A systematic literature review of evidence for the use of assistive exoskeletons in defence and security use cases.

Advances in assistive exoskeleton technology, and a boom in related scientific literature, prompted a need to review the potential use of exoskeletons in defence and security. A systematic review examined the evidence for successful augmentation of human performance in activities deemed most relevant to military tasks. Categories of activities were determined a priori through literature scoping and Human Factors workshops with military stakeholders. Workshops identified promising opportunities and risks for integration of exoskeletons into military use cases. The review revealed promising evidence for exoskeletons' capacity to assist with load carriage, manual lifting, and working with tools. However, the review also revealed significant gaps in exoskeleton capabilities and likely performance levels required in the use case scenarios. Consequently, it was recommended that a future roadmap for introducing exoskeletons to military environments requires development of performance criteria for exoskeletons that can be used to implement a human-centred approach to research and development.

We assessed the state-of-the-art for the use of wearable assistive exoskeletons in UK defence and security use cases. A full systematic review of the literature was undertaken, informed by use cases developed in military stakeholder workshops. Clear gaps in exoskeleton capability and use case requirements were identified, leading to recommendations for future work.

Spin density distributions on graphene clusters and ribbons with carbene-like active sites.

Aiming to better understand the reactivity of graphene-based materials, the present work employs density functional theory that provides detailed information about spin-density distributions for single and contiguous pairs of carbene-like active sites. In order to examine the extent to which different models, methodologies, and approximations affect the outcome, our calculations employ the AIMPRO, QuantumEspresso and Gaussian program packages. Models are in the form of polycyclic aromatic hydrocarbons (PAHs) and graphene nanoribbons (GNRs), both isolated and within supercells with periodic boundary conditions. Benchmarking calculations for the phenyl radical and cation are also presented. General agreement is found among the methods and also with previous studies. A significant electron spin polarization (spin density >1.096 electron spin) on the active sites is seen in both periodic and cluster systems, but it tends to be lower for GNRs than graphene clusters. The effect of the functional seems to be much more important than the position of singularities at the edges of the GNRs. Finally, we show the interactions and effects on spin density when a single site lies at the edge of a bilayer GNR, where bonding between layers may occur under specific circumstances.

Predicting experimentally stable allotropes: Instability of penta-graphene.

In recent years, a plethora of theoretical carbon allotropes have been proposed, none of which has been experimentally isolated. We discuss here criteria that should be met for a new phase to be potentially experimentally viable. We take as examples Haeckelites, 2D networks of sp(2)-carbon-containing pentagons and heptagons, and "penta-graphene," consisting of a layer of pentagons constructed from a mixture of sp(2)- and sp(3)-coordinated carbon atoms. In 2D projection appearing as the "Cairo pattern," penta-graphene is elegant and aesthetically pleasing. However, we dispute the author's claims of its potential stability and experimental relevance.

Resonant electronic coupling enabled by small molecules in nanocrystal solids.

The future exploitation of the exceptional properties of nanocrystal (NC) thin films deposited from liquid dispersions of nanoparticles relies upon our ability to produce films with improved electrical properties by simple and inexpensive means. Here, we demonstrate that the electronic conduction of solution-processed NC films can be strongly enhanced without the need of postdeposition treatments, via specific molecules adsorbed at the surfaces of adjacent NCs. This effect is demonstrated for Si NC films doped with the strong molecular oxidizing agent tetrafluoro-tetracyanoquinodimethane (F4-TCNQ). Density functional calculations were carried out with molecule-doped superlattice solid models. It is shown that, when populated by electrons, hybrid molecule/NC states edge (and may actually resonate with) the conduction-band states of the NC solid. This provides extra electronic connectivity across the NC network as the molecules effectively flatten the electronic potential barriers for electron transfer across the otherwise vacuum-filled network interstitialcies.

Increased electronic coupling in silicon nanocrystal networks doped with F4-TCNQ.

The modification of the electronic structure of silicon nanocrystals using an organic dopant, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), is investigated using first-principles calculations. It is shown that physisorbed F4-TCNQ molecules have the effect of oxidizing the nanocrystal, attracting the charge density towards the F4-TCNQ-nanocrystal interface, and decreasing the excitation energy of the system. In periodic F4-TCNQ/nanocrystal superlattices, F4-TCNQ is suggested to enhance exciton separation, and in the presence of free holes, to serve as a bridge for electron/hole transfer between adjacent nanocrystals.

Electronic and optical properties of chlorinated silicon nanoparticles.

