Search Results (62)

This study presents the first comprehensive theoretical investigation of the antioxidant mechanisms of trans-isoferulic acid against hydroperoxyl (HOO^•) radicals in aqueous solution, using the DFT/M062X/6-311+G(d,p)/PCM method. Thermodynamic and kinetic parameters, including reaction energy barriers and bimolecular rate constants, were determined for the three major pathways: hydrogen transfer (HT), radical adduct formation (RAF), and single electron transfer (SET). The results indicate that, at physiological pH, the RAF mechanism is both more exergonic and approximately eight-times faster than HT. At a higher pH, where the phenolate anion dominates, antioxidant activity is enhanced by an additional fast, diffusion-limited SET pathway. Isoferulic acid was also found to effectively chelate Fe²⁺ ions at pH 7.4 and above, forming stable complexes that could inhibit Fenton-type hydroxyl radical generation. Moreover, its strong UV absorption suggests a role in limiting photo-induced free radical formation. These findings not only clarify the antioxidant behavior of isoferulic acid but also provide novel theoretical insights applicable to related phenolic compounds. The compound’s multi-target antioxidant profile highlights its potential as a photoprotective agent in sunscreen formulations. Full article

Background: Balance and gait are critical for functional recovery and fall prevention following total hip (THA) and knee arthroplasty (TKA). Despite improvements in pain and joint function, residual impairments often persist. The Timed Up and Go (TUG) test and Tinetti Performance-Oriented Mobility Assessment (POMA) objectively measure postoperative mobility and balance, while patient-reported outcome measures (PROMs) assess perceived function and well-being. This study longitudinally evaluates functional measurement and PROMs to explore their interrelationships and compare recovery trajectories in THA and TKA cohorts. Methods: In this prospective study, 22 THA and 21 TKA patients were assessed preoperatively and at 4–6 days, 6 weeks, 3 months, and 12 months postoperatively using TUG, Tinetti, Hip Disability and Osteoarthritis Outcome Score (HOOS), Knee Injury and Osteoarthritis Outcome Score (KOOS), and clinical scores (Harris Hip Score (HHS) for THA, Knee Society Score (KSS) for TKA). Pearson correlation assessed relationships between measures. Results: Both cohorts demonstrated significant immediate postoperative declines in balance and mobility, recovering to baseline by 6 weeks and surpassing it by 3 and 12 months (p < 0.001). PROMs showed earlier and sustained improvements. Objective balance and mobility measures showed minimal correlation with PROMs but were highly interrelated from 6 weeks onward. Conclusions: THA and TKA patients experience early postoperative balance impairments, suggesting heightened fall risk, with functional recovery lagging behind perceived well-being, highlighting the need for cautious rehabilitation strategies. Full article

Introduction: The present study investigates the five-year outcomes of hip arthroscopy for cam or pincer-type femoroacetabular impingement (FAI) and associated labral tears in a defined patient population. Methods: Patients who underwent hip arthroscopy for cam or pincer-type arthroscopy femoroacetabular impingement (FAI) and labral tears at our hospital in the past five years were included. All patients who underwent revision—like a total hip arthroplasty (THA), a subsequent hip arthroscopy at another hospital, or had primary osseous diseases—were excluded. Patients were contacted via mail and asked to answer a clinical questionnaire called the “Hip Osteoarthritis Outcome Score” (HOOS) and to indicate whether there was a second surgery like a subsequent arthroscopy or THA. Results: There were 77 hip arthroscopies in 75 patients the last 5 years. A total of 29 patients responded. Those who did not respond were contacted via phone. All in all, we obtained the results of 49 patients (50 hips—29 right, 19 left, and 1 bilateral) who underwent hip arthroscopy over the past five years. The mean age at the time of operation was 41 years. Our results were as follows: 24 hips had an isolated labral tear, 49 hips a combined FAI pathology with cam and/or pincer-type impingement and labral tears, 3 patients had a posttraumatic FAI, and 1 patient suffered from hip chondromatosis, who was subsequently excluded; further, 22 patients (23 procedures) were lost to follow-up. HOOS contains various subscales; only the postoperative result of subscale 1 (symptoms) did not show a statistically significant improvement compared with the preoperative value. All other subscales showed a statistically significant improvement in comparison with the preoperative condition. Five patients (10.2%) still experienced symptoms, so we performed a total hip arthroplasty (THA) as a second surgical procedure. One patient was revised due to chondromatosis. One patient was revised at another center, and another was excluded because of chondromatosis. Conclusions: The five-year follow-up results of hip arthroscopy proved successful outcomes. Hip arthroscopy is an effective treatment for FAI in order to delay primary THA, regaining mobility and range of motion and reducing pain. Longer-term studies with a larger cohort are necessary. Full article

