Elbow flexion contractures in neonatal brachial plexus palsy: A one-year comparison of dynamic orthosis and serial casting.

OBJECTIVE: Elbow flexion contractures are common complications of neonatal brachial plexus palsy, but evidence on how to treat these contractures is weak. This study compared the treatment of elbow flexion contractures using a dynamic orthosis or serial circular casting. METHODS: A randomized controlled trial was conducted with one-year follow-up. Children with an elbow flexion contracture of ≥30° were treated with either a night-worn dynamic orthosis for one year or serial casting for four weeks followed by night splinting. For pragmatic reasons, some participants were included in an open part of this study, this group was also analyzed separately. Degree of contracture and goal attainment scaling was evaluated at baseline and after 8, 20 and 54 weeks. RESULTS: 55 patients were analyzed in this trial, 32 of whom were randomized to treatment. At one-year follow-up of the randomized group, both dynamic splinting (median -8.5°, interquartile range [IQR] -13.5, -5) and serial casting (median -11.0°, IQR -16, -5) resulted in significant reduction of contracture (P < 0.001). The reduction was significantly greater with serial casting in the first 20 weeks, but not at one-year follow-up (P = 0.683). In the entire cohort, the individual functional goals had been reached in 24 out of 32 cases (80%) of dynamic splinting and 18 out of 23 cases (82%) of serial casting, respectively. CONCLUSION: The dynamic night orthosis is comparable to serial casting for treating elbow flexion contractures in children with brachial plexus birth injury. We recommend selecting one of these treatment modalities in close consultation with parents and patients.

Evidence for sustained cortical involvement in peripheral stretch reflex during the full long latency reflex period.

Adaptation of reflexes to environment and task at hand is a key mechanism in optimal motor control, possibly regulated by the cortex. In order to locate the corticospinal integration, i.e. spinal or supraspinal, and to study the critical temporal window of reflex adaptation, we combined transcranial magnetic stimulation (TMS) and upper extremity muscle stretch reflexes at high temporal precision. In twelve participants (age 49 ± 13 years, eight male), afferent signals were evoked by 40 ms ramp and subsequent hold stretches of the m. flexor carpi radialis (FCR). Motor conduction delays (TMS time of arrival at the muscle) and TMS-motor threshold were individually assessed. Subsequently TMS pulses at 96% of active motor threshold were applied with a resolution of 5-10 ms between 10 ms before and 120 ms after onset of series of FCR stretches. Controlled for the individually assessed motor conduction delay, subthreshold TMS was found to significantly augment EMG responses between 60 and 90 ms after stretch onset. This sensitive temporal window suggests a cortical integration consistent with a long latency reflex period rather than a spinal integration consistent with a short latency reflex period. The potential cortical role in reflex adaptation extends over the full long latency reflex period, suggesting adaptive mechanisms beyond reflex onset.

Cranial translation of the humeral head on radiographs in rotator cuff tear patients: the modified active abduction view.

Cranial translation of the humeral head is related to massive rotator cuff tears; however, it may be unapparent in early-stage tears. The goal of this study was to investigate whether active abduction leads to increased active cranial humeral translation in early-stage tears. We assessed 20 consecutive patients (9 full-thickness supraspinatus tears, 11 posterosuperior tears) using the newly introduced modified active abduction view: acromiohumeral (AH) distance was measured on radiographs acquired during rest and active isometric abduction and adduction tasks with the arm alongside the body. Rest AH was 7.5 mm (SD = 1.53); during abduction and adduction, it decreased to 2.1 mm (95 % CI 1.28-3.01, p < 0.001) and 1.1 mm (95 % CI 0.46-1.65, p = 0.001), respectively. Cranial translation during abduction was more severe in shoulders with posterosuperior cuff tears (∆AH = 3 mm, SD = 1.5) compared to supraspinatus tears (∆AH = 1 mm, SD = 1.6), with a mean difference of 2 mm (95 % CI 0.64-3.58, p = 0.007). Both active isometric abduction and adduction leads to active cranial translation in cuff tear patients. Cranial translation is largest during active abduction. Furthermore, there is significant more cranial translation in posterosuperior cuff tear patients compared to supraspinatus cuff tear patients. Possibly, radiographs combined with active tasks offer new possibilities in diagnosing early-stage rotator cuff tears.

Cranial humerus translation, deltoid activation, adductor co-activation and rotator cuff disease - different patterns in rotator cuff tears, subacromial impingement and controls.

BACKGROUND: Arm adductor co-activation during abduction has been reported as a potential compensation mechanism for a narrow subacromial space in patients with rotator cuff dysfunction. We assessed differences in acromiohumeral distance at rest and the amount of humerus translation during active abduction and adduction in patients with rotator cuff tears (n=20) and impingement (n=30) and controls (n=10), controlled for deltoid, pectoralis major, latissimus dorsi and teres major activation (electromyography). METHODS: During the acquirement of shoulder radiographs, subjects performed standardized isometric arm abduction and adduction tasks. EMG's were normalized between -1 and 1 using the "Activation Ratio", where low values express (pathologic) co-activation, e.g. adductor activation during abduction. FINDINGS: In patients with cuff tears mean rest acromiohumeral distance was 7.6mm (SD=1.6): 3.5mm narrower compared to patients with impingement (95%-CI: 2.4-4.5) and 1.3mm narrower compared to controls (95%-CI: -0.1-2.7). Both during abduction and adduction tasks, cranial translation was observed with equal magnitudes for patients and controls, with average values of 2.3 and 1.7mm, respectively. Where patients with cuff tears had lower adductor Activation Ratios (i.e. more adductor co-activation during abduction), no association between abductor/adductor muscle activation and acromiohumeral distance was found. INTERPRETATION: The subacromial space is narrower in patients with rotator cuff tears compared to patients with impingement and controls. We found additional subacromial narrowing during isometric abduction and, to a lesser amount, during adduction in all subjects and more adductor co-activation in patients with cuff tears. We found no association between subacromial space and activation of the deltoid and main adductors.