First-principles calculations are used to investigate the structure, electronic and optical properties of silicon nanocystals with chlorine-passivated surface. The nanocrystals considered were approximately spherical, with diameters between 1.5 and 3.0 nm. We show that the nanocrystals with chlorinated surface have a smaller bandgap, lower optical absorption threshold, and greater ionization energy and electron affinity than hydrogenated silicon nanocrystals of the same size.

Development of an accelerometer-based multivariate model to predict free-living energy expenditure in a large military cohort.

This study developed a multivariate model to predict free-living energy expenditure (EE) in independent military cohorts. Two hundred and eighty-eight individuals (20.6 ± 3.9 years, 67.9 ± 12.0 kg, 1.71 ± 0.10 m) from 10 cohorts wore accelerometers during observation periods of 7 or 10 days. Accelerometer counts (PAC) were recorded at 1-minute epochs. Total energy expenditure (TEE) and physical activity energy expenditure (PAEE) were derived using the doubly labelled water technique. Data were reduced to n = 155 based on wear-time. Associations between PAC and EE were assessed using allometric modelling. Models were derived using multiple log-linear regression analysis and gender differences assessed using analysis of covariance. In all models PAC, height and body mass were related to TEE (P < 0.01). For models predicting TEE (r (2) = 0.65, SE = 462 kcal · d(-1) (13.0%)), PAC explained 4% of the variance. For models predicting PAEE (r (2) = 0.41, SE = 490 kcal · d(-1) (32.0%)), PAC accounted for 6% of the variance. Accelerometry increases the accuracy of EE estimation in military populations. However, the unique nature of military life means accurate prediction of individual free-living EE is highly dependent on anthropometric measurements.

Physiological responses of Police Officers during job simulations wearing chemical, biological, radiological and nuclear personal protective equipment.

The aim of this study was to quantify the physiological responses of Police Officers wearing chemical, biological, radiological and nuclear personal protective equipment (CBRN PPE) during firearms house entry (FE) unarmed house entry (UE) and crowd control (CC) simulations. Participants volunteered from the UK Police Force [FE (n = 6, age 33 ± 4 years, body mass 85.3 ± 7.9 kg, (·)VO2max 53 ± 5 ml · kg⁻¹ · min⁻¹), UE and CC (n = 11, age 34 ± 5 years, body mass 88.5 ± 13.8 kg, (·)VO2max 51 ± 5 ml · kg⁻¹ · min⁻¹)]. Heart rate reserve (HRR) during FE was greater than UE (74 ± 7 vs. 62 ± 6%HRR, p = 0.01) but lower in CC (39 ± 7%HRR, p < 0.01). Peak core body temperature was greater during FE (39.2 ± 0.3°C) than UE (38.9 ± 0.4°C, p < 0.01) and CC (37.5 ± 0.3°C, p < 0.01), with similar trends in skin temperature. There were no differences in the volume of water consumed (1.13 ± 0.44 l, p = 0.51) or change in body mass (-1.68 ± 0.65 kg, p = 0.74) between simulations. The increase in body temperature was a primary physiological limitation to performance. Cooling strategies and revised operating procedures may improve Police Officers' physical performance while wearing CBRN PPE. PRACTITIONER SUMMARY: In recent years, the likelihood of Police Officers having to respond to a chemical, biological, nuclear or radiological (CBRN) incident wearing personal protective equipment (PPE) has increased. Such apparel is likely to increase physiological strain and impair job performance; understanding these limitations may help improve Officer safety and operational effectiveness.

Accurate rate constants for decomposition of aqueous nitrous acid.

Decomposition of nitrous acid in aqueous solution has been studied by stopped flow spectrophotometry to resolve discrepancies in literature values for the rate constants of the decomposition reactions. Under the conditions employed, the rate-limiting reaction step comprises the hydrolysis of NO(2). A simplified rate law based on the known elementary reaction mechanism provides an excellent fit to the experimental data. The rate constant, 1.34 × 10(-6) M(-1) s(-1), is thought to be of higher accuracy than those in the literature as it does not depend on the rate of parallel reaction pathways or on the rate of interphase mass transfer of gaseous reaction products. The activation energy for the simplified rate law was established to be 107 kJ mol(-1). Quantum chemistry calculations indicate that the majority of the large activation energy results from the endothermic nature of the equilibrium 2HNO(2) ⇆ NO + NO(2) + H(2)O. The rate constant for the reaction between nitrate ions and nitrous acid, which inhibits HNO(2) decomposition, was also determined.

