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The polarization state of the excitation light used in two Raman systems was controlled to study its effect in the unpolarized Raman spectra of unstructured samples. Both systems work in different regions of the electromagnetic spectrum (NIR and visible). Four polarization states (linear, linear at 45° and 90°, and circular) were used to excite liquid samples (ethanol, acetone, and their mixture). The results show that the Raman peaks intensities' ratio varies according to the polarization state of the excitation light. Peaks related to functional groups and C-H stretching modes increase their intensity when circular polarization (CP) is applied. The latter may help to study liquid mixtures with low concentrations. Different polarizing light states give a more detailed spectroscopic analysis since it gathers more structural information of the samples tested in this work with an undefined structure., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The effects of the vibronic coupling in quantum cellular automata (QCA) based on the square planar mixed valence (MV) molecular cells comprising four paramagnetic centers (spin cores) and two excess mobile electrons are analyzed in the important particular case when the Coulomb energy gap between the ground antipodal diagonal-type two-electron configurations and the excited side-type configurations considerably exceeds both the one-electron transfer parameter (strong U-limit) and the vibronic stabilization energy. Under such conditions the developed model involves the second-order double exchange, the Heisenberg-Dirac-Van Vleck (HDVV) exchange and the vibronic coupling of the excess electrons with the molecular B 1g -vibration composed of four full-symmetric local vibrations. The latter interaction is shown to significant amplify the ability of the electric field produced by the driver-cell to polarize the excess electrons in the working cell, which can be termed "the effect of the vibronic enhancement of the cell-cell interaction". This effect leads to a redetermination of the conditions for switching between different spin-states, as well as to a significant change in the shapes of the cell-cell response functions. The obtained results demonstrate the importance of the vibronic coupling in all aspects (such as description of a free cell and cell-cell response) of the theory of molecular QCA based on MV clusters., (© 2021 Wiley-VCH GmbH.)

The 1 : 2 and 1 : 1 Co(ii) complexes of the L ligand (L = 6-(3,5-diamino-2,4,6-triazinyl)2,2'-bipyridine) with formulas [CoII(L)2](ClO4)2·0.5MeCN·Et2O (1) and [CoII(L)(CH3CN)2(H2O)](ClO4)2·MeCN (2) have been prepared. The structural and magnetic characterization of the two compounds shows that they contain octahedral high-spin Co(ii) and present a field-induced slow relaxation of the magnetization. 1 has been inserted into a bimetallic oxalate-based network leading to a novel achiral 3D compound of formula [CoII(L)2][MnIICrIII(ox)3]2·(solvate) (3) exhibiting ferromagnetic ordering below 4.6 K. EPR measurements suggest a weak magnetic coupling between the two sublattices.

Penile carcinoma (PeCa) is an important public health issue in poor and developing countries, and has only recently been explored in terms of genetic and epigenetic studies. Integrative data analysis is a powerful method for the identification of molecular drivers involved in cancer development and progression. miRNA and mRNA expression profiles followed by integrative analysis were investigated in 23 PeCa and 12 non-neoplastic penile tissues (NPT). Expression levels of eight miRNAs and 10 mRNAs were evaluated in the same set of samples used for microarray and in a validation set of cases (PeCa = 36; NPT = 27). Eighty-one miRNAs and 2,697 mRNAs were identified as differentially expressed in PeCa. Integrative data analysis revealed 255 mRNAs potentially regulated by 68 miRNAs. Using RT-qPCR, eight miRNAs and nine transcripts were confirmed as altered in PeCa. We identified that MMP1, MMP12 and PPARG and hsa-miR-31-5p, hsa-miR-224-5p, and hsa-miR-223-3p were able to distinguish tumors from NPT with high sensitivity and specificity. Higher MMP1 expression was detected as a better predictor of lymph node metastasis than the clinical-pathological data. In addition, PPARG and EGFR were highlighted as potential pathways for targeted therapy in PeCa. The analysis based on HPV positivity (7 of 23 cases) revealed five miRNA and 13 mRNA differentially expressed. Although in a limited number of cases, HPV positive PeCa presented less aggressive phenotype in comparison with negative cases. Overall, an integrative analysis using mRNA and miRNA profiles revealed markers related with tumor development and progression. Furthermore, MMP1 expression level was a predictive marker for lymph node metastasis in patients with PeCa.

The Fe(ii) complex of the L 1 ligand (L 1 = 6-(3,5-diamino-2,4,6-triazinyl)-2,2'-bipyridine) has been used as a templating cation for the growth of oxalate-based networks. The magnetic characterization of the [Fe II (L 1 ) 2 ](ClO 4 ) 2 ·CH 3 CN (1) precursor in the solid state has been performed for the first time showing that the low-spin (LS) state is predominating from 2 to 400 K with 10% of Fe(ii), which undergoes a gradual and irreversible spin-crossover above 350 K. 1 presents the LIESST effect with a photo-conversion close to 25% and a T(LIESST) of 49 K. During the preparation of 1, a secondary product of the formula [Fe II (L 1 )(CH 3 CN) 2 (H 2 O)](ClO 4 ) 2 ·CH 3 CN (2) has been obtained. The magnetic characterization of 2 shows that it contains high-spin (HS) Fe(ii). 1 has afforded two novel oxalate-based compounds, the 2D compound of the formula [Fe II (L 1 ) 2 ][Mn II Cr III (ox) 3 ] 2 ·(CH 3 NO 2 ) 6 ·(CH 3 OH)·(H 2 O) 2 (3) and the 3D compound of the formula [Fe II (L 1 ) 2 ][Mn II Cr III (ox) 3 ] 2 ·(CH 3 CN) 3 (4), which have been obtained by changing the synthetic conditions. The magnetic properties show that in 3 the inserted Fe(ii) cation remains in the LS state from 2 to 340 K and presents a partial and irreversible spin-crossover of ∼20% at higher temperatures. In 4, most of the Fe(ii) complexes remain in the LS state from 2 to 230 K and present a partial and irreversible spin-crossover of ∼50% from 230 to 400 K. 3 and 4 do not present the LIESST effect.

