Racial differences in serological markers across the first year of injury in spinal cord injury: a retrospective analysis of a multi-center interventional study.

STUDY DESIGN: Secondary analysis of a randomized, multi-center, placebo-controlled study(Sygen®). OBJECTIVES: To evaluate racial differences in serological markers in individuals with spinal cord injury(SCI) across the first year of injury. SETTING: Hospitals in North America. METHODS: Serological markers (e.g.,cell count, liver, kidney, and pancreatic function, metabolism, and muscle damage) were assessed among 316 participants (247 White, 69 Black) at admission, weeks 1, 2, 4, 8, and 52 post-injury. Linear mixed models were employed to explore the main effects of time, race (Black vs. White), and their interaction, with adjustment of covariates such as study center, polytrauma, injury (level, completeness), treatment group, and sex. RESULTS: A main effect of race was observed where White individuals had higher alanine transaminase, blood urea nitrogen(BUN), BUN/Creatinine ratio, sodium, and chloride, while Black individuals had higher calcium, total serum protein, and platelets. For markers with interaction effects, post-hoc comparisons showed that at week 52, White individuals had higher mature neutrophils, hematocrit, hemoglobin, mean corpuscular hemoglobin, albumin, and triglycerides, and Black individuals had higher amylase. Eosinophils, monocytes, red blood cells, aspartate aminotransferase, bilirubin, cholesterol, partial thromboplastin time, urine specific gravity, urine pH, CO2, and inorganic phosphorus did not differ between races. CONCLUSIONS: Our results revealed racial differences in serological markers and underscores the importance of considering race as a determinant of physiological responses. Future studies are warranted to explore the causes and implications of these racial disparities to facilitate tailored clinical management and social policy changes that can improve health equity.

Effect of high-intensity interval training on cardiometabolic component risks in persons with paraplegia: Results of a randomized controlled trial.

The aim of this work is to determine the effect of upper-body high intensity interval training (HIIT) on cardiometabolic risks in individuals with chronic paraplegia. Twenty-seven individuals (14 females, 13 males, mean ± SD age: 46 ± 9 years) with chronic paraplegia (spinal cord injury between T2 and L5 >1-year post-injury) took part in a randomized controlled trial and were included in the final analysis. Participants in the HIIT group (n = 18) performed ∼30 min of arm crank exercise (60 s intervals at 80%-90% peak heart rate) four times per week, for 6 weeks. Participants in the control (CON) group (n = 9) were asked to maintain their habitual diet and physical activity patterns over the study period. Outcome measures were taken at baseline and follow-up. The primary outcome measures were fasting insulin, peak power output (PPO) and peak aerobic capacity ( V ̇ O 2 peak ${{\dot{V}}_{{{{\mathrm{O}}}_{\mathrm{2}}}{\mathrm{peak}}}}$ ). Secondary outcome measures included body composition, postprandial glycaemic control, fasting blood lipids, inflammatory biomarkers and resting blood pressure. Differences between groups were assessed by ANCOVA, using baseline values as a covariate. PPO was higher in the HIIT (101 W, 97-106) compared to the CON (90 W, 83-96) group at follow-up (P = 0.006). There were no differences in fasting insulin (P = 0.415) or relative V ̇ O 2 peak ${{\dot{V}}_{{{{\mathrm{O}}}_{\mathrm{2}}}{\mathrm{peak}}}}$ (P = 0.417). Postprandial Matsuda insulin sensitivity index (ISIMatsuda) was higher in the HIIT (5.42, 4.69-6.15) compared to the CON (3.75, 2.46-5.04) group at follow-up (P = 0.036). Six weeks of upper-body HIIT increased PPO and ISIMatsuda, with no other beneficial effect on cardiometabolic component risks in persons with chronic paraplegia. HIGHLIGHTS: What is the central question of this study? What is the effect of upper-body high intensity interval training (HIIT) on cardiometabolic component risks in individuals with chronic paraplegia? What is the main finding and its importance? Six weeks of upper-body HIIT increased PPO and improved insulin sensitivity, but had no beneficial effect on other cardiometabolic component risks in persons with chronic paraplegia. The large effect size observed for insulin sensitivity may be important in terms of reducing the risk of type-2 diabetes in this population.

