Running Alterations Pre- and Postarthroscopy for Femoroacetabular Impingement Syndrome and Labral Tears.

ABSTRACT: Freemyer, B, Beeler, D, Crawford, S, Durkin, R, and Stickley, C. Running alterations pre- and postarthroscopy for femoroacetabular impingement syndrome and labral tears. J Strength Cond Res 38(3): 501-509, 2024-Running is essential to sports participation and activity over the lifespan; however, running biomechanics are not fully described in patients with femoroacetabular impingement (FAIS). The purpose was to compare FAIS patient report outcome surveys (PRO) and running biomechanics preoperatively and 6 months postoperatively with controls. Nineteen subjects (FAIS, n = 10 and age-matched controls, n = 9) were included. The UCLA, Hip Outcome Score activity of daily living (HOS ADL ) and sports subscale (HOS SS ), and 3-D running biomechanics were evaluated. Statistical parametric mapping was conducted on biomechanics data. Statistical significance was set at p ≤ 0.05. Femoroacetabular impingement had similar UCLA activity scores compared with controls by 6 months (FAIS: 8.4 ± 1.7, CON: 8.6 ± 2.0, p = 0.80), despite lower HOS ADL (FAIS-Six: 89.3 ± 6.3, CON: 100 ± 0, p = 0.04) and HOS SS (FAIS-Six: 82.6 ± 18.5, CON: 100 ± 0, p = 0.05). The FAIS group had lower knee adduction moments (KAM) around 22-27% of stance ( p = 0.05) and lower sagittal plane ankle power generation during the final 5% of stance compared with the controls ( p = 0.04) preoperatively. The FAIS also had lower vertical ground reaction forces the first 2% of stance ( p = 0.05) and lower KAM from 20 to 30% stance ( p = 0.03) at the postoperative time vs. controls. Femoroacetabular impingement had higher hip external rotation angles the first 5% stance ( p = 0.05) and the last 20% of stance ( p = 0.01) vs. controls. This is the first study to describe FAIS running pre- and postoperatively. Despite higher activity and health 6 months postarthroscopy, the patients with FAIS had altered running biomechanics. Clinicians should consider these findings when creating rehabilitation protocols and during running progressions across the postoperative care of patients with FAIS.

Regional shear wave elastography of Achilles tendinopathy in symptomatic versus contralateral Achilles tendons.

OBJECTIVES: Ultrasound often corroborates clinical diagnosis of Achilles tendinopathy (AT). Traditional measures assess macromorphological features or use qualitative grading scales, primarily focused within the free tendon. Shear wave imaging can non-invasively quantify tendon elasticity, yet it is unknown if proximal structures are affected by tendon pathology. The purpose of the study was to determine the characteristics of both traditional sonographic measures and regional shear wave speed (SWS) between limbs in patients with AT. METHODS: Twenty patients with chronic AT were recruited. Traditional sonographic measures of tendon structure were measured. Regional SWS was collected in a resting ankle position along the entire length of the tendon bilaterally. SWS measures were extracted and interpolated across evenly distributed points corresponding to the free tendon (FT), soleus aponeurosis (SA), and gastrocnemius aponeurosis (GA). Comparisons were made between limbs in both traditional sonographic measures and regional SWS. RESULTS: Symptomatic tendons were thicker (10.2 (1.9) vs. 6.8 (1.8) mm; p < 0.001) and had more hyperemia (p = 0.001) and hypoechogenicity (p = 0.002) than the contralateral tendon. Regional SWS in the FT was lower in the symptomatic limb compared to the contralateral limb (11.53 [10.99, 12.07] vs. 10.97 [10.43, 11.51]; p = 0.03). No differences between limbs were found for the SA (p = 0.13) or GA (p = 0.99). CONCLUSIONS: Lower SWS was only observed in the FT in AT patients, indicating that alterations in tendon elasticity associated with AT were localized to the FT and did not involve the proximal passive tendon structures. KEY POINTS: • Baseline characteristics of a pilot sample of 20 subjects suffering from chronic Achilles tendinopathy showed differences in conventional sonographic measures of tendon thickness, qualitatively assessed hypoechogenicity, hyperemia, and quantitative measures of shear wave speed. • Regional shear wave speeds were lower in the free tendon but not in the proximal regions of the soleus or gastrocnemius aponeuroses in Achilles tendinopathy patients. • Using shear wave imaging to estimate tendon stiffness may prove beneficial for clinical validation studies to address important topics such as return to activity and the effectiveness of rehabilitation protocols.

