Synthesis and crystal structures of μ-oxido- and μ-hydroxido-bridged dinuclear iron(III) complexes with an N2O donor ligand - a theoretical study on the influence of weak forces on the Fe-O-Fe bridging angle

The synthesis and crystal structures of three nonheme di-iron(III) complexes with a tridentate N,N,O Schiff-base ligand, 2-({[2-(dimethylamino) ethyl] imino} methyl) phenol (HL), are reported. Complexes [Fe2OL2(NCO)(2)] (1a) and [Fe2OL2(SAL)(2)]center dot H2O [SAL = o-(CHO)C6H4O-] (1b) are unsupported mu-oxido-bridged dimers, and [Fe-2(OH)L-2(HCOO)(2)-(Cl)] (2) is a mu-hydroxido-bridged dimer supported by a formato bridging ligand. All complexes have been characterized by X-ray crystallography and spectroscopic analysis. Complex 1b has been reported previously; however, it has been reinvestigated to confirm the presence of a crucial water molecule in the solid state. Structural analyses show that in 1a the iron atoms are pentacoordinate with a bent Fe-O-Fe angle [142.7(2)degrees], whereas in 2 the metal centers are hexacoordinate with a normal Fe-OH-Fe bridging angle [137.9(2)degrees]. The Fe-O-Fe angles in complexes 1a and 1b differ significantly to those usually shown by (mu-oxido) Fe-III complexes. A theoretical study has been performed in order to rationalize this deviation. Moreover, the influence of the water molecule observed in the solid-state structure of 1b on the Fe-O-Fe angle is also analyzed theoretically.

Molecular characterization and phylogenetic analysis of JussuMP-I: A RGD-P-III class hemorrhagic metalloprotease from Bothrops jararacussu snake venom

Snake venom metalloproteases (SVMPs) embody zinc-dependent multidomain enzymes responsible for a relevant pathophysiology in envenomation. including local and systemic hemorrhage. The molecular features responsible for hemorrhagic potency of SVMPs have been associated with their multidomains structures which can target these proteins them to several receptors of different tissues and cellular types. BjussuMP-I. a SVMP isolated from the Bothrops jararacussu venom, has been characterized as a P-III hemorrhagic metalloprotease. The complete cDNA sequence of BjussuMP-I with 1641bp encodes open reading frames of 547 amino acid residues, which conserve the common domains of P-III high molecular weight hemorrhagic metalloproteases: (i) pre-pro-peptide, (ii) metalloprotease, (iii) disintegrin-like and (iv) rich cysteine domain. BjussuMP-I induced lyses in fibrin clots and inhibited collagen- and ADP-induced platelet aggregation. We are reporting, for the first time, the primary structure of an RGD-P-III class snake venom metalloprotease. A phylogenetic analysis of the BjussuMP-1 metalloprotease/catalytic domain was performed to get new insights into the molecular evolution of the metalloproteases. A theoretical molecular model of this domain was built through folding recognition (threading) techniques and refined by molecular dynamics simulation. Then, the final BjussuMP-I catalytic domain model was compared to other SVMPs and Reprolysin family proteins in order to identify eventual structural differences, which could help to understand the biochemical activities of these enzymes. The presence of large hydrophobic areas and some conserved surface charge-positive residues were identified as important features of the SVMPs and other metalloproteases. (C) 2006 Elsevier B.V. All rights reserved.

Purification, crystallization and preliminary X-ray diffraction analysis of a class P-III metalloproteinase (BmMP-III) from the venom of Bothrops moojeni

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Avaliação do crescimento natural e induzido pelo aparelho extrabucal de thurow modificado em crianças hiperdivergentes com má-oclusão classe II, divisão 1 de angle

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Comparative analysis of the anterior and posterior length and deflection angle of the cranial base, in individuals with facial pattern I, II and III

Objective: This study evaluated the variations in the anterior cranial base (S-N), posterior cranial base (S-Ba) and deflection of the cranial base (SNBa) among three different facial patterns (Pattern I, II and III). Method: A sample of 60 lateral cephalometric radiographs of Brazilian Caucasian patients, both genders, between 8 and 17 years of age was selected. The sample was divided into 3 groups (Pattern I, II and III) of 20 individuals each. The inclusion criteria for each group were the ANB angle, Wits appraisal and the facial profile angle (G’.Sn.Pg’). To compare the mean values obtained from (SNBa, S-N, S-Ba) each group measures, the ANOVA test and Scheffé’s Post-Hoc test were applied. Results and Conclusions: There was no statistically significant difference for the deflection angle of the cranial base among the different facial patterns (Patterns I, II and III). There was no significant difference for the measures of the anterior and posterior cranial base between the facial Patterns I and II. The mean values for S-Ba were lower in facial Pattern III with statistically significant difference. The mean values of S-N in the facial Pattern III were also reduced, but without showing statistically significant difference. This trend of lower values in the cranial base measurements would explain the maxillary deficiency and/or mandibular prognathism features that characterize the facial Pattern III.

