Pseudocyclic Arylbenziodoxaboroles as Water-Triggered Aryne Precursors in Reactions with Organic Sulfides.

Pseudocyclic arylbenziodoxaboroles are unique aryne precursors under neutral aqueous conditions that selectively react with organic sulfides, forming the corresponding sulfonium salts. This reaction is compatible with various substituents (alkyl, halogen, CN, NO2, CHO, and cyclopropyl) in the aromatic ring or alkyl group of the sulfide. Similar reactions of sulfoxides afford o-hydroxy-substituted sulfonium salts. The structures of key products were confirmed by X-ray analysis.

Preparation and X-ray Structural Study of Dibenzobromolium and Dibenzochlorolium Derivatives.

Various five-membered cyclic dibenzobromolium salts (dibenzo[b,d]bromol-5-ium chloride, nitrate, hydrogen sulfate, dihydrogen phosphate, trifluoroacetate, and tetrafluoroborate) were prepared by diazotization-cyclization of 2'-bromo-[1,1'-biphenyl]-2-amine in solution of appropriate acids. The chlorolium analogues (iodide, trifluoroacetate, and tetrafluoroborate) were obtained by a similar procedure. Additional dibenzohalolium derivatives (dibenzo[b,d]bromol-5-ium and dibenzo[b,d]chlorol-5-ium azides, bis(trifluoromethanesulfonyl)imidates, thiocyanates, and trifluoromethanesulfonates) were prepared by anion exchange. Structures of ten of these dibenzohalolium derivatives were established by X-ray analysis. Bond distances and angles for the halogen atoms in different dibenzohalolium derivatives were summarized and discussed.

The effective use of adaptogens of various origins on the cattle productivity.

Background: In conditions of industrial animal husbandry, it is necessary to pay attention to the immune system, which regulates metabolic processes in the body of animals. To do this, additives with adaptive properties attract attention. Aim: The aim is to define a way to increase productivity using adaptogens of plant and animal origin in feeding cattle. Methods: In the farms of the Orenburg region and the Republic of Bashkortostan, which differ in climatic conditions, scientific and economic experiments were done on Kazakh white-headed bulls and first-calf cows of black-and-white breed, whose diet was introduced in the form of tinctures (at the rate of 0.01 ml of tincture per 1 kg of body weight), adaptogen may change (for animals of the II experimental group), drone homogenate (experimental group III), and pantocrine (experimental group IV), while the animals of group I were assigned to the control group and did not receive additives. Results: The results of the evaluation of the live weight of bulls by age periods indicate that young animals consuming plant adaptogen exceeded control peers by 18 months of age by 18.60 kg (3.72%); animal origin-by 28.50 kg (5.71%; p < 0.05) and 21.00 kg (4.21%). A similar pattern was observed in cows, in which, against the background of the use of may chang, the milk yield for 305 days of lactation increased by 312 kg (5.61%; p < 0.05), drone homogenate-by 726.1 kg (13.04%; p < 0.001), pantocrine-by 494.4 kg (8.88%; p < 0.001). In all animals participating in the experiment, blood values were within the limits of physiological norms but with a slight increase toward the upper regulatory limits in the experimental samples. There is an improvement in the qualitative composition of the final livestock products. Thus, the indicator of the biological usefulness of beef was higher in samples taken from experimental animals by 0.18-0.36 units (p ≤ 0.05). Conclusion: The most significant nutritional, biological, and energy value was characterized by milk obtained from cows, in whose diet drone homogenate was introduced. Thus, the results of complex studies indicate the effectiveness of introducing adaptogens of both plant and animal nature into the diet. Still, the best effect is obtained from drone homogenate.

Aryl-, Akynyl-, and Alkenylbenziodoxoles: Synthesis and Synthetic Applications.

Hypervalent iodine reagents are in high current demand due to their exceptional reactivity in oxidative transformations, as well as in diverse umpolung functionalization reactions. Cyclic hypervalent iodine compounds, known under the general name of benziodoxoles, possess improved thermal stability and synthetic versatility in comparison with their acyclic analogs. Aryl-, alkenyl-, and alkynylbenziodoxoles have recently received wide synthetic applications as efficient reagents for direct arylation, alkenylation, and alkynylation under mild reaction conditions, including transition metal-free conditions as well as photoredox and transition metal catalysis. Using these reagents, a plethora of valuable, hard-to-reach, and structurally diverse complex products can be synthesized by convenient procedures. The review covers the main aspects of the chemistry of benziodoxole-based aryl-, alkynyl-, and alkenyl- transfer reagents, including preparation and synthetic applications.

Efficient Catalytic Synthesis of Condensed Isoxazole Derivatives via Intramolecular Oxidative Cycloaddition of Aldoximes.