Personal academic tutors (PATs): A student perspective.

INTRODUCTION: Personal academic tutors (PATs) have an important role in providing academic and non-academic support for university students. This study sought to assess the effectiveness of a PAT system developed for pharmacy students. METHODS: A student-led survey was developed using a mix of single answer, Likert-style scale, and free text responses. The questionnaire was peer reviewed by students and other researchers and was piloted before being made available online to pharmacy students. RESULTS: One hundred fifty-nine responses were received from students across all stages of the programme. In general, students expressed high levels of satisfaction with their PATs. Despite high levels of recognition of positive attributes of the PAT system, students had low levels of willingness to discuss personal issues with their PAT. Male students were more comfortable than female students in discussing personal issues. The level of comfort expressed by female participants was not significantly different with male or female PATs. Often students turn to friends and family who may provide advice that is unhelpful or outdated, particularly for issues such as poor mental health. Reasons for not speaking to PATs included concerns about being judged and academic records being affected. Worryingly, 18% of respondents (n = 28) had personal issues that had not been disclosed to anyone. CONCLUSIONS: Satisfaction with more traditional academic tutoring was high but the reluctance to discuss wellbeing issues was concerning. Further work involving the student body is planned to co-create strategies to overcome reluctance to discuss personal issues.

The Effect of Lower Limb Combined Neuromuscular Electrical Stimulation on Skeletal Muscle Signaling for Glucose Utilization, Myofiber Distribution, and Metabolic Function after Spinal Cord Injury.

Maintaining healthy myofiber type and metabolic function early after spinal cord injury (SCI) may prevent chronic metabolic disorders. This study compares the effects of a 2-5 week combined (aerobic + resistance) neuromuscular electrical stimulation (Comb-NMES) regimen versus a sham control treatment on muscle protein signaling for glucose uptake, myofiber type distribution, and metabolic function. Twenty participants (31 ± 9 years of age) with an SCI (C4-L1, AIS level A-C) within 14 days of the SCI were randomly assigned to control (N = 8) or Comb-NMES (N = 12). Sessions were given three times per week. Fasting blood samples and vastus lateralis muscle biopsies were collected 24-48 h before or after the last session. Western blots were performed to quantify proteins, immunohistochemical analyses determined muscle myofiber distribution, and enzymatic assays were performed to measure serum glucose, insulin, and lipids. Our main findings include a decrease in fasting glucose (p < 0.05) and LDL-C (p < 0.05) levels, an upregulation of CamKII and Hexokinase (p < 0.05), and an increase in type I (+9%) and a decrease in type IIx (-36%) myofiber distribution in response to Comb-NMES. Our findings suggest that maintaining healthy myofiber type and metabolic function may be achieved via early utilization of Comb-NMES.

Assessing student perception of the integration of portable wireless ultrasound imaging in undergraduate anatomy education.

Anatomy is the foundation of many physiology and healthcare-related degrees. With limited access to cadavers in many universities, it is essential to investigate techniques that could be utilized to support and enhance the teaching of anatomy. Ultrasound is used clinically to aid the diagnosis of a wide range of conditions by visualizing the anatomy of the patient. While research has investigated the advantages of ultrasound in medical education, the potential benefits of ultrasound in undergraduate bioscience degrees remain to be investigated. The aim of this study was to identify if a portable ultrasound probe that wirelessly attaches to a smartphone or tablet was perceived by students as beneficial for their understanding and learning of anatomy, and to identify if there were any barriers for students partaking in ultrasound sessions. Following five ultrasound-teaching sessions, 107 undergraduate students completed a 5-point likert questionnaire on their perception of the integration of portable ultrasound machines in anatomy education. The data indicated that 93% of students perceived that the ultrasound teaching sessions improved their anatomical understanding, 94% perceived that ultrasound increased their ability to understand the clinical relevance of learning anatomy, 97% enjoyed the sessions, and 95% of students believed that ultrasound should be integrated into anatomy teaching. In this study, we also found several barriers for students taking part in ultrasound sessions, including religious beliefs, and lacking adequate background knowledge. In conclusion, these findings demonstrate, for the first time, that students perceive portable ultrasound to enhance their anatomy studies, demonstrating the potential benefit the integration of ultrasound into the anatomy curriculum may serve within undergraduate bioscience courses.