Here we describe a new vibronic model of mixed valence (MV) dimer inspired by the conventional Piepho, Krausz, and Schatz (PKS) approach. We attempted to partially lift the main restriction of the PKS model dealing with the vibronically independent moieties of a MV molecule. The refined version of the PKS model in which the bridging ligands are included deals with the three main interactions: electron transfer (integral t0) related to the high-symmetric ligand configuration, on-site vibronic coupling (parameter υ) arising from the modulation of the crystal field on the metal sites by the breathing displacements of their nearest ligand surroundings, and intercenter vibronic coupling (parameter ζ) describing the dependence of the electron transfer on ligand positions in the course of their breathing movement. We apply the modified model to the analysis of the adiabatic potentials and electronic density distributions in the minima of their lower sheets for the cases of one-electron MV dimer with long and short bridges and for the two-electron MV dimer exhibiting a valence disproportionation effect. The inclusion of the intercenter interaction in addition to the conventional PKS coupling is shown to produce a strong effect on the degree of localization in MV dimers and, in particular, on the assignments to the Robin and Day classes and on the conditions of stabilization of valence disproportionated states in bielectron transfer systems.

Objectives: The aim of this study was to ascertain the factors associated with non-achievement of triglyceride (TG) goals in a cohort of hypertriglyceridemic patients attending the lipid clinics of the Spanish Arteriosclerosis Society (LC-SAS)., Methods: Patients with high TG levels (>2.2 mmol/L; 200 mg/dL) were included in this multicenter, prospective, observational study and followed up for 1 year. The TG goal was ≤2.2 mmol/L (200 mg/dL). Main limitations of this study are that etiologic diagnosis of hypertriglyceridemia was not done under unified criteria and drug compliance was not evaluated., Results: From 1394 patients initially included in the study, 929 (age range: 50 ± 12 years, 26% women) were followed up for 1 year; 523 patients (56%) failed to reach the TG target. These patients were younger, had a higher body mass index (BMI), were more frequently smokers, hypertensive and diabetic and had more severe dyslipidemia. They were also more sedentary, their diet was of poorer quality and they had higher alcohol consumption. The independent predictors of treatment failure were hypertriglyceridemia severity, low high density lipoprotein cholesterol (HDL-C), and high non-HDL-C, alcohol consumption and a raised BMI, while drug treatment had no predictive power., Conclusion: Independent predictors of failure to achieve hypertriglyceridemia treatment goals are inappropriate lifestyle, evidenced by insufficient weight loss, alcohol consumption and dyslipidemia severity.

The substantial increase in female employment rates in Europe over the past two decades has often been linked in political and public rhetoric to negative effects on child development, including obesity. We analyse this association between maternal employment and childhood obesity using rich objective reports of various anthropometric and other measures of fatness from the IDEFICS study of children aged 2-9 in 16 regions of eight European countries. Based on such data as accelerometer measures and information from nutritional diaries, we also investigate the effects of maternal employment on obesity's main drivers: calorie intake and physical activity. Our analysis provides little evidence for any association between maternal employment and childhood obesity, diet or physical activity., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A robust, stable and processable family of mononuclear lanthanoid complexes based on polyoxometalates (POMs) that exhibit single-molecule magnetic behavior is described here. Preyssler polyanions of general formula [LnP(5)W(30)O(110)](12-) (Ln(3+) = Tb, Dy, Ho, Er, Tm, and Yb) have been characterized with static and dynamic magnetic measurements and heat capacity experiments. For the Dy and Ho derivatives, slow relaxation of the magnetization has been found. A simple interpretation of these properties is achieved by using crystal field theory.

We report ac susceptibility and continuous wave and pulsed EPR experiments performed on GdW10 and GdW30 polyoxometalate clusters, in which a Gd3+ ion is coordinated to different polyoxometalate moieties. Despite the isotropic character of gadolinium as a free ion, these molecules show slow magnetic relaxation at very low temperatures, characteristic of single molecule magnets. For T≲200  mK, the spin-lattice relaxation becomes dominated by pure quantum tunneling events, with rates that agree quantitatively with those predicted by the Prokof'ev and Stamp model [Phys. Rev. Lett. 80, 5794 (1998)]. The sign of the magnetic anisotropy, the energy level splittings, and the tunneling rates strongly depend on the molecular structure. We argue that GdW30 molecules are also promising spin qubits with a coherence figure of merit Q(M)≳50.

To explain the single-molecule magnet behavior of the mononuclear complex [(tpaMes)Fe](-) we have developed a model that takes into account the trigonal ligand field splitting of the atomic (5)D term of the Fe(II) ion, and the spin-orbital splitting and mixing of the ligand field terms. The ground ligand field term is shown to be the orbital doublet (5)E possessing an unquenched orbital angular momentum. We demonstrate that the splitting of this term cannot be described by the conventional zero-field splitting Hamiltonian proving thus the irrelevance of the spin-Hamiltonian formalism in the present case. The first-order orbital angular momentum is shown to lead to the strong magnetic anisotropy with the trigonal axis being the easy axis of the magnetization.