The intramolecular oxidative cycloaddition reaction of alkyne- or alkene-tethered aldoximes was catalyzed efficiently by hypervalent iodine(III) species to afford the corresponding polycyclic isoxazole derivatives in up to a 94% yield. The structure of the prepared products was confirmed by various methods, including X-ray crystallography. Mechanistic study demonstrated the crucial role of hydroxy(aryl)iodonium tosylate as a precatalyst, which is generated from 2-iodobenzoic acid and m-chloroperoxybenzoic acid in the presence of a catalytic amount of p-toluenesulfonic acid.

The effect of an energy additive on the metabolism of cattle.

The objective of this study was to determine the effect of an energy additive on the metabolism of cattle. This article provides information on the analysis of the diet of young cattle calculated for when the animals were both indoors and outdoors. The ration was prepared for 40 heifers, divided into 4 groups consisting of 10 animals in each group. Three of these groups were fed different amounts of a high-energy additive, which was not fed to the control group. The effectiveness of the additive was analyzed according to the balance experiment and by calculating digestibility coefficients. It was determined that the percentage of nitrogen use in young animals was higher in the groups that were fed the additive than in the control group. Increasing the dose of the additive increased the level of nitrogen use. Comparative analysis of live weight indicated intergroup differences in favor of heifers in the groups that were fed the additive of 1.34% to 2.41% at the age of 9 mo; 2.51% to 4.16% at 12 mo; 3.14% to 5.46% at 15 mo; and 3.57% to 6.30% at 18 mo. The average daily growth dynamics indicated a gradual increase in all animals up to 15 mo, with a slight decrease by 18 mo of age. The difference among the groups ranged from 5.08% to 8.85% at 6 to 9 mo of age; 7.08% to 10.79% at 9 to 12 mo; 5.64% to 10.97% at 12 to 15 mo; and 6.05% to 11.11% at 18 mo. It was concluded that feeding the energy additive Tanrem to heifers increased their metabolism so that nitrogen use was improved, and feed was digested more efficiently, which in turn improved the growth of animals. Using an energy additive at the mid-range dose of 500 g a day per animal is recommended, since the effect was similar at the mid-range and maximum dosages.

L'objectif de cette étude était de déterminer l'effet d'un additif énergétique sur le métabolisme des bovins. Cet article fournit des informations sur l'analyse du régime alimentaire des jeunes bovins calculé lorsque les animaux étaient à la fois à l'intérieur et à l'extérieur. La ration a été préparée pour 40 génisses, réparties en quatre groupes constitués de 10 animaux dans chaque groupe. Trois de ces groupes ont reçu différentes quantités d'un additif à haute énergie, qui n'a pas été donné au groupe témoin. L'efficacité de l'additif a été analysée selon l'expérience du bilan et en calculant les coefficients de digestibilité. Il a été déterminé que le pourcentage d'utilisation d'azote chez les jeunes animaux était plus élevé dans les groupes ayant reçu l'additif que dans le groupe témoin. L'augmentation de la dose de l'additif a augmenté le niveau d'utilisation d'azote. L'analyse comparative du poids vif a indiqué des différences intergroupes en faveur des génisses dans les groupes ayant reçu l'additif de 1,34 % à 2,41 % à l'âge de 9 mois; 2,51 % à 4,16 % à 12 mois; 3,14 % à 5,46 % à 15 mois; et 3,57 % à 6,30 % à 18 mois. La dynamique de croissance quotidienne moyenne a indiqué une augmentation graduelle chez tous les animaux jusqu'à 15 mois, avec une légère diminution à l'âge de 18 mois. La différence entre les groupes variait de 5,08 % à 8,85 % à l'âge de 6 à 9 mois; 7,08 % à 10,79 % à 9 à 12 mois; 5,64 % à 10,97 % à 12 à 15 mois; et 6,05 % à 11,11 % à 18 mois. Il a été conclu que l'alimentation de l'additif énergétique Tanrem aux génisses augmentait leur métabolisme, de sorte que l'utilisation de l'azote était améliorée et que les aliments étaient digérés plus efficacement, ce qui à son tour améliorait la croissance des animaux. L'utilisation d'un additif énergétique à la dose moyenne de 500 g par jour par animal est recommandée, car l'effet était similaire aux doses moyenne et maximale.(Traduit par Docteur Serge Messier).

Efficiency of high-carbohydrate fodder in the diets of Holstein cows.

