37 research outputs found
Analysis of Indirect Measurement of Cutting Forces Turning Metal Cylindrical Shells
Cutting forces measurement is an important component of the ma- chining processes development and control. The use of conventional direct meas- urement systems is often impossible as they interfere in the process’s dynamics. This work proposes a method of cutting force indirect estimation during turning thin-walled cylindrical shells. Calculation of the flexibility matrix has enabled us to relate measured displacements of certain workpiece’s points to the cutting force. An optimization approach for choosing the measurement points location has been proposed, based on the best conditioning of the flexibility matrix
Stereoselective chromium- and molybdenum-mediated transformations of arenes
Tricarbonylchromium-mediated dearomatization provides a rapid access to substituted cyclohexadienes. Efficient asymmetric routes to planar chiral arene complexes and to substituted cyclohexadienes have been developed. The article sums up the main features of this chemistry. Highly enantiomerically enriched ortho-substituted benzaldehyde complexes are accessible via asymmetric lithiation followed by trapping with electrophiles. In different solvents, the trimethylsilyl complex exhibits [alpha] values ranging from −174 to +108 for the same enantiomer. Details of two asymmetric syntheses of natural products are given: the alkaloid lasubine I starting from a highly enantiomerically enriched planar chiral arene complex and the marine furanosesquiterpene acetoxytubipofuran. The latter is assembled via asymmetric dearomatization of a benzaldehyde imine complex. Other key steps include an Eschenmoser-Claisen rearrangement and a regio- and diastereoselective Pd-catalyzed allylic substitution. The final section deals with labile arene metal complexes. For the first time, dearomatization reactions mediated by the Mo(CO)3 group have been realized. The reactions show strong analogies to the Cr(CO)3-mediated reactions, but exhibit also marked differences: the arene-Mo bond is stronger, but more labile, and the sequential double additions show different selectivities compared to the chromium analog
Stereoselective chromium-and molybdenum- mediated transformations of arenes*
Abstract: Tricarbonylchromium-mediated dearomatization provides a rapid access to substituted cyclohexadienes. Efficient asymmetric routes to planar chiral arene complexes and to substituted cyclohexadienes have been developed. The article sums up the main features of this chemistry. Highly enantiomerically enriched ortho-substituted benzaldehyde complexes are accessible via asymmetric lithiation followed by trapping with electrophiles. In different solvents, the trimethylsilyl complex exhibits [α] values ranging from -174 to +108 for the same enantiomer. Details of two asymmetric syntheses of natural products are given: the alkaloid lasubine I starting from a highly enantiomerically enriched planar chiral arene complex and the marine furanosesquiterpene acetoxytubipofuran. The latter is assembled via asymmetric dearomatization of a benzaldehyde imine complex. Other key steps include an Eschenmoser-Claisen rearrangement and a regio-and diastereoselective Pd-catalyzed allylic substitution. The final section deals with labile arene metal complexes. For the first time, dearomatization reactions mediated by the Mo(CO) 3 group have been realized. The reactions show strong analogies to the Cr(CO) 3 -mediated reactions, but exhibit also marked differences: the arene-Mo bond is stronger, but more labile, and the sequential double additions show different selectivities compared to the chromium analogs. The search for ever more efficient chemo-, regio-, and stereoselective routes to complex molecules from simple starting materials is an important task in organic synthesis. Progress in this area continues to advance at a fast pace. Arenes, the subject of this article, are widely available, highly stable, and readily derivatized through reactions such as electrophilic and nucleophilic aromatic substitution [1], ortholithiation followed by reaction with electrophiles [2], or metal-catalyzed substitution and coupling reactions This notwithstanding, the synthesis of complex organic molecules via elegant dearomatization chemistry has undergone intensive investigation. Examples involve the Birch reduction, which achieves *Plenary and invited lectures presented at th
Care of patients with inborn errors of immunity in thirty J Project countries between 2004 and 2021