We present a FORTRAN code based on a new powerful and efficient computational approach to solve the double exchange problem for high-nuclearity MV clusters containing arbitrary number of localized spins and itinerant electrons. We also report some examples in order to show the possibilities of the program., (2009 Wiley Periodicals, Inc.)

Background: The electronic Schizophrenia Treatment Adherence Registry (e-STAR) is a prospective, observational study of patients with schizophrenia designed to evaluate long-term treatment outcomes in routine clinical practice., Methods: Parameters were assessed at baseline and at 3 month intervals for 2 years in patients initiated on risperidone long-acting injection (RLAI) (n=1345) or a new oral antipsychotic (AP) (n=277; 35.7% and 36.5% on risperidone and olanzapine, respectively) in Spain. Hospitalization prior to therapy was assessed by a retrospective chart review., Results: At 24 months, treatment retention (81.8% for RLAI versus 63.4% for oral APs, p<0.0001) and reduction in Clinical Global Impression Severity scores (-1.14 for RLAI versus -0.94 for APs, p=0.0165) were significantly higher with RLAI. Compared to the pre-switch period, RLAI patients had greater reductions in the number (reduction of 0.37 stays per patient versus 0.2, p<0.05) and days (18.74 versus 13.02, p<0.01) of hospitalizations at 24 months than oral AP patients., Conclusions: This 2 year, prospective, observational study showed that, compared to oral antipsychotics, RLAI was associated with better treatment retention, greater improvement in clinical symptoms and functioning, and greater reduction in hospital stays and days in hospital in patients with schizophrenia. Improved treatment adherence, increased efficacy and reduced hospitalization with RLAI offer the opportunity of substantial therapeutic improvement in schizophrenia.

A general approach to the problem of electron delocalization in the high-nuclearity mixed-valence (MV) clusters containing an arbitrary number of localized spins and itinerant electrons is developed. Along with the double exchange, we consider the isotropic magnetic exchange between the localized electrons as well as the Coulomb intercenter repulsion. As distinguished from the previous approaches dealing with the MV systems in which itinerant electrons are delocalized over all constituent metal sites, here, we consider a more common case of systems exhibiting partial delocalization and containing several delocalized domains. Taking full advantage of the powerful angular momentum technique, we were able to derive closed form analytical expressions for the matrix elements of the full Hamiltonian. These expressions provide an efficient tool for treating complex mixed-valence systems, because they contain only products of 6j-symbols (that appear while treating the delocalized parts) and 9j-symbols (exchange interactions in localized parts) and do not contain high-order recoupling coefficients and 3j-symbols that essentially constrained all previous theories of mixed valency. The approach developed here is accompanied by an efficient computational procedure that allows us to calculate the bulk thermodynamic properties (magnetic susceptibility, magnetization, and magnetic specific heat) of high-nuclearity MV clusters. Finally, this approach has been used to discuss the magnetic properties of the octanuclear MV cluster [Fe(8)(mu(4)-O)(4)(4-Cl-pz)(12)Cl(4)](-) and the diphthalocyanine chains [YPc(2)].CH(2)Cl(2) and [ScPc(2)].CH(2)Cl(2) composed of MV dimers interacting through the magnetic exchange and Coulomb repulsion.

This study questioned the effect of living and training at moderate altitude on cardiac morphological and functional adaptations and tested the incidences of potential specific adaptations compared with aerobic sea level training on maximal left ventricular performance. Sea level-native rats were randomly assigned to N (living in normoxia), NT (living and training 5 days/wk for 5 wk in normoxia), CH (living in hypoxia, 2,800 m), and CHT (living and training 5 days/wk for 5 wk in hypoxia, 2,800 m) groups. Cardiac adaptations were evaluated throughout the study period by Doppler echocardiography. Maximal stroke volume (LV(SVmax)) was measured during volume overloading before and after the study period. Finally, at the end of the study period, passive pressure-volume relationships on isolated heart and cardiac weighing were obtained. Altitude training resulted in a specific left ventricular (LV) remodeling compared with NT, characterized by an increase in wall thicknesses without any alteration in internal dimensions. These morphological adaptations associated with hypoxia-induced alterations in pulmonary outflow and preload conditions led to a decrease in LV filling and subsequently no improvement in LV performance during resting physiological conditions in CHT compared with NT. Such a lack of improvement was confirmed during volume overloading that simulated maximal effort (LV(SVmax) pretest: NT = 0.58 +/- 0.05, CHT = 0.57 +/- 0.08 ml; posttest: NT = 0.72 +/- 0.06, CHT = 0.58 +/- 0.07 ml; NT vs. CHT in posttest session, P < 0.05). Maximal aerobic velocities increased to the same extent in NT and CHT rats despite marked polycythemia in the latter. The lack of LV(SVmax) improvement resulting from altitude training-induced cardiac morphological and functional adaptations could be responsible for this phenomenon.