AIM: This study aimed to analyze the efficiency of carbohydrate-enriched rations fed to pasture and stall-housed cows. MATERIALS AND METHODS: Forty Holstein cows were divided into four groups of 10 animals each. The experiment lasted 305 days. All animals were kept under the same conditions, except for the amount of energy-carbohydrate rations fed. The control cows were on a standard diet. Experimental groups 1, 2, and 3 received a ration enriched with energy-carbohydrate components at 250, 500, and 700 g/head/day, respectively. Feed intake was measured on 2 consecutive days each month. During the balance trial, when young animals reached 13 months, feed intake was examined daily. Fodder, its residues, feces, and urine collected during the balance trial were used to determine nutrient digestibility and nitrogen exchange. RESULTS: Nitrogen balance was positive in all experimental animals. Cows in Group 3 made better use of the digested nitrogen. A biochemical blood test showed higher total protein content in the serum of the experimental cows than in the control by 1.47-3.49% (p≤0.05-0.001) in winter and 0.24-0.98% (p≤0.01) in summer. In winter, the serum protein level increased due to changed feeding routines and shorter exercise times, but did not exceed physiological requirements. The alpha- and gammα-globulins levels increased to 0.2-0.5 g/L in winter and 0.3-0.6 g/L in summer, and 0.5-1.4 g/L in winter and 0.1-0.2 g/L in summer, respectively. Beta-globulins decreased. The supplement had a positive effect on milk output, which increased by 67.1-137.3 kg (1.93-3.95%; p≤0.05-0.001) in the first 100 lactation days, then by 198.2-458.8 kg (2.39-5.53%; p≤0.05-0.001) for the remaining days. All animals had a high milk yield coefficient, with the experimental groups having 0.64-2.64% more milk yield than the control. The lactation curves showed that the average daily milk yield of all experimental cows increased, then gradually decreased along the physiological trajectory from the 3rd month until the end of lactation. Milk quality analysis in the experimental groups indicated an increase in the dry matter content by 0.17-0.27% (p≤0.001) in summer and 0.16-0.27% (p≤0.001) in winter; higher protein levels by 0.04-0.06% in summer and 0.03-0.07% (p≤0.05) in winter; increased fat by 0.09-0.14% (p≤0.05-0.001) in summer and 0.09-0.13% (p≤0.05-0.001) in winter; increased density by 0.47-0.61°A (p≤0.05) in summer and 0.17-0.27°A in winter; and increased energy by 1.70-2.63% (p≤0.001) in summer and 1.57-2.54% (p≤0.01-0.001) in winter. CONCLUSION: The energy-carbohydrate feed "Tanrem" can provide the required energy intake of Holstein cows. The maximum biological and economic effect wads attained at 500 g per animal.

Spectra of high energy electron precipitation and atmospheric ionization rates retrieval from balloon measurements.

The bremsstrahlung from high and relativistic energy electron precipitation (HEEP) measured with balloon based instruments provides information on energy spectra and fluence of the precipitating energetic electrons allowing calculations of the atmospheric ionization. HEEP from the outer radiation belt at the subauroral region causes an increase in the ionization rates down to about 20 km altitudes. We study the variability in the ionization rate using the balloon observations of secondary bremsstrahlung initiated by HEEP. For the first time the changes of atmospheric ionization rates on an hourly and minute time scale at different altitudes was retrieved from balloon observations. These new highlights are important for atmospheric electricity that is sensitive to the local condition in the atmosphere including the local ionization rate.

The representation of ionospheric potential in the global chemistry-climate model SOCOL.

In this paper, we present the first results of the ionospheric potential (IP) calculations with the chemistry-climate model (CCM) SOCOL (Solar Climate Ozone Links). For the study, we exploit a parameterization of the difference in electric potential between Earth's surface and lower boundary of the ionosphere as a function of thunderstorm and electrified cloud properties. The model shows a good enough agreement with the IP obtained by balloon soundings. The simulated UT variation of IP exhibits a maximum at 20 Universal time (UT) and minimum at about 2 UT which agree with the UT cycle of the lightning activity. The obtained results allow understanding of IP variability pattern at diurnal, seasonal and annual timescales. We also compare our results with the IP simulated with the climate model INMCM4 using similar IP parameterization. The comparison shows a good agreement of UT cycles especially before 12 UT. Simulated IP annual cycle reaches its maximum in late spring in both models. However, the comparison also reveals some differences in amplitudes of IP variability on different time scales. The large deviations occur after 12 UT for all seasons except summer where the maximum of both results happens before 12 UT. The UT cycle of IP simulated with CCM SOCOL is in a better agreement with observations after 12 UT in terms of phase with similar timing of maximum values. The calculation of IP using climate models can help to fill up the gaps when the observed IP is not available. The interactive calculation of IP is also a step forward in coupling atmospheric and ionospheric processes.

