Substituent effects on the nitrogen-15 and carbon-13 shieldings of some N-arylguanidinium chlorides

The 13C and 15N chemical shifts of five N-arylguanidinium chlorides carrying polar substituents, ranging in character from 4-methoxy to 4-nitro groups, have been determined by NMR spectroscopy at the natural-abundance level of 13C and 15N in dimethyl sulfoxide solution. Comparison of the 13C shifts of these salts with those of monosubstituted benzenes shows that the guanidinium group induces an average downfield shift of -5.8 ppm of the resonance of the aryl carbon to which it is attached (C1), an average upfield shift of +4.2 ppm for C2 and C6, and a small upfield shift of +1.9 ppm for C4. The shifts of C3 and C5 are small and erratic relative to the corresponding carbons in monosubstituted benzenes. The 15N resonances of the guanidinium nitrogens are quite sensitive to electric effects resulting from substitution of polar groups at C4. The 15N shift of the ==NAr nitrogen relative to that of the salts suggests that the predominant tautomer for N-arylguanidines is (H2N)2C==NAr. The 15N shifts of the (NH2) 2 nitrogens correlate rather well with σp- parameters, whereas the shifts of the -NHAr nitrogens seem to correlate only with R values derived from the σp- substituent constants

Technical note: Design flood under hydrological uncertainty

Planning and verification of hydraulic infrastructures require a design estimate of hydrologic variables, usually provided by frequency analysis, and neglecting hydrologic uncertainty. However, when hydrologic uncertainty is accounted for, the design flood value for a specific return period is no longer a unique value, but is represented by a distribution of values. As a consequence, the design flood is no longer univocally defined, making the design process undetermined. The Uncertainty Compliant Design Flood Estimation (UNCODE) procedure is a novel approach that, starting from a range of possible design flood estimates obtained in uncertain conditions, converges to a single design value. This is obtained through a cost–benefit criterion with additional constraints that is numerically solved in a simulation framework. This paper contributes to promoting a practical use of the UNCODE procedure without resorting to numerical computation. A modified procedure is proposed by using a correction coefficient that modifies the standard (i.e., uncertainty-free) design value on the basis of sample length and return period only. The procedure is robust and parsimonious, as it does not require additional parameters with respect to the traditional uncertainty-free analysis. Simple equations to compute the correction term are provided for a number of probability distributions commonly used to represent the flood frequency curve. The UNCODE procedure, when coupled with this simple correction factor, provides a robust way to manage the hydrologic uncertainty and to go beyond the use of traditional safety factors. With all the other parameters being equal, an increase in the sample length reduces the correction factor, and thus the construction costs, while still keeping the same safety level

Fretting wear of alloy steels at the blade tip of steam turbines

In order to reduce blade resonant vibration amplitude in turbomachinery, blades are assembled with a mutual interlocking at the tip. The aim of this study is to investigate the wear mechanism at the contact interface of the blade shroud in steam turbines. Experimental data are available concerning the wear mechanism at interfaces of aircraft engines blades, while the literature regarding the same effect on steam turbines is less rich. Moreover, the transposition of the results from the aero-engine to the steam turbine is difficult, because materials and working conditions are different. To overcome this lack of knowledge an experimental campaign was set up to investigate this wear mechanism under the specific conditions and with the distinctive materials used in steam turbines. Two base materials (alloy steels) were tested under different conditions: surface treatment (with and without laser quenching), temperature and normal load. Dissipated energies were determined from the hysteresis loops measured during the tests and were correlated to the test conditions. Profiles of worn surfaces were measured, and volume losses were accurately computed with a procedure that takes into account the roughness of the surfaces. Experiments were conducted both at room and low temperature (150 °C). At room temperature the surface temperature increased to 60-70 °C, due to the heat generated in the wear process. Comparison of volume losses at room and low temperature showed that at 150°C the volume losses decreased dramatically. This behavior was explained with a brittle-ductile transition. In other words, the same wear mechanism, adhesion and abrasion respectively in stick and gross slip condition, give very different results for a small softening effect of the material. Moreover, experimental results showed much more sensitive wear rates to the heat treatment than to the steel type

Experimental and numerical investigation of contact parameters in a dovetail type of blade root joints

This paper focuses on the contact characteristics of the blade root joints subjected to the dry friction damping under periodic excitation. The numerical method and experimental procedure are combined to trace the contact behavior in the nonlinear vibration conditions. In experimental procedure, a novel excitation method alongside the accurate measurements is used to determine the frequencies of the blade under different axial loads. In numerical simulations, local behavior of contact areas is investigated using the reduction method as a reliable and fast solver. Subsequently, by using both experimental measurements and numerical outcomes in a developed code, the global stiffness matrix is calculated. This leads to find the normal and tangential stiffness in the contact areas of a dovetail blade root joints. The results indicate that the proposed method can provide an accurate quantitative assessment for investigation the dynamic response of the joints with focusing the contact areas

