Measuring the viscoelastic relaxation function of cells with a time-dependent interpretation of the Hertz-Sneddon indentation model.

The Hertz-Sneddon elastic indentation model is widely adopted in the biomechanical investigation of living cells and other soft materials using atomic force microscopy despite the explicit viscoelastic nature of these materials. In this work, we demonstrate that an exact analytical viscoelastic force model for power-law materials, can be interpreted as a time-dependent Hertz-Sneddon-like model. Characterizing fibroblasts (L929) and osteoblasts (OFCOLII) demonstrates the model's accuracy. Our results show that the difference between Young's modulus EY obtained by fitting force curves with the Hertz-Sneddon model and the effective Young's modulus derived from the viscoelastic force model is less than 3%, even when cells are probed at large forces where nonlinear deformation effects become significant. We also propose a measurement protocol that involves probing samples at different indentation speeds and forces, enabling the construction of the average viscoelastic relaxation function of samples by conveniently fitting the force curves with the Hertz-Sneddon model.

Sublinear drag regime at mesoscopic scales in viscoelastic materials.

Stressed soft materials commonly present viscoelastic signatures in the form of power-law or exponential decay. Although exponential responses are the most common, power-law time dependencies arise peculiarly in complex soft materials such as living cells. Understanding the microscale mechanisms that drive rheologic behaviors at the macroscale shall be transformative in fields such as material design and bioengineering. Using an elastic network model of macromolecules immersed in a viscous fluid, we numerically reproduce those characteristic viscoelastic relaxations and show how the microscopic interactions determine the rheologic response. The macromolecules, represented by particles in the network, interact with neighbors through a spring constant k and with fluid through a non-linear drag regime. The dissipative force is given by γvα, where v is the particle's velocity, and γ and α are mesoscopic parameters. Physically, the sublinear regime of the drag forces is related to micro-deformations of the macromolecules, while α ≥ 1 represents rigid cases. We obtain exponential or power-law relaxations or a transitional behavior between them by changing k, γ, and α. We find that exponential decays are indeed the most common behavior. However, power laws may arise when forces between the macromolecules and the fluid are sublinear. Our findings show that in materials not too soft not too elastic, the rheological responses are entirely controlled by α in the sublinear regime. More specifically, power-law responses arise for 0.3 ⪅ α ⪅ 0.45, while exponential responses for small and large values of α, namely, 0.0 ⪅ α ⪅ 0.2 and 0.55 ⪅ α ⪅ 1.0.

Molecular One- and Two-Qubit Systems with Very Long Coherence Times.

General-purpose quantum computation and quantum simulation require multi-qubit architectures with precisely defined, robust interqubit interactions, coupled with local addressability. This is an unsolved challenge, primarily due to scalability issues. These issues often derive from poor control over interqubit interactions. Molecular systems are promising materials for the realization of large-scale quantum architectures, due to their high degree of positionability and the possibility to precisely tailor interqubit interactions. The simplest quantum architecture is the two-qubit system, with which quantum gate operations can be implemented. To be viable, a two-qubit system must possess long coherence times, the interqubit interaction must be well defined and the two qubits must also be addressable individually within the same quantum manipulation sequence. Here results are presented on the investigation of the spin dynamics of chlorinated triphenylmethyl organic radicals, in particular the perchlorotriphenylmethyl (PTM) radical, a mono-functionalized PTM, and a biradical PTM dimer. Extraordinarily long ensemble coherence times up to 148 µs are found at all temperatures below 100 K. Two-qubit and, importantly, individual qubit addressability in the biradical system are demonstrated. These results underline the potential of molecular materials for the development of quantum architectures.

Boron nitride nanotube peapods at ultrasonic velocity impacts: a fully atomistic molecular dynamics investigation.

Boron nitride nanotube peapods (BNNT-peapod) are composed of linear chains of C60molecules encapsulated inside BNNTs, they were first synthesized in 2003. In this work, we investigated the mechanical response and fracture dynamics of BNNT-peapods under ultrasonic velocity impacts (from 1 km s-1up to 6 km s-1) against a solid target. We carried out fully atomistic reactive molecular dynamics simulations using a reactive force field. We have considered the case of horizontal and vertical shootings. Depending on the velocity values, we observed tube bending, tube fracture, and C60ejection. Furthermore, the nanotube unzips for horizontal impacts at certain speeds, forming bi-layer nanoribbons 'incrusted' with C60molecules. The methodology used here is applicable to other nanostructures. We hope it motivates other theoretical investigations on the behavior of nanostructures at ultrasonic velocity impacts and aid in interpreting future experimental results. It should be stressed that similar experiments and simulations were carried out on carbon nanotubes trying to obtain nanodiamonds. The present study expands these investigations to include BNNT.

