A Highly Efficient Solvent-Free Acetalization of Aldehydes to 1,1-Diacetates Catalyzed by SiO2-Pr-SO3H

1,1-Diacetates are prepared in excellent yields from aldehydes and acetic anhydride under solvent-free conditions at room temperature in short reaction times using catalytic amount of sulfonic acid functionalized silica (SiO2-Pr-SO3H) which could be easily handled and removed from the mixture of reaction.Keywords: 1,1-Diacetates, sulfonic acid functionalized silica, acetalization, solvent-free reaction, SiO2-Pr-SO3

Precision bond lengths for Rydberg Matter clusters KN (N = 19, 37, 61 and 91) in excitation levels n = 4 - 8 from rotational radio-frequency emission spectra

Clusters of the electronically excited condensed matter Rydberg Matter (RM) are planar and six-fold symmetric with magic numbers N = 7, 19, 37, 61 and 91. The bond distances in the clusters are known with a precision of +- 5% both from theory and Coulomb explosion experiments. Long series of up to 40 consecutive lines from rotational transitions in such clusters are now observed in emission in the radio-frequency range 7-90 MHz. The clusters are produced in five different vacuum chambers equipped with RM emitters. The most prominent series with B = 0.9292 +- 0.0001 MHz agrees accurately with expectation (within 2%) for the planar six-fold symmetric cluster K19 in excitation level n = 4. Other long series agree even better with K19 at n = 5 and 6. The ratio between the interatomic distance and the theoretical electron orbit radius (the dimensional ratio) for K19 in n = 4 is found to be 2.8470 +- 0.0003. For clusters K19 (n = 6) and K37 (n = 7 and 8) the dimensional ratio 2.90 is the highest value that is found, which happens to be exactly the theoretical value. Clusters K61 and K91 in n = 5 and 6 have slightly lower dimensional ratios. This is expected since the edge effects are smaller. Intensity alternations are observed of approximately 7:3. The nuclear spins interact strongly with the magnetic field from the orbiting electrons. Spin transitions are observed with energy differences corresponding accurately (within 0.6%) to transitions with apparent total (delta)F = -3 at excitation levels n = 5 and 6. The angular momentum coupling schemes in the clusters are complex but well understood.Comment: 37 pages, 14 figure

Quantification of the uterine involution and dimensions, hormonal response and reproductive performance of pyometric and healthy dairy cows treated with Dinoprost

The aim of the present study was to investigate the effects of a PGF2α analogue (Dinoprost) on involution of the puerperal uterus, especially with pyometra during 35 to 45 days postpartum in multiparous high yielding Holstein dairy cows. At days 40 ± 5 postpartum, 1250 cows were ultrasonographically examined. Fifty cows were diagnosed as pyometric. Fifty pyometric and 50 clinically healthy cows were assigned randomly to one of four groups. Groups were: 1.) Pyometric+Dinoprost cows (PD, n = 25 treated with 25 mg of Dinoprost), 2.) Pyometric+Saline cows (PS, n = 25 treated with saline), 3.) Healthy+Dinoprost cows (HD, n = 25 treated with 25 mg of Dinoprost), and 4.) Healthy+Saline cows (HS, n = 25 treated with saline). All treatments were given intramuscularly. Ultrasonography was performed at the time of examination and 7 days later to evaluate changes in uterine diameter. Treatment with Dinoprost significantly reduced gross uterine diameter in PD in comparison to the PS group in the presence or absence (P4 concentrations <1 ng/ml) of an active corpus luteum. Dinoprost treatment did not decrease gross uterine diameter in groups HD and HS. Luminal diameter was significantly smaller in the PD than in the PS group. Pregnancy rate of PD was greater than PS cows (36% vs 20%, respectively). Days to first service (110 d vs. 140 d) and open days (160 d vs. 190 d) were shorter in PD cows than PS cows. It was concluded that injection of 25 mg of Dinoprost to pyometric cows had uterotonic effects in presence or absence of functional corpus luteum. Therefore, this treatment can help uterine involution in puerperal dairy cows affected by pyometra and consequently improved reproductive performance.Keywords: Cattle, Dinoprost, pregnancy rate, pyometra, uterine healt

Synthesis of 1,2-Disubstituted Benzimidazoles in the Presence of SBA-Pr-SO 3 H as a Nano Solid Acid Catalyst

Abstract In this article, simple, convenient synthesis of 2-aryl-1-arylmethyl-1H-1,3-benzimidazole (1,2-disubstituted benzimidazoles) via condensation of 1,2-phenylenediamine and aromatic aldehydes using SBA-Pr-SO 3 H as a nanoporous solid acid catalyst in green protocol was reported. JNS All rights reserve