Mice lacking C1q or C3 show accelerated rejection of minor H disparate skin grafts and resistance to induction of tolerance

Complement activation is known to have deleterious effects on organ transplantation. On the other hand, the complement system is also known to have an important role in regulating immune responses. The balance between these two opposing effects is critical in the context of transplantation. Here, we report that female mice deficient in C1q (C1qa(−/−)) or C3 (C3(−/−)) reject male syngeneic grafts (HY incompatible) at an accelerated rate compared with WT mice. Intranasal HY peptide administration, which induces tolerance to syngeneic male grafts in WT mice, fails to induce tolerance in C1qa(−/−) or C3(−/−) mice. The rejection of the male grafts correlated with the presence of HY D(b)Uty-specific CD8(+) T cells. Consistent with this, peptide-treated C1qa(−/−) and C3(−/−) female mice rejecting male grafts exhibited more antigen-specific CD8(+)IFN-γ(+) and CD8(+)IL-10(+) cells compared with WT females. This suggests that accumulation of IFN-γ- and IL-10-producing T cells may play a key role in mediating the ongoing inflammatory process and graft rejection. Interestingly, within the tolerized male skin grafts of peptide-treated WT mice, IFN-γ, C1q and C3 mRNA levels were higher compared to control female grafts. These results suggest that C1q and C3 facilitate the induction of intranasal tolerance

Unbalanced Langmuir kinetics affects TASEP dynamical transitions: mean-field theory

In a previous study we developed a mean-field theory of dynamical transitions for the totally-asymmetric simple-exclusion process (TASEP) with open boundaries and Langmuir kinetics, in the so-called balanced regime, characterized by equal binding and unbinding rates. Here we show that simply including the possibility of unbalanced rates gives rise to an unexpectedly richer dynamical phase diagram. In particular, the current work predicts an unusual type of dynamical transition, which exhibits certain similarities with first-order phase transitions of equilibrium systems. We also point out that different types of dynamical transition are accompanied by different structural changes in the (mean-field) relaxation spectrum.Comment: 32 pages, 8 figure

C1q acts in the tumour microenvironment as a cancer-promoting factor independently of complement activation

Complement C1q is the activator of the classical pathway. However, it is now recognized that C1q can exert functions unrelated to complement activation. Here we show that C1q, but not C4, is expressed in the stroma and vascular endothelium of several human malignant tumours. Compared with wild-type (WT) or C3- or C5-deficient mice, C1q-deficient (C1qa(-/-)) mice bearing a syngeneic B16 melanoma exhibit a slower tumour growth and prolonged survival. This effect is not attributable to differences in the tumour-infiltrating immune cells. Tumours developing in WT mice display early deposition of C1q, higher vascular density and an increase in the number of lung metastases compared with C1qa(-/-) mice. Bone marrow (BM) chimeras between C1qa(-/-) and WT mice identify non-BM-derived cells as the main local source of C1q that can promote cancer cell adhesion, migration and proliferation. Together these findings support a role for locally synthesized C1q in promoting tumour growth

Nonlinear dynamic analysis of gas turbine combustor leaf seal

The leaf seals are one of the typical sealing systems in gas turbine and jet engines. In Baker Hughes LT family gas turbines, they are used to create sealing between the combustion chamber and the first stage nozzle. The leaf seals are thin metallic plates and subjected to dynamic loads and high temperatures. They have curved contacts, and depending on the inclination, they can experience partial contact. Furthermore, when excited by dynamic loads, the leaf seal can be subject to intermittent contact, possibly triggering wear out or vibratory phenomena. Due to its flexibility and its partial seating, it exhibits a complex nonlinear dynamic behaviour, strongly variable with the operating conditions. This study presents a numerical investigation using coupled static/dynamic harmonic balance method (HBM) frequency-based solution technique. The reported solutions include nonlinear forced response and contact studies for various operating and kinematic conditions along with brief insights

Comparison of contact parameters measured with two different friction rigs for nonlinear dynamic analysis

The accurate measurement of contact interface parameters is of great importance for nonlinear dynamic response computations since there is a lack of predictive capabilities for such input parameters. Several test rigs have been developed at different institutions, and a series of measurements published, but their reliability remains unknown due to a lack of direct comparisons. To somehow address this issue, a Round-Robin test campaign was performed including the high frequency friction rigs of Imperial College London and Politecnico di Torino. Comparable hysteresis loops were recorded on specimen pairs manufactured from the same batch of raw stainless steel, for a wide range of test conditions, including varying normal loads, sliding distances and nominal areas of contact. Measurements from the two rigs were compared to quantify the level of agreement between the two very different experimental setup, showing a reasonably good matching in the results, but also highlighting some differences. Results also demonstrated that loading conditions can strongly affect the contact parameters, and consequently their effect must be included in future nonlinear dynamic simulations for more reliable predictions