Comparison of the physical demands of single-sex training for male and female recruits in the British Army.

This study compared the physical demands and progression of basic training for male and female British Army recruits in single-sex platoons. Thirty male and 30 female recruits were monitored for energy expenditure (EE) (doubly labeled water), physical activity (3-dimensional accelerometry) and cardiovascular strain (percent heart rate reserve) during 6 weeks over the 14-week course. First time pass rate was similar for male (60%) and female (57%) recruits. Average daily percent heart rate reserve (female 31 +/- 4%; male 32 +/- 5%), physical activity levels (female 2.2 +/- 0.2; male 2.3 +/- 0.2) and percentage improvements in 2.4-km run time (female 10 +/- 4%; male 10 +/- 5%) were similar for both sexes (p > 0.05), although male recruits had 12% higher physical activity counts (p < 0.01). Although the absolute physical demands of basic training were greater for male recruits, the relative cardiovascular strain experienced was similar between sexes.

Aqueous carbonation of peridotites for carbon utilisation: a critical review.

Peridotite and serpentinites can be used to sequester CO2 emissions through mineral carbonation. Olivine dissolution rate is directly proportional with temperature, presence of CO2, surface area of mineral particles and presence of ligands and is inversely proportional to pH. Olivine dissolution is better under air flow and increases seven times when rock-inhibiting fungus (Knufia petricola) is used. Olivine dissolution retards as silica layers form during reaction. Sonication, acoustic and concurrent grinding using various grinding medias have been used to artificially break these silica layers and achieve high magnesium extraction. Wet grinding using 50 wt.% ethanol enhanced CO2 uptake of dunite 6.9 times and CO2 uptake of harzburgite by 4.5 times. The best economical process is single-stage concurrent grinding at 130 bar, 185 °C, 15 wt.% solids and 50 wt.% grinding media (zirconia) using 0.64 M NaHCO3. Ratio of grinding media to feed should not be less than 3:1. Yield increases with temperature, pressure, time of reaction, pH and rpm and using additives and grinding media and reducing particle size. This review aims to investigate the progress from 1970s to 2021 on aqueous mineral carbonation of olivine and its naturally available rocks (harzburgite and dunite). This paper comprehensively reviews all aspects of olivine carbonation including olivine dissolution kinetics, effects of grinding and concurrent grinding, thermal activation of olivine feedstock (dunites and harzburgites) as well as chemistry of olivine mineral carbonation. The effects of different reaction parameters on the carbonation yield, role of mineral carbonation accelerators and costs of mineral carbonation process are discussed.

Low-energy termination of graphene edges via the formation of narrow nanotubes.

We demonstrate that free graphene sheet edges can curl back on themselves, reconstructing as nanotubes. This results in lower formation energies than any other nonfunctionalized edge structure reported to date in the literature. We determine the critical tube size and formation barrier and compare with density functional simulations of other edge terminations including a new reconstructed Klein edge. Simulated high resolution electron microscopy images show why such rolled edges may be difficult to detect. Rolled zigzag edges serve as metallic conduction channels, separated from the neighboring bulk graphene by a chain of insulating sp(3)-carbon atoms, and introduce van Hove singularities into the graphene density of states.

Experimental study of decomposition of aqueous nitrosyl thiocyanate.

This study has examined the kinetics of the decomposition of nitrosyl thiocyanate (ONSCN) by stopped flow UV-vis spectrophotometry, with the reaction products identified and quantified by infrared spectroscopy, membrane inlet mass spectrometry, ion chromatography, and CN(-) ion selective electrode. The reaction results in the formation of nitric oxide and thiocyanogen, the latter decomposing to sulfate and hydrogen cyanide in aqueous solution. The rate of consumption of ONSCN depends strongly on the concentration of SCN(-) ions and is inhibited by nitric oxide. We have developed a reaction mechanism that comprises three parallel pathways for the decomposition of ONSCN. At high thiocyanate concentrations, two reaction pathways operate including a second order reaction to generate NO and (SCN)(2) and a reversible reaction between ONSCN and SCN(-) producing NO and (SCN)(2)(-), with the rate limiting step corresponding to the consumption of (SCN)(2)(-) by reaction with ONSCN. The third reaction pathway, which becomes significant at low thiocyanate concentrations, involves formation of a previously unreported species, ONOSCN, via a reaction between ONSCN and HOSCN, the latter constituting an intermediate in the hydrolysis of (SCN)(2). ONOSCN contributes to the formation of NO via homolysis of the O-NO bond and subsequent dimerization and hydrolysis of OSCN. Fitting the chemical reactions of the model to the experimental measurements, which covered a wide range of reactant concentrations, afforded estimation of all relevant kinetic parameters and provided an excellent match. The reaction mechanism developed in this contribution may be applied to predict the rates of NO formation from ONSCN during the synthesis of azo dyes, the gassing of explosive emulsions, or nitrosation reactions occurring in the human body.

