein detected by immunoblot in that both proteins showed the same change in electrophoretic mobility after digestion by N-Glycanase. The precipitated protein was indentified as CFTR by two criteria. First, the same protein was immunoprecipitated with an antibody to a different CFTR peptide, [Lys102]CFTR-(102-116). Second, two-dimensional phosphopeptide mapping was used to compare the immunoprecipitated protein with a bacterially expressed protein known to contain most of the predicted protein kinase A phosphorylation sites in CFTR. Because the six most prominent peptides in each map were equivalent, these maps confirm that the precipitated protein is CFTR. By using these antibodies for immunofluorescence and immunoperoxidase staining, CFTR was localized to the apical region of T84 cells grown in tumors and in monolayers. Thus, T84 cells express CFTR at sufficient levels to permit identification and immunochemical studies of this protein in its endogenously occurring form.

Amino Acid Sequence↗

Ribonucleotide reductase in melanoma tissue. EPR detection in human amelanotic melanoma and quenching of the tyrosine radical by 4-hydroxyanisole.

The characteristic EPR doublet of tyrosine radicals of the growth-regulating enzyme ribonucleotide reductase was detected in human melanoma tissue grown in nude mice. This was possible through the use of an amelanotic melanoma that does not exhibit disturbing EPR signals from melanin. The content of tyrosine radicals is higher in young tumor tissues than in older ones. The clinically applied antimelanotic drug, 4-hydroxyanisole, inhibits ribonucleotide reductase in Ehrlich ascites tumor cells as demonstrated by a pronounced quenching of tyrosine radicals (IC50 = 5 microM). In amelanotic melanoma tissue tyrosine radicals of the enzyme are also quenched by 4-hydroxyanisole in concentrations down to 50 microM. Thus, the inactivation of ribonucleotide reductase, which provides deoxyribonucleotides for DNA synthesis, may be a hitherto unexpected mechanism for the antitumor action of 4-hydroxyanisole.

Animals↗

Spectroscopy of NbO: Characterization of the Doublet Manifold

Doublet bands of NbO in the near infrared region have been observed in emission with FTS techniques using an electrodeless 2450 MHz discharge as a source. Transitions involving the vibrational levels v = 0-4 of a low-lying a2Delta state of configuration sigma2delta and four additional doublet states (c2Pi, d2Deltai, e2Phi, and f2Pii) have been recorded at high resolution. Furthermore, a 2Sigma state, assigned as b2Sigma-, has been observed through the c2Pi (v = 0) --> b2Sigma- (v = 0, 1) transitions in the 1.6 &mgr;m region. Rotational analyses of the doublet bands have been performed. Most of the excited doublet states lie only slightly above or below the well-known B4Pi state. The density of states is fairly high immediately above B4Pi, and characterizations of some of the states in this region involve difficulties. A currently unanalyzed band, centered at 11 820 cm-1, has been preliminarily attributed to the A4Pi --> X4Sigma- (0, 0) transition. Nuclear hyperfine effects are barely detectable in orbitally degenerate states of the doublet manifold at Doppler-limited resolution, while the b2Sigma- state of configuration sigmadelta2 shows partly resolved magnetic hyperfine structure (b = -0.08191 cm-1). Large-scale all-electron CI calculations have been performed on doublet and quartet manifolds of NbO up to 22 000 cm-1. The calculations have been performed in two steps. In the first step, the spin-orbit effects within electronic states were not considered. An excellent overall agreement with experimental energies was obtained, except for the d2Deltai state. In the second step, all spin-orbit interactions were included. Also these calculations resulted in a good agreement with the experimental observations. The calculations also predict three hitherto unobserved low-lying states: 4Phi at 8545 cm-1, 2Gamma at 8430 cm-1 and 2Sigma+ at 9648 cm-1. Copyright 1997 Academic Press. Copyright 1997Academic Press

Journal Article↗

The third molecule associated with interleukin 2 receptor alpha and beta chain.

