Parameterizing a tumor humeral prosthesis and development of a set.

BACKGROUND: The reconstruction of the proximal humerus is possible from the resection of the tumor and the placement of a prosthesis. In some cases, they do not meet the anthropometric aspects of the patients. OBJECTIVE: To determine the parameters to size the components of a humeral prosthesis and the development of a set, using design software. METHOD: Forty patients were selected for prostheses, radiographs and CT scans were analyzed and statistical tests were applied to the measurements. RESULTS: The length of the tumors was 8-20 cm. The minimum length of the humerus was 28 cm and 33 cm the maximum. Correlation was observed between the humerus and the tumor and the height of the patient with p = 0.93088 and p = 0.904564, respectively; humerus diameter, p = 0.2345. The set will include three components, diameter 6-10 mm, and length of 24, 26 and 28 cm. Three modular spacers with lengths of 6, 8.5 and 13 cm. Crowns 6.5 and 8.5 cm long, 1.3 cm in diameter and 5 mm nut. CONCLUSION: With the development of the set, poorly calculated resections and adaptation to any humerus size can be resolved.

ANTECEDENTES: La reconstrucción del húmero proximal es posible a partir de la resección del tumor y la colocación de una prótesis. En algunos casos, las prótesis no cumplen con los aspectos antropométricos de los pacientes. OBJETIVO: Determinar los parámetros para dimensionar los componentes de una prótesis de húmero y el desarrollo de un set, mediante software de diseño. MÉTODO: Se seleccionaron 40 pacientes para prótesis, se analizaron radiografías y tomografías computarizadas, y se aplicaron pruebas estadísticas a las mediciones. RESULTADOS: La longitud de los tumores fue de 8-20 cm. La longitud mínima del húmero fue de 28 cm y la máxima fue de 33 cm. Se observó correlación entre el húmero y el tumor y la altura del paciente, con p = 0.93088 y p = 0.904564, respectivamente; para el diámetro del húmero, p = 0.2345. El set incluye tres componentes, con diámetro de 6-10 mm y longitud de 24, 26 y 28 cm; tres espaciadores modulares con longitudes de 6, 8,5 y 13 cm; coronas de 6,5 y 8,5 cm de largo, 1,3 cm de diámetro y tuerca de 5 mm. CONCLUSIÓN: Con el desarrollo del set se pueden resolver resecciones mal calculadas y la adaptación a cualquier tamaño de húmero.

BIMP-Catalyzed 1,3-Prototropic Shift for the Highly Enantioselective Synthesis of Conjugated Cyclohexenones.

A bifunctional iminophosphorane (BIMP)-catalysed enantioselective synthesis of α,ß-unsaturated cyclohexenones through a facially selective 1,3-prototropic shift of ß,γ-unsaturated prochiral isomers, under mild reaction conditions and in short reaction times, on a range of structurally diverse substrates, is reported. α,ß-Unsaturated cyclohexenone products primed for downstream derivatisation were obtained in high yields (up to 99 %) and consistently high enantioselectivity (up to 99 % ee). Computational studies into the reaction mechanism and origins of enantioselectivity, including multivariate linear regression of TS energy, were carried out and the obtained data were found to be in good agreement with experimental findings.

Highly Enantioselective Extraction of Phenylglycine by a Chiral Macrocyclic Receptor Based on Supramolecular Interactions.

Using supramolecular interactions, a novel macrocyclic receptor is able to selectively extract zwitterionic phenylglycine from neutral aqueous solutions into chloroform with up to 91.8% ee. Modeling studies, nuclear magnetic resonance experiments, and X-ray diffraction analysis were carried out to explain the high enantioselectivity observed.

Volumetric measurement of the acetabular cavity in patients with unilateral neglected developmental dysplasia of the dislocated hip operated in a single time.

BACKGROUND: Plain radiography is the most often imaging method used for postoperative assessment of inveterate developmental dysplasia of the hip. This technique does not permit to achieve an accurate diagnose of intra-articular changes, specifically articular congruity. OBJECTIVE: analyze the morphological changes of the acetabular volume by computed tomography, in patients operated by medium adductor myotomy, psoas tenotomy, open hip reduction, diaphysectomy, varus osteotomy and derotating and Dega-type acetabuloplasty. METHOD: A pilot clinical trial was conducted including six patients with unilateral inveterate dysplasia admitted to the Rehabilitation National Institute. Computed tomography were analyzed using an engineering design software. RESULTS: It was found that in all cases analyzed, operated acetabular volume was greater than the contralateral (8 to 48%), however, no significant difference between the volumes was found (p = 2.46). Significant difference between the volume and the age of patients, in multifactorial ANOVA tests (p = 0.006), Cochran's (p = 0.00019) and Kruskal-Wallis (p = 2.925 × 10-8) was found. CONCLUSION: It is clear that the proposed measurement technique is able to identify differences between volumes (operated and contralateral). The clinical monitoring of these patients can validate the results obtained by this measurement technique, and it will serve to estimate the effectiveness of the surgical technique applied in patients.