Embracing ligands. Synthesis, characterisation and the correlation between 59Co NMR and ligand field parameters of Co(III) complexes with a new class of nitrogen-thioether multidentate ligand

The syntheses of the hexadentate ligands 2,2,10,10-tetra(methyleneamine)-4,8-dithiaundecane (PrN(4)S(2)amp), 2,2,11,11-tetra(methyleneamine)-4,9-dithiadodecane (BuN(4)S(2)amp), and 1,2-bis(4,4-methyleneamine)-2-thiapentyl)benzene (XyN(4)S(2)amp) are reported and the complexes [Co(RN(4)S(2)amp)](3+) (R = Pr, Bu, Xy) characterised by single crystal X-ray study. The low-temperature (11 K) absorption spectra have been measured in Nafion films. From the observed positions of both spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(1g) and (1)A(1g) --> T-3(2g) bands, octahedral ligand-field parameters (10D(q), B and C) have been determined. DFT calculations suggest that significant interaction between the d-d and CT excitations occurs for the complexes. The calculations offer an explanation for the observed deviations from linearity of the relationship between Co-59 magnetogyric ratio and beta(DeltaE)(-1) (beta = the nephelauxetic ratio; DeltaE the energy of the (1)A(1g) --> T-1(1g) transition) for a series of amine and mixed amine/thioether donor complexes.

Investigating high-achieving sixth grade students' erroneous answers on the angle concept in Yozgat

The angle concept is a multifaceted concept having static and dynamic definitions. The static definition of the angle refers to “the space between two rays” or “the intersection of two rays at the same end point” (Mitchelmore & White, 1998), whereas the dynamic definition of the angle concept highlights that the size of angle is the amount of rotation in direction (Fyhn, 2006). Since both definitions represent two diverse situations and have unique limitations (Henderson & Taimina, 2005), students may hold misconceptions about the angle concept. In this regard, the aim of this research was to explore high achievers’ knowledge regarding the definition of the angle concept as well as to investigate their erroneous answers on the angle concept.

104 grade 6 students drawn from four well-established elementary schools of Yozgat, Turkey were participated in this research. All participants were selected via a purposive sampling method and their mathematics grades were 4 or 5 out of 5, and. Data were collected through four questions prepared by considering the learning competencies set out in the grade 6 curriculum in Turkey and the findings of previous studies whose purposes were to identify students’ misconceptions of the angle concept. The findings were analyzed by two researchers, and their inter-rater agreement was calculated as 0.91, or almost perfect. Thereafter, coding discrepancies were resolved, and consensus was established.

The angle concept is a multifaceted concept having static and dynamic definitions.The static definition of the angle refers to “the space between two rays” or“the intersection of two rays at the same end point” (Mitchelmore & White, 1998), whereas the dynamicdefinition of the angle concept highlights that the size of angle is the amountof rotation in direction (Fyhn, 2006). Since both definitionsrepresent two diverse situations and have unique limitations (Henderson & Taimina, 2005), students may holdmisconceptions about the angle concept. In this regard, the aim of thisresearch was to explore high achievers’ knowledge regarding the definition ofthe angle concept as well as to investigate their erroneous answers on theangle concept.

class="MsoNormal" style="text-align:justify;text-indent:0cm;line-height:normal">104grade 6 students drawn from four well-established elementary schools of Yozgat,Turkey were participated in this research. All participants were selected via a purposive sampling method and their mathematics grades were 4 or 5 out of 5,and. Data were collected through four questions prepared by considering the learning competencies set out in the grade 6 curriculum in Turkey and the findings of previous studies whose purposes were to identify students’ misconceptions of the angle concept. The findings were analyzed by two researchers, and their inter-rater agreement was calculated as 0.91, or almost perfect. Thereafter, coding discrepancies were resolved, and consensus was established.