Preparation and X-ray structure of 2-iodoxybenzenesulfonic acid (IBS) - a powerful hypervalent iodine(V) oxidant.

The selective preparation of 2-iodoxybenzenesulfonic acid (IBS, as potassium or sodium salts) by oxidation of sodium 2-iodobenzenesulfonate with Oxone or sodium periodate in water is reported. The single crystal X-ray diffraction analysis reveals a complex polymeric structure consisting of three units of IBS as potassium salt and one unit of 2-iodoxybenzenesulfonic acid linked together by relatively strong I=O···I intermolecular interactions. Furthermore, a new method for the preparation of the reduced form of IBS, 2-iodosylbenzenesulfonic acid, by using periodic acid as an oxidant, has been developed. It has been demonstrated that the oxidation of free 2-iodobenzenesulfonic acid under acidic conditions affords an iodine(III) heterocycle (2-iodosylbenzenesulfonic acid), while the oxidation of sodium 2-iodobenzenesulfonate in neutral aqueous solution gives the iodine(V) products.

Predictors of Intrathoracic Injury after Blunt Torso Trauma in Children Presenting to an Emergency Department as Trauma Activations.

BACKGROUND: Thoracic injuries are a major cause of death associated with blunt trauma in children. Screening for injury with chest x-ray study, compared with chest computed tomography (CT) scan, has been controversial, weighing the benefits of specificity with the detriment of radiation exposure. OBJECTIVE: To identify predictors of thoracic injury in children presenting as trauma activations to a Level I trauma center after blunt torso trauma, and to compare these predictors with those previously reported in the literature. METHODS: We performed a retrospective chart review of pediatric patients (<18 years of age) who presented to the Emergency Department of a Level I trauma center between June 2010 and June 2013 as a trauma activation after sustaining a blunt torso trauma and who received diagnostic imaging of the chest as part of their initial evaluation. RESULTS: Data analysis was performed on 166 patients. There were 33 patients (20%) with 45 abnormalities detected on diagnostic imaging of the chest, with the most common abnormalities being lung contusion (36%), pneumothorax (22%), and rib fracture (13%). Statistically significant predictors of abnormal diagnostic imaging of the chest included Glasgow Coma Scale score (GCS) < 15 (27% with abnormality vs. 13% without abnormality), hypoxia (22% vs. 5%), syncope/loss of consciousness (55% vs. 35%), cervical spine tenderness (12% vs. 3%), thoraco-lumbar-sacral spine tenderness (41% vs. 17%), and abdominal/pelvic tenderness (12% vs. 3%). CONCLUSIONS: Based on our data, predictors of thoracic injury in children after blunt torso trauma include GCS < 15, hypoxia, syncope/dizziness, cervical spine tenderness, thoraco-lumbar-sacral spine tenderness, and abdominal/pelvic tenderness.

Microphysical aerosol parameters from multiwavelength lidar.

The hybrid regularization technique developed at the Institute of Mathematics of Potsdam University (IMP) is used to derive microphysical properties such as effective radius, surface-area concentration, and volume concentration, as well as the single-scattering albedo and a mean complex refractive index, from multiwavelength lidar measurements. We present the continuation of investigations of the IMP method. Theoretical studies of the degree of ill-posedness of the underlying model, simulation results with respect to the analysis of the retrieval error of microphysical particle properties from multiwavelength lidar data, and a comparison of results for different numbers of backscatter and extinction coefficients are presented. Our analysis shows that the backscatter operator has a smaller degree of ill-posedness than the operator for extinction. This fact underlines the importance of backscatter data. Moreover, the degree of ill-posedness increases with increasing particle absorption, i.e., depends on the imaginary part of the refractive index and does not depend significantly on the real part. Furthermore, an extensive simulation study was carried out for logarithmic-normal size distributions with different median radii, mode widths, and real and imaginary parts of refractive indices. The errors of the retrieved particle properties obtained from the inversion of three backscatter (355, 532, and 1064 nm) and two extinction (355 and 532 nm) coefficients were compared with the uncertainties for the case of six backscatter (400, 710, 800 nm, additionally) and the same two extinction coefficients. For known complex refractive index and up to 20% normally distributed noise, we found that the retrieval errors for effective radius, surface-area concentration, and volume concentration stay below approximately 15% in both cases. Simulations were also made with unknown complex refractive index. In that case the integrated parameters stay below approximately 30%, and the imaginary part of the refractive index stays below 35% for input noise up to 10% in both cases. In general, the quality of the retrieved aerosol parameters depends strongly on the imaginary part owing to the degree of ill-posedness. It is shown that under certain constraints a minimum data set of three backscatter coefficients and two extinction coefficients is sufficient for a successful inversion. The IMP algorithm was finally tested for a measurement case.