Zinc deficiency as a codeterminant for airway epithelial barrier dysfunction in an ex vivo model of COPD

There is now convincing evidence that the airway epithelium drives the pathogenesis of COPD. A major aspect of this is the disease-related reduction in barrier function that is potentiated by dysregulation of tight junction (TJ) protein complexes. However, a significant number of studies using in vitro smoke exposure models have not observed alterations in barrier permeability. We have previously shown that zinc (Zn) is an influential cytoprotective factor for the airway epithelium, and its depletion by cigarette smoke produces disease-related modifications consistent with inflammatory changes in COPD. We hypothesized that Zn deficiency is a significant co-stimulus with cigarette smoke extract (CSE) for potentiating the leaky barrier phenotype exhibited in COPD. We employed an ex vivo model of differentiated human airway epithelium exposed to Zn depletion and CSE to determine the contribution of Zn in maintaining normal epithelial permeability. Western blot analysis demonstrated a significant downregulation of the TJ proteins such as ZO-1 (-1.93-fold, P<0.05) and Claudin-1 (-3.37-fold, P<0.01) with the combination exposure. Assessment of barrier function via paracellular ionic conductance and tracer permeability also showed that Zn depletion was an important factor, which potentiated an increase in epithelial permeability (P<0.001 for both) compared to Zn depletion or CSE exposures in isolation. Visual inspection of the epithelium using transmission electron microscopy revealed a marked reduction in junction complexes between the adjacent airway epithelial cells treated with a combination of Zn depletion and CSE. These observations identify Zn deficiency as a significant codeterminant with CSE as a factor leading to an increase in airway epithelial permeability. Hence, as Zn dyshomeostasis has been reported in the airway epithelium exposed to chronic cigarette smoke and inflammation, targeting these phenomena may represent a promising strategy to ameliorate the leaky barrier phenotype that is synonymous with COPD.Eugene Roscioli, Hubertus PA Jersmann, Susan Lester, Arash Badiei, Andrew Fon, Peter Zalewski, Sandra Hodg

Associations of physical activity and quality of life in parapneumonic effusion patients

Introduction Little is known about activity behaviours and quality of life (QoL) of patients with parapneumonic pleural effusions (PPE) after hospital discharge. This study is a secondary analysis of a randomised trial (dexamethasone versus placebo) for hospitalised patients with PPE. We: 1) described the patients’ activity behaviour patterns and QoL measured at discharge and at 30 days post-discharge; and 2) examined the association between activity behaviours and QoL scores. Methods Activity behaviour (7-day accelerometry; Actigraph GT3X+) and QoL (Medical Outcomes Study Short-Form 36) were assessed. Repeated measures analysis of covariance controlling for baseline values and a series of linear regression models were undertaken. Results 36 out of 53 eligible participants completed accelerometry assessments. Despite modest increases in light physical activity (+7.5%) and some domains of QoL ( \u3e 2 points) from discharge to 30 days post-discharge, patients had persistently high levels of sedentary behaviour ( \u3e 65% of waking wear time) and poor QoL ( ⩽ 50 out of 100 points) irrespective of treatment group ( p=0.135–0.903). Increasing moderate-to-vigorous physical activity was associated with higher scores on most QoL domains ( p=0.006–0.037). Linear regression indicates that a clinically important difference of 5 points in physical composite QoL score can be achieved by reallocating 16.1 min·day−1 of sedentary time to moderate-to-vigorous physical activity. Conclusion Patients with PPE had low levels of physical activity and QoL at discharge and 30 days post-discharge irrespective of treatment. Moderate-to-vigorous physical activity participation was associated with higher QoL scores. Increasing moderate-to-vigorous physical activity following discharge from the hospital may be associated with improvements in QoL. © The authors 2023

Effects of unidirectional flow shear stresses on the formation, fractal microstructure and rigidity of incipient whole blood clots and fibrin gels