Understanding the role of physical activity on the pathway from intra-articular knee injury to post-traumatic osteoarthritis disease in young people: a scoping review protocol.

INTRODUCTION: The prevalence of intra-articular knee injuries and reparative surgeries is increasing in many countries. Alarmingly, there is a risk of developing post-traumatic osteoarthritis (PTOA) after sustaining a serious intra-articular knee injury. Although physical inactivity is suggested as a risk factor contributing to the high prevalence of the condition, there is a paucity of research characterising the association between physical activity and joint health. Consequently, the primary aim of this review will be to identify and present available empirical evidence regarding the association between physical activity and joint degeneration after intra-articular knee injury and summarise the evidence using an adapted Grading of Recommendations Assessment, Development and Evaluations. The secondary aim will be to identify potential mechanistic pathways through which physical activity could influence PTOA pathogenesis. The tertiary aim will be to highlight gaps in current understanding of the association between physical activity and joint degeneration following joint injury. METHODS: A scoping review will be conducted using the Preferred Reporting Items for Systematic reviews and Meta-Analyses extension for Scoping Reviews checklist and best-practice recommendations. The review will be guided by the following research question: what is the role of physical activity in the trajectory from intra-articular knee injury to PTOA in young men and women? We will identify primary research studies and grey literature by searching the electronic databases Scopus, Embase: Elsevier, PubMed, Web of Science: all databases, and Google Scholar. Reviewing pairs will screen abstracts, full texts and will extract data. Data will be presented descriptively using charts, graphs, plots and tables. ETHICS AND DISSEMINATION: This research does not require ethical approval due to the data being published and publicly available. This review will be submitted for publication in a peer-reviewed sports medicine journal irrespective of discoveries and disseminated through scientific conference presentations and social media. TRIAL REGISTRATION NUMBER: https://osf.io/84pnh/.

In jars: The integration of historical anatomical and pathological potted specimens in undergraduate education.

INTRODUCTION: Across the UK, many anatomy departments possess historical potted wet cadaveric specimen collections, such as organs preserved in fluid-filled jars. Although considered obsolete by some for anatomical education, there is immense potential for their utilisation in teaching, particularly in institutes that have limited access to cadavers or have had body donation rates impacted by the Covid-19 pandemic. Another benefit of historical potted cadaveric specimens is that severe pathology, often not seen today, can be observed by the student. MATERIAL AND METHODS: The aim of this study was to understand students' opinions and attitudes towards the use of historical anatomical and pathological potted wet specimen collections in undergraduate science teaching. Following their integration into the anatomy program of a Clinical Sciences degree, seventy-seven undergraduate students completed a five-point Likert questionnaire on their perspective for the integration of the historical potted specimens in anatomical education. This study was approved by the Research Ethics committee at the University of Bradford RESULTS: The study demonstrated that 90 % of students found the collection useful in teaching, 92 % would like to see the collection used more in teaching, and 76 % of students found that the collection encouraged them to consider medical ethics and the donor. CONCLUSIONS: In conclusion, the survey findings suggest that further utilisation of historical potted wet specimen collections would be useful in the teaching of anatomy and that these collections could potentially encourage conversations on post-mortem bodily integrity, ethics, and organ donation.

Prior arm-crank exercise has no effect on postprandial lipaemia in nondisabled adults.

