Investigation of the Relationship between Quantum Yield, Charge-Transfer State, and Structure of the Ligands in Red-Emitting Heteroleptic Iridium(III) Complexes.

Iridium(III) organometallic complexes have been a key component in commercialization of organic light-emitting diodes, but the direct relationship between their structural features and photophysical properties has not yet been fully established. Here, combined experimental and theoretical studies are carried out to elucidate the main factors governing the quantum efficiency of red phosphorescent emitters by using two heteroleptic iridium(III) complexes with high geometrical similarity. It is found that two red-emitting heteroleptic iridium complexes differing only in the steric direction of phenylquinoline (pq) and phenylisoquinoline (piq) ligands, annotated Red-pq and Red-piq, show clearly different degrees of distortion of the ligand geometry in the excited state, which leads to the higher quantum yield of Red-piq than that of Red-pq. This larger distortion of the piq ligand causes more suppressed nonradiative decay of Red-piq than that of Red-pq which is the important factor governing the higher quantum yield of Red-piq.

Unsupervised machine learning for clustering forward head posture, protraction and retraction movement patterns based on craniocervical angle data in individuals with nonspecific neck pain.

OBJECTIVES: The traditional understanding of craniocervical alignment emphasizes specific anatomical landmarks. However, recent research has challenged the reliance on forward head posture as the primary diagnostic criterion for neck pain. An advanced relationship exists between neck pain and craniocervical alignment, which requires a deeper exploration of diverse postures and movement patterns using advanced techniques, such as clustering analysis. We aimed to explore the complex relationship between craniocervical alignment, and neck pain and to categorize alignment patterns in individuals with nonspecific neck pain using the K-means algorithm. METHODS: This study included 229 office workers with nonspecific neck pain who applied unsupervised machine learning techniques. The craniocervical angles (CCA) during rest, protraction, and retraction were measured using two-dimensional video analysis, and neck pain severity was assessed using the Northwick Park Neck Pain Questionnaire (NPQ). CCA during sitting upright in a comfortable position was assessed to evaluate the resting CCA. The average of midpoints between repeated protraction and retraction measures was considered as the midpoint CCA. The K-means algorithm helped categorize participants into alignment clusters based on age, sex and CCA data. RESULTS: We found no significant correlation between NPQ scores and CCA data, challenging the traditional understanding of neck pain and alignment. We observed a significant difference in age (F = 140.14, p < 0.001), NPQ total score (F = 115.83, p < 0.001), resting CCA (F = 79.22, p < 0.001), CCA during protraction (F = 33.98, p < 0.001), CCA during retraction (F = 40.40, p < 0.001), and midpoint CCA (F = 66.92, p < 0.001) among the three clusters and healthy controls. Cluster 1 was characterized by the lowest resting and midpoint CCA, and CCA during pro- and -retraction, indicating a significant forward head posture and a pattern of retraction restriction. Cluster 2, the oldest group, showed CCA measurements similar to healthy controls, yet reported the highest NPQ scores. Cluster 3 exhibited the highest CCA during protraction and retraction, suggesting a limitation in protraction movement. DISCUSSION: Analyzing 229 office workers, three distinct alignment patterns were identified, each with unique postural characteristics; therefore, treatments addressing posture should be individualized and not generalized across the population.

Effects of isolated shoulder versus core-shoulder chain exercises on motor control and isokinetic torque in baseball pitchers with shoulder impingement syndrome: A single-blinded randomized controlled trial.

Recent biomechanical evidence suggests that shoulder impingement syndrome (SIS) is closely linked with altered core-shoulder kinetic chain, resulting pain, altered external shoulder muscle activation, and external muscle weakness. We aimed to compare the effects of conventional isolated shoulder exercise (ISE) and core-shoulder chain exercises (CCE) during isokinetic shoulder rotation in baseball pitchers with SIS. Forty male college baseball pitchers with SIS were randomly allocated to ISE and CCE groups and they performed the exercises 3 times a week for 6 weeks. The standardised numerical pain rating scale (NPRS), shoulder pain and disability index (SPADI), electromyography (EMG) amplitude, and concentric (CON) and eccentric (ECC) torques were measured. Substantial improvements in NPRS and SPADI scores were observed after CCE compared to ISE (p ≤ 0.046). Internal oblique/transversus abdominis, rectus abdominis, external oblique, serratus anterior, and infraspinatus muscle activation were significantly higher after CCE than ISE (p ≤ 0.033). CON and ECC torques were higher after CCE than ISE (p ≤ 0.002). The present findings demonstrated superior therapeutic effects of CCE in improving pain, disability level, shoulder muscle activation, and torque (muscle strength) in baseball pitchers with SIS compared to the conventional ISE, highlighting the importance of the chain exercise concept.