Lacticaseibacillus (L.) rhamnosus CRL75 is a lactic acid bacterium (LAB) isolated from local dairy products, demonstrating significant adaptation in skimmed milk (FM75). In this context, CRL75 exhibited high microbial growth (3.63 ± 0.18 log CFU·mL⁻¹), strong acidification (9.20 ± 0.10 g·L⁻¹ lactic acid, and 2.40 ± 0.10 pH units), and increased viscosity in FM75 after 16 h of fermentation. Additionally, this LAB strain produces both capsular polysaccharides (CPS+) and extracellular polysaccharides (EPS75), contributing to a ropy phenotype (>10 cm). The purified EPS75 (70.70 ± 3.25 mg·L⁻¹) displayed low molecular weight (12.7 kDa), with galactose and glucose as its primary monomers in a 4:1 ratio. In aqueous environments, EPS75 exhibited an extended size (147 nm), a random coil structure, and macromolecular aggregation. Furthermore, vibrational spectroscopy confirmed the presence of a neutral EPS with high thermal stability. Additionally, EPS75 exhibited dose-dependent antioxidant activity, effectively reducing metal ions (Fe³⁺, Mo⁶⁺, and Mn⁷⁺) and stabilizing radicals (ABTS^•+, HO^•, O₂^•−, and HOO^•). The biopolymer also demonstrated immunostimulatory and anti-inflammatory effects in RAW 264.7 cells. In vivo assays using Balb/c mice indicated that both EPS75 and FM75 prevented constipation, suggesting their potential as natural and safe agents for constipation-related disorders. Due to its viscosifying and health-promoting attributes, CRL75 offers promising applications for functional dairy products. Full article

Background/Objectives: In 2020, 595 million world citizens had osteoarthritis, and the largest growth in OA morbidity refers to the hip joint. Effective OA therapies have been sought for years. Assessing the treatment effectiveness and QoL improvement in hip OA after intra-articular administration of fresh peripheral blood hematopoietic CD34+ stem cells. Methods: The study comprised 49 adults (median age: 63). The SCs were injected into hip joints and straight to the bone. Hip manipulation was conducted. Patients were subjected to a standardized rehabilitation protocol. Hip degeneration was graded by Kellgren–Lawrence. Multi-factor statistical analyses, with replications, were performed. The study was an R&D project, co-financed by the E.U. Results: Patient-reported outcomes (HOOS, SF-36) ameliorated remarkably over 24 months (p < 0.0001). Ranges of movement improved significantly (p < 0.0001). The most noticeable improvement manifested 6 months after the SC administration. Its furtherance was maintained. Conclusions: Intra-articular administration of CD34+ cells significantly reduces pain and improves hip joint function, regardless of the severity of OA, according to K-L, over a 24-month follow-up period. The combination of CD34+ cell therapy with joint mobilization and rehabilitation allows for the postponement of hip arthroplasty by significantly improving patients’ QoL over the 24-month follow-up period. Full article

Bromophenols (BPs), particularly those derived from marine sources, are known for their potent radical scavenging activity, effectively neutralizing reactive oxygen species (ROS). However, their exact mechanism of action remains largely unexplored, limiting our understanding of their potential as natural antioxidants. In this study, the antiradical mechanisms of two BP derivatives (1 and 2), previously isolated from the marine red alga Polysiphonia urceolata, were systematically investigated using thermodynamic and kinetic calculations. Both compounds demonstrated potent hydroperoxyl radical (HOO^•) scavenging activity in polar and lipid environments, with rate constants surpassing those of the well-known antioxidant standards Trolox and BHT. In lipid media, BP 2 exhibited approximately 600-fold greater activity than BP 1, with rate constants of 9.75 × 10⁵ and 1.64 × 10³ M⁻¹ s⁻¹, respectively. In contrast, both BPs showed comparable activity in aqueous media, with rate constants of 3.46 × 10⁸ and 9.67 × 10⁸ M⁻¹ s⁻¹ for 1 and 2, respectively. Mechanistic analysis revealed that formal hydrogen atom transfer (f-HAT) is the predominant pathway for radical scavenging in both lipid and polar environments. These findings provide critical insights into the antiradical mechanisms of natural BPs and underscore the potential of BP 1 and BP 2 as highly effective hydroperoxyl radical scavengers under physiological conditions. Full article