Stable Organic Radical for Enhancing Metal-Monolayer-Semiconductor Junction Performance.

The preparation of monolayers based on an organic radical and its diamagnetic counterpart has been pursued on hydrogen-terminated silicon surfaces. The functional monolayers have been investigated as solid-state metal/monolayer/semiconductor (MmS) junctions showing a characteristic diode behavior which is tuned by the electronic characteristics of the organic molecule. The eutectic gallium-indium liquid metal is used as a top electrode to perform the transport measurements and the results clearly indicate that the SOMO-SUMO molecular orbitals impact the device performance. The junction incorporating the radical shows an almost two orders of magnitude higher rectification ratio (R(|J1V/J-1V|) = 104.04) in comparison with the nonradical one (R(|J1V/J-1V|) = 102.30). The high stability of the fabricated MmS allows the system to be interrogated under irradiation, evidencing that at the wavelength where the photon energy is close to the band gap of the radical there is a clear enhancement of the photoresponse. This is translated into an increase of the photosensitivity (Sph) value from 68.7 to 269.0 mA/W for the nonradical and radical based systems, respectively.

Accuracy and economic evaluation of screening tests for undiagnosed COPD among hypertensive individuals in Brazil.

In Brazil, prevalence of diagnosed COPD among adults aged 40 years and over is 16% although over 70% of cases remain undiagnosed. Hypertension is common and well-recorded in primary care, and frequently co-exists with COPD because of common causes such as tobacco smoking, therefore we conducted a cross-sectional screening test accuracy study in nine Basic Health Units in Brazil, among hypertensive patients aged ≥40 years to identify the optimum screening test/combinations to detect undiagnosed COPD. We compared six index tests (four screening questionnaires, microspirometer and peak flow) against the reference test defined as those below the lower limit of normal (LLN-GLI) on quality diagnostic spirometry, with confirmed COPD at clinical review. Of 1162 participants, 6.8% (n = 79) had clinically confirmed COPD. Peak flow had a higher specificity but lower sensitivity than microspirometry (sensitivity 44.3% [95% CI 33.1, 55.9], specificity 95.5% [95% CI 94.1, 96.6]). SBQ performed well compared to the other questionnaires (sensitivity 75.9% [95% CI 65.0, 84.9], specificity 59.2% [95% CI 56.2, 62.1]). A strategy requiring both SBQ and peak flow to be positive yielded sensitivity of 39.2% (95% CI 28.4, 50.9) and specificity of 97.0% (95% CI 95.7, 97.9). The use of simple screening tests was feasible within the Brazilian primary care setting. The combination of SBQ and peak flow appeared most efficient, when considering performance of the test, cost and ease of use (costing £1690 (5554 R$) with 26.7 cases detected per 1,000 patients). However, the choice of screening tests depends on the clinical setting and availability of resources.ISRCTN registration number: 11377960.

Domiciliation and sympatry of Triatoma maculata and Rhodnius prolixus, risk of Trypanosoma cruzi transmission in villages of Anzoátegui, Venezuela.

The domiciliation of Triatoma maculata and Rhodnius prolixus and the entomological risk indicators for the transmission of Trypanosoma cruzi, an etiological agent of Chagas Disease-CD, were studied in rural villages of Anzoátegui state, Venezuela. Nightly home visits were made for 4 months/year, for 2 years, to search for and capture triatomines in human settlements. For six of the evaluated villages, 16.4% (11/67) of houses were found with triatomine infestation; obtaining 151 triatomines in all their ontogenetic stages, of which 54.3% (82/151) corresponded to T. maculata and 45.7% (69/151) to R. prolixus. In 7.5% of the evaluated houses, both species were presented in sympatry. Entomological indicators of transmission risk were higher for T. maculata in relation to R. prolixus. Inoculation of fecal flagellates of triatomines produced 2.92 × 105 flagellates/mL of blood in mean and 100% mortality in the murine model. Molecular tests (satellite DNA, kDNA and DTUs studies) demonstrated the presence of T. cruzi, all compatible with TcI. The food source determined by IESPA, revealed that R. prolixus showed less eclecticism in relation to T. maculata in the use of blood sources. This could be an indicator of an older domiciliation with low dispersion between ecotopes. The sympatry of T. maculata and R. prolixus had been recorded in natural niches, but for the first time it is recorded inside the houses in rural villages of the Anzoátegui state. Human dwellings can constitute an adequate niche, with available food sources for both triatomines species and with the risk of establishing AT/CD as zoonosis or zooanthroponosis.