The Impact of Community Health Information Exchange Usage on Time to Reutilization of Hospital Services.

PURPOSE: Few studies have determined whether clinician usage of a community health information exchange (HIE) directly improves patient care transitions. We hypothesized that lookup in the HIE by primary care physicians of patients recently released from the hospital would increase the time until hospital reuse. METHODS: We identified a retrospective cohort of 8,216 hospital inpatients aged over 18 years that were discharged from January 1, 2021 through November 30, 2021 using the Paso del Norte Health Information Exchange, in El Paso County, Texas. All patients had a primary care physician visit within 30 days after hospital discharge, and we identified patients that were looked up in the HIE close to that visit. Of the cohort, 2,627 were rehospitalized and 3,809 visited an emergency department (ED) during the follow-up window. The remaining 1,780 patients were controls. We conducted survival analysis, censoring at the second ED or inpatient visit or end of the study window (January 31, 2022). The model was adjusted by ethnicity, gender, insurance, and age. RESULTS: Lookup in the HIE was significantly associated with reducing the likelihood of visiting the ED by 53% and being rehospitalized by 61%. Lookup in the HIE was associated with an increased median time to use of the ED after inpatient discharge from 99 to 238 patient days. Ethnicity, insurance, gender, and age were also significant predictors of hospital reuse. CONCLUSIONS: Increased utilization of community HIEs by primary care physicians on behalf of their recently discharged patients may dramatically increase the time until inpatient or ED reuse.

Influence of ultrasound machine settings on quantitative measures derived from spatial frequency analysis of muscle tissue.

BACKGROUND: Ultrasound is a powerful tool for diagnostic purposes and provides insight into both normal and pathologic tissue structure. Spatial frequency analysis (SFA) methods characterize musculoskeletal tissue organization from ultrasound images. Both sonographers in clinical imaging and researchers may alter a minimized range of ultrasound settings to optimize image quality, and it is important to know how these small adjustments of these settings affect SFA parameters. The purpose of this study was to investigate the effects of making small adjustments in a typical default ultrasound machine setting on extracted spatial frequency parameters (peak spatial frequency radius (PSFR), Mmax, Mmax%, and Sum) in the biceps femoris muscle. METHODS: Longitudinal B-mode images were collected from the biceps femoris muscle in 36 participants. The window depth, foci locations, and gain were systematically adjusted consistent with clinical imaging procedures for a total of 27 images per participant. Images were analyzed by identifying a region of interest (ROI) in the middle portion of the muscle belly in a template image and using a normalized two-dimensional cross-correlation technique between the template image and subsequent images. The ROI was analyzed in the frequency domain using conventional SFA methods. Separate linear mixed effects models were run for each extracted parameter. RESULTS: PSFR was affected by modifications in focus location only (p < 0.001) with differences noted between all locations. Mmax% was influenced by the interaction of gain and focus location (p < 0.001) but was also independently affected by increasing window depth (p < 0.001). Both Mmax and Sum parameters were sensitive to small changes in machine settings with the interaction of focus location and window depth (p < 0.001 for both parameters) as well as window depth and gain (p < 0.001 for both) influencing the extracted values. CONCLUSIONS: Frequently adjusted imaging settings influence some SFA statistics. PSFR and Mmax% appear to be most robust to small changes in image settings, making them best suited for comparison across individuals and between studies, which is appealing for the clinical utility of the SFA method.