ANTECEDENTES: El método más utilizado para la evaluación posquirúrgica de la displasia del desarrollo de la cadera inveterada es la radiografía convencional, lo que impide medir con precisión cambios intraarticulares. OBJETIVO: Analizar los cambios morfológicos del volumen acetabular mediante tomografía computarizada en pacientes operados con miotomía de aductor mediano, tenotomía de psoas, reducción abierta de cadera, diafisectomía, osteotomía varizante y desrotadora, y acetabuloplastia tipo Dega. MÉTODO: Se realizó un estudio piloto en el que se analizaron tomografías de seis pacientes del Instituto Nacional de Rehabilitación con displasia inveterada unilateral, por medio de software de diseño para determinar el volumen acetabular. RESULTADOS: Se encontró que el volumen acetabular operado fue mayor que el contralateral (8 vs. 48%), pero no se halló diferencia significativa entre los volúmenes (p = 2.46). Se encontraron diferencias significativas entre los volúmenes y la edad de los pacientes, evaluadas mediante ANOVA multifactorial (p = 0.006), Cochran (p = 2.925 × 10−8) y Kruskal-Wallis (p = 0.00019). CONCLUSIÓN: Es claro que la técnica de medición propuesta permite identificar diferencias entre volúmenes (operado y contralateral). El seguimiento clínico de estos pacientes podrá validar los resultados obtenidos por este método y servirá para poder estimar la eficacia de la técnica quirúrgica aplicada en los pacientes.

Low-Power Highly Robust Resistance-to-Period Converter.

This paper presents a novel structure of Resistance- to-Period (R-T) Converter highly robust to supply and temperature variations. Robustness is achieved by using the ratiometric approach so that complex circuits or high accuracy voltage references are not necessary. To prove the proposed architecture of R-T converter, a prototype was implemented in a 0.18 µ m CMOS process with a single supply voltage of 1.8 V and without any stable reference voltage. Experimental results show a maximum ±1.5% output signal variation for ±10% supply voltage variation and in a 3⁻95 ° C temperature range.

The True Catalyst Revealed: The Intervention of Chiral Ca and Mg Phosphates in Brønsted Acid Promoted Asymmetric Mannich Reactions.

The acetylacetone-benzaldimine Mannich reaction catalyzed by Mg(II) and Ca(II) salts of chiral phosphoric acids (CPA) has been investigated computationally by QM/MM methods. Enantioselectivity in this reaction is both larger than and in the opposite sense to that observed for the same reaction catalyzed by the protic CPA catalyst alone. We present a mechanistic model from which the characteristic differences between these metal and metal-free catalysts, which can coexist in the same reaction mixture, can be understood. Alkaline earth salts with chiral phosphate counterions are found to be more catalytically active than the protic form, and the Ca(II) and Mg(II) CPA salts react via different mechanisms, with a higher coordination number favored by calcium over magnesium. In the well-ordered chiral cavities around these metal centers, asymmetric induction arises from the steric interaction with the imine protecting group in the unfavorable pathway, with both substrates adopting well-defined conformations. These mechanistic models have allowed us to rationalize the stereochemical outcome across a range of bimolecular reactions promoted by divalent metal phosphates formed with different CPAs.

Enantioselectivity in CPA-catalyzed Friedel-Crafts reaction of indole and N-tosylimines: a challenge for guiding models.

Qualitative reaction models or predicting guides are a very useful outcome of theoretical investigations of organocatalytic reaction mechanism that allow forecasting of the degree and sense of the enantioselectivity of reactions involving novel substrates. However, application of these models can be unexpectedly challenging in reactions affected by a large number of conformations and potential control of the enantioselectivity by different reaction steps. The QM/MM study of the Friedel-Crafts reaction between indole and the N-tosylimide of benzaldehyde catalysed by different CPA reveals that the reaction consists of two CPA-assisted steps: the addition of the two reagents to yield a Wheland intermediate, and its re-aromatization. The relevance of the second step depends on the catalyst: it changes the sense of the expected stereoselectivity for a BINOP-derived CPA but is irrelevant in the reaction catalysed by a VAPOL-derived imidodiphosphoric acid catalyst. Although the relative energies of the TSs can be rationalized considering the steric interactions with the catalyst, the possibility of additional H-bonds, or the relative stability of the conformation of the reagents, predicting the enantioselectivity is not possible using qualitative guides.