class="MsoNormal" style="text-align:justify;text-indent:0cm;line-height:normal">In the first question, students were asked to answer a multiple choice questions consisting of two statics definitions and one dynamic definition of the angle concept. Only 38 of 104 students were able to recognize these three definitions. Likewise, Mitchelmore and White (1998) investigated that less than10% of grade 4 students knew the dynamic definition of the angle concept. Additionally,the purpose of the second question was to figure out how well students could recognize 0-degree angle. We found that 49 of 104 students were unable to recognize MXW as an angle. While 6 students indicated that the size of MXW is0, other 6 students revealed that the size of MXW is 360. Therefore, 12 of 104students correctly answered this questions. On the other hand, 28 of 104students recognized the MXW angle as 180-degree angle. This finding demonstrated that these students have difficulties in naming the angles.Moreover, the third question consisted of three concentric circles with center O and two radiuses of the outer circle, and the intersection of the radiuses with these circles were named. Then, students were asked to compare the size of AOB, GOD and EOF angles. Only 36 of 104 students answered correctly by indicating that all three angles are equal, whereas 68 of 104 students incorrectly responded this question by revealing AOB<GOD< EOF. These students erroneously thought the size of the angle is related to either the size of the arc marking the angle or the area between the arms of the angle and the arc marking angle. These two erroneous strategies for determining the size of angles have been found by a few studies (Clausen-May,2008; Devichi & Munier, 2013; Kim & Lee, 2014; Mithcelmore, 1998;Wilson & Adams, 1992). The last question, whose aim was to determine how well students can adapt theangle concept to real life, consisted of an observer and a barrier, and students were asked to color the hidden area behind the barrier. Only 2 of 104students correctly responded this question, whereas 19 of 104 students drew rays from the observer to both sides of the barrier, and colored the area covered by the rays, the observer and barrier. While 35 of 104 students just colored behind the barrier without using any strategies, 33 of 104 students constructed two perpendicular lines at the both end of the barrier, and colored behind the barrier. Similarly, Munier, Devinci and Merle (2008) found that this incorrect strategy was used by 27% of students.

class="MsoNormal" style="text-align:justify;text-indent:0cm;line-height:normal">Consequently, we found that although the participants in this study were high achievers, they still held several misconceptions on the angle concept and had difficulties in adapting the angle concept to real life.

class="MsoNormal" style="text-align:justify;text-indent:0cm;line-height:normal">Keywords: the angle concept;misconceptions; erroneous answers; high achievers

class="MsoBibliography" style="text-align:justify;line-height:normal">Clausen-May, T. (2008). AnotherAngle on Angles. Australian Primary Mathematics Classroom, 13(1),4–8.

class="MsoBibliography" style="text-align:justify;line-height:normal">Devichi, C., & Munier, V.(2013). About the concept of angle in elementary school: Misconceptions andteaching sequences. The Journal of Mathematical Behavior, 32(1),1–19. http://doi.org/10.1016/j.jmathb.2012.10.001

class="MsoBibliography" style="text-align:justify;line-height:normal">Fyhn, A. B. (2006). A climbinggirl’s reflections about angles. The Journal of Mathematical Behavior, 25(2),91–102. http://doi.org/10.1016/j.jmathb.2006.02.004

class="MsoBibliography" style="text-align:justify;line-height:normal">Henderson, D. W., & Taimina,D. (2005). Experiencing geometry: Euclidean and non-Euclidean with history(3rd ed.). New York, USA: Prentice Hall.

class="MsoBibliography" style="text-align:justify;line-height:normal">Kim, O.-K., & Lee, J. H.(2014). Representations of Angle and Lesson Organization in Korean and AmericanElementary Mathematics Curriculum Programs. KAERA Research Forum, 1(3),28–37.

class="MsoBibliography" style="text-align:justify;line-height:normal">Mitchelmore, M. C., & White,P. (1998). Development of angle concepts: A framework for research. MathematicsEducation Research Journal, 10(3), 4–27.

class="MsoBibliography" style="text-align:justify;line-height:normal">Mithcelmore, M. C. (1998). Youngstudents’ concepts of turning and angle. Cognition and Instruction, 16(3),265–284.

class="MsoBibliography" style="text-align:justify;line-height:normal">Munier, V., Devichi, C., &Merle, H. (2008). A Physical Situation as a Way to Teach Angle. TeachingChildren Mathematics, 14(7), 402–407.

class="MsoBibliography" style="text-align:justify;line-height:normal">Wilson, P. S., & Adams, V.M. (1992). A Dynamic Way to Teach Angle and Angle Measure. ArithmeticTeacher, 39(5), 6–13.