It is known that the affinity cross-linking study of the human high-affinity Interleukin 2 (IL-2) receptor reveals triplet bands consisting of 70 kDa alpha chain(Tac)-IL-2 and the 90/80 kDa doublet. We found the cell lines lacking the lower band of the doublet in spite of the expression of both alpha and beta chains. No IL-2 binding was detectable in the presence of anti-Tac antibody in these cells. Immunoprecipitation from the cell extract of [125 I] IL-2-cross-linked T cells with anti-beta chain polyclonal IgG detected the upper band, but not lower band of the doublet. These data suggest that the lower band of the doublet represents an unknown IL-2-binding protein (p65) distinct from the beta chain and this molecule may be involved in the intermediate-affinity IL-2 binding together with the beta chain.

3T3 Cells↗

Sm60, a mannose-binding protein from Schistosoma mansoni with inflammatory property.

We demonstrate here that a mannose-binding protein from Schistosoma mansoni, termed Sm60, was recovered in the mannose-eluted fraction (Man(+)) upon affinity chromatography on immobilised mannose of the soluble antigen fraction from adult worm tegument and cercariae. Sm60 was detected in the Man(+) fraction as a prominent doublet with an apparent molecular mass of 60-66 kDa by SDS-PAGE and appeared as a single band with a pI of approximately 6.9 by isoelectrofocusing. Sm60 was also detected in preparations of schistosomula extract and soluble egg antigens using a mouse polyclonal anti-Sm60 serum on immunoblotting assay. This antiserum demonstrated that Sm60 was localised on the tegument of S. mansoni adult worm. In order to determine the role of Sm60 in host-parasite interactions, we showed that Sm60 induced in vitro migration of human neutrophil in a dose-dependent manner and in vitro mast cell degranulation. Sm60 triggered these activities through its carbohydrate-binding site, since these activities were selectively inhibited by 0.2 M D-mannose, but not by 0.2 M D-galactose. Furthermore, Sm60 induced in vivo neutrophil migration. In contrast, mast cell-depleted rats presented a significant reduction of the neutrophil migration induced by Sm60 as compared with non-depleted controls. These data suggest that in vivo neutrophil migration induced by Sm60 is modulated by mast cell-dependent mechanisms. Sm60 might play a key role in the host-parasite interaction, and its characterization opens perspective to examine the role of this molecule in the biology of S. mansoni.

Animals↗

Tubulin and tektin in sea urchin embryonic cilia: pathways of protein incorporation during turnover and regeneration.

Axonemal precursor tubulin is the major protein component of the detergent-soluble membrane/matrix fraction of sea urchin embryonic cilia. Its unusual abundance may reflect the rapid turnover of these cilia, a process that is further documented here. However, whether during induced regeneration or normal turnover and growth, most other newly synthesized axonemal proteins are not detectable in the membrane/matrix fraction, raising the question of how non-tubulin precursors transit the growing cilium to the distal tip where assembly is generally thought to occur. Three potential explanations were considered: (1) the assembly of these components is proximal; (2) their relative concentration is too low to detect; or (3) tubulin alone is conveyed via a membrane/matrix pathway while most other axonemal proteins are transported in association with the axoneme. Light microscope autoradiography of axonemes pulse-chase labeled with [3H]leucine showed relatively uniform labeling, with no evidence for proximal incorporation. Fully grown cilia and cilia at early stages of regeneration were isolated from labeled embryos, fractionated into membrane/matrix, axonemal tubulin and architectural remnant components, and their labeled protein compositions were compared. Heavily labeled axonemal proteins, most notably the integral microtubule doublet component tektin-A, were not detected in the membrane/matrix fraction of emerging cilia, even though nearly half of the total ciliary tubulin appeared in that fraction, arguing against membrane-associated or soluble matrix transit for the architectural proteins at low concentrations. However, after thermal fractionation of axonemes from growing cilia, labeled proteins characteristic of the architectural remnant dominated the solubilized microtubule fraction, supporting axoneme-associated transport of the non-tubulin proteins during growth, in contrast to a membrane/matrix pathway for tubulin.