Applying Responsive Survey Design to Small-Scale Surveys: Campus Surveys of Sexual Misconduct.

Responsive survey design is a technique aimed at improving the efficiency or quality of surveys by using incoming data from the field to make design changes. The technique was pioneered on large national surveys, but the tools can also be applied on the smaller-scale surveys most commonly used by sociologists. We demonstrate responsive survey design in a small-scale, list-based sample survey of students on the topic of sexual misconduct. We investigate the impact of individual incentive levels and a two-phase responsive design with changes to mode of contact as approaches for limiting the potential of nonresponse bias in data from such surveys. Our analyses demonstrate that a two-phase design introducing telephone and face-to-face reminders to complete the survey can produce stronger change in response rates and characteristics of those who respond than higher incentive levels. These findings offer tools for sociologists designing smaller-scale surveys of special populations or sensitive topics.

Association Between Birthplace and Time in the United States With Diet Quality in US Adolescents: Findings from the National Health and Nutrition Examination Survey, 2007 to 2018.

BACKGROUND: During adolescence, diet quality reaches its lowest point compared to other childhood life stages. Acculturation is associated with decreased diet quality among many groups of US immigrant adults, but research is limited among adolescents. OBJECTIVES: We investigated the associations between birthplace and length of time living in the United States, 2 proxy measures of acculturation, and diet quality among adolescents (12-19 years old). METHODS: Data were from the NHANES (2007-2018), which included two 24-hour dietary recalls (n = 6113) to estimate Healthy Eating Index 2015 (HEI-2015) total scores and component scores. Multivariate linear regression and generalized linear models were performed to compare HEI-2015 total scores and component scores between US-born adolescents (n = 5342) and foreign-born adolescents with <5 years (n = 244), 5 to <10 years (n = 201), and ≥10 years (n = 290) of US residency. RESULTS: Foreign-born adolescents with <5 years (53.3 ± 1.2), 5 to <10 years (51.4 ± 1.5), and ≥10 years of US residency (49.9 ± 0.8) had higher HEI-2015 total scores than US-born adolescents (47.0 ± 0.3; P < 0.0001) and higher component scores for total vegetables, seafood and plant proteins, and added sugars (P values ≤ 0.0001). Foreign-born adolescents with more years of US residency had higher component scores for total fruits, whole fruits, and saturated fats than those with fewer years of US residency. A sensitivity analysis revealed this pattern held for Mexican-American and other Hispanic adolescents. CONCLUSIONS: Being born outside the United States and living in the United States for less time (among foreign-born adolescents) are associated with higher diet quality. Culturally informed health promotion programs may help to reduce diet-related disparities related to acculturation among adolescents.

Assessment of nationally recommended antibiotics for treatment of UTI in U.S.-Mexico border emergency departments.