Comparison of acromiohumeral distance and glenohumeral internal rotation angle between the empty can test and modified empty can test: "thumb pointing down" versus "elbow pointing laterally".

BACKGROUND: During the empty can test, the direction of the thumb (downward) has been widely used as an instruction for producing glenohumeral internal rotation. However, the combination of forearm pronation and thumb motion as a compensatory movement could contribute to the lack of glenohumeral internal rotation during the empty can test. This study aimed to compare the glenohumeral internal rotation angle between the conventional empty can (with thumb direction) and modified empty can tests (with elbow direction), as well as the acromiohumeral distance between the full can, conventional empty can, and modified empty can tests. METHODS: In this laboratory study, we measured the glenohumeral internal rotation angle using a motion sensor and the acromiohumeral distance using ultrasonography during the following tests: full can test (thumb pointing up), conventional empty can test (thumb pointing down), and modified empty can test (elbow pointing laterally) in 20 healthy subjects. RESULTS: Compared with the conventional empty can test, the glenohumeral internal rotation angle was significantly greater during the modified empty can test (p < 0.05). Furthermore, the acromiohumeral distance measured in the modified empty can test was significantly less than that in the full can test (p < 0.001) and conventional empty can test (p < 0.001). However, there was no difference in the acromiohumeral distance between the full can test and the conventional empty can test (p > 0.017). CONCLUSIONS: During the empty can test, the instructions should be given to patients based on the elbow direction (elbow pointing laterally). The modified empty can test can produce full glenohumeral internal rotation, compared with instructions based on the thumb direction (thumb pointing down). Consequently, the modified empty can test can produce a more decreased subacromial space.

Prediction model of subacromial pain syndrome in assembly workers using shoulder range of motion and muscle strength based on support vector machine.

Subacromial pain syndrome (SAPS) is the most common upper-extremity musculoskeletal problem among workers. In this study, a machine learning model was built to predict and classify the presence or absence of SAPS in assembly workers with shoulder joint range of motion (ROM) and muscle strength data using support vector machine (SVM). Permutation importance was used to determine important variables for predicting workers with or without SAPS. The accuracy of the support vector classifier (SVC) polynomial model for classifying workers with SAPS was 82.4%. The important variables in model construction were internal rotation and abduction of shoulder ROM and internal rotation of shoulder muscle strength. It is possible to accurately perform SAPS classification of workers with relatively easy-to-obtain shoulder ROM and muscle strength data using this model. In addition, preventing SAPS in workers is possible by adjusting the factors affecting model building using exercise or rehabilitation programs.Practitioner summary: This study aimed to create a machine learning model that can predict and classify SAPS using shoulder ROM and muscle strength and identify the variables that are of high importance in model construction. This model could be used to predict or classify workers' SAPS and manage or prevent SAPS.

Dealkenylative Alkynylation Using Catalytic FeII and Vitamin C.

In this paper, we report the synthesis of alkyl-tethered alkynes through ozone-mediated and FeII-catalyzed dealkenylative alkynylation of unactivated alkenes in the presence of alkynyl sulfones. This one-pot reaction, which employs a combination of a catalytic FeII salt and l-ascorbic acid, proceeds under mild conditions with good efficiency, high stereoselectivity, and broad functional group compatibility. In contrast to our previous FeII-mediated reductive fragmentation of α-methoxyhydroperoxides, the FeII-catalyzed process was devised through a thorough kinetic analysis of the multiple competing radical (redox) pathways. We highlight the potential of this dealkenylative alkynylation through multiple post-synthetic transformations and late-stage diversifications of complex molecules, including natural products and pharmaceuticals.

Enantioselective Synthesis of Quaternary Oxindoles: Desymmetrizing Staudinger-Aza-Wittig Reaction Enabled by a Bespoke HypPhos Oxide Catalyst.

This paper describes a catalytic asymmetric Staudinger-aza-Wittig reaction of (o-azidoaryl)malonates, allowing access to chiral quaternary oxindoles through phosphine oxide catalysis. We designed a novel HypPhos oxide catalyst to enable the desymmetrizing Staudinger-aza-Wittig reaction through the PIII/PV═O redox cycle in the presence of a silane reductant and an IrI-based Lewis acid. The reaction occurs under mild conditions, with good functional group tolerance, a wide substrate scope, and excellent enantioselectivity. Density functional theory revealed that the enantioselectivity in the desymmetrizing reaction arose from the cooperative effects of the IrI species and the HypPhos catalyst. The utility of this methodology is demonstrated by the (formal) syntheses of seven alkaloid targets: (-)-gliocladin C, (-)-coerulescine, (-)-horsfiline, (+)-deoxyeseroline, (+)-esermethole, (+)-physostigmine, and (+)-physovenine.