Incipient clot formation in whole blood and fibrin gels was studied by the rheometric techniques of controlled stress parallel superposition (CSPS) and small amplitude oscillatory shear (SAOS). The effects of unidirectional shear stress on incipient clot microstructure, formation kinetics and elasticity are reported in terms of the fractal dimension (df ) of the fibrin network, the gel network formation time (TGP ) and the shear elastic modulus, respectively. The results of this first haemorheological application of CSPS reveal the marked sensitivity of incipient clot microstructure to physiologically relevant levels of shear stress, these being an order of magnitude lower than have previously been studied by SAOS. CSPS tests revealed that exposure of forming clots to increasing levels of shear stress produces a corresponding elevation in df , consistent with the formation of tighter, more compact clot microstructures under unidirectional flow. A corresponding increase in shear elasticity was recorded. The scaling relationship established between shear elasticity and df for fibrin clots and whole blood confirms the fibrin network as the dominant microstructural component of the incipient clot in terms of its response to imposed stress. Supplementary studies of fibrin clot formation by rheometry and microscopy revealed the substantial additional network mass required to increase df and provide evidence to support the hypothesis that microstructural changes in blood clotted under unidirectional shear may be attributed to flow enhanced thrombin generation and activation. CSPS also identified a threshold value of unidirectional shear stress above which no incipient clot formation could be detected. CSPS was shown to be a valuable haemorheological tool for the study of the effects of physiological and pathological levels of shear on clot properties

The application of large amplitude oscillatory stress in a study of fully formed fibrin clots

The suitability of controlled stress large amplitude oscillatory shear (LAOStress) for the characterisation of the nonlinear viscoelastic properties of fully formed fibrin clots is investigated. Capturing the rich nonlinear viscoelastic behaviour of the fibrin network is important for understanding the structural behaviour of clots formed in blood vessels which are exposed to a wide range of shear stresses. We report, for the first time, that artefacts due to ringing exist in both the sample stress and strain waveforms of a LAOStress measurement which will lead to errors in the calculation of nonlinear viscoelastic properties. The process of smoothing the waveforms eliminates these artefacts whilst retaining essential rheological information. Furthermore, we demonstrate the potential of LAOStress for characterising the nonlinear viscoelastic properties of fibrin clots in response to incremental increases of applied stress up to the point of fracture. Alternating LAOStress and small amplitude oscillatory shear measurements provide detailed information of reversible and irreversible structural changes of the fibrin clot as a consequence of elevated levels of stress. We relate these findings to previous studies involving large scale deformations of fibrin clots. The LAOStress technique may provide useful information to help understand why some blood clots formed in vessels are stable (such as in deep vein thrombosis) and others break off (leading to a life threatening pulmonary embolism)

Abnormal clot microstructure formed in blood containing HIT-like antibodies

IntroductionThrombosis is a severe and frequent complication of heparin-induced thrombocytopenia (HIT). However, there is currently no knowledge of the effects of HIT-like antibodies on the resulting microstructure of the formed clot, despite such information being linked to thrombotic events. We evaluate the effect of the addition of pathogenic HIT-like antibodies to blood on the resulting microstructure of the formed clot.Materials and methodsPathogenic HIT-like antibodies (KKO) and control antibodies (RTO) were added to samples of whole blood containing Unfractionated Heparin and Platelet Factor 4. The formed clot microstructure was investigated by rheological measurements (fractal dimension; df) and scanning electron microscopy (SEM), and platelet activation was measured by flow cytometry.Results and conclusionsOur results revealed striking effects of KKO on clot microstructure. A significant difference in df was found between samples containing KKO (df = 1.80) versus RTO (df = 1.74; p < 0.0001). This increase in df was often associated with an increase in activated platelets. SEM images of the clots formed with KKO showed a network consisting of a highly branched and compact arrangement of thin fibrin fibres, typically found in thrombotic disease. This is the first study to identify significant changes in clot microstructure formed in blood containing HIT-like antibodies. These observed alterations in clot microstructure can be potentially exploited as a much-needed biomarker for the detection, management and monitoring of HIT-associated thrombosis

The phases of deuterium at extreme densities

We consider deuterium compressed to higher than atomic, but lower than nuclear densities. At such densities deuterium is a superconducting quantum liquid. Generically, two superconducting phases compete, a "ferromagnetic" and a "nematic" one. We provide a power counting argument suggesting that the dominant interactions in the deuteron liquid are perturbative (but screened) Coulomb interactions. At very high densities the ground state is determined by very small nuclear interaction effects that probably favor the ferromagnetic phase. At lower densities the symmetry of the theory is effectively enhanced to SU(3), and the quantum liquid enters a novel phase, neither ferromagnetic nor nematic. Our results can serve as a starting point for investigations of the phase dynamics of deuteron liquids, as well as exploration of the stability and dynamics of the rich variety of topological objects that may occur in phases of the deuteron quantum liquid, which range from Alice strings to spin skyrmions to Z_2 vortices.Comment: 9 pages, 6 figures; v2: fixed typo