BACKGROUND: Urinary tract infections (UTIs) seen in the emergency department are commonly treated as an outpatient with oral antibiotics. Given that antibiotics are available for over-the-counter purchase in Mexico, there is speculation that potential misuse and overuse of antibiotics in United States-Mexico border areas could lead to antibiotic resistance patterns that would render some empiric treatments for UTIs less effective. The purpose of this study was to examine the effectiveness of Infectious Disease Society of America (IDSA) guideline-recommended antibiotics for treatment of outpatient UTI diagnosed in the emergency department. Data were collected from a county hospital on the U.S.-Mexico border with a metropolitan area of over 2 million people. Secondary analysis included frequency of urine culture isolated, resistance rates of urine pathogens, and prescriber habits. METHODS: This study was a retrospective chart review of adult patients diagnosed and treated for UTI from August 1, 2019, to February 29, 2020. Culture results of included patients were analyzed against in vitro-tested antibiotics. Bacterial isolate frequency, resistance rates, and prescribing habits were collected. RESULTS: A total of 985 patient charts were reviewed, of which 520 patients met inclusion criteria for analysis of prescribing habits. Of these, 329 positive bacterial culture growths were included in the analysis of antibiotic resistance rates. Oral antibiotics with comparatively lower resistance rates were amoxicillin/clavulanate, cefdinir, cefuroxime, and nitrofurantoin. Oral antibiotics with notably high resistance rates included trimethoprim-sulfamethoxazole (TMP-SMX), tetracycline, ciprofloxacin, levofloxacin, and cephalexin. Nitrofurantoin was prescribed most frequently for outpatient treatment of UTI/cystitis (41.6%) while cephalexin was the most commonly prescribed antibiotic for outpatient treatment of pyelonephritis (50%). CONCLUSION: Our findings suggest that, while part of standard IDSA guidelines, fluoroquinolones and TMP-SMX are not ideal empiric antibiotics for treatment of outpatient UTI in the U.S.-Mexico border region studied due to high resistance rates. Although not listed as first line agents per current IDSA recommendations, 2nd and 3rd generation cephalosporins, and amoxicillin/clavulanate would be acceptable options given resistance patterns demonstrated in accordance with IDSA allowance for tailoring selection to local resistance. Nitrofurantoin appears to be consistent with recommendations and demonstrates a favorable resistance profile for treatment of outpatient UTI within this region.

Spatial frequency analysis detects altered tissue organization following hamstring strain injury at time of injury but not return to sport.

BACKGROUND: Hamstring strain injury (HSI) diagnosis is often corroborated using ultrasound. Spatial frequency analysis (SFA) is a quantitative ultrasound method that has proven useful in characterizing altered tissue organization. The purpose of this study was to determine changes in muscular tissue organization using SFA following HSI. METHODS: Ultrasound B-mode images were captured at time of injury (TOI) and return to sport (RTS) in collegiate athletes who sustained an HSI. Spatial frequency parameters extracted from two-dimensional Fourier Transforms in user-defined regions of interest (ROI) were analyzed. Separate ROIs encompassed injured and adjacent tissue within the same image of the injured limb and mirrored locations in the contralateral limb at TOI. The ROIs for RTS images were drawn to correspond to the injury-matched location determined from TOI imaging. Peak spatial frequency radius (PSFR) and the fascicular banded pattern relative to image background (Mmax%) were compared between injured and adjacent portions within the same image with separate paired t-tests. Within-image differences of SFA parameters in the injured limb were calculated and compared between TOI and RTS with Wilcoxon rank sum tests. RESULTS: Within the injured limb at TOI, PSFR differences in injured and healthy regions did not strictly meet statistical significance (p = 0.06), while Mmax% was different between regions (p < 0.001). No differences were observed between regions in the contralateral limb at TOI (PSFR, p = 0.16; Mmax%, p = 0.30). Significant within-image differences in PSFR (p = 0.03) and Mmax% (p = 0.04) at RTS were detected relative to TOI. CONCLUSIONS: These findings are a first step in determining the usefulness of SFA in muscle injury characterization and provide quantitative assessment of both fascicular disruption and edema presence in acute HSI.

Spatial-frequency Analysis of the Anatomical Differences in Hamstring Muscles.

Spatial frequency analysis (SFA) is a quantitative ultrasound method that characterizes tissue organization. SFA has been used for research involving tendon injury, but may prove useful in similar research involving skeletal muscle. As a first step, we investigated if SFA could detect known architectural differences within hamstring muscles. Ultrasound B-mode images were collected bilaterally at locations corresponding to proximal, mid-belly, and distal thirds along the hamstrings from 10 healthy participants. Images were analyzed in the spatial frequency domain by applying a two-dimensional Fourier Transform in all 6.5 × 6.5 mm kernels in a region of interest corresponding to the central portion of the muscle. SFA parameters (peak spatial frequency radius [PSFR], maximum frequency amplitude [Mmax], sum of frequencies [Sum], and ratio of Mmax to Sum [Mmax%]) were extracted from each muscle location and analyzed by separate linear mixed effects models. Significant differences were observed proximo-distally in PSFR (p = .039), Mmax (p < .0001), and Sum (p < .0001), consistent with architectural descriptions of the hamstring muscles. These results suggest that SFA can detect regional differences of healthy tissue structure within the hamstrings-an important finding for future research in regional muscle structure and mechanics.