A single bout of cycling or running performed in the evening can reduce postprandial lipaemia (PPL) the following morning, although this is currently unknown for upper-body exercise. The aim of this study was to determine if a bout of arm-crank exercise (high-intensity interval [HIIE] or moderate-intensity continuous [MICE]), can attenuate PPL in noninjured individuals. Eleven healthy and recreationally active participants (eight males, three females; age: 27 ± 7 years; body mass index: 23.5 ± 2.5 kg·m-2) volunteered to participate in three trials: HIIE (10 × 60 s at 80% peak power output), MICE (50% peak power output of isocaloric duration), and a no-exercise control condition. Each exercise bout was performed at 18:00, and participants consumed a standardised evening meal at 20:00. Following an overnight fast, a 5-h mixed-macronutrient tolerance test was performed at 08:00. There were no significant differences in triglyceride incremental area under the curve between HIIE (192 ± 94 mmol·L-1 per 300 min), MICE (184 ± 111 mmol·L-1 per 300 min), and the no-exercise condition (175 ± 90 mmol·L-1 per 300 min) (P = 0.46). There were no significant differences in incremental area under the curve for glucose (P = 0.91) or insulin (P = 0.59) between conditions. Upper-body MICE and HIIE performed in the evening do not influence PPL the following morning, in normotriglyceridemic individuals. Clinical Trials Registration: NCT04277091. Novelty: Arm-crank exercise has no effect on PPL when performed the evening prior to a mixed-macronutrient meal test. Upper-body sprint interval exercise should be investigated as a potential solution to reduce PPL.

Effect of high-intensity interval training on cardiometabolic component risks in persons with paraplegia: Protocol for a randomized controlled trial.

Individuals with a spinal cord injury (SCI) are at an increased risk of developing cardiovascular disease and present with a multitude of elevated cardiometabolic component risks. Although upper-body exercise appears an effective strategy to improve some of these outcomes, the effectiveness of high-intensity interval training (HIIT) has yet to be determined for this population. Therefore, a randomized controlled trial will be conducted to determine the effectiveness of a 6 week home-based upper-body HIIT intervention on biomarkers of cardiometabolic health in persons with spinal cord injury, in comparison to a control (CON) group. We will recruit 40 individuals with chronic (>1 year post-injury) paraplegia (spinal cord lesion between the second thoracic and second lumbar vertebrae), aged between 18 and 65 years. After baseline testing, participants will be assigned randomly, using a 2:1 allocation, to the home-based exercise intervention (HIIT, n = 26) or control group (CON, n = 14). The HIIT intervention will consist of 30 min of arm crank-based HIIT (60 s intervals at 80-90% peak heart rate) four times per week. Participants in the CON group will be asked to maintain their habitual diet and physical activity patterns over the study period. Baseline and follow-up assessments will be made for determination of body composition, postprandial glycaemic control, fasting blood lipids and systemic inflammation, aerobic capacity, physical activity and energy intake, resting metabolic rate, resting blood pressure, and subjective measures of health and well-being. ClinicalTrials.gov, ID: NCT04397250. Registered on 21 May 2020.

A Single Bout of Upper-Body Exercise Has No Effect on Postprandial Metabolism in Persons with Chronic Paraplegia.

PURPOSE: The acute effects of a single bout of upper-body exercise on postprandial metabolism in persons with spinal cord injury are currently not well understood. The primary aim of this study was to evaluate the effects of a single bout of upper-body high-intensity interval exercise (HIIE) and moderate-intensity continuous exercise (MICE) in comparison with a no-exercise control (REST) condition on postprandial metabolic responses in persons with chronic paraplegia. METHODS: Ten participants (eight males, two females; age, 49 ± 10 yr; time since injury, 22 ± 13 yr) with chronic paraplegia took part in a randomized crossover study, consisting of three trials: HIIE (8 × 60 s at 70% peak power output [PPEAK]), MICE (25 min at 45% PPEAK), and REST, at least 3 d apart. Exercise was performed in the fasted state, and participants consumed a mixed-macronutrient liquid meal 1-h postexercise. Venous blood and expired gas samples were collected at regular intervals for 6-h postmeal consumption. RESULTS: There were no significant differences in postprandial incremental area under the curve for triglycerides (P = 0.59) or glucose (P = 0.56) between conditions. Insulin incremental area under the curve tended to be lower after MICE (135 ± 85 nmol·L-1 per 360 min) compared with REST (162 ± 93 nmol·L-1 per 360 min), but this did not reach statistical significance (P = 0.06, d = 0.30). Participants reported a greater fondness (P = 0.04) and preference for HIIE over MICE. CONCLUSIONS: After an overnight fast, a single bout of upper-body exercise before eating has no effect on postprandial metabolism in persons with chronic paraplegia, irrespective of exercise intensity. This suggests that alternative exercise strategies may be required to stimulate postprandial substrate oxidation for this population.