Background: Cardiac troponins I (cTnI) and T (cTnT) have been shown to be highly sensitive and specific markers of myocardial cell injury. We investigated the diagnostic value of cTnI and cTnT for the diagnosis of myocardial damage in a rat model of doxorubicin (DOX)-induced cardiomyopathy, and we examined the relationship between serial cTnI and cTnT with the development of cardiac disorders monitored by echocardiography and histological examinations in this model., Methods: Thirty-five Wistar rats were given 1.5 mg/kg DOX, i.v., weekly for up to 8 weeks for a total cumulative dose of 12 mg/kg BW. Ten rats received saline as a control group. cTnI was measured with Access(R) (ng/ml) and a research immunoassay (pg/ml), and compared with cTnT, CK-MB mass and CK. By using transthoracic echocardiography, anterior and posterior wall thickness, LV diameters and LV fractional shortening (FS) were measured in all rats before DOX or saline, and at weeks 6 and 9 after treatment in all surviving rats. Histology was performed in DOX-rats at 6 and 9 weeks after the last DOX dose and in all controls., Results: Eighteen of the DOX rats died prematurely of general toxicity during the 9-week period. End-diastolic (ED) and end-systolic (ES) LV diameters/BW significantly increased, whereas LV FS was decreased after 9 weeks in the DOX group (p<0.001). These parameters remained unchanged in controls. Histological evaluation of hearts from all rats given DOX revealed significant slight degrees of perivascular and interstitial fibrosis. In 7 of the 18 rats, degeneration and myocyte vacuolisation were found. Only five of the controls exhibited evidence of very slight perivascular fibrosis. A significant rise in cTnT was found in DOX rats after cumulative doses of 7.5 and 12 mg/kg in comparison with baseline (p<0.05). cTnT found in rats after 12 mg/kg were significantly greater than that found after 7.5 mg/kg DOX. Maximal cTnI (pg/ml) and cTnT levels were significantly increased in DOX rats compared with controls (p=0.006, 0.007). cTnI (ng/ml), CK-MB mass and CK remained unchanged in DOX rats compared with controls. All markers remained stable in controls. Analysis of data revealed a significant correlation between maximal cTnT and ED and ES LV diameters/BW (r=0.81 and 0.65; p<0.0001). A significant relationship was observed between maximal cTnT and the extent of myocardial morphological changes, and between LV diameters/BW and histological findings., Conclusions: Among markers of ischemic injury after DOX in rats, cTnT showed the greatest ability to detect myocardial damage assessed by echocardiographic detection and histological changes. Although there was a discrepancy between the amount of cTnI and cTnT after DOX, probably due to heterogeneity in cross-reactivities of mAbs to various cTnI and cTnT forms, it is likely that cTnT in rats after DOX indicates cell damage determined by the magnitude of injury induced and that cTnT should be a useful marker for the prediction of experimentally induced cardiotoxicity and possibly for cardioprotective experiments.

A new polynuclear copper(II) complex [Cu7(OH)6Cl2(pn)6(H2O)2](C(CN)3)4Cl2 with hydroxo-bridging ligands has been prepared; the centrosymmetric cluster cation can be described as two Cu4O3Cl distorted cubane units sharing one copper cation.

The ground-state properties of the pentameric Co(II) cluster [Co(3)W(D(2)O)(2)(CoW(9)O(34))(2)](12-) were investigated by combining magnetic susceptibility and low-temperature magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated polycrystalline sample of Na(12)[Co(3)W(D(2)O)(2)(CoW(9)O(34))(2)].46D(2)O. The encapsulated magnetic Co(5) unit consists of three octahedral and two tetrahedral oxo-coordinated Co(II) ions. Thus, two different types of exchange interactions are present within this cluster: a ferromagnetic interaction between the octahedral Co(II) ions and an antiferromagnetic interaction between the octahedral and the tetrahedral Co(II) ions. As a result of the single-ion anisotropy of the octahedral Co(II) ions, the appropriate exchange Hamiltonian to describe the ground-state properties of the Co(5) spin cluster is anisotropic and is expressed as H = -2 summation operator(i= x,y,z)J(1)(i)[S(1)(i)S(2)(i) + S(2)(i)S(3)(i)] + J(2)(i)[S(1)(i)S(5)(i) + S(2)(i)S(5)(i) + S(2)(i)S(6)(i) + S(3)(i)S(6)(i)], where J(1)(i) are the components of the exchange interaction between the octahedral Co(II) ions and J(2)(i) are the components of the exchange interaction between the octahedral and tetrahedral Co(II) ions (see Figure 1d). The study of the exchange interactions in the two structurally related polyoxoanions [Co(4)(H(2)O)(2)(PW(9)O(34))(2)](10)(-) and [Co(3)W(H(2)O)(2)(ZnW(9)O(34))(2)](12)(-) allowed an independent determination of the ferromagnetic exchange parameters J(1)(x) = 0.70 meV, J(1)(y) = 0.43 meV, and J(1)(z) = 1.51 meV (set a) and J(1)(x) = 1.16 meV, J(1)(y) = 1.16 meV and J(1)(z) = 1.73 meV (set b), respectively. Our analysis proved to be much more sensitive to the size and anisotropy of the antiferromagnetic exchange interaction J(2). We demonstrate that this exchange interaction exhibits a rhombic anisotropy with exchange parameters J(2)(x) = -1.24 meV, J(2)(y) = -0.53 meV, and J(2)(z) = -1.44 meV (set a) or J(1)(x) = -1.19 meV, J(1)(y) = -0.53 meV, and J(1)(z) = -1.44 meV (set b). The two parameter sets reproduce in a satisfactory manner the susceptibility, magnetization, and INS properties of the title compound.