A cleft type receptor which combines an oxyanion hole with electrostatic interactions.

A receptor for carboxylic acids which combines an oxyanion-hole structure with electrostatic forces has been prepared. X-ray diffraction studies have been carried out to evaluate the geometry of both the free receptor and its associated species with several carboxylic acids and many different arrangements have been discovered for the H-bond pattern in the associated species.

Phosphazene Catalyzed Addition to Electron-Deficient Alkynes: The Importance of Nonlinear Allenyl Intermediates upon Stereoselectivity.

An ONIOM(QM/MM) study on the mechanism of the Michael addition to triple bonds catalyzed by chiral diiminophosphorane catalysts has been performed to understand the stereoselectivity of the product olefin. Our results are consistent with the experimental enantioselectivity, but more importantly, reveal that the Z vs E preference depends on the influence of the catalyst upon the geometry of the allenyl enolate formed in the addition step. These intermediates show an innate preference for a (Z)-configuration, although this can be suppressed by steric interactions due to a catalyst. This leads to two distinct mechanisms in which the kinetic basis for (E) or (Z)-stereoselectivity is determined by a different step. Bifunctional iminophosphorane catalysts are found to use steric interactions to override innate stereoelectronic effects of the allenyl enolate reactive intermediate.

A molecular receptor selective for zwitterionic alanine.

A molecular receptor has been synthesized joining an aza-crown ether with a chiral chromane which mimics the oxyanion hole of the enzymes. With this receptor an apolar host-guest complex with zwitterionic alanine has been achieved through the formation of up to seven H-bonds. This complex allows the extraction of aqueous alanine to a chloroform phase, while other natural amino acids are poorly extracted or are not extracted at all. Due to the chiral nature of the receptor, enantioselective extraction from the aqueous alanine solution to a chloroform phase takes place. X-Ray analysis combined with anisotropic effects, NOE and CD studies revealed the absolute configuration of both strong and weak complexes. Modelling studies also support the proposed structures. The presence of an oxyanion-hole motif in this structure was corroborated by X-ray diffraction studies.

A bio-inspired enantioselective small-molecule artificial receptor for ß adrenergic agonists and antagonists and its application for enantioselective extraction.

Administration of enantiomerically pure ß-adrenergic agonists and antagonists increases their activity and reduces side effects. We report here a small-molecule artificial receptor (SMAR) that, by mimicking the ß-adrenergic receptor, is able to enantioselectively extract commercial ß-adrenergic interacting drugs. The selectivity is justified according to DFT calculations and X-ray diffraction experiments.

A Practical Guide for Predicting the Stereochemistry of Bifunctional Phosphoric Acid Catalyzed Reactions of Imines.

Chiral phosphoric acids have become powerful catalysts for the stereocontrolled synthesis of a diverse array of organic compounds. Since the initial report, the development of phosphoric acids as catalysts has been rapid, demonstrating the tremendous generality of this catalyst system and advancing the use of phosphoric acids to catalyze a broad range of asymmetric transformations ranging from Mannich reactions to hydrogenations through complementary modes of activation. These powerful applications have been developed without a clear mechanistic understanding of the reasons for the high level of stereocontrol. This Account describes investigations into the mechanism of the phosphoric acid catalyzed addition of nucleophiles to imines, focusing on binaphthol-based systems. In many cases, the hydroxyl phosphoric acid can form a hydrogen bond to the imine while the P═O interacts with the nucleophile. The single catalyst, therefore, activates both the electrophile and the nucleophile, while holding both in the chiral pocket created by the binaphthol and constrained by substituents at the 3 and 3' positions. Detailed geometric and energetic information about the transition states can be gained from calculations using ONIOM methods that combine the advantages of DFT with some of the speed of force fields. These high-level calculations give a quantitative account of the selectivity in many cases, but require substantial computational resources. A simple qualitative model is a useful complement to this complex quantitative model. We summarize our calculations into a working model that can readily be sketched by hand and used to work out the likely sense of selectivity for each reaction. The steric demands of the different parts of the reactants determine how they fit into the chiral cavity and which of the competing pathways is favored. The preferred pathway can be found by considering the size of the substituents on the nitrogen and carbon atoms of the imine electrophile, and the position of the nucleophilic site on the nucleophile in relation to the hydrogen-bond which holds it in the catalyst active site. We present a guide to defining the pathway in operation allowing the fast and easy prediction of the stereochemical outcome and provide an overview of the breadth of reactions that can be explained by these models including the latest examples.