Muscle deterioration due to rheumatoid arthritis: assessment by quantitative MRI and strength testing.

OBJECTIVES: RA patients often present with low muscle mass and decreased strength. Quantitative MRI offers a non-invasive measurement of muscle status. This study assessed whether MRI-based measurements of T2, fat fraction, diffusion tensor imaging and muscle volume can detect differences between the thigh muscles of RA patients and healthy controls, and assessed the muscle phenotype of different disease stages. METHODS: Thirty-nine RA patients (13 'new RA'-newly diagnosed, treatment naïve, 13 'active RA'-persistent DAS28 >3.2 for >1 year, 13 'remission RA'-persistent DAS28 <2.6 for >1 year) and 13 age and gender directly matched healthy controls had an MRI scan of their dominant thigh. All participants had knee extension and flexion torque and grip strength measured. RESULTS: MRI T2 and fat fraction were higher in the three groups of RA patients compared with healthy controls in the thigh muscles. There were no clinically meaningful differences in the mean diffusivity. The muscle volume, handgrip strength, knee extension and flexion were lower in all three groups of RA patients compared with healthy controls. CONCLUSION: Quantitative MRI and muscle strength measurements can potentially detect differences within the muscles between RA patients and healthy controls. These differences may be seen in RA patients who are yet to start treatment, those with persistent active disease, and those who were in clinical remission. This suggests that the muscles in RA patients are affected in the early stages of the disease and that signs of muscle pathology and muscle weakness are still observed in clinical remission.

Novel Muscle Imaging in Inflammatory Rheumatic Diseases-A Focus on Ultrasound Shear Wave Elastography and Quantitative MRI.

In recent years, imaging has played an increasing role in the clinical management of patients with rheumatic diseases with respect to aiding diagnosis, guiding therapy and monitoring disease progression. These roles have been underpinned by research which has enhanced our understanding of disease pathogenesis and pathophysiology of rheumatology conditions, in addition to their key role in outcome measurement in clinical trials. However, compared to joints, imaging research of muscles is less established, despite the fact that muscle symptoms are very common and debilitating in many rheumatic diseases. Recently, it has been shown that even though patients with rheumatoid arthritis may achieve clinical remission, defined by asymptomatic joints, many remain affected by lingering constitutional systemic symptoms like fatigue, tiredness, weakness and myalgia, which may be attributed to changes in the muscles. Recent improvements in imaging technology, coupled with an increasing clinical interest, has started to ignite new interest in the area. This perspective discusses the rationale for using imaging, particularly ultrasound and MRI, for investigating muscle pathology involved in common inflammatory rheumatic diseases. The muscles associated with rheumatic diseases can be affected in many ways, including myositis-an inflammatory muscle condition, and myopathy secondary to medications, such as glucocorticoids. In addition to non-invasive visual assessment of muscles in these conditions, novel imaging techniques like shear wave elastography and quantitative MRI can provide further useful information regarding the physiological and biomechanical status of the muscle.

Effect of Exercise on Cardiometabolic Risk Factors in Adults With Chronic Spinal Cord Injury: A Systematic Review.