Altered muscle recruitment patterns during isometric shoulder abduction in individuals with chronic upper trapezius pain: a cross sectional study.

BACKGROUND: Upper trapezius (UT) pain with myofascial trigger points (MTrPs) can affect movement at the glenohumeral joint as well as at the scapulothoracic joint. The investigation of muscle recruitment patterns can discern motor control strategies. The purpose of this study was to compare shoulder muscle recruitment patterns and muscle activity according to various loads between individuals with and without chronic UT pain. METHODS: In this cross-sectional study, twenty-four participants that had UT pain with MTrPs and sex, age, body weight matched 24 controls with no UT pain were recruited. Surface EMG electrodes were attached to the UT, the serratus anterior (SA), the lower trapezius (LT) and the middle deltoid (MD). All participants performed isometric shoulder abduction with a load of 25%, 50%, or 75% of the maximum strength at 60° of shoulder abduction. The EMG activity, the activity ratio (SA/UT, LT/UT, MD/UT), and the relative contribution of each muscle activity were calculated. RESULTS: MD activity was significantly decreased in the UT pain group compared to that in the control group (p < 0.05). The EMG activity ratio of SA/UT (p < 0.025) and the relative contribution of SA activity to shoulder abduction (p < 0.05) were significantly greater in the UT pain group than in the control group in the 25% loading condition. CONCLUSION: The results of present study showed that UT pain with MTrPs may increase the relative contribution of SA activity and decrease MD activity at low loads. Altered recruitment patterns of scapular upward rotators can be altered in the proper scapular position, which results in decreased MD activity. Clinicians should consider altered recruitment patterns when managing UT pain. TRIAL REGISTRATION: Clinical Research Information Service: Clinical Research Information Service (KCT0007370; 08/06/2022).

Subgrouping of Peripheral Neuropathic Pain Patients According to Sensory Symptom Profile Using the Korean Version of the PainDETECT Questionnaire.

BACKGROUND: A culturally validated Korean version of the PainDETECT Questionnaire (PD-Q) was used to identify neuropathic pain components (NeP) in patients suffering from chronic pain. The purpose of this study was to determine if the Korean PD-Q can be used to subgroup patients with peripheral NeP according to sensory symptom profiles. METHODS: This study included 400 Korean patients with peripheral neuropathic pain diagnosed as probable or definite NeP. The total scores and subscores for each item in PD-Q were transformed into a Z-score for standardization. Hierarchical cluster analysis was performed to identify clusters of subjects by PD-Q scores. RESULTS: The mean total PD-Q score of the study participants was 14.57 ± 6.46. A hierarchical cluster analysis identified 5 clusters with distinct pain characteristic profiles. Cluster 1 had relatively severe burning and tingling sensations. The mean total PD-Q score for cluster 2 was the lowest of the 5 clusters. Cluster 3 tended to be vulnerable to pain in response to cold/heat stimulation. Cluster 4 showed relatively severe pain induced by physical stimuli, such as light touch or slight pressure. Cluster 5 had high scores for all NeP symptoms. CONCLUSION: This study demonstrates the ability of patients to cluster by symptoms using the Korean PD-Q. Subgrouping of peripheral neuropathic pain by sensory symptom profile may be useful in making effective drug treatment decisions.

Comparison of MOG and AQP4 antibody seroprevalence in Korean adults with inflammatory demyelinating CNS diseases.

We aimed to compare seroprevalence of anti-myelin oligodendrocyte glycoprotein (MOG) and anti-aquaporin-4 (AQP4) antibodies in Korean adults with inflammatory demyelinating diseases (IDDs) of the central nervous system (CNS), based on a multicenter nationwide database. Sera were analyzed using a live cell-based assay for MOG and AQP4 antibodies. Of 586 Korean adults with IDDs of the CNS, 36 (6.1%) and 185 (31.6%) tested positive for MOG and AQP4 antibodies, respectively. No participant showed double positivity. Seroprevalence of MOG antibodies was about five times lower than that of AQP4 antibodies in a large cohort of Korean adults with IDDs of the CNS.