Allocation of Ambipolar Charges on an Organic Diradical with a Vinylene-Phenylenediyne Bridge.

Two redox and magnetically active perchlorotriphenylmethyl (•PTM) radical units have been connected as end-capping groups to a bis(phenylene)diyne chain through vinylene linkers. Negative and positive charged species have been generated, and the influence of the bridge on their stabilization is discussed. Partial reduction of the electron-withdrawing •PTM radicals results in a class-II mixed-valence system with the negative charge located on the terminal PTM units, proving the efficiency of the conjugated chain for the electron transport between the two terminal sites. Counterintuitively, the oxidation process does not occur along the electron-rich bridge but on the vinylene units. The •PTM radicals play a key role in the stabilization of the cationic species, promoting the generation of quinoidal ring segments.

Interaction of Luminescent Defects in Carbon Nanotubes with Covalently Attached Stable Organic Radicals.

The functionalization of single-walled carbon nanotubes (SWCNTs) with luminescent sp3 defects has greatly improved their performance in applications such as quantum light sources and bioimaging. Here, we report the covalent functionalization of purified semiconducting SWCNTs with stable organic radicals (perchlorotriphenylmethyl, PTM) carrying a net spin. This model system allows us to use the near-infrared photoluminescence arising from the defect-localized exciton as a highly sensitive probe for the short-range interaction between the PTM radical and the SWCNT. Our results point toward an increased triplet exciton population due to radical-enhanced intersystem crossing, which could provide access to the elusive triplet manifold in SWCNTs. Furthermore, this simple synthetic route to spin-labeled defects could enable magnetic resonance studies complementary to in vivo fluorescence imaging with functionalized SWCNTs and facilitate the scalable fabrication of spintronic devices with magnetically switchable charge transport.

On the Mechanical Properties of Popgraphene-Based Nanotubes: a Reactive Molecular Dynamics Study.

Carbon-based tubular materials have sparked a great interest in future electronics and optoelectronics device applications. In this work, we computationally studied the mechanical properties of nanotubes generated from popgraphene (PopNTs). Popgraphene is a 2D carbon allotrope composed of 5-8-5 rings. We carried out fully atomistic reactive (ReaxFF) molecular dynamics for PopNTs of different chiralities ( n,0 and 0,n ) and/or diameters and at different temperatures (from 300 up to 1200 K). Results showed that the tubes are thermally stable (at least up to 1200 K). All tubes presented stress/strain curves with a quasi-linear behavior followed by an abrupt drop of stress values. Interestingly, armchair-like PopNTs ( 0,n ) can stand a higher strain load before fracturing when contrasted to the zigzag-like ones ( n,0 ). Moreover, it was obtained that Young's modulus (YMod ) (750-900 GPa) and ultimate strength (σUS ) (120-150 GPa) values are similar to the ones reported for conventional armchair and zigzag carbon nanotubes. YMod values obtained for PopNTs are not significantly temperature-dependent. While the σUS values for the 0,n showed a quasi-linear dependence with the temperature, the n,0 exhibited no clear trends.

Robust principal component analysis for compositional tables.

A data table arranged according to two factors can often be considered a compositional table. An example is the number of unemployed people, split according to gender and age classes. Analyzed as compositions, the relevant information consists of ratios between different cells of such a table. This is particularly useful when analyzing several compositional tables jointly, where the absolute numbers are in very different ranges, e.g. if unemployment data are considered from different countries. Within the framework of the logratio methodology, compositional tables can be decomposed into independent and interactive parts, and orthonormal coordinates can be assigned to these parts. However, these coordinates usually require some prior knowledge about the data, and they are not easy to handle for exploring the relationships between the given factors. Here we propose a special choice of coordinates with direct relation to centered logratio (clr) coefficients, which are particularly useful for an interpretation in terms of the original cells of the tables. With these coordinates, robust principal component analysis (rPCA) is performed for dimension reduction, allowing to investigate relationships between the factors. The link between orthonormal coordinates and clr coefficients enables to apply rPCA, which would otherwise suffer from the singularity of clr coefficients.

Respiratory medicine curriculum in Portuguese family medicine training: A Delphi study.