Background/Objectives: Reported patient results after total hip arthroplasty (THA) have been described as a function of surgical approach. Such results have commonly been subjective. Though self-reported outcomes are of value and often utilized, inclusion of functional performance measures represents an objective measure to compare THA techniques. Methods: Patients that underwent primary THA surgery at our institution were grouped by surgical approach (Direct Anterior vs Posterior). Patient data were collected pre-operatively, as well as post-operatively at three and twelve months. Hip Dysfunction and Osteoarthritis Outcome Score (HOOS JR) was utilized, and function was assessed with the timed up and go test (TUGT), 4-m walk test (4MWT), and 30 s sit-to-stand (30STS) test. Unpaired T tests were used to compare mean results and differences between the groups. Results: Functional outcome scores were improved to a similar degree for both surgical approach groups at all the time points post-operatively. At 3 months, the TUGT was improved by 2.33 s for the posterior group, the 30STS was increased by 2.71 repetitions, and the 4MWT was increased by 1.23 s; the anterior group had 2.66 s, 2.49 repetition, and 1.18 s improvements in the three functional tests, respectively. At 12 months, the posterior group had improvements of 2.86 s, 3.99 repetition, and 1.19 s, while the anterior group had improvements of 3.15 s, 3.83 repetition, and 1.23 s, respectively. No clinical and statistical significant differences in surgical approach were noted in these measures. In contrast, the anterior group showed a statistically significant but not clinically significant improvement in self-reported HOOS JR scores compared to the posterior group at the 3-month post-operative mark (p = 0.045). Conclusions: This study suggests both anterior and posterior surgical approaches to total hip arthroplasty yield equivalent functional results at 3 months and one year post-operatively, while the anterior approach demonstrates more improved patient satisfaction than the posterior approach at the 3-month post-operative assessment. Full article

Background: Despite the popularity of the modified Harris Hip Score (mHHS) to monitor patient-reported outcome measures (PROMs) following Total Hip Arthroplasty (THA) over the last 5 decades, International Joint Registries have recently favoured the Hip disability and Osteoarthritis Outcome Score (HOOS). The ability to convert mHHS collected in historical and ongoing studies would be beneficial to benchmark more recent HOOS reports. Hence, this study aimed to create multi-directional crosswalks between mHHS and HOOS. Methods: Forty-nine patients undergoing primary THA prospectively completed both HHS and HOOS forms pre-operatively and at either 3, 6 and/or 12 months postoperatively. The Equipercentile (EQ) and Linear Regression (LR) crosswalk methodology were used. The Mean Absolute Error (MAE) of the crosswalk-derived scores was established against patient-derived (PD) scores. Results: There was a strong correlation between PD mHHS and HOOS (0.90) and HOOS-12 (0.90). The MAE of mHHS-to-HOOS-12 crosswalk was 10.4 (EQ) and 10.1 (LR). Subcategory activity had a larger contribution towards the error in the crosswalks than pain. Conclusions: This is the first crosswalk to facilitate conversion of mHHS and HOOS scores, which are required in long-term THA quality-assurance and research studies, which often span 2 decades of expected implant survivorship. Full article

Background: Clinical guidelines for physiotherapy following total hip and knee arthroplasty (THA/TKA) recommend using Patient-Reported Outcome Measures (PROMs) like the Hip disability and Knee injury Osteoarthritis Outcome Score (HOOS/KOOS). However, it remains unclear how physiotherapists use these PROMs in daily clinical practice. Objective: To explore primary care physiotherapists’ experiences with the HOOS/KOOS in daily clinical practice following THA and TKA. Methods: Thirteen physiotherapists in the Netherlands were recruited via convenience sampling. Data were collected through semi-structured interviews, which explored HOOS/KOOS use in clinical practice, administrative regulations, and applications beyond patient care, as well as think-aloud interviews to capture perceptions of the content of these PROMs and interpretations of hypothetical patient scores. Interviews were analysed using reflexive thematic analysis. Results: The physiotherapists’ ages ranged from 25 to 54y, with annual THA/TKA volumes from 5 to 50 patients. Three themes emerged, as follows: (1) “Physiotherapists use the HOOS/KOOS for various purposes in daily clinical practice”, including complementing history taking and monitoring patient progress; (2) “Perceptions of the relevance of the HOOS/KOOS for daily clinical practice vary per item, domain, and version,” with items related to daily life activities and psychosocial factors being perceived as more valuable; and (3) “Practical aspects of HOOS/KOOS administration influence their use in daily clinical practice,” with electronic health records (EHRs) that facilitate PROM administration enhancing their use, while administrative regulations limit this. Conclusions: Physiotherapists experience HOOS/KOOS items related to daily life activities and psychosocial factors useful for history-taking and monitoring patient progress, particularly when embedded in EHRs that facilitate PROM administration. Full article