Surface Chemistry-Mediated Near-Infrared Emission of Small Coinage Metal Nanoparticles.

From size-dependent luminescence to localized surface plasmon resonances, the optical properties that emerge from common materials with nanoscale dimensions have been revolutionary. As nanomaterials get smaller, they approach molecular electronic structures, and this transition from bulk to molecular electronic properties is a subject of far-reaching impact. One class of nanomaterials that exhibit particularly interesting optoelectronic features at this size transition are coinage metal (i.e., group 11 elements copper, silver, and gold) nanoparticles with core diameters between approximately 1 to 3 nm (∼25-200 atoms). Coinage metal nanoparticles can exhibit red or near-infrared photoluminescence features that are not seen in either their molecular or larger nanoscale counterparts. This emission has been exploited both as a probe of electronic behavior at the nanoscale as well as in critical applications such as biological imaging and chemical sensing. Interestingly, it has been demonstrated that their photoluminescence figures of merit such as emission quantum yield, energy, and lifetime are largely independent of particle diameter. Instead, emission from particles at this size range depends heavily on the particle surface chemistry, which includes both its metallic composition and the capping ligand architecture. The strong influence of surface chemistry on these emergent optoelectronic phenomena has powerful implications for both the study and use of these particles, primarily due to the theoretically limitless possible surface ligand architectures and metallic compositions. In this Account, we highlight recent work that studies and uses surface chemistry-mediated photoluminescence from coinage metal nanoparticles. Specifically, we emphasize the distinct, as well as synergistic, roles of the nanoparticle capping ligand and the nanoparticle core for controlling and/or enhancing their near-infrared photoluminescence. We then discuss the implications of surface chemistry-mediated photoluminescence as it relates to downstream applications such as energy transfer, sensing, and biological imaging. We conclude by discussing current challenges that remain in the field, including opportunities to develop new particle synthetic routes, analytical tools, and physical frameworks with which to understand small nanoparticle emission. Taken together, we anticipate that these materials will be foundational both in understanding the unique transition from molecular to bulk electronic structures and in the development of nanomaterials that leverage this transition.

Plasmon-Enhanced Chemical Conversion Using Copper Selenide Nanoparticles.

The syntheses, properties, and broad utility of noble metal plasmonic nanomaterials are now well-established. To capitalize on this exceptional utility, mitigate its cost, and potentially expand it, non-noble metal plasmonic materials have become a topic of widespread interest. As new plasmonic materials come online, it is important to understand and assess their ability to generate comparable or complementary plasmonic properties to their noble metal counterparts, including as both sensing and photoredox materials. Here, we study plasmon-driven chemistry on degenerately doped copper selenide (Cu2- xSe) nanoparticles. In particular, we observe plasmon-driven dimerization of 4-nitrobenzenethiol to 4,4'-dimercaptoazobenzene on Cu2- xSe surfaces with yields comparable to those observed from noble metal nanoparticles. Overall, our results indicate that doped semiconductor nanoparticles are promising for light-driven chemistry technologies.

Sensitivity of a bedside reagent strip for the detection of spontaneous bacterial peritonitis in ED patients with ascites.