IntroductionThe J Project (JP) physician education and clinical research collaboration program was started in 2004 and includes by now 32 countries mostly in Eastern and Central Europe (ECE). Until the end of 2021, 344 inborn errors of immunity (IEI)-focused meetings were organized by the JP to raise awareness and facilitate the diagnosis and treatment of patients with IEI.ResultsIn this study, meeting profiles and major diagnostic and treatment parameters were studied. JP center leaders reported patients’ data from 30 countries representing a total population of 506 567 565. Two countries reported patients from JP centers (Konya, Turkey and Cairo University, Egypt). Diagnostic criteria were based on the 2020 update of classification by the IUIS Expert Committee on IEI. The number of JP meetings increased from 6 per year in 2004 and 2005 to 44 and 63 in 2020 and 2021, respectively. The cumulative number of meetings per country varied from 1 to 59 in various countries reflecting partly but not entirely the population of the respective countries. Altogether, 24,879 patients were reported giving an average prevalence of 4.9. Most of the patients had predominantly antibody deficiency (46,32%) followed by patients with combined immunodeficiencies (14.3%). The percentages of patients with bone marrow failure and phenocopies of IEI were less than 1 each. The number of patients was remarkably higher that those reported to the ESID Registry in 13 countries. Immunoglobulin (IgG) substitution was provided to 7,572 patients (5,693 intravenously) and 1,480 patients received hematopoietic stem cell therapy (HSCT). Searching for basic diagnostic parameters revealed the availability of immunochemistry and flow cytometry in 27 and 28 countries, respectively, and targeted gene sequencing and new generation sequencing was available in 21 and 18 countries. The number of IEI centers and experts in the field were 260 and 690, respectively. We found high correlation between the number of IEI centers and patients treated with intravenous IgG (IVIG) (correlation coefficient, cc, 0,916) and with those who were treated with HSCT (cc, 0,905). Similar correlation was found when the number of experts was compared with those treated with HSCT. However, the number of patients treated with subcutaneous Ig (SCIG) only slightly correlated with the number of experts (cc, 0,489) and no correlation was found between the number of centers and patients on SCIG (cc, 0,174).Conclusions1) this is the first study describing major diagnostic and treatment parameters of IEI care in countries of the JP; 2) the data suggest that the JP had tremendous impact on the development of IEI care in ECE; 3) our data help to define major future targets of JP activity in various countries; 4) we suggest that the number of IEI centers and IEI experts closely correlate to the most important treatment parameters; 5) we propose that specialist education among medical professionals plays pivotal role in increasing levels of diagnostics and adequate care of this vulnerable and still highly neglected patient population; 6) this study also provides the basis for further analysis of more specific aspects of IEI care including genetic diagnostics, disease specific prevalence, newborn screening and professional collaboration in JP countries
Feasibility of measuring EDM in spin transparent colliders
A new polarization control mode called a Spin Transparency (ST) mode is currently being actively developed for new rings. The ST mode is an intrinsic feature of figure-8 rings such as the JLEIC at Jefferson Lab. A racetrack collider can be converted to the ST mode by inserting two identical Siberian snakes into its opposite straights as at NICA, JINR. The ST mode allows one to develop a completely new approach to the measurement of the EDMs of both protons and deuterons. The idea of the method is to use the significant enhancement of the EDM signal by the interaction of the EDM with arc magnets, which has an interference effect. A unique feature of this technique is the conceptual capability of measuring the EDM signal in the whole energy range of a ring without introducing additional electric fields using only its magnetic fields. We describe an experimental setup and provide estimates of the limiting EDM values that can be measured at the JLEIC and NICA colliders
New Chromium Carbonyl Catalysts for [6+2] Cycloaddition Reactions
The complexes, (benzene)chromiumdicarbonyl(methyl acrylate) and chromiumdicarbonylbis(cyclohexadiene), are precursors for the highly coordinatively unsaturated chromium dicarbonyl fragment 3, a catalyst for the cycloaddition of activated olefins to cycloheptatriene