Objective: The aim of this study was to evaluate changes in the wall mechanics of small-diameter arteries after endovascular placement of three different stents., Subjects and Methods: Five self-expandable stents (Wallstent), five balloon-expandable noncovered Palmaz stents, and three balloon-expandable covered stents (Jostent) were placed in the infrarenal aorta of 13 New Zealand white rabbits. Systolic blood pressure changes, blood-flow velocity, systolic diameter, and diameter changes were measured and used to calculate the diameter compliance, the distensibility coefficient, and the pulsatility index., Results: Compliance (10(-3) mm kPa(-1)) was 75.3 +/- 20.1 before stenting and reached 94.7 +/- 42.2 upstream, 38.8 +/- 14.2 at the stent level (p < 0.05), and 70.8 +/- 23.2 downstream from the stent. Distensibility (10(-3) kPa(-1)) was 24.3 +/- 6.3 before stenting and reached 27.8 +/- 10.3 upstream, 10.5 +/- 4.4 at the stent level (p < 0.001), and 21.9 +/- 8.6 downstream from the stent. Compliance and distensibility were significantly lower at the stent level than upstream and downstream (p < 0.05). Aortic diameter increased significantly at the stent level from 3.11 +/- 0.40 mm before to 3.76 +/- 0.42 mm after stenting. No significant difference was found among the three stent designs for all the studied data., Conclusion: Regardless of the three tested stent designs, endovascular stenting produces a significant decrease in arterial wall compliance of the rabbit aorta.

The synthesis, crystal structure, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O (1), [Ni(en)2][Fe(CN)5NO]x3H2O (2), [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO] (3), and [Mn(5-Brsalen)]2[Fe(CN)5NO] (4) are presented. 1 crystallizes in the monoclinic space group P2(1)/n (a = 7.407(4) A, b = 28.963(6) A, c = 14.744(5) A, alpha = 90 degrees, beta = 103.26(4) degrees, gamma = 90 degrees, Z = 2). Its structure consists of branched linear chains formed by cis-[Ni(en)2]2+ cations and ferrocyanide and nitroprusside anions. The presence of two kinds of iron(II) sites has been demonstrated by Mössbauer spectroscopy. 2 crystallizes in the monoclinic space group P2(1)/c (a = 11.076(3) A, b = 10.983(2) A, c = 17.018(5) A, alpha = 90 degrees, beta = 107.25(2) degrees, gamma = 90 degrees, Z = 4). Its structure consists of zigzag chains formed by an alternated array of cis-[Ni(en)2]2+ cations and nitroprusside anions. 3 crystallizes in the triclinic space group P1 (a = 8.896(5) A, b = 10.430(5) A, c = 12.699(5) A, alpha = 71.110(5) degrees, beta = 79.990(5) degrees, gamma = 89.470(5) degrees, Z = 1). Its structure comprises neutral trinuclear bimetallic complexes in which a central [Fe(CN)5NO]2- anion is linked to two [Mn(3-MeOsalen)]+ cations. 4 crystallizes in the tetragonal space group P4/ncc (a = 13.630(5) A, c = 21.420(8) A, Z = 4). Its structure shows an extended 2D neutral network formed by cyclic octameric [-Mn-NC-Fe-CN-]4 units. The magnetic properties of these compounds indicate the presence of quasi-isolated paramagnetic Ni2+ and Mn3+. Irradiated samples of the four compounds have been studied by differential scanning calorimetry to detect the existence of the long-lived metastable states of nitroprusside.

The tetranuclear [Ni4(pypentO)(pym)(mu 3-OH)2(mu-Oac)2(NCS)2(OH2)] cubane-like complex has been prepared, and its structure and magnetic properties have been studied (pypentO and pym are the deprotonated forms of 1,5-bis[(2-pyridylmethyl)amino]pentane-3-ol and 2-pyridylmethanol, respectively). The X-ray diffraction analysis of this novel nickel complex (C61H74N14O25.5S4Ni8, monoclinic, P2(1), a = 13.9375(14) A, b = 20.6604(18) A, c = 16.6684(19) A, beta = 110.619(12) degrees, Z = 2) showed a Ni4O4 cubane arrangement of four nickel atoms, four mu 3-O bridging ligands (one pypentO, one pym, and two OH-), two syn-syn bridging acetates, and three terminal monodentate ligands (two NCS- and one OH2). In this low-symmetry elongated cubane, the four Ni-Ni long distances (3.18 A) correspond to the faces of the cube including two mu 3-OR bridges, and the two Ni-Ni short distances (2.94 A) correspond to the faces including two mu 3-OR and one acetate bridges. The temperature dependence of the magnetic susceptibility was fitted with J1 = -3.09 cm-1, J2 = 15.0 cm-1, J3 = 6.72 cm-1, and g = 2.27. The differences in sign among the J1, J2, and J3 superexchange interactions is in good agreement with the different types of faces present in this Ni4O4 cubane core. The two faces of the cube, including two mu 3-OR bridges associated with one acetate bridge, exhibit ferromagnetic interactions, while the four faces which include only mu 3-OR bridges exhibit antiferromagnetic interactions. The very small zero field splitting may be attributed to the fact that the ground state is diamagnetic. The nature of the ground state is confirmed by the good simulation of the magnetization curves at 2 and 5 K (diagonalization of the full matrix taking into account all energy levels obtained with the parameter set resulting from the fit of the susceptibility curve). The large differences in J values resulting from small differences in Ni-O-Ni angles in this Ni4O4 core of very low symmetry reflect a quite strong magnetostructural correlation.