OBJECTIVE: To determine the effects of exercise on individual cardiometabolic syndrome (CMS) risk factors in adults with chronic spinal cord injury (SCI). DATA SOURCES: English language searches of PubMed, Web of Science, EMBASE, and Scopus (January 1, 1970, to July 31, 2019). STUDY SELECTION: Articles were included if they met the following criteria: (1) original articles with statistical analysis, (2) participants were adults with a SCI sustained ≥1 year ago, (3) exercise intervention duration ≥2 weeks, and (4) included any CMS risk factor as an outcome. DATA EXTRACTION: The methodological quality of articles was assessed using the Downs and Black score. DATA SYNTHESIS: Sixty-five studies were included for the final analysis, including 9 studies classified as high quality (≥66.7%), 35 studies classified as fair quality (50%-66.6%), and 21 studies classified as low quality (<50%). Improvements in waist circumference (4/6 studies) and markers of hepatic insulin sensitivity (4/5 studies) were reported following upper body aerobic exercise training, but no improvements in fasting glucose (8/8 studies), lipid profile (6/8 studies), systolic blood pressure (8/9 studies), or diastolic blood pressure (9/9 studies) were observed. Improvements in markers of peripheral insulin sensitivity (5/6 studies) were observed following functional electrical stimulation (FES) cycling. Improvements in lipid profile (4/5 studies) were observed following upper body resistance training (RT) (with or without aerobic exercise). No consistent improvements in CMS risk factors were observed following assisted ambulation, FES hybrid, FES rowing, and FES RT. CONCLUSIONS: Upper body aerobic exercise training (>75% maximum heart rate) appears to improve waist circumference and hepatic insulin sensitivity but appears insufficient for improving fasting glucose, lipid profile, or resting blood pressure. The addition of RT to upper body aerobic exercise may elicit favorable changes in the lipid profile. More high-quality studies are needed to confirm if FES cycling is effective at improving peripheral insulin sensitivity.

Normal values and test-retest variability of stimulated-echo diffusion tensor imaging and fat fraction measurements in the muscle.

OBJECTIVES: To assess the test-retest variability of both diffusion parameters and fat fraction (FF) estimates in normal muscle, and to assess differences in normal values between muscles in the thigh. METHODS: 29 healthy volunteers (mean age 37 years, range 20-60 years, 17/29 males) completed the study. Magnetic resonance images of the mid-thigh were acquired using a stimulated echo acquisition mode-echoplanar imaging (STEAM-EPI) imaging sequence, to assess diffusion, and 2-point Dixon imaging, to assess FF. Imaging was repeated in 19 participants after a 30 min interval in order to assess test-retest variability of the measurements. RESULTS: Intraclass correlation coefficients (ICCs) for test-retest variability were 0.99 [95% confidence interval, (CI): 0.98, 1] for FF, 0.94 (95% CI: 0.84, 0.97) for mean diffusivity and 0.89 (95% CI: 0.74, 0.96) for fractional anisotropy (FA). FF was higher in the hamstrings than the quadriceps by a mean difference of 1.81% (95% CI:1.63, 2.00)%, p < 0.001. Mean diffusivity was significantly lower in the hamstrings than the quadriceps (0.26 (0.13, 0.39) x10-3 mm2s-1, p < 0.001) whereas fractional anisotropy was significantly higher in the hamstrings relative to the quadriceps with a mean difference of 0.063 (0.05, 0.07), p < 0.001. CONCLUSIONS: This study has shown excellent test-retest, variability in MR-based FF and diffusion measurements and demonstrated significant differences in these measures between hamstrings and quadriceps in the healthy thigh. ADVANCES IN KNOWLEDGE: Test-retest variability is excellent for STEAM-EPI diffusion and 2-point Dixon-based FF measurements in the healthy muscle. Inter- and intraobserver variability were excellent for region of interest placement for STEAM-EPI diffusion and 2-point Dixon-based FF measurements in the healthy muscle. There are significant differences in FF and diffusion measurements between the hamstrings and quadriceps in the normal muscle.

Virtual-reality exergaming improves performance during high-intensity interval training.

