18 research outputs found

    Design of innovation in a technical subject

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    Copyright (2009) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in AIP Conf. Proc. 1181, 738 (2009) and may be found at http://dx.doi.org/10.1063/1.3273695.The greatest motivation found in the teaching of the subject Mechanical Technology is the ability to speak to students about manufacturing technologies. The main objective of learning in this subject is a global vision of the manufacturing process, and its optimization in terms of applicability to the real world. The best way for students to learn these concepts is for the teacher to explain them with a more global view aimed at reaching a comprehensive vision with a high degree of detail.Juárez Varón, D.; Peydro, MA.; Reig Pérez, MJ.; Parres, F. (2009). Design of innovation in a technical subject. American Institute of Physics (AIP). doi:10.1063/1.3273695

    Genetic Differentiation in a Sample from Northern Mexico City Detected by HLA System Analysis: Impact in the Study of Population Immunogenetics

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    The major histocompatibility complex is directly involved in the immune response and thus the genes coding for its proteins are useful markers for the study of genetic diversity, susceptibility to disease (autoimmunity and infections), transplant medicine, and pharmacogenetics, among others. The polymorphism of the system also allows researchers to use it as a proxy for population genetics analysis, such as genetic admixture and genetic structure. In order to determine the immunogenetic characteristics of a sample from the northern part of Mexico City and to use them to analyze the genetic differentiation from other admixed populations, including those from previous studies of Mexico City population, we analyzed molecular typing results of donors and patients from the Histocompatibility Laboratory of the Central Blood Bank of the Centro Médico Nacional La Raza selected according to their geographic origin. HLA-A, -B, -DRB1, and -DQB1 alleles were typed by PCR-SSP procedures. Allelic and haplotypic frequencies, as well as population genetics parameters, were obtained by maximum likelihood methods. The most frequent haplotypes found included HLA-A*02/-B*39/- DRB1*04/-DQB1*03:02P; HLA-A*02/-B*35/-DRB1*04/-DQB1*03:02P; HLA-A*68/-B*39/- DRB1*04/-DQB1*03:02P, and HLA-A*02/-B*35/-DRB1*08/-DQB1*04. Important to observe is that the second most frequent haplotype found in our sample (HLA-A*02/-B*35/-DRB1*04/- DQB1*03:02P) has not been previously reported in any mixed ancestry populations from Mexico but it is commonly encountered in Native American human groups, which can be a reflection on the impact of migration dynamics in the genetic conformation of the northern part of Mexico City, and the limitations of previous studies with regard to the genetic diversity of the analyzed groups. Differences found in haplotypic frequencies demonstrated that large urban conglomerates cannot be analyzed as one homogeneous entity, but rather should be understood as a set of structures in which social, political, and economical factors influence their genesis and dynamics

    Impact of opioid-free analgesia on pain severity and patient satisfaction after discharge from surgery: multispecialty, prospective cohort study in 25 countries

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    Background: Balancing opioid stewardship and the need for adequate analgesia following discharge after surgery is challenging. This study aimed to compare the outcomes for patients discharged with opioid versus opioid-free analgesia after common surgical procedures.Methods: This international, multicentre, prospective cohort study collected data from patients undergoing common acute and elective general surgical, urological, gynaecological, and orthopaedic procedures. The primary outcomes were patient-reported time in severe pain measured on a numerical analogue scale from 0 to 100% and patient-reported satisfaction with pain relief during the first week following discharge. Data were collected by in-hospital chart review and patient telephone interview 1 week after discharge.Results: The study recruited 4273 patients from 144 centres in 25 countries; 1311 patients (30.7%) were prescribed opioid analgesia at discharge. Patients reported being in severe pain for 10 (i.q.r. 1-30)% of the first week after discharge and rated satisfaction with analgesia as 90 (i.q.r. 80-100) of 100. After adjustment for confounders, opioid analgesia on discharge was independently associated with increased pain severity (risk ratio 1.52, 95% c.i. 1.31 to 1.76; P < 0.001) and re-presentation to healthcare providers owing to side-effects of medication (OR 2.38, 95% c.i. 1.36 to 4.17; P = 0.004), but not with satisfaction with analgesia (beta coefficient 0.92, 95% c.i. -1.52 to 3.36; P = 0.468) compared with opioid-free analgesia. Although opioid prescribing varied greatly between high-income and low- and middle-income countries, patient-reported outcomes did not.Conclusion: Opioid analgesia prescription on surgical discharge is associated with a higher risk of re-presentation owing to side-effects of medication and increased patient-reported pain, but not with changes in patient-reported satisfaction. Opioid-free discharge analgesia should be adopted routinely