Animals↗

Diaspirin crosslinked hemoglobin (DCLHb): absence of increased free radical generation following administration in a rabbit model of renal ischemia and reperfusion.

In control rabbits, a renal ischemia of 60 min followed by 10 min of reperfusion resulted in an enhanced free radical production in cortical tissue, as assessed by a significant decrease of free glutathione (42%), protein-bound GSH (17%), and vitamin E (49%). In contrast, catalase or glutathione peroxidase activities were not affected by these experimental conditions. Free radical production in this model was also measured directly using electron spin resonance (ESR) spectroscopy associated with a PBN (alpha-phenyl N-tert-butyl-nitrone) spin trap agent in the venous blood arising from the ischemic kidney. The signal consisted of a triplet of doublets. In contrast, no signal could be detected in control blood samples taken prior to inducing ischemia. The burst of free radical production occurred in the early phase after restoration of flow in the kidneys rendered ischemic, as evidenced by a signal of weak intensity which generally appeared within the third minute after reperfusion and progressively increased to form a well-defined asymmetric signal following 10 min of reperfusion. The precise nature of free radicals trapped by the PBN agent remains, however, to be elucidated, but analysis of the coupling constants (aN = 14.5-15 G; a beta H = 2.5-3 G) and asymmetry of the central doublets suggests that the ESR signal may arise from a nitorxy-radical adduct resulting from the spin trapping by PBN of both oxygen- or carbon-centered radicals of lipid origin. As evidenced by both direct and indirect measurements, exchange of rabbit blood immediately after inducing renal ischemia with 30 ml/kg of Diaspirin Crosslinked Hemoglobin (7.5 g/dl in lactated electrolyte) or human serum albumin (7.5 g/dl in lactated electrolyte) did not exacerbate free radical production mediated by an ischemia reperfusion phenomenon, a typical situation found in a resuscitation setting.

Animals↗

Protease-induced alteration of insulin-like growth factor binding protein-3 as detected by radioimmunoassay. Agreement with ligand blotting data.

Structural alteration of insulin-like growth factor binding protein-3 (IGFBP-3) resulting from limited proteolysis by one or more serine proteases in vivo was first described in the serum of pregnant women and in certain pathological conditions. Western immunoblotting has since been employed to detect the phenomenon in normal serum, using a polyclonal antibody raised against recombinant human IGFBP-3 and a highly sensitive technique of visualization by chemiluminescence. The major proteolytic fragment of 30 kDa, which fails to be detected in native serum by ligand blotting owing to its weak affinity for IGFs, has proved clearly visible in all serum samples tested, sometimes accompanied by smaller fragments of 20 and 16 kDa. Among the serum samples analysed, increasing proportions of proteolysed IGFBP-3 were found in the following order: acromegalic patients, normal subjects, GH-deficient patients, pregnant women. In RIAs done with the same antibody, many of the serum samples yielded dose-response curves which were not parallel with standard curves, with lower gradients. In the samples where measurements were possible, apparent IGFBP-3 levels proved lower in pregnant women (2.28 +/- 0.23 mg/l, mean +/- SEM) than in normal adults (4.26 +/- 0.33 mg/l, P < 0.001). These observations, which contradict earlier reports of higher levels in pregnant women, suggest that the 30 kDa proteolytic fragment has a weaker affinity for the antibody than the intact IGFBP-3 (which in ligand- and immunoblotting appears as a characteristic 42-39 kDa doublet and which is barely or not detectable in pregnancy serum).(ABSTRACT TRUNCATED AT 250 WORDS)

Acromegaly↗

Association of the human papillomavirus type 11 E1()E4 protein with cornified cell envelopes derived from infected genital epithelium.