BACKGROUND: Respiratory diseases (RD) constitute a significant part of the workload of family physicians. There is no consensus on what family doctors should know in this area but established methods for achieving consensus may help to overcome this. OBJECTIVES: The purpose of the study was to obtain a national consensus on the required knowledge and skills in respiratory medicine for family medicine trainees after vocational training. METHODS: A Delphi study was conducted via e-mail with a diverse panel of experts. We developed a Learning Curriculum Framework (LCF) with 399 items adapted from the Royal Australasian College of Physicians - Respiratory Medicine Advanced Training Curriculum. The LCF was submitted to the experts in two rounds for consensus. Consensus was considered for items that had an agreement of 80% in the classifications above 4 on a scale of importance that ranged from 1 (not important) to 5 (very important). RESULTS: Consensus was obtained for 159 items (38.8%). These included structure and function of the respiratory tract (0.6%), presenting problems (21.4%), diagnosis (7.5%), interventions and prevention (11.3%), COPD-emphysema (12.6%), tumours (3.1%), infections (10.7%), tuberculosis (5.7%), HIV (1.3%), thromboembolic disease (2.5%), pleural-pulmonary disease (3.1%), pregnancy (0.6%) and sleep disorders (3.8%). Items on iatrogenic diseases and respiratory research did not reach consensus. CONCLUSIONS: Consensus on the respiratory medicine curriculum may contribute to further development of the vocational training curriculum in Portugal. This approach may help teachers in other countries in Europe to develop curricula for respiratory medicine and other areas of general practice.

Electrocatalytic oxidative Z/E isomerization of a stilbene favoured by the presence of an electroactive persistent radical.

A push-pull-functionalized stilbene has been prepared, with an electroactive perchlorotriphenylmethyl (PTM˙) radical and dimethylamine units as electron-withdrawing and -donating moieties, respectively, showing an electrocatalytic redox-induced Z→E isomerization where the open-shell nature of PTM˙ plays a key role in the isomerization ocurrance.

Selection of Patients for Treatment of Brain Arteriovenous Malformations by the Transvenous Approach: Relationship with Venous Anatomy and Risk of Hemorrhagic Complications.

BACKGROUND AND PURPOSE: Intracranial hemorrhage represents a severe complication of brain arteriovenous malformation treatment. The aim of this cohort was to report the rate of hemorrhagic complications after transvenous endovascular embolization and analyze the potential angioarchitectural risk factors as well as clinical outcomes. MATERIALS AND METHODS: During an 11-year period, 57 patients underwent transvenous endovascular embolization. All cases of hemorrhagic complications were identified. We analyzed the following variables: sex, age, hemorrhagic presentation, Spetzler-Martin grade, size of the AVM before the transvenous treatment, number of venous collectors, pattern of drainage, presence of dilated veins, and technical aspects. Univariate and multivariate multiple regression analyses were performed to evaluate the potential risk factors for procedure-related hemorrhagic complications. RESULTS: Hemorrhagic complications (either intraprocedural or periprocedural) unrelated to a perforation due to micronavigation occurred in 8 (14.0%) procedures. Significant (mRS > 2) and persistent neurologic deficits were present in 2 (3.5%) patients at 6-month control. Larger nidi, especially >3 cm (P = .03), and a larger number of venous collectors have shown a statistically significant correlation with hemorrhagic complications. Only the number of venous collectors was identified as an independent predictor of hemorrhagic complications in the multivariate analysis (OR, 8.7; 95% confidence interval, 2.2-58.2) (P = .006). CONCLUSIONS: Larger nidus sizes and an increased number of venous collectors may increase the risk of hemorrhagic complications when implementing transvenous endovascular treatment of AVMs. The technique is effective and promising, especially with small nidi and single venous collectors.

Exploiting the versatile alkyne-based chemistry for expanding the applications of a stable triphenylmethyl organic radical on surfaces.

The incorporation of terminal alkynes into the chemical structure of persistent organic perchlorotriphenylmethyl (PTM) radicals provides new chemical tools to expand their potential applications. In this work, this is demonstrated by the chemical functionalization of two types of substrates, hydrogenated SiO2-free silicon (Si-H) and gold, and, by exploiting the click chemistry, scarcely used with organic radicals, to synthesise multifunctional systems. On one hand, the one-step functionalization of Si-H allows a light-triggered capacitance switch to be successfully achieved under electrochemical conditions. On the other hand, the click reaction between the alkyne-terminated PTM radical and a ferrocene azide derivative, used here as a model azide system, leads to a multistate electrochemical switch. The successful post-surface modification makes the self-assembled monolayers reported here an appealing platform to synthesise multifunctional systems grafted on surfaces.

Double power-law viscoelastic relaxation of living cells encodes motility trends.