STUDY OBJECTIVE: To determine the sensitivity of a highly sensitive bedside leukocyte esterase reagent strip (RS) for detection of spontaneous bacterial peritonitis (SBP) in emergency department (ED) ascites patients undergoing paracentesis. METHODS: We conducted a prospective, observational cohort study of ED ascites patients undergoing paracentesis at two academic facilities. Two practitioners, blinded to each other's results, did a bedside RS analysis of the peritoneal fluid in each patient and documented the RS reading at 3-min according to manufacturer-specified colorimetric strip reading as either "negative", "trace", "small", or "large". The primary outcome measure was sensitivity of the RS strip for SBP (absolute neutrophil count ≥ 250 cells/mm3) at the "trace" threshold (positive equals trace or greater). RESULTS: There were 330 cases enrolled, with 635 fluid analyses performed. Of these, 40 fluid samples had SBP (6%). Bedside RS had a sensitivity, specificity, positive predictive value, and negative predictive value of 95% (95% CI 82%-99%), 48% (95% CI 44%-52%), 11% (95% CI 10%-11%), and 99% (95% CI 97%-99%) respectively at the "trace" threshold for the detection of SBP. CONCLUSION: Bedside use of the RS in ED ascites patients demonstrated high sensitivity for SBP. Given the wide confidence intervals, we cannot currently recommend it as a stand-alone test. We recommend further study with a larger number of SBP patients, potentially combining a negative RS result with low clinical suspicion to effectively rule out SBP without formal laboratory analysis.

Efficient Energy Transfer from Near-Infrared Emitting Gold Nanoparticles to Pendant Ytterbium(III).

Here, we demonstrate efficient energy transfer from near-infrared-emitting ortho-mercaptobenzoic acid-capped gold nanoparticles (AuNPs) to pendant ytterbium(III) cations. These functional materials combine the high molar absorptivity (1.21 × 106 M-1 cm-1) and broad excitation features (throughout the UV and visible regions) of AuNPs with the narrow emissive properties of lanthanides. Interaction between the AuNP ligand shell and ytterbium is determined using both nuclear magnetic resonance and electron microscopy measurements. In order to identify the mechanism of this energy transfer process, the distance of the ytterbium(III) from the surface of the AuNPs is systematically modulated by changing the size of the ligand appended to the AuNP. By studying the energy transfer efficiency from the various AuNP conjugates to pendant ytterbium(III) cations, a Dexter-type energy transfer mechanism is suggested, which is an important consideration for applications ranging from catalysis to energy harvesting. Taken together, these experiments lay a foundation for the incorporation of emissive AuNPs in energy transfer systems.

A Divergent Route to Eravacycline.

A convergent route to eravacycline (1) has been developed by employing Michael-Dieckmann cyclization between enone 3 and a fully built and protected left-hand piece (LHP, 2). After construction of the core eravacycline structure, a deprotection reaction was developed, allowing for the isoxazole ring opening and global deprotection to be achieved in one pot. The LHP is synthesized from readily available 4-fluoro-3-methylphenol in six steps featuring a palladium-catalyzed phenyl carboxylation in the last step.

High dietary phosphate intake induces hypertension and augments exercise pressor reflex function in rats.

An increasing number of studies have linked high dietary phosphate (Pi) intake to hypertension. It is well established that the rise in sympathetic nerve activity (SNA) and blood pressure (BP) during physical exertion is exaggerated in many forms of hypertension, which are primarily mediated by an overactive skeletal muscle exercise pressor reflex (EPR). However, it remains unknown whether high dietary Pi intake potentiates the EPR-mediated SNA and BP response to exercise. Accordingly, we measured renal SNA (RSNA) and mean BP (MBP) in normotensive Sprague-Dawley rats fed a normal Pi diet (0.6%, n = 13) or high Pi diet (1.2%, n = 13) for 3 mo. As previously reported, we found that resting BP was significantly increased by 1.2% Pi diet in both conscious and anesthetized animals. Activation of the EPR by electrically induced hindlimb contraction triggered greater increases in ΔRSNA and ΔMBP in the 1.2% compared with 0.6% Pi group (126 ± 25 vs. 42 ± 9%; 44 ± 5 vs. 14 ± 2 mmHg, respectively, P < 0.01). Activation of the muscle mechanoreflex, a component of the EPR, by passively stretching hindlimb muscle also evoked greater increases in ΔRSNA and ΔMBP in the 1.2% compared with 0.6% Pi group (109 ± 27 vs. 24 ± 7%, 38 ± 7 vs. 8 ± 2 mmHg, respectively, P < 0.01). A similar response was produced by hindlimb intra-arterial capsaicin administration to stimulate the metaboreflex arm of the EPR. Thus, our data demonstrate a novel action of dietary Pi loading in augmenting EPR function through overactivation of both the muscle mechanoreflex and metaboreflex.