Cardiac troponins I (cTnI) and T (cTnT) have been shown to be highly sensitive and specific markers of myocardial cell injury. The purpose of this study was to investigate the diagnostic value of cTnI and cTnT with regard to creatine kinase (CK) and lactate dehydrogenase (LD) and to determine whether they can be used for early diagnosis of myocardial damage in rats, and to examine the relationship between cTnl and cTnT release with histological examinations, using isoprenaline-induced cardiac muscle damage as an experimental model in the rat. Eighteen Wistar rats per group were treated with a single dose of either isoprenaline (iso) or with normal saline as a control group. The anti-cTnI and cTnT monoclonal antibodies (mAbs) employed in the cTnI (Access) and cTnT (Elecsys) assays cross-react with cTnI and cTnT of the rat. A highly significant rise of cTnl or cTnT was found already 2 h after iso. The time-courses of cTnI and cTnT were monophasic in form. The highest cTnI (mean+/-S.D., 1.1+/-2.3 ng/ml) and cTnT (mean+/-S.D. 3.6+/-30 ng/ml) were found 4 h after iso. cTnI and cTnT significantly increased in iso-treated rats in comparison with controls whether the differences between 2-, 4- and 6-h levels and basal levels were considered or not. The areas under cTnl and cTnT curves (AUC) (0-6 h) and the maximal cTnI and cTnT (0-6 h) after iso were significantly different from the controls. For CK and LD, no elevation in comparison with controls could be detected (except a trend for LD whether or not the difference between 6-h levels and basal levels were considered (P=0.08) and for LD AUC (0-6 h) (P=0. 059)). Correlations between maximal cTnI and cTnT and AUC were 0.69 (P=0.0001) and 0.60 (P=0.0066), respectively. Histological examinations of iso-treated rats revealed acute focal or multifocal myofibrillar degeneration of the myocardial tissue in ten out of 14 rats and showed the earliest alterations 4 h after iso in one treated rat. Only four of the controls exhibited evidence of mild changes and slight mononuclear cell infiltration. cTnl and cTnT peak values to at least 0.35 and 1.3 ng/ml, respectively, were necessary to detect histological myocardial cell injury after iso. cTnI and cTnT were found to be early markers for diagnosing iso-induced myocardial damage in comparison with CK and LD. Elevations of cTnI and cTnT appeared to relate to the severity of histologic changes after myocardial injury. Although there was a difference in the absolute concentration of results between cTnI and cTnT assays, due to a lack of standardization and heterogeneity in the cross-reactivities of mAbs to various troponin I and T forms, cTnI and cTnT can be used as easily measurable target parameters for detection of cardiotoxic and/or cardiodegenerative effects in rats.

Purpose: To evaluate mechanical property changes after endovascular stent placement in small-diameter arteries., Materials and Methods: Self-expanding stents (Wallstent) were placed in the infrarenal aorta of five New Zealand White rabbits via a surgical right femoral approach. Blood pressure changes (deltaP) were monitored in the aorta. Blood flow velocity was measured with a 20-MHz, pulsed Doppler probe (n = 4) to calculate the pulsatility index. Aortic diameter (dA) and diameter changes (delta(d)) were measured with a 20-MHz probe in echo-tracking mode. Diameter compliance (Cd) and distensibility coefficient (DC) were calculated as Cd = 2(delta)d/(delta)P and DC = 2delta(d)/delta(P)/dA., Results: Aortic diameter increased from 3.360 +/- 0.4033 mm to 4.020 +/- 0.3033 mm after stent placement at the stent level only. Compliance decreased from 77.644 +/- 24.306 mm kPa(-1) to 31.150 +/-8.245 x 10(-3) mm kPa(-1) at the stent level, and was then significantly lower than upstream (98.500 +/- 53.196 mm kPa(-1)) and down-stream (59.047 +/- 13.833 mm kPa(-1)). There was no significant change in pulsatility index., Conclusions: Endovascular stent placement produces a significant decrease in arterial wall compliance of the rabbit abdominal aorta.

A general solution of the exchange problem in the high-nuclearity spin clusters (HNSC) containing arbitrary number of exchange-coupled centers and topology is developed. All constituent magnetic centers are supposed to possess well-isolated orbitally non-degenerate ground states so that the isotropic Heisenberg-Dirac-Van Vleck (HDVV) term is the leading part of the exchange spin Hamiltonian. Along with the HDVV term, we consider higher-order isotropic exchange terms (biquadratic exchange), as well as the anisotropic terms (anisotropic and antisymmetric exchange interactions and local single-ion anisotropies). All these terms are expressed as irreducible tensor operators (ITO). This allows us to take full advantage of the spin symmetry of the system. At the same time, we have also benefitted by taking into account the point group symmetry of the cluster, which allows us to work with symmetrized spin functions. This results in an additional reduction of the matrices to diagonalize. The approach developed here is accompanied by an efficient computational procedure that allows us to calculate the bulk magnetic properties (magnetic susceptibility, magnetization, and magnetic specific heat) as well as the spectroscopic properties of HNSC. Special attention is paid to calculate the magnetic excitations observed by inelastic neutron scattering (INS), their intensities, and their Q and temperature dependencies. This spectroscopic technique provides direct access to the energies and wave functions of the different spin states of the cluster; thus, it can be applied to spin clusters in order to obtain deep and detailed information on the nature of the magnetic exchange phenomenon. The general expression for the INS cross-section of spin clusters interacting by all kinds of exchange interactions, including also the single-ion zero-field splitting term, is derived for the first time. A closed-form expression is also derived for the particular case in which only the isotropic exchange interactions are involved. Finally this approach has been used to model the magnetic properties as well as the INS spectra of the polyoxometalate anion [Ni(9)(OH)(3)(H(2)O)(6)(HPO(4))(2)(PW(9)O(34))(3)](16)(-), which contains a central magnetic cluster formed by nine exchange-coupled Ni(II) ions surrounded by diamagnetic phosphotungstate ligands (PW(9)O(34))(9)(-).