    Influencia de las emociones en el juicio clínico de los profesionales de la salud a propósito del diagnóstico de enfermedad terminal

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    In Spain, the dying process is sometimes described as «bad» or even «awful». There are many reasons for this situation, the most important being the difficulties health care professionals have to face with death and their lack of ability to help and assist patients to go through the dying process. The influence of the current cultural context regarding death and the way people die is paired with other factors. These factors are both clinical and professional in nature such as for example: the moment of diagnosis of a terminally ill patient that entails important emotional implications for the health care professionals, the patient and their family. All these factors have a direct influence on the health care assistance. We conducted Grounded Theory-based, phenomenological, qualitative research using a final sample of 42 indepth interviews with doctors and nurses from different fields in Granada (Spain) in order to understand their point of view, as health care providers, on the assistance given to terminally ill patients. The results were analysed with Atlas-tí software using thematic coding. The results show the effect the emotional factor has on the clinical judgment of health care professionals and support the need for broader and more comprehensive study. KEYWORDS. Emotions. Terminally ill. End of life processes. Health care professionals. Qualitative stud

    Half-Sandwich Ruthenium-Phosphine Complexes with Pentadienyl and Oxo- and Azapentadienyl Ligands

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    Treatment of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> and RuHCl­(PPh<sub>3</sub>)<sub>3</sub> with the tin compound CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>SnMe<sub>3</sub> gives the corresponding acyclic pentadienyl half-sandwich (η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>)­RuX­(PPh<sub>3</sub>)<sub>2</sub> [X = Cl, (<b>2</b>); H, (<b>3</b>)]. The steric congestion in <b>2</b> is most effectively relieved by formation of the cyclometalated complex (η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>)­Ru(C<sub>6</sub>H<sub>4</sub>PPh<sub>2</sub>)­(PPh<sub>3</sub>) (<b>4</b>). Addition of 1 equiv of PHPh<sub>2</sub> to (η<sup>5</sup>-CH<sub>2</sub>CHCHCHCH<sub>2</sub>)­RuCl­(PPh<sub>3</sub>)<sub>2</sub> (<b>1</b>) affords the chiral complex (η<sup>5</sup>-CH<sub>2</sub>CHCHCHCH<sub>2</sub>)­RuCl­(PPh<sub>3</sub>)­(PHPh<sub>2</sub>) (<b>5</b>), while compound (η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>)­RuCl­(PPh<sub>3</sub>)­(PHPh<sub>2</sub>)] (<b>6</b>) is directly obtained from the reaction of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>Sn­(Me)<sub>3</sub> and PHPh<sub>2</sub>. Treatment of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with the corresponding Me<sub>3</sub>SnCH<sub>2</sub>CHCHCHNR (R = Cy, <i>t-</i>Bu) affords (1-3,5-η-CH<sub>2</sub>CHCHCHNCy)­RuCl­(PPh<sub>3</sub>)<sub>2</sub> (<b>7</b>) and [1-3,5-η-CH<sub>2</sub>CHCHCHN­(<i>t</i>-Bu)]RuCl­(PPh<sub>3</sub>)<sub>2</sub> (<b>8</b>). The hydrolysis of <b>7</b>, on a silica gel chromatography column, allows the isolation of RuCl­(η<sup>5</sup>-CH<sub>2</sub>CHCHCHO)­(PPh<sub>3</sub>)<sub>2</sub> (<b>9</b>). The azapentadienyl complex <b>7</b> reacts with 1 equiv of PHPh<sub>2</sub> to afford [1-3,5-η-CH<sub>2</sub>CHCHCHN­(Cy)]­RuCl­(PPh<sub>3</sub>)­(PHPh<sub>2</sub>) (<b>10</b>), while the corresponding product [1-3,5-η-CH<sub>2</sub>CHCHCHN­(<i>t</i>-Bu)]­RuCl­(PPh<sub>3</sub>)­(PHPh<sub>2</sub>) (<b>11</b>) from <b>8</b> is only observed through <sup>1</sup>H and <sup>31</sup>P NMR spectroscopy as a mixture of isomers. Two equivalents of PHPh<sub>2</sub> gives spectroscopic evidence of [η<sup>3</sup>-CH<sub>2</sub>CHCHCHN­(<i>t</i>-Bu)]­RuCl­(PHPh<sub>2</sub>)<sub>3</sub>. A mixture of products [η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­O]­RuCl­(PPh<sub>3</sub>)<sub>2</sub> (<b>12</b>) and [η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­O]­RuH­(PPh<sub>3</sub>)<sub>2</sub> (<b>13</b>) is obtained from reaction of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with Li­[CH<sub>2</sub>C­(Me)­CHC­(Me)­O]. In contrast, the oxopentadienyl compound <b>13</b> is cleanly formed from RuHCl­(PPh<sub>3</sub>)<sub>3</sub> and Li­[CH<sub>2</sub>C­(Me)­CHC­(Me)­O]. An attempt to separate compounds <b>12</b> and <b>13</b> by crystallization gives an orthometalated product [η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­O]­Ru­(C<sub>6</sub>H<sub>4</sub>PPh<sub>2</sub>)­(PPh<sub>3</sub>) (<b>14</b>), which is the oxopentadienyl analogue to <b>4</b>. The bulky [1-3,5-η-CH<sub>2</sub>C­(<i>t</i>-Bu)­CHC­(<i>t</i>-Bu)­O]­RuH­(PPh<sub>3</sub>)<sub>2</sub> (<b>15</b>) analogue to <b>13</b> has also been prepared from RuHCl­(PPh<sub>3</sub>)<sub>3</sub> and Li­[CH<sub>2</sub>C­(<i>t</i>-Bu)­CHC­(<i>t</i>-Bu)­O]. Compounds <b>3</b>, <b>5</b>, <b>6</b>, <b>7</b>, and <b>12</b>–<b>15</b> have been structurally characterized. The preferred heteropentadienyl orientations and the relative positions of the H, Cl, PPh<sub>3</sub>, and PHPh<sub>2</sub> ligands have been established in the piano-stool structures for all compounds, and it can be definitively surmised that the chemistry involved in the heteropentadienyl half-sandwich compounds studied is dominated by steric effects