Five representatives of a novel type of di(hydroperoxy)alkane adducts of phosphine oxides have been synthesized and fully characterized, including their solubility in organic solvents. The phosphine oxide Cy₃PO (1) has been used in combination with the corresponding aldehydes to create the adducts Cy₃PO·(HOO)₂CHCH₃ (2), Cy₃PO·(HOO)₂CHCH₂CH₃ (3), Cy₃PO·(HOO)₂CH(CH₂)₂CH₃ (4), Cy₃PO·(HOO)₂CH(CH₂)₃CH₃ (5), and Cy₃PO·(HOO)₂CH(CH₂)₇CH₃ (6). All adducts crystallize easily and contain the peroxide and phosphine oxide hydrogen-bonded in 1:1 ratios. The single crystal X-ray structures of 2–6 and their unique features are discussed. The ³¹P NMR spectra of the adducts 2–6 show downfield-shifted signals as compared to Cy₃PO. In the IR spectra, the ν(P=O) wavenumbers of the adducts have smaller values than the neat phosphine oxide. All spectroscopic results of 2–6 show that the P=O bond is weakened by hydrogen-bonding to the di(hydroperoxy)alkane moieties. Adduct 6 selectively oxidizes PPh₃ to OPPh₃ within minutes, and nonanal is reformed in the process. The easy synthesis, handling, and administration of these stable, solid, and soluble peroxides with well-defined composition will have a positive impact on synthetic chemistry. Full article

In this study, the antioxidant and prooxidant potency of protocatechuic aldehyde (PCA) was evaluated using density functional theory (DFT). The potency of direct scavenging of hydroperoxyl (HOO^•) and lipid peroxyl radicals (modeled by vinyl peroxyl, H₂C=CHOO^•) involved in lipid peroxidation was estimated. The repair of oxidative damage in biomolecules (lipids, proteins and nucleic acids) and the prooxidant ability of PCA phenoxyl radicals were considered. The repairing potency of PCA was investigated for damaged tryptophan, cysteine, leucine, DNA base guanine and linolenic acid. The thermodynamics and kinetics of the single electron transfer (SET) and formal hydrogen atom transfer (fHAT) mechanisms underlying the studied processes were investigated under physiological conditions in aqueous and lipid environments using the SMD/M06-2X/6-311++G(d,p) level of theory. Sequestration of catalytic Fe²⁺ and Fe³⁺ ions by PCA, which prevents HO^• production via Fenton-like reactions, was modeled. Molecular docking was used to study the inhibitory capability of PCA against xanthine oxidase (XO), one of the enzymes producing reactive oxygen species. The attained results show that PCA has the capability to scavenge lipid peroxyl radicals, repair damaged tryptophan, leucine and guanine, chelate catalytic iron ions and inhibit XO. Thus, PCA could be considered a possible multifunctional antioxidant. Full article

In this study, the DFT/M062X/PCM method was applied to investigate thermodynamic and kinetic aspects of reactions involved in possible mechanisms of antioxidant activity of caffeic acid against HOO^● radicals in aqueous medium at different pH values. Kinetic parameters of the reactions involved in HAT (Hydrogen Atom Transfer), RAF (Radical Adduct Formation), and SET (Single Electron Transfer) mechanisms, including reaction energy barriers and bimolecular rate constants, were determined, and identification and characterization of stationary points along the reaction pathways within HAT and RAF mechanisms were performed. Inspection of geometrical parameters and spin densities of the radical products formed within HAT and RAF mechanisms revealed that they are stabilized by hydrogen bonding interactions and the odd electron originated through the reaction with the HOO^● radical is spread over the entire molecule, resulting in significant radical stabilization. Thermodynamic and kinetic data collected in this study indicated that increasing pH of the medium boosts the antioxidant activity of caffeic acid by reducing the energy required to generate radicals within the RAF and/or HAT mechanism and, at extremely high pH, where the trianionic form of caffeic acid is a dominant species, by the occurrence of an additional fast, diffusion-limited electron-related channel. Full article