Differential expression of 12 histone deacetylase (HDAC) genes in astrocytomas and normal brain tissue: class II and IV are hypoexpressed in glioblastomas

Background: Glioblastoma is the most lethal primary malignant brain tumor. Although considerable progress has been made in the treatment of this aggressive tumor, the clinical outcome for patients remains poor. Histone deacetylases (HDACs) are recognized as promising targets for cancer treatment. In the past several years, HDAC inhibitors (HDACis) have been used as radiosensitizers in glioblastoma treatment. However, no study has demonstrated the status of global HDAC expression in gliomas and its possible correlation to the use of HDACis. The purpose of this study was to evaluate and compare mRNA and protein levels of class I, II and IV of HDACs in low grade and high grade astrocytomas and normal brain tissue and to correlate the findings with the malignancy in astrocytomas. Methods: Forty-three microdissected patient tumor samples were evaluated. The histopathologic diagnoses were 20 low-grade gliomas (13 grade I and 7 grade II) and 23 high-grade gliomas (5 grade III and 18 glioblastomas). Eleven normal cerebral tissue samples were also analyzed (54 total samples analyzed). mRNA expression of class I, II, and IV HDACs was studied by quantitative real-time polymerase chain reaction and normalized to the housekeeping gene beta-glucuronidase. Protein levels were evaluated by western blotting. Results: We found that mRNA levels of class II and IV HDACs were downregulated in glioblastomas compared to low-grade astrocytomas and normal brain tissue (7 in 8 genes, p < 0.05). The protein levels of class II HDAC9 were also lower in high-grade astrocytomas than in low-grade astrocytomas and normal brain tissue. Additionally, we found that histone H3 (but not histone H4) was more acetylated in glioblastomas than normal brain tissue. Conclusion: Our study establishes a negative correlation between HDAC gene expression and the glioma grade suggesting that class II and IV HDACs might play an important role in glioma malignancy. Evaluation of histone acetylation levels showed that histone H3 is more acetylated in glioblastomas than normal brain tissue confirming the downregulation of HDAC mRNA in glioblastomas.

Relationship between maxillary and mandibular base lengths and dental crowding in patients with complete Class II malocclusions

Objective: To verify the relationship between maxillary and mandibular effective lengths and dental crowding in patients with Class II malocclusions. Materials and Methods: The sample comprised 80 orthodontic patients with complete Class II malocclusions in the permanent dentition (47 male, 33 female) who were divided into two groups according to the amount of mandibular tooth-arch size discrepancy. The maxillary and mandibular effective lengths (Co-A and Co-Gn) and tooth-arch size discrepancies were measured on the initial cephalograms and dental casts, respectively. Intergroup comparisons of apical base lengths were performed with independent t-tests. Correlation between base length and dental crowding was examined by means of Pearson's correlation coefficient (P < .05). Results: Patients with Class II malocclusion and moderate to severe crowding had significantly smaller maxillary and mandibular effective lengths than subjects with the same malocclusion and slight mandibular crowding. A weak inverse correlation was also found between maxillary and mandibular effective lengths and the severity of dental crowding. Conclusion: Decreased maxillary and mandibular effective lengths constitute an important factor associated with dental crowding in patients with complete Class II malocclusion. (Angle Orthod. 2011;81:217-221.)

Class II Correction with the Cantilever Bite Jumper

Objective: To identify the skeletal, dentoalveolar, and soft tissue changes that occur during Class II correction with the Cantilever Bite Jumper (CBJ). Materials and Methods: This prospective cephalometric study was conducted on 26 subjects with Class II division 1 malocclusion treated with the CBJ appliance. A comparison was made with 26 untreated subjects with Class II malocclusion. Lateral head films from before and after CBJ therapy were analyzed through conventional cephalometric and Johnston analyses. Results: Class II correction was accomplished by means of 2.9 mm apical base change, 1.5 mm distal movement of the maxillary molars, and 1.1 mm mesial movement of the mandibular molars. The CBJ exhibited good control of the vertical dimension. The main side effect of the CBJ is that the vertical force vectors of the telescope act as lever arms and can produce mesial tipping of the mandibular molars. Conclusions: The Cantilever Bite Jumper corrects Class II malocclusions with similar percentages of skeletal and dentoalveolar effects. (Angle Orthod. 2009:79;)