    Half-Sandwich Ruthenium-Phosphine Complexes with Pentadienyl and Oxo- and Azapentadienyl Ligands

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    Treatment of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> and RuHCl­(PPh<sub>3</sub>)<sub>3</sub> with the tin compound CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>SnMe<sub>3</sub> gives the corresponding acyclic pentadienyl half-sandwich (η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>)­RuX­(PPh<sub>3</sub>)<sub>2</sub> [X = Cl, (<b>2</b>); H, (<b>3</b>)]. The steric congestion in <b>2</b> is most effectively relieved by formation of the cyclometalated complex (η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>)­Ru(C<sub>6</sub>H<sub>4</sub>PPh<sub>2</sub>)­(PPh<sub>3</sub>) (<b>4</b>). Addition of 1 equiv of PHPh<sub>2</sub> to (η<sup>5</sup>-CH<sub>2</sub>CHCHCHCH<sub>2</sub>)­RuCl­(PPh<sub>3</sub>)<sub>2</sub> (<b>1</b>) affords the chiral complex (η<sup>5</sup>-CH<sub>2</sub>CHCHCHCH<sub>2</sub>)­RuCl­(PPh<sub>3</sub>)­(PHPh<sub>2</sub>) (<b>5</b>), while compound (η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>)­RuCl­(PPh<sub>3</sub>)­(PHPh<sub>2</sub>)] (<b>6</b>) is directly obtained from the reaction of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with CH<sub>2</sub>C­(Me)­CHC­(Me)­CH<sub>2</sub>Sn­(Me)<sub>3</sub> and PHPh<sub>2</sub>. Treatment of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with the corresponding Me<sub>3</sub>SnCH<sub>2</sub>CHCHCHNR (R = Cy, <i>t-</i>Bu) affords (1-3,5-η-CH<sub>2</sub>CHCHCHNCy)­RuCl­(PPh<sub>3</sub>)<sub>2</sub> (<b>7</b>) and [1-3,5-η-CH<sub>2</sub>CHCHCHN­(<i>t</i>-Bu)]RuCl­(PPh<sub>3</sub>)<sub>2</sub> (<b>8</b>). The hydrolysis of <b>7</b>, on a silica gel chromatography column, allows the isolation of RuCl­(η<sup>5</sup>-CH<sub>2</sub>CHCHCHO)­(PPh<sub>3</sub>)<sub>2</sub> (<b>9</b>). The azapentadienyl complex <b>7</b> reacts with 1 equiv of PHPh<sub>2</sub> to afford [1-3,5-η-CH<sub>2</sub>CHCHCHN­(Cy)]­RuCl­(PPh<sub>3</sub>)­(PHPh<sub>2</sub>) (<b>10</b>), while the corresponding product [1-3,5-η-CH<sub>2</sub>CHCHCHN­(<i>t</i>-Bu)]­RuCl­(PPh<sub>3</sub>)­(PHPh<sub>2</sub>) (<b>11</b>) from <b>8</b> is only observed through <sup>1</sup>H and <sup>31</sup>P NMR spectroscopy as a mixture of isomers. Two equivalents of PHPh<sub>2</sub> gives spectroscopic evidence of [η<sup>3</sup>-CH<sub>2</sub>CHCHCHN­(<i>t</i>-Bu)]­RuCl­(PHPh<sub>2</sub>)<sub>3</sub>. A mixture of products [η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­O]­RuCl­(PPh<sub>3</sub>)<sub>2</sub> (<b>12</b>) and [η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­O]­RuH­(PPh<sub>3</sub>)<sub>2</sub> (<b>13</b>) is obtained from reaction of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with Li­[CH<sub>2</sub>C­(Me)­CHC­(Me)­O]. In contrast, the oxopentadienyl compound <b>13</b> is cleanly formed from RuHCl­(PPh<sub>3</sub>)<sub>3</sub> and Li­[CH<sub>2</sub>C­(Me)­CHC­(Me)­O]. An attempt to separate compounds <b>12</b> and <b>13</b> by crystallization gives an orthometalated product [η<sup>5</sup>-CH<sub>2</sub>C­(Me)­CHC­(Me)­O]­Ru­(C<sub>6</sub>H<sub>4</sub>PPh<sub>2</sub>)­(PPh<sub>3</sub>) (<b>14</b>), which is the oxopentadienyl analogue to <b>4</b>. The bulky [1-3,5-η-CH<sub>2</sub>C­(<i>t</i>-Bu)­CHC­(<i>t</i>-Bu)­O]­RuH­(PPh<sub>3</sub>)<sub>2</sub> (<b>15</b>) analogue to <b>13</b> has also been prepared from RuHCl­(PPh<sub>3</sub>)<sub>3</sub> and Li­[CH<sub>2</sub>C­(<i>t</i>-Bu)­CHC­(<i>t</i>-Bu)­O]. Compounds <b>3</b>, <b>5</b>, <b>6</b>, <b>7</b>, and <b>12</b>–<b>15</b> have been structurally characterized. The preferred heteropentadienyl orientations and the relative positions of the H, Cl, PPh<sub>3</sub>, and PHPh<sub>2</sub> ligands have been established in the piano-stool structures for all compounds, and it can be definitively surmised that the chemistry involved in the heteropentadienyl half-sandwich compounds studied is dominated by steric effects