Injuries and injury risk factors among British army infantry soldiers during predeployment training.

PURPOSE: This prospective cohort study examined injuries and injury risk factors in 660 British Army infantry soldiers during a predeployment training cycle. METHODS: Soldiers completed a questionnaire concerning physical characteristics, occupational factors, lifestyle characteristics (including physical training time) and previous injury. Direct measurements included height, body mass, sit-ups, push-ups and run time. Electronic medical records were screened for injuries over a 1-year period before operational deployment. Backward-stepping Cox regression calculated HR and 95% CI to quantify independent injury risk factors. RESULTS: One or more injuries were experienced by 58.5% of soldiers. The new injury diagnosis rate was 88 injuries/100 person-years. Most injuries involved the lower body (71%), especially the lower back (14%), knee (19%) and ankle (15%). Activities associated with injury included sports (22%), physical training (30%) and military training/work (26%). Traumatic injuries accounted for 83% of all injury diagnoses. Independent risk factors for any injury were younger age (17-19 years (HR 1.0), 20-24 years (HR 0.71, 95% CI 0.55 to 0.93), 25-29 years (HR 0.89, 95% CI 0.66 to 1.19) and 30-43 years (HR 0.41, 95% CI 0.27 to 0.63), previous lower limb injury (yes/no HR 1.49, 95% CI 1.19 to 1.87) and previous lower back injury (yes/no HR 1.30, 95% CI 1.03 to 1.63). CONCLUSION: British infantry injury rates were lower than those reported for US infantry (range 101-223 injuries/100 soldier-years), and younger age and previous injury were identified as independent risk factors. Future efforts should target reducing the incidence of traumatic injuries, especially those related to physical training and/or sports.

Health, fitness, and responses to military training of officer cadets in a Gulf Cooperation Council country.

OBJECTIVE: To quantify the health, fitness, and physiological responses to military training of Officer Cadets from a Gulf Cooperation Council country. METHODS: One hundred and nineteen Officer Cadets volunteered; body composition, core body temperature, aerobic fitness, hydration status (urine osmolality), cardiovascular strain, physical activity (3-dimensional accelerometry), and energy expenditure (doubly labelled water) were measured over 5-days of Basic Training (BT), Army Training (AT), Navy Training (NT), and Air Force Training (AFT). RESULTS: There were no differences between courses for body mass index (mean all courses: 24.1 +/- 4.1 kg x m2) or peak core body temperature (mean all courses: 38.1 +/- 0.4 degrees C) (p > 0.05). AT body fat (19.8 +/- 3.6%) and BT VO2 max (36.8 +/- 11.6 mL x kg(-1) x min(-1)) were lower than the other courses (BT, 26.1 +/- 8.1; NT, 26.0 +/- 6.0; AFT, 24.7 +/- 6.1%) and (AT, 44.8 +/- 9.6; NT, 45.0 +/- 7.5; AFT, 44.6 +/- 5.2 mL x kg(-1) x min(-1)), respectively (p < 0.05). NT urine osmolality (979 +/- 90 mOsmol x kg(-1)) was similar to BT (946 +/- 181 mOsmol x kg(-1) p > 0.05) but lower in AT (868 +/- 144 mOsmol x kg(-1), p < 0.05) and AFT (883 +/- 121 mOsmol x kg(-1), p < 0.05). Cardiovascular strain during NT (22 +/- 5% HRR) was lower than other courses (range, 25 +/- 4-29 +/- 3% Heart Rate Reserve) (p < 0.05). Physical activity level during AFT (1.70 +/- 0.18 AU) was lower than other courses (range, 1.86 +/- 0.21-1.92 +/- 0.18 AU) (p > 0.05). CONCLUSION: Positive developments were apparent from BT leading into other courses. Potential exists to increase physical training volume on all courses, which may improve participants' aerobic fitness, body composition, and health.

Development of physical employment standards of specialist paramedic roles in the National Ambulance Resilience Unit (Naru).