PAR evaluation of treated Class I extraction patients

Objective: To evaluate treatment changes and quality of finishing occlusion in Class I patients treated with four premolar extractions. Material and Methods: Dental casts of 94 subjects (50 males and 44 females) were evaluated. Mean pretreatment age was 13.46 years, and mean treatment time was 2.09 years. The peer assessment rating (PAR) index was obtained from pretreatment and posttreatment dental casts. Results: The mean pretreatment PAR index of 29.46 was reduced to 6.32 at posttreatment stage, achieving a reduction of 78.54% with treatment. There was correlation between the initial PAR and correction during treatment, that is, the more severe the malocclusion the greater the treatment changes. Conclusion: The cases evaluated showed a high-standard orthodontic finishing.

Can metal complexes serve as hypoxia activated prodrugs? Investigations of a Co(III) complex of the MMP inhibitor marimastat

For many years proof that the hypoxic nature of malignant tumours can be used to selectively target anticancer drugs has been sought. Several classes of potential redox activated anticancer drugs have been developed to take advantage of the reducing environment resulting from the hypoxia. Drug complexes with redox active metal centres as carriers have been investigated, but have largely been employed with cytotoxic drugs that require release of the drug intracellularly, complicating the design of such complexes. MMP inhibitors, a new class of anticancer drug, conversely act in the extracellular environment and we have investigated inhibitor complexes with several redox active transition metals. Marimastat is an MMP inhibitor with potent in-vitro antimetastatic activity and was recently in Phase III clinical trials for a variety of cancer types. We have synthesised a Co(II1) complex of marimastat incorporating the tetradentate ligand tpa (tris(2-methylpyridyl)amine) as a carrier ligand. The complex was structurally characterised in the solid state by single crystal X-ray diffraction, the first example of a crystal structure containing marimastat. 2D COSY and NOESY NMR spectra showed that the complex exists in two isomeric forms in solution, corresponding to the cis and trans isomers yet only crystallises in one of these forms. Biological testing of the complex in mice with 4T1.2 tumours showed interesting and unexpected outcomes. Initial results of the tumour growth inhibition study showed that a significant inhibition of growth was exhibited by the complex over the free inhibitor and the control. However, the metastatic potential of both free marimastat and the complex were higher than the control indicating likely problems with the experimental protocol. Further experiments are needed to determine the potential of such complexes as hypoxia activated prodrugs but there appears at least to be some promise.

Metabolic syndrome determinants in an urban population from Brazil: Social class and gender-specific interaction

Introduction: The metabolic syndrome (MS) is characterized by multiple cardiovascular risk factors such as central obesity, arterial hypertension, dislipidemia and hyperinsulinemia and is associated with a higher incidence of cardiovascular events and mortality. The aim of the present work is to describe the prevalence of MS in an urban population from a highly admixed developing country and to characterize the different correlations between this diagnosis, cardiovascular risk factors and demographic variables distributed in this population. Materials and methods: A cross-sectional study of risk factors for cardiovascular diseases was performed in the urban population of Vitoria, Brazil (n= 1507). Major cardiovascular risk factors such as smoking habits, alcohol intake, amount of physical activity, diabetes and hypertension were inquired. Blood biochemical assays were performed by standard techniques in 12 h fasting blood sample and Metabolic Syndrome (MS) was characterizes following the ATP III criteria. Results: The analysis of 1507 individuals showed a 25.43% general prevalence of MS without any significant difference between sexes, but a clear relation of the prevalence with progressing age (p=<0.0001). Even though both sexes showed similar prevalence rates, distribution of risk factors that defined MS was different between men and women, with the prevalence of hypertension, fasting hyperglycemia and hypertriglyceridemia being higher in men. Race was not an important risk factor for MS in this population as opposed to social economic class that was highly associated with the risk of MS in women as their social class was lower, but not in men. Conclusion: This cross-sectional study from a large urban population in Brazil showed a high general prevalence of MS (25.4%), which is increased as the population becomes older (especially in women) and poorer. Although prevalence was very similar in both genders, the frequency of components defining the syndrome varied greatly amongst them. In particular, a significant interaction between gender and social class was observed and may shed light in our understanding of the complex interplay between demographic and biological risk factors for metabolic syndrome. (C) 2007 Elsevier Ireland Ltd. All rights reserved.