Purpose: To determine if: (i) mean power output and enjoyment of high-intensity interval training (HIIT) are enhanced by virtual-reality (VR)-exergaming (track mode) compared to standard ergometry (blank mode), (ii) if mean power output of HIIT can be increased by allowing participants to race against their own performance (ghost mode) or by increasing the resistance (hard mode), without compromising exercise enjoyment. Methods: Sixteen participants (8 males, 8 females, VO2max: 41.2 ± 10.8 ml-1·kg-1·min-1) completed four VR-HIIT conditions in a partially-randomised cross-over study; (1a) blank, (1b) track, (2a) ghost, and (2b) hard. VR-HIIT sessions consisted of eight 60 s high-intensity intervals at a resistance equivalent to 70% (77% for hard) maximum power output (PMAX), interspersed by 60 s recovery intervals at 12.5% PMAX, at a self-selected cadence. Expired gases were collected and VO2 measured continuously. Post-exercise questionnaires were administered to identify differences in indices related to intrinsic motivation, subjective vitality, and future exercise intentions. Results: Enjoyment was higher for track vs. blank (difference: 0.9; 95% CI: 0.6, 1.3) with no other differences between conditions. There was no difference in mean power output for track vs. blank, however it was higher for track vs. ghost (difference: 5 Watts; CI: 3, 7), and hard vs. ghost (difference: 19 Watts; 95% CI: 15, 23). Conclusions: These findings demonstrate that VR-exergaming is an effective intervention to increase enjoyment during a single bout of HIIT in untrained individuals. The presence of a ghost may be an effective method to increase exercise intensity of VR-HIIT.

Open-Source, Python-Based Redevelopment of the ChemShell Multiscale QM/MM Environment.

ChemShell is a scriptable computational chemistry environment with an emphasis on multiscale simulation of complex systems using combined quantum mechanical and molecular mechanical (QM/MM) methods. Motivated by a scientific need to efficiently and accurately model chemical reactions on surfaces and within microporous solids on massively parallel computing systems, we present a major redevelopment of the ChemShell code, which provides a modern platform for advanced QM/MM embedding models. The new version of ChemShell has been re-engineered from the ground up with a new QM/MM driver module, an improved parallelization framework, new interfaces to high performance QM and MM programs, and a user interface written in the Python programming language. The redeveloped package is capable of performing QM/MM calculations on systems of significantly increased size, which we illustrate with benchmarks on zirconium dioxide nanoparticles of over 160000 atoms.

Thermodynamically accessible titanium clusters TiN, N = 2-32.

We have performed a genetic algorithm search on the tight-binding interatomic potential energy surface (PES) for small TiN (N = 2-32) clusters. The low energy candidate clusters were further refined using density functional theory (DFT) calculations with the PBEsol exchange-correlation functional and evaluated with the PBEsol0 hybrid functional. The resulting clusters were analysed in terms of their structural features, growth mechanism and surface area. The results suggest a growth mechanism that is based on forming coordination centres by interpenetrating icosahedra, icositetrahedra and Frank-Kasper polyhedra. We identify centres of coordination, which act as centres of bulk nucleation in medium sized clusters and determine the morphological features of the cluster.

The adsorption of Cu on the CeO2(110) surface.

We report a detailed density functional theory (DFT) study in conjunction with extended X-ray absorption fine structure (EXAFS) experiments on the geometrical and local electronic properties of Cu adatoms and Cu(ii) ions in presence of water molecules and of CuO nanoclusters on the CeO2(110) surface. Our study of (CuO)n(=1,2&4) clusters on CeO2(110) shows that based on the Cu-O environment, the geometrical properties of these clusters may vary and their presence may lead to relatively high localization of charge on the exposed surfaces. We find that in the presence of an optimum concentration of water molecules, Cu has a square pyramidal geometry, which agrees well with our experimental findings; we also find that Cu(ii) facilitates water adsorption on the CeO2(110) surface. We further show that a critical concentration of water molecules is required for the hydrolysis of water on Cu(OH)2/CeO2(110) and on pristine CeO2(110) surfaces.

Room temperature methoxylation in zeolites: insight into a key step of the methanol-to-hydrocarbons process.

Neutron scattering methods observed complete room temperature conversion of methanol to framework methoxy in a commercial sample of methanol-to-hydrocarbons (MTH) catalyst H-ZSM-5, evidenced by methanol immobility and vibrational spectra matched by ab initio calculations. No methoxylation was observed in a commercial HY sample, attributed to the dealumination involved in high silica HY synthesis.