The COVID-19 pandemic has triggered the adoption of new technologies to reduce the need for in-person physical therapy (PT). This study evaluated the impact of the COVID-19 pandemic on PT utilization and outcomes of patients prescribed a smartphone-based care management platform (sbCMP) for self-directed rehabilitation (SDR). A secondary analysis of data collected in a multicenter, prospective cohort trial investigating a mobile platform to deliver SDR after arthroplasty was performed. Patients who used the sbCMP for 2 weeks prior to undergoing partial knee arthroplasty (PKA), total knee arthroplasty (TKA), or total hip arthroplasty (THA) and provided 3 months of post-operative data were included. Use of adjunct PT at 3 months, step counts, and KOOS JR and HOOS JR scores were compared during the early versus late pandemic period. The cohort data was available for 1665 patients. Use of SDR without adjunct PT was higher in the early period of the COVID-19 pandemic in TKA (35.3% vs. 27.6%, p = 0.03) and THA (72.5% vs. 59.3%, p < 0.001), but not in the PKA cohort (58.9% vs. 53.3%, p = 0.53). Post-operative step counts improved at 3 months compared to pre-operative levels in all procedure types. Change in HOOS JR and KOOS JR scores from pre-operative to post-operative levels were similar by pandemic period in all cohorts. Use of SDR increased early during the COVID-19 pandemic, corresponding to pandemic restrictions, without negatively impacting patient outcomes. SDR facilitated via a sbCMP may be beneficial for patients unable or unwilling to participate in traditional PT visits. Full article

Hip Disability and Osteoarthritis Outcome Survey (HOOS) was developed as a region- and disease-specific outcome to assess hip disability. Despite the use of the HOOS in clinical practice and research, psychometric analyses of the scale in a large dataset of patients have not been performed. As such, the purposes of this study were to assess the structural validity of the HOOS in patients who underwent a total hip arthroplasty. Data were obtained from the Surgical Outcome System (SOS) global registry. Confirmatory factor analysis (CFA) was conducted to assess the scale structure of the 40-item HOOS and exploratory factor analysis (EFA) was conducted to identify a parsimonious scale structure. The parsimonious model identified was subjected to multi-group and longitudinal invariance testing and LGC modeling. The original five-factor, 40-item HOOS did not meet recommended model fit indices values (CFI = 0.822, TLI = 0.809, IFI = 0.822, RMSEA = 0.085). Alternate model generation identified an alternative model (i.e., HOOS-9). Sound model fit was identified for the HOOS-9 (CFI = 0.974, TLI = 0.961, RMSEA = 0.046). Invariance testing criteria were also met between groups (i.e., age and sex) and across time. Lastly, a nonlinear growth trajectory was identified in responses pertaining to hip disability. The original scale structure of the 40-item HOOS was not supported. The HOOS-9 met contemporary model fit recommendations, along with multi-group and longitudinal invariance testing. Our findings support the preliminary use of the HOOS-9 to assess hip function and disability in research and clinical practice. Full article

The oxidation of benzylic alcohols is an important transformation in modern organic synthesis. A plethora of photoredox protocols have been developed to achieve the aerobic oxidation of alcohols into carbonyls. Recently, several groups described that ultraviolet (UV) or purple light can initiate the aerobic oxidation of benzylic alcohols in the absence of an external catalyst, and depicted different mechanisms involving the photoinduction of ^•O₂⁻ as a critical reactive oxygen species (ROS). However, based on comprehensive mechanistic investigations, including control experiments, radical quenching experiments, EPR studies, UV–vis spectroscopy, kinetics studies, and density functional theory calculations (DFT), we elucidate here that HOO^•, which is released via the H₂O₂ elimination of α-hydroxyl peroxyl radicals [ArCR(OH)OO^•], serves as the real chain carrier for the autocatalytic photooxidation of benzylic alcohols. The mechanistic ambiguities depicted in the precedent literature are clarified, in terms of the crucial ROS and its evolution, the rate-limiting step, and the primary radical cascade. This work highlights the necessity of stricter mechanistic analyses on UV-driven oxidative reactions that involve aldehydes’ (or ketones) generation. Full article