AIM: To develop evidence-based role-specific physical employment standards and tests for National Ambulance Resilience Unit (NARU) specialist paramedics. METHODS: Sixty-two (53 men, 9 women) paramedics performed an array of (1) realistic reconstructions of critical job-tasks (criterion job performance); (2) simplified, easily-replicable simulations of those reconstructions and; (3) fitness tests that are portable and/or practicable to administer with limited resources or specialist equipment. Pearson's correlations and ordinary least products regression were used to assess relationships between tasks and tests. Performance on reconstructions, subject-matter expert and participant ratings were combined to derive minimum acceptable job performance levels, which were used to determine cut-scores on appropriate correlated simulations and tests. RESULTS: The majority of performance times were highly correlated with their respective simulations (range of r: 0.73-0.90), with the exception of those replicating water rescue (r range: 0.28-0.47). Regression compatibility intervals provided three cut-scores for each job-task on an appropriate simulation and fitness test. CONCLUSION: This study provides a varied and easily-implementable physical capability assessment for NARU personnel, empirically linked to job performance, with flexible options depending on organisational requirements.

Theoretical study of the ammonia-hypochlorous acid reaction mechanism.

A mechanism for the oxidation of ammonia by hypochlorous acid to form nitrogen gas has been developed at the B3LYP/6-31G(d,p) level of theory using the Gaussian 03 software package. The formation of NH(2)Cl, NHCl(2), and NCl(3) was studied in the gas phase, with explicit water molecules included to examine the transition state energy in aqueous solution. The inclusion of explicit water molecules in the transition state dramatically reduced the reaction barrier in reactions involving transfer of a hydrogen atom between molecules, effects that were not taken into account through use of a solvation model alone. Three mechanisms were identified for the decomposition of chloramine species to form N(2), involving the combination of two chloramine species to form hydrazine, dichlorohydrazine and tetrachlorohydrazine intermediates. The highest barrier in each pathway was found to be the formation of the hydrazine derivative.

Influence of hydration volume and ambient temperature on physiological responses while wearing CBRN protective clothing.

This study examined a low (L; 5 ml/kg per h) and high (H, 10 ml/kg per h) rate of fluid replacement in moderate (18°C) and hot (30°C) conditions on physiological responses while wearing personal protective equipment (PPE). PPE included the gas-tight suit (GTS), the powered respirator protective suit (PRPS) and the civil responder 1 (CR1). Relative to the moderate condition, physiological responses were greater in the hot condition. The percentage change in body mass was different (p < 0.05) between L and H in the hot (L vs. H, GTS: -0.83 vs. -0.38%; PRPS: -1.18 vs. -0.71%; CR1: -1.62 vs. -0.57%) and moderate conditions, although in GTS and CR1 body mass increased (L vs. H, GTS: -0.48 vs. 0.06%; PRPS: -0.66 vs. -0.11%; CR1: -0.18 vs. 0.67%). Fluid replacement strategies for PPE should be adjusted for environmental conditions in order to avoid >1% body mass loss and/or net body mass gain. STATEMENT OF RELEVANCE: Currently, the UK Emergency Services do not have specific evidence-based fluid replacement guidelines to follow when wearing chemical, biological, radiological and/or nuclear (CBRN) PPE. Although ad libitum fluid replacement is encouraged (when breathing apparatus permits), recommendations from evidence-based findings specific to different PPE and to different environmental conditions are lacking. This study provides novel evidence supporting the need to develop fluid replacement strategies during CBRN deployments in both moderate and hot environmental conditions for CBRN PPE.

Gender differences in the physical demands of British Army recruit training.

This study examined gender differences in the physical demands of British Army recruit training in 3 platoons with different gender compositions. Subjects wore heart rate monitors to measure cardiovascular strain and accelerometers to measure physical activity during weeks 1, 6, and 9 of the 12-week program. There was no difference in physical activity between platoons or genders (p > 0.05). In the mixed gender platoon, males operated at a lower cardiovascular strain than females (24 +/- 2 vs. 33 +/- 2% heart rate reserve (HRR), p < 0.001), probably because of their greater aerobic fitness (p < 0.001). Males in the mixed gender platoon experienced lower cardiovascular strain than the male-only platoon (24 +/- 2 vs. 33 +/- 2% HRR, p < 0.001). Females experienced the same degree of cardiovascular strain, irrespective of platoon (33 +/- 2 vs. 33 +/- 3% HRR, p = 0.814). The additional cardiovascular strain experienced by female recruits may increase fatigue and predisposition to overuse musculoskeletal injury.