The cornified cell envelope (CCE) is an insoluble matrix of covalently linked proteins assembled in differentiating keratinocytes, providing a barrier against external insults. CCEs derived from HPV 11-infected tissue are fragile compared to those derived from healthy epithelium. To study a possible role for the E1()E4 protein, HPV 11-infected epithelium was examined for the distribution of this protein and three CCE proteins. CCEs were then purified from genital epithelium, fragmented, washed to remove nonassociated proteins, and analyzed for E1()E4 protein. In HPV 11-infected tissue, the E1()E4 protein was detected in the region of the CCE in differentiated keratinocytes. Loricrin and cytokeratin 10 (K10) were absent in E1()E4-positive cells, and E1()E4 protein was not detected in cells containing these proteins. E1()E4 protein was detected in immunoblots as a 10- to 11-kDa doublet in extracts of intact CCEs from infected tissue and in extracts of CCE fragments prepared without using reducing agents. Extraction with reducing agents eliminated E1()E4 detection, suggesting that disulfide bonding was involved in the association with CCE fragments. In addition, cyanogen bromide degradation experiments, immunofluorescence, and immunoelectron microscopy provided evidence that E1()E4 protein was associated with CCE fragments by covalent bonds other than disulfide bonds. We conclude that E1()E4 protein expression is associated with profound alterations in detection of loricrin and K10 in HPV 11-infected genital epithelium. The E1()E4 protein copurified with CCEs derived from infected epithelium and could be identified in CCE fragments, suggesting a possible role for E1()E4 in the development of CCE abnormalities.

Blotting, Western↗

FTIR microspectroscopic study of cell types and potential confounding variables in screening for cervical malignancies.

FTIR microscopy was applied to the analysis of cell types and other variables present in Pap smears to ascertain the limitations of infrared spectroscopy in the diagnosis of cervical cancer and dysplasia. It was found that leukocytes, and in particular lymphocytes, have spectral features in the phosphodiester region (1300-900 cm[-1]) suggestive of what has previously been described as changes indicative of malignancy. Endocervical cells and fibroblasts have similar spectral features to HeLa cells and consequently could also confound diagnosis. The use of ethanol as a fixative and dehydrating agent results in retention of glycogen in cervical cell types and thus minimizes spectral changes in the glycogen region due to sampling technique. Spectra of seminal fluids exhibit strong bands in the phosphodiester/carbohydrate region; however, sperm contamination should be easily detectable by the presence of a distinctive doublet at 981/968 cm(-1). Erythrocyte spectra exhibit a reduction in glycogen band intensity, but can be discerned by a relatively low-intensity nu(s) PO2- band. Endocervical mucin spectra exhibit a reduction in glycogen bands and a very pronounced nu(s) PO2- band, which is similar in intensity to the corresponding band in HeLa cells. Thrombocytes have strong bands in the phosphodiester region, but thrombocytes can be discerned from other cell types by the presence of two small broad bands at 980 and 935 cm(-1). Candida albicans is characterized by strong bands in the polysaccharide region which could potentially obscure diagnostic bands if C. albicans is present in large numbers. Spectra of bacteria common to the female genital tract, in general, also have strong absorptions in the polysaccharide region; however, bacterial contamination is usually minimal and would not be expected to obscure cervical cell spectra. Nylon threads and bristles from cervical sampling implements produce characteristic IR profiles which allow for easy identification. Given the number of potential confounding variables associated with cervical cytology, a multivariate statistical or neural network analysis would appear to be necessary before the implementation of FTIR technology in clinical laboratories.

Biopsy↗

Determination of the Chemical-Shift Difference between the Lactate Multiplets and Its pH Dependence

A volume-selective NMR method is presented for very exact determination of the difference of the Larmor frequencies between the coupled resonances of homonuclear AX3 spin systems, as, for example, lactate. The frequency difference can be determined with an accuracy of 0.003 ppm even if only the doublet of the spin system can be detected. The method is based on the effects of homonuclear polarization transfer which occurs in localized double-spin-echo spectroscopy. It is used for determination of the chemical-shift difference of the lactate multiplets, which depends on the degree of dissociation and consequently on pH. Measurements were performed with a 1.5 T Siemens Magnetom SP 63 whole-body imager on solutions of lactate and acetic acid in physiological sodium chloride solution with pH from 1 to 11. As a consequence of these measurements, conclusions are possible for the optimum echo time for PRESS measurements which avoid signal losses from polarization transfer. Furthermore, the possibility of localized pH determination by this effect is discussed.