Ligand density quantification on colloidal inorganic nanoparticles.

Colloidal inorganic nanoparticles are being used in an increasingly large number of applications ranging from biological imaging to television displays. In all cases, nanoparticle surface chemistry can significantly impact particle physical properties, processing, and performance. The first step in leveraging this tunability is to develop analytical approaches to describe surface chemical features. Some of the most basic descriptors of particle surface chemistry include the quantity, identity, and arrangement of ligands appended to the particle core. Here, we review approaches to quantify molecular ligand densities on nanoparticle surfaces and consider fundamental barriers to the accuracy of this analysis including parameters such as dispersity in colloidal nanoparticle samples, particle-ligand interactions, and currently available analytical techniques. Techniques reviewed include widely studied methods such as optical, atomic, vibrational, and nuclear magnetic resonance spectroscopies as well as emerging or niche approaches including electrospray-differential mobility analysis, pH-based methods, and X-ray photoelectron spectroscopy. Collectively, these studies elucidate surface chemistry architectures that accelerate both fundamental understanding of nanoscale physical phenomena and the implementation of these materials in a wide range of technologies.

Ligand-Mediated "Turn On," High Quantum Yield Near-Infrared Emission in Small Gold Nanoparticles.

Small gold nanoparticles (∼1.4-2.2 nm core diameters) exist at an exciting interface between molecular and metallic electronic structures. These particles have the potential to elucidate fundamental physical principles driving nanoscale phenomena and to be useful in a wide range of applications. Here, we study the optoelectronic properties of aqueous, phosphine-terminated gold nanoparticles (core diameter = 1.7 ± 0.4 nm) after ligand exchange with a variety of sulfur-containing molecules. No emission is observed from these particles prior to ligand exchange, however the introduction of sulfur-containing ligands initiates photoluminescence. Further, small changes in sulfur substituents produce significant changes in nanoparticle photoluminescence features including quantum yield, which ranges from 0.13 to 3.65% depending on substituent. Interestingly, smaller ligands produce the most intense, highest energy, narrowest, and longest-lived emissions. Radiative lifetime measurements for these gold nanoparticle conjugates range from 59 to 2590 µs, indicating that even minor changes to the ligand substituent fundamentally alter the electronic properties of the luminophore itself. These results isolate the critical role of surface chemistry in the photoluminescence of small metal nanoparticles and largely rule out other mechanisms such as discrete (Au(I)-S-R)n impurities, differences in ligand densities, and/or core diameters. Taken together, these experiments provide important mechanistic insight into the relationship between gold nanoparticle near-infrared emission and pendant ligand architectures, as well as demonstrate the pivotal role of metal nanoparticle surface chemistry in tuning and optimizing emergent optoelectronic features from these nanostructures.

Quantitative analysis of thiolated ligand exchange on gold nanoparticles monitored by 1H NMR spectroscopy.

We use nuclear magnetic resonance spectroscopy methods to quantify the extent of ligand exchange between different types of thiolated molecules on the surface of gold nanoparticles. Specifically, we determine ligand density values for single-moiety ligand shells and then use these data to describe ligand exchange behavior with a second, thiolated molecule. Using these techniques, we identify trends in gold nanoparticle functionalization efficiency with respect to ligand type, concentration, and reaction time as well as distinguish between functionalization pathways where the new ligand may either replace the existing ligand shell (exchange) or add to it ("backfilling"). Specifically, we find that gold nanoparticles functionalized with thiolated macromolecules, such as poly(ethylene glycol) (1 kDa), exhibit ligand exchange efficiencies ranging from 70% to 95% depending on the structure of the incoming ligand. Conversely, gold nanoparticles functionalized with small-molecule thiolated ligands exhibit exchange efficiencies as low as 2% when exposed to thiolated molecules under identical exchange conditions. Taken together, the reported results provide advances in the fundamental understanding of mixed ligand shell formation and will be important for the preparation of gold nanoparticles in a variety of biomedical, optoelectronic, and catalytic applications.