QM/MM study on the enantioselectivity of spiroacetalization catalysed by an imidodiphosphoric acid catalyst: how confinement works.

The mechanism for the spiroacetalization of enol-ethers 1 and 2 promoted by chiral phosphoric acid (CPA) catalyst (I) and by chiral imidodiphosphoric acid catalyst (II) has been investigated by QM/MM methods. The computed levels of enantioselectivity following exhaustive conformational analysis is in close agreement with the sense and magnitude of experimental results. Small substrates fit inside catalyst I to yield both enantiomers, in agreement with the absence of asymmetric induction for this reaction, while for catalyst II chiral discrimination between TS structures is possible. Unlike reactions catalysed by CPA or CPA derivatives in which steric effects and substrate distortion controls enantioselectivity, we show that chiral discrimination results from the restricted area and direction of possible hydrogen-bonding interactions with a more confined catalyst structure.

Prevalence of Dirofilaria immitis in dogs from Barcelona: Validation of a geospatial prediction model.

Like other vector borne infections, the distribution of dirofilariosis caused by Dirofilaria immitis is influenced by climatic factors, which regulate the diversity and abundance of mosquito species able to transmit the parasite. Geographical Information Systems (GIS) can predict the distribution and epidemiological behavior of dirofilariosis based on temperature and humidity data. This study analyses the prevalence and current distribution of canine dirofilariosis in the province of Barcelona (Northeastern Spain), and uses a GIS model to evaluate the relationship between the spatial distribution of positive cases and different geo-environmental factors. Canine dirofilariosis is present in all the studied regions but unevenly distributed. The general prevalence is 2.4%, being located most of positive dogs in areas where the model predict both high number of annual generations of D. immitis in vectors and humidity, as a consequence of the presence of irrigated crops or the proximity to the sea. Furthermore, in the urban area of Barcelona, infected dogs were located in districts surrounded or close to parks and green areas. The model can be used as a tool to determine the need of implementation of prophylactic protocols in pets living in municipalities from these regions, based on the geo-environmental characteristics of the area.

Application of matrix-assisted laser desorption and ionization time of flight mass spectrometry to the study of the proteinaceous binders in paint: blue paint composition in the series "The Life of Virgin" by Alonso Cano (17th century) as a case study.

The identification of proteinaceous materials in paint constituents provides very valuable information regarding the techniques used by the painter and the most suitable procedures for conserving and restoring their works. Although the analysis of proteinaceous materials is nowadays a common task when dealing with works of art, the reliable detection and identification of protein traces is still complicated, particularly when very small samples can be taken that may contain a mixture of different organic materials (oils, waxes, resins, gums etc.). We therefore proposed a proteomic approach to investigate protein materials in paintings at trace levels in order to obtain a better understanding of the painter's technique. After trypsin digestion of the paint samples, mass spectra were obtained by matrix-assisted laser desorption and ionization time of flight mass spectrometry (MALDI-TOF-MS) and they were compared with the Mascot database and with theoretical digested proteins. This study contributes to the knowledge about the technique used by Alonso Cano (Granada, Spain, 1601-1667), one of the most original and brilliant artists from the Spanish Golden Age (17th century), in the series called the Life of the Virgin (six paintings), part of the iconographic program about the life of the Virgin Mary, nowadays seen in the main chapel of Granada Cathedral. The objective of the present study was to test the use of proteinaceous material, mainly egg yolk, in the paint used by Cano, as suggested in previous research, although this would have been unusual at that time when most artists used oil paints. Based on the results of the analysis here presented, the use of protein in the binding media can most likely be excluded.

Origins of asymmetric phosphazene organocatalysis: computations reveal a common mechanism for nitro- and phospho-aldol additions.

We report a hybrid density functional theory-molecular mechanics study of the mechanism of the addition of nitroalkanes and phosphonates to benzaldehyde catalyzed by a chiral phosphacene catalyst developed by Ooi and co-workers. Our results are consistent with a reaction mechanism in which a catalyst molecule simultaneously interacts by hydrogen bonds with the nucleophile and the electrophile, transferring a proton to the aldehyde in concert with carbon-carbon bond formation. Despite the C2 symmetry of this class of organocatalyst, substrate recognition, and asymmetric induction in both reaction classes studied relies on interactions with nonequivalent N-H bonds that break symmetry. The origin of the stereo and diastereoselectivity is discussed in terms of steric effects and of the conformations adopted by the reactants, and the most favorable transition structure results from minimal geometric distortion energies. A rational model for predicting the major stereoisomer of reactions catalyzed by this chiral phosphacene, based on the qualitative assessment of steric interactions, is given.