The study was designed to determine the time-course of cardiac troponin I (cTn-I) release in isolated and Langendorff-perfused rat hearts during hypoxia and reoxygenation (H/Reox), and after various durations of total ischemia and subsequent reperfusion (I/R). For this purpose, in H/Reox, cTn-I was measured with the conventional Access immunoassay (ng/ml) and a new immunoassay which operates at pg/ml, and compared with creatine kinase (CK), lactate dehydrogenase (LD) and cardiac troponin T (cTn-T). In I/R, cTn-I was compared with CK and LD. The anti-Tn-I mAbs used in cTn-I assays cross-react with cTn-I of the rat. A clear difference between time-courses and concentration levels of cTn-I in I/R and H/Reox models was found. In I/R, maximum release of cTn-I, CK and LD similarly occurred within minutes following reperfusion; however cTn-I did not return to baseline values. cTn-I levels were not linked to the duration of ischemia. In I/R, we were only able to detect small cTn-I concentrations. In H/Reox experiments, cTn-I, CK and LD increased time-dependently. We found higher cTn-I maximal peak levels detected with the Access immunoassay than with the new assay (median, 0.346 ng/ml per min/g dry wt vs 132 pg/ml per min/g dry wt). cTn-T maximal concentrations were lower than maximal cTn-I levels (median, 0.117 ng/ml per min/g dry wt). Time-courses of cTn-I release were roughly similar with both assays in the H/Reox model (r = 0.90). These data indicate that the cTn-I time-course is related to experimental model (I/R or H/Reox), but also likely depends on the sensitivity of cTn-I assays in such experimental conditions.

The aim of the study was to determine whether facilitation of reentry by potassium-channel openers is related to dispersion of refractoriness and/or modification of anisotropic properties of ventricular myocardium. The dispersion of ventricular effective refractory period (VERP), longitudinal and transverse ventricular conduction velocities (thetaL and thetaT, respectively), and wavelength [lambda = VERP x theta(L or T)] were studied in Langendorff-perfused left ventricular epicardium in 20 rabbits during infusion of incremental doses of levcromakalim or nicorandil. Dispersion of refractoriness was assessed using standard deviation of VERP mean (SD-VERP), dispersion index (DI; SD-VERP/mean VERP), and maximum dispersion (Dmax = VERPmax - VERPmin). Ventricular conduction velocities and anisotropic ratio were not modified, whatever the dose used. VERP and lambda were significantly shortened at high concentrations of levcromakalim and nicorandil. At these doses, SD-VERP, DI, and Dmax were increased significantly. Analysis of ventricular tachycardia induction, performed using a high-resolution ventricular mapping system, confirmed that heterogeneity and shortening of VERP were factors inducing functional conduction block. Our data suggest that, in rabbit left ventricular epicardium, functional conduction block facilitating the occurrence of reentry could be initiated by shortening and, especially, by dispersion of refractoriness during infusion of potassium-channel openers.

The value of immunotherapy (IT) in allergic rhinitis is debated. The results of a retrospective study of 67 patients treated with IT from 1985 to the end of 1995 are reported. Patients were classified as cured, improved, or not improved. Variables such as age, number and type of allergens, improvement, release, duration of evolution, and initial and final IgE levels were analyzed. Response to IT was favorable in 81.1% of cases. Improvement and cure were age-dependent, with the cure rate being significantly higher in patients over 30.

Background: The aims of the study were to verify the effects of ketamine on ventricular conduction velocity and on the ventricular effective refractory period, to determine its effects on anisotropy and on homogeneity of refractoriness, and to use wavelength to determine whether ketamine has antiarrhythmic or arrhythmogenic properties., Methods: A high-resolution epicardial mapping system was used to study the effects of 50, 100, 150, and 200 microM racemic ketamine in 15 isolated, Langendorff-perfused rabbit hearts. Five hearts were kept intact to study the effects of ketamine on spontaneous sinus cycle length (RR) interval and its putative arrhythmogenic effects. In 10 other hearts, a thin epicardial layer was obtained by an endocardial cryoprocedure (frozen hearts) to study ventricular conduction velocity, ventricular effective refractory periods (five sites), and ventricular wavelength., Results: Ketamine induced a concentration-dependent lengthening of the RR interval. Ketamine slowed longitudinal and transverse ventricular conduction velocity with no anisotropic change, and it prolonged the ventricular effective refractory period with no significant increase in dispersion. Ventricular longitudinal and transverse wavelengths tend to increase, but this was not statistically significant. Finally, no arrhythmia could be induced regardless of the ketamine concentration., Conclusion: Ketamine slowed ventricular conduction and prolonged refractoriness without changing anisotropy or increasing dispersion of refractoriness. Although these effects should result in significant antiarrhythmic effects of ketamine, this should not be construed to suggest a protective effect in ischemic or other abnormal myocardium.