Transverse forces in skeletal muscle with massage-like loading in a rabbit model.

BACKGROUND: The objective of this study was to quantify the transverse forces in skeletal muscle subjected to constant compressive massage-like loading (MLL) following eccentric exercise (ECC). METHODS: Twenty-eight New Zealand White rabbits were used for this two-part study. For all testing, a customized electromechanical device was utilized to apply a constant compressive force MLL to the tibialis anterior (TA) muscle and the resultant transverse forces were quantified. The device consisted of two stepper motors that were positioned orthogonally to each other and connected to separate sliding tracks. A stainless steel cylindrical massage tip was mounted to a customized two-axis sensor consisting of two strain gauges with which forces along the two axes were measured. First, we determined the effects of tissue loading frequency and compression magnitude on transverse forces in the TA. Following a bout of ECC, sixteen rabbits were randomly assigned to a protocol with MLL frequency of 0.25 Hz or 0.5 Hz at a constant compressive force of 5 N or 10 N. Secondly, we utilized a protocol of 0.5 Hz, 10 N, 15 min MLL that was performed on 4 consecutive days commencing immediately post ECC (n = 6 animals) or 48 hours following ECC (n = 6 animals). Transverse forces were measured during all 4 MLL sessions for the entire 15 min duration for both the immediate and the delayed groups. RESULTS: Both frequency and magnitude of compressive force due to MLL showed an effect on the magnitude of transverse force (p < 0.05 for each parameter). Furthermore, MLL beginning immediately following ECC produced higher transverse forces than MLL delayed by 48 hours with an average 20% difference between the two MLL groups over the four day protocol. Forces were higher in the middle 5 minutes compared to the first 5 minutes for all MLL bouts in both groups. CONCLUSIONS: Frequency and magnitude of MLL and timing for delivery of MLL following ECC affect resultant transverse force values for exercised muscle. The application of our findings to humans receiving massage following exercise remains unknown at this time.

Sensing at the Nanoscale Using Nitrogen-Vacancy Centers in Diamond: A Model for a Quantum Pressure Sensor.

The sensing of stress under harsh environmental conditions with high resolution has critical importance for a range of applications including earth's subsurface scanning, geological CO2 storage monitoring, and mineral and resource recovery. Using a first-principles density functional theory (DFT) approach combined with the theoretical modelling of the low-energy Hamiltonian, here, we investigate a novel approach to detect unprecedented levels of pressure by taking advantage of the solid-state electronic spin of nitrogen-vacancy (NV) centers in diamond. We computationally explore the effect of strain on the defect band edges and band gaps by varying the lattice parameters of a diamond supercell hosting a single NV center. A low-energy Hamiltonian is developed that includes the effect of stress on the energy level of a ±1 spin manifold at the ground state. By quantifying the energy level shift and split, we predict pressure sensing of up to 0.3 MPa/Hz using the experimentally measured spin dephasing time. We show the superiority of the quantum sensing approach over traditional optical sensing techniques by discussing our results from DFT and theoretical modelling for the frequency shift per unit pressure. Importantly, we propose a quantum manometer that could be useful to measure earth's subsurface vibrations as well as for pressure detection and monitoring in high-temperature superconductivity studies and in material sciences. Our results open avenues for the development of a sensing technology with high sensitivity and resolution under extreme pressure limits that potentially has a wider applicability than the existing pressure sensing technologies.