Journal Article↗

Channel activators reduce the expression of sodium channel alpha-subunit mRNA in developing neurons.

The expression of rat brain sodium channel alpha-subunit (Na+I, Na+II and Na+III) and beta 1-subunit mRNAs was examined in rat fetal brain neurons in culture. A combined technique of reverse transcription and polymerase chain reaction (RT-PCR) was used. Two different PCR primer sets were designed to obtain simultaneous amplification of the three alpha-subunit mRNAs. All three molecules were detected in fetal neurons but the expression pattern (Na+III > Na+II > > Na+I) was different than that observed in adult tissue (Na+II > Na+I > Na+III). Expression of the beta 1-subunit mRNA was detected using a specific PCR primer set. Doublet bands were amplified, from fetal cells and adult brain mRNA. To get further insight into the molecular mechanism that underlie activity dependent plasticity of sodium channels, we studied the effect on the expression of sodium channel subunits mRNA of a 60 h incubation of cells in the presence of a scorpion neurotoxin that blocks channel inactivation. An overall decrease in the expression of all three alpha-subunit mRNAs was observed whereas the beta 1-subunit mRNA was unaffected by the same treatment. When cells were incubated with the scorpion neurotoxin together with tetrodotoxin, to block Na+ influx through channels, the decrease in mRNA expression was not observed. Finally, a 60 h continuous depolarization of cells induced by application of a high concentration KC1 solution did not mimic the effect of the scorpion toxin. These observations suggest that a persistent activation of the sodium channels is able to down-regulate mRNA expression for alpha-subunits but not for the beta 1-subunit.

Animals↗

Thermal and Light-Induced Spin Transition in the High- and Low-Temperature Structure of [Fe(0.35)Ni(0.65)(mtz)(6)](ClO(4))(2).

The thermal and light induced spin transition in [Fe(0.35)Ni(0.65)(mtz)(6)](ClO(4))(2) (mtz = 1-methyl-1H-tetrazole) was studied by (57)Fe Mössbauer spectroscopy and magnetic susceptibility measurements. In addition to the spin transition of the iron(II) complexes the compound undergoes a structural phase transition. The high-temperature structure could be determined by X-ray crystallography of the isomorphous [Fe(0.25)Ni(0.75)(mtz)(6)](ClO(4))(2) complex at room temperature. The X-ray structural analysis shows this complex to be rhombohedric, space group R&thremacr;, with a = 10.865(2) Å and c = 23.65(1) Å with three molecules in the unit cell. The transition to the low-temperature structure occurs at approximately 60 K without changing the spin state of the molecules. By subsequent heating of the complex the high-temperature structure is reached again between ca. 170 and 200 K. The spin transition behavior is strongly influenced by the structural changes, and the observed spin transition curves are completely different for the high- and low-temperature phases. In the high-temperature structure a complete and gradual spin transition between 220 and 120 K (T(1/2)(gamma(HS) = 0.5) = 185 K) is detected; the high-spin (HS) state is represented by one HS doublet in the Mössbauer spectra. In the low-temperature structure a two-step transition curve is detected in the heating mode. About 36% of the molecules show a LS (low-spin) --> HS transition between ca 50 and 75 K. Then the HS fraction stays constant up to 150 K. A further increase in the high-spin fraction is observed at temperatures above 150 K. In this structural phase the HS state is represented by two different HS doublets in the Mössbauer spectra. The formation of metastable HS states by making use of the LIESST effect is only possible in the low-temperature structure. By excitation of the LS molecules with green light, two different HS states are populated which show very different relaxation behavior. One HS state shows a relaxation to the LS state even at 10 K; the other HS state shows a very slow HS --> LS relaxation at 60 K (within days), leading to the HS fraction corresponding to the thermal equilibrium value.

Journal Article↗