Human subcutaneous/ocular dirofilariasis in the Russian Federation and Belarus, 1997-2013.

OBJECTIVES: This study was performed to determine the yearly frequency, trends in spread, and clinical-epidemiological characteristics of human subcutaneous/ocular dirofilariasis (HSOD) in the Russian Federation and Belarus. METHODS: The surveillance data of HSOD cases occurring between January 1997 and June 2013, obtained from the regional health administrations of the Russian Federation and Belarus, were analyzed. The spatial distribution of cases was assessed using a GIS map, and the clinical-epidemiological characteristics were defined using 719 cases for which information on anatomical location, age, sex, and area of residence was available. The statistical analysis was performed using the Chi-square test. RESULTS: One thousand two hundred and seventy-two clinical cases of HSOD were identified, the majority of them reported in the south-western regions of the Russian Federation. The disease has spread into northern areas, changing its limit from latitude 45°N in 1997 to latitude 61°N in 2013. The statistical analysis of the data showed that the disease is more frequent in the ocular location, in women, in patients aged between 41 and 60 years, and in patients living in urban areas. CONCLUSIONS: Alternative sources to the scientific literature could be necessary to assess the epidemiological situation regarding HSOD in some areas where it has become an emerging condition. There is an urgent need for uniform criteria for reporting and retrieving human cases of dirofilariasis.

An integrated low-power lock-in amplifier and its application to gas detection.

This paper presents a new micropower analog lock-in amplifier (LIA) suitable for battery-operated applications thanks to its reduced size and power consumption as well as its operation with single-supply voltage. The proposed LIA was designed in a 0.18 µm CMOS process with a single supply voltage of 1.8 V. Experimental results show a variable DC gain ranging from 24.7 to 42 dB, power consumption of 417 µW and integration area of 0.013 mm2. The LIA performance was demonstrated by measuring carbon monoxide concentrations as low as 1 ppm in dry N2. The experimental results show that the response to CO of the sensing system can be considerably improved by means of the proposed LIA.

Regional warming and emerging vector-borne zoonotic dirofilariosis in the Russian Federation, Ukraine, and other post-Soviet states from 1981 to 2011 and projection by 2030.

We analyze through a climatic model the influence of regional warming on the geographical spreading and potential risk of infection of human dirofilariosis in Russia, Ukraine, and other post-Soviet states from 1981 to 2011 and estimate the situation by 2030. The model correctly predicts the spatiotemporal location of 97.10% of 2154 clinical cases reported in the area during the studied period, identified by a retrospective review of the literature. There exists also a significant correlation between annual predicted Dirofilaria generations and calculated morbidity. The model states the progressive increase of 14.8% in the potential transmission area, up to latitude 64 °N, and 14.7% in population exposure. By 2030 an increase of 18.5% in transmission area and 10.8% in population exposure is expected. These findings strongly suggest the influence of global warming in both geographical spreading and increase in the number of Dirofilaria generations. The results should alert about the epidemiological behavior of dirofilariosis and other mosquito-borne diseases in these and other countries with similar climatic characteristics.

Intergrative health care method based on combined complementary medical practices: rehabilitative acupuncture, homeopathy and chiropractic.

BACKGROUND: There are various models of health care, such as the epidemiological, psychosocial, sociological, economic, systemic of Neuman, cognitive medicine or ecological, ayurvedic, supraparadigmatic among others. All of them are seeking to combine one or more elements to integrate a model of health care. The article presents a systemic approach to health care with complementary medicines such as rehabilitative acupuncture, homeopathy and chiropractic through the application of a method of holistic care and integrated approach. MATERIALS AND METHODS: There was a participatory action research in January 2012 to January 2013, with a comprehensive approach in 64 patients using the clinical method. We included the environmental aspects, biological, emotional, and behavioral to identify, recognize and integrate the form of manifestation of the disease. Later, it was ordered in a coherent way the etiologic factors, precipitating factors and identified the vulnerability of the patients as well as the structural alterations, classifying them in immediate, mediate and late. Referred to the three disciplines: rehabilitative acupuncture, homeopathy and chiropractic to be seen doing references and against-references between them, evaluating the current state of health and each meeting by noting the clinical and behavioral changes submitted and thus the area of attention to which would be forwarded to continue their treatment. RESULTS: 64 patients rotated by the 3 areas taking an average of 30 meetings with rehabilitative acupuncture, 12 with homeopathy and 10 with chiropractic. The changes were submitted clinical attitudinal, behavioral, clinical and organic. CONCLUSIONS: The model of care was multifaceted and interdisciplinary with a therapeutic approach of individualization and a holistic view to carry out a comprehensive diagnosis and provide quality health care to the population.