Living cells are constantly exchanging momentum with their surroundings. So far, there is no consensus regarding how cells respond to such external stimuli, although it reveals much about their internal structures, motility as well as the emergence of disorders. Here, we report that twelve cell lines, ranging from healthy fibroblasts to cancer cells, hold a ubiquitous double power-law viscoelastic relaxation compatible with the fractional Kelvin-Voigt viscoelastic model. Atomic Force Microscopy measurements in time domain were employed to determine the mechanical parameters, namely, the fast and slow relaxation exponents, the crossover timescale between power law regimes, and the cell stiffness. These cell-dependent quantities show strong correlation with their collective migration and invasiveness properties. Beyond that, the crossover timescale sets the fastest timescale for cells to perform their biological functions.

COPD: Analysing factors associated with a successful treatment.

OBJECTIVES: To evaluate if non-adherence to inhaled medications, inhalers mishandling or the prescribers' non-adherence to GOLD strategy are associated with mMRC grade, CAT score, COPD acute exacerbations or FEV1%. METHODS: A cross-sectional study on COPD was conducted in the ambulatory pulmonary clinic of Hospital de Guimarães. Patients ≥40 years diagnosed according to GOLD criteria were recruited consecutively. A survey of demographic and clinical data was used. Adherence was assessed by using the Measure of Treatment Adherence (MTA) questionnaire. Inhalation technique was evaluated by using checklists of correct steps and critical errors, and inhalers' misuse was defined when one or more critical errors were made, whatever the number or types of inhalers in use. To evaluate the prescriber non-adherence to GOLD strategy, the patients' current medication was compared with therapeutic standards proposed by the GOLD 2017 strategy for the same ABCD groups. A statistical analysis was performed with IBM SPSS Statistics for Windows, Version 23.0. Armonk, NY: IBM Corp. RESULTS: We studied 303 participants, 79.5% males, mean age=67.5 years. A total of 285 completed the MTA questionnaire. Non-adherence was referred by 47 (16.5%) patients, and a significant negative association was found between adherence and CAT score and FEV1%. 285 patients performed 499 inhalations manoeuvres with 10 different IDs. Inhaler misuse was observed in 113 (39.6%) patients, and was not associated with CAT score, mMRC grade, ECOPD or FEV1%. We found deviations from the GOLD strategy in 133 (44.3%) patients, which were negatively related to CAT score, mMRC grade and ECOPD. CONCLUSIONS: In the present study we failed to prove a positive association between non-adherence to medication, inhalers mishandling or prescribers' non-adherence to GOLD strategy with symptoms, exacerbations and airflow limitation. Conversely, more symptomatic and more obstructed patients were more adherent to medication, previous ECOPD seems to improve prescribers' adherence to treatment guidelines, and symptoms, ECOPD and FEV1% were not significantly associated with inhaler technique.

Stability of radical-functionalized gold surfaces by self-assembly and on-surface chemistry.

We have investigated the radical functionalization of gold surfaces with a derivative of the perchlorotriphenylmethyl (PTM) radical using two methods: by chemisorption from the radical solution and by on-surface chemical derivation from a precursor. We have investigated the obtained self-assembled monolayers by photon-energy dependent X-ray photoelectron spectroscopy. Our results show that the molecules were successfully anchored on the surfaces. We have used a robust method that can be applied to a variety of materials to assess the stability of the functionalized interface. The monolayers are characterized by air and X-ray beam stability unprecedented for films of organic radicals. Over very long X-ray beam exposure we observed a dynamic nature of the radical-Au complex. The results clearly indicate that (mono)layers of PTM radical derivatives have the necessary stability to withstand device applications.

Payload for Contact Inspection Tasks with UAV Systems.

This paper presents a payload designed to perform semi-autonomous contact inspection tasks without any type of positioning system external to the UAV, such as a global navigation satellite system (GNSS) or motion capture system, making possible inspection in challenging GNSS- denied sites. This payload includes two LiDAR sensors which measure the distance between the UAV and the target structure and their inner orientation angle. The system uses this information to control the approaching of the UAV to the structure and the contact between both, actuating over the pitch and yaw signals. This control is performed using a hybrid automaton with different states that represent all the possible UAV status during the inspection tasks. It uses different control strategies in each state. An ultrasonic gauge has been used as the inspection sensor of the payload to measure the thickness of a metallic sheet. The sensor requires a stable contact in order to collect reliable measurements. Several tests have been performed on the system, reaching accurate results which show it is able to maintain a stable contact with the target structure.