This study was designed (a) to test and (b) to compare proarrhythmic effects of levcromakalim and nicorandil; and (c) determine the mechanism of arrhythmia initiation by using high-resolution ventricular epicardial mapping on 44 Langendorff-perfused rabbit hearts. Eighteen hearts were kept intact and received incremental doses (1-500 microM) of levcromakalim, nicorandil, and isosorbide dinitrate. In 26 hearts, a thin layer of epicardium was obtained after endocardial cryotechnique (frozen hearts). In intact hearts, isosorbide dinitrate did not produce any arrhythmia. In contrast, levcromakalim induced spontaneous ventricular fibrillation (VF) in all hearts at 50 microM, whereas only one VF occurred at 500 microM nicorandil. These three drugs produced a dose-dependent bradycardia in intact hearts. In frozen hearts, arrhythmias were induced by 5 microM levcromakalim and 50 microM nicorandil. Isosorbide dinitrate had no proarrhythmogenic effect. Epicardial mapping showed that most of induced ventricular tachycardias were based on reentry around an arc of functional conduction block. Ventricular conduction velocities did not change, but levcromakalim and nicorandil shortened ventricular effective refractory period. We conclude that (a) levcromakalim and nicorandil, used in toxic concentrations, have direct proarrhythmic effects; (b) nicorandil proarrhythmogenic effects are 10 times less marked than those of levcromakalim (arrhythmia is solely the result of the potassium channel opener property of nicorandil); and (c) most of ventricular tachycardias induced are based on reentry.

Electrophysiologic and proarrhythmogenic effects of imipramine were studied by use of 21 Langendorff-perfused rabbit hearts and high-resolution mapping to analyze epicardial activation of the left ventricle. In 16 hearts, a thin layer of epicardium was obtained by an endocardial cryotechnique (frozen hearts). Five hearts were kept intact (nonfrozen imipramine-treated group). Preparation stability was verified in six frozen hearts. In 10 frozen and in 5 nonfrozen hearts, 0.01, 0.1, 1.0, 2.0 and 5.0 micrograms/ml imipramine were administered. In nonfrozen imipramine-treated hearts, imipramine induced bradycardia at 5.0 micrograms/ml (291.8 +/- 40.5 vs. 495.2 +/- 54.4 msec, P = .02), one A-V block at 5.0 micrograms/ml and two monomorphic ventricular tachycardias (MVT) at 2.0 and 5.0 micrograms/ml. In 4/10 frozen hearts, three MVT were induced at 1.0 microgram/ml imipramine and one MVT at 2.0 micrograms/ml imipramine. All MVT were based on reentry around a line of functional conduction blocks. Imipramine (2.0 micrograms/ml) slowed longitudinal and transversal ventricular conduction velocities at a pacing cycle length of 1000 msec from 71.7 +/- 6.1 to 63.0 +/- 7.7 cm/sec (P = .008) and from 32.9 +/- 2.6 to 27.7 +/- 2.8 cm/sec (P = .009), respectively, and prolonged ventricular effective refractory period from 141.9 +/- 9.3 to 279.1 +/- 112.6 msec (P = .03). Imipramine induced dose- and use-dependent slowing of ventricular conduction velocity facilitating functional conduction blocks and reentrant MVT.

Serious complications may occur after "blind" profound venous puncture in intensive care units. To secure these punctures, we designed a new fingertip pulsed Doppler (FPD) 5 MHz probe with a lateral to center indentation to guide the needle into the ultrasonic flux. A specific ultrasound analyzer indicating depth and diameter of the vessel was made for this use. The material was first tested in an experimental animal study. Results of animal venous punctures were successful 20/21. This material was then tested on patients with previous failure of "blind" punctures: results of 4 FPD punctures were successful in all 12 cases but one (catheterization not completed). We started a prospective multi-unit randomized study with various operators (junior residents, senior staff members), compared the success rate and type, the procedure duration of blind standard versus FPD punctures. We conclude in the safety and easy use of the FPD for central venous punctures.

A series of direct carotid end-to-end laser anastomosis vs. direct manual suture was carried out on a series of 70 Wistar rats (mean weight 260 g). Both common carotids (0.8-1.2 mm) were sectioned and repaired. The left side (n = 70) was submitted to laser-assisted microvascular anastomosis (LAMA) performed by means of a diode laser device (wavelength 830 nm and power output 3 W in continuous wave) without chromophore. The right side (n = 70) underwent a control manual suture (CMA). The diode laser energy was delivered into a micromanipulator coupled to a Zeiss operating microscope with a focused spot of 300 microns in diameter. After placement of three 10.0 stitches for edge coaptation, the LAMA was achieved using laser shots (average 3) of 500 mW power, 4.5 s duration, and 700 W/cm2 irradiance each. The CMA was performed by means of six 10.0 stitches. The good vascular flow was confirmed by Doppler spectral analysis (n = 466) carried out from day 0 to day 90. Light and scanning electron microscopy (n = 82) showed that re-endothelialization after LAMA was gaining ground on day 3, whereas collagenous network developed in the media scar by day 10. In contrast, after CMA the arterial repair was delayed on day 20, inducing a media fibrotic scar. The patency rate was 93% in both anastomoses. The shorter operating time (13 min for LAMA vs. 22 min for CMA) and the noncontact laser technique are the main intraoperative advantages. The technical benefits of the diode laser are pointed out.

After a pelvic trauma, in a 78 years old women, systematic radiograms showed a polycyclic mass in the left side of the pelvis. This finding was confirmed by B-mode ultrasound echography. The vaginal touch found a pulsatile and expanding mass. At surgery, the diagnosis of a fissuring aneurysm of the internal iliac artery was confirmed, and a curative treatment was undertaken. Reviewing the literature, the authors emphasize the diagnostic usefulness of rectal and vaginal touch, and the importance of an early diagnosis using noninvasive imaging techniques. Surgery is the only treatment for isolated internal iliac aneurysms.