    QSAR Models for P-450 (2D6) Substrate Activity

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    Halogen compounds are capable of playing an important role in the manipulation of nanoparticle shapes and properties. In a new approach, we examined the shape evolution of CdSe nanorods to hexagonal pyramids in a hot-injection synthesis under the influence of halogenated additives in the form of organic chlorine, bromine and iodine compounds. Supported by density functional theory calculations, this shape evolution is explained as a result of X-type ligand coordination to sloped and flat Cd-rich facets and an equilibrium shape strongly influenced by halides. Synchrotron XPS measurements and TXRF results show that the shape evolution is accompanied by a modification in the chemical composition of the ligand sphere. Our experimental results suggest that the molecular structure of the halogenated compound is related to the degree of the effect on both rod growth and further shape evolution. This presents a new degree of freedom in nanoparticle shape control and highlights the role of additives in nanoparticle synthesis and their possible in situ formation of ligands

    Line-Focused Optical Excitation of Parallel Acoustic Focused Sample Streams for High Volumetric and Analytical Rate Flow Cytometry

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    Flow cytometry provides highly sensitive multiparameter analysis of cells and particles but has been largely limited to the use of a single focused sample stream. This limits the analytical rate to ∼50K particles/s and the volumetric rate to ∼250 μL/min. Despite the analytical prowess of flow cytometry, there are applications where these rates are insufficient, such as rare cell analysis in high cellular backgrounds (e.g., circulating tumor cells and fetal cells in maternal blood), detection of cells/particles in large dilute samples (e.g., water quality, urine analysis), or high-throughput screening applications. Here we report a highly parallel acoustic flow cytometer that uses an acoustic standing wave to focus particles into 16 parallel analysis points across a 2.3 mm wide optical flow cell. A line-focused laser and wide-field collection optics are used to excite and collect the fluorescence emission of these parallel streams onto a high-speed camera for analysis. With this instrument format and fluorescent microsphere standards, we obtain analysis rates of 100K/s and flow rates of 10 mL/min, while maintaining optical performance comparable to that of a commercial flow cytometer. The results with our initial prototype instrument demonstrate that the integration of key parallelizable components, including the line-focused laser, particle focusing using multinode acoustic standing waves, and a spatially arrayed detector, can increase analytical and volumetric throughputs by orders of magnitude in a compact, simple, and cost-effective platform. Such instruments will be of great value to applications in need of high-throughput yet sensitive flow cytometry analysis
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