Pathologic deltoid activation in rotator cuff tear patients: normalization after cuff repair?

Rotator cuff (RC) tears have a high prevalence, and RC repair surgery is frequently performed. Evaluation of deltoid activation has been reported as an easy to measure proxy for RC functionality. Our goal was to test the success of RC repair in restoring muscle function, by assessing deltoid activation with varying arm abduction moment loading tasks in controls and in RC tear patients before and 1 year after RC repair. Averaged rectified electromyography recordings (rEMG) of the deltoid during 2-s isometric arm abduction tasks were assessed in 22 controls and 33 patients before and after RC repair. Changes in deltoid activation as a response to increased arm abduction moment loading (large vs. small moment), without changing task force magnitude, were expressed as: R = (rEMGLarge - rEMGSmall)/(rEMGLarge + rEMGSmall), where R > 0 indicates an increase in muscle activation with larger moment loading. In controls, a significant increase in deltoid activation was observed with large abduction moment loading: R = 0.11 (95 % CI 0.06-0.16). In patients, R was larger: 0.20 (95 % CI 0.13-0.27) preoperatively and 0.16 (95 % CI 0.09-0.22) postoperatively. Increased compensatory deltoid activation was found in pre-operative RC tear patients. The post-operative decrease in compensatory deltoid activation, although not significant, could indicate (partially) restored RC function in at least some patients.

The Supraspinatus and the Deltoid - not just two arm elevators.

BACKGROUND: The debate on the clinical and functional role of the Supraspinatus in relation to the Deltoid necessitates experimental assessment of their contributions to arm elevation. Our goal was to evaluate the responses of both muscles to increased elevation moment loading. METHODS: Twenty-three healthy volunteers applied 30N elevation forces at the proximal and distal humerus, resulting in small and large glenohumeral elevation moment tasks. The responses of the Deltoid and Supraspinatus were recorded with surface and fine-wire electromyography, quantified by (EMGdistal-EMGproximal), and normalized by the summed activations (EMGdistal+EMGproximal) to RMuscle ratios. RESULTS: Deltoid activity increased with large elevation moment loading (RDE=.11, 95%-CI [.06-.16]). Surprisingly, there was no significant average increase in Supraspinatus activation (RSSp=.06, 95%-CI [-.08 to .20]) and its response was significantly more variable (Levene's test, F=11.7, p<.001). There was an inverse association between the responses (ß=-1.02, 95%-CI [-2.37 to .32]), indicating a potential complementary function of the Supraspinatus to the Deltoid. CONCLUSION: The Deltoid contributes to the glenohumeral elevation moment, but the contribution of the Supraspinatus is variable. We speculate there is inter-individual or intra-muscular function variability for the Supraspinatus, which may be related to the frequently reported variations in symptoms and treatment outcome of Supraspinatus pathologies.

Arm adductor with arm abduction in rotator cuff tear patients vs. healthy -- design of a new measuring instrument [corrected].

The incidence of (a)symptomatic rotator cuff tears is high, but etiologic mechanisms are unclear and treatment outcomes vary. A practical tool providing objective outcome measures and insight into etiology and potential patient subgroups is desirable. Symptomatic cuff tears coincide with humerus cranialization. Adductor co-activation during active arm abduction has been reported to reduce subacromial narrowing and pain in cuff patients. We present an easy-to-use method to evaluate adductor co-activation. Twenty healthy controls and twenty full-thickness cuff tear patients exerted EMG-recorded isometric arm abduction and adduction tasks. Ab- and adductor EMG's were expressed using the "Activation Ratio (AR)" (-1 ≤ AR ≤ 1), where lower values express more co-activation. Mean control AR's ranged from .7 to .9 with moderate to good test-retest reliability (ICC: .60-.74). Patients showed significantly more adductor co-activation during abduction, with adductor AR's ranging between .3 (teres major) and .5 (latissimus dorsi). In conclusion, the introduced method discriminates symptomatic cuff tear patients from healthy controls, quantifies adductor co-activation in an interpretable measure, and provides the opportunity to study correlations between muscle activation and humerus cranialization in a straightforward manner. It has potential as an objective outcome measure, for distinguishing symptomatic from asymptomatic cuff tears and as a tool for surgical or therapeutic decision-making.

Glenohumeral stability in simulated rotator cuff tears.

Rotator cuff tears disrupt the force balance in the shoulder and the glenohumeral joint in particular, resulting in compromised arm elevation torques. The trade-off between glenohumeral torque and glenohumeral stability is not yet understood. We hypothesize that compensation of lost abduction torque will lead to a superior redirection of the reaction force vector onto the glenoid surface, which will require additional muscle forces to maintain glenohumeral stability. Muscle forces in a single arm position for five combinations of simulated cuff tears were estimated by inverse dynamic simulation (Delft Shoulder and Elbow Model) and compared with muscle forces in the non-injured condition. Each cuff tear condition was simulated both without and with an active modeling constraint for glenohumeral stability, which was defined as the condition in which the glenohumeral reaction force intersects the glenoid surface. For the simulated position an isolated tear of the supraspinatus only increased the effort of the other muscles with 8%, and did not introduce instability. For massive cuff tears beyond the supraspinatus, instability became a prominent factor: the deltoids were not able to fully compensate lost net abduction torque without introducing destabilizing forces; unfavorable abductor muscles (i.e. in the simulated position the subscapularis and the biceps longum) remain to compensate the necessary abduction torque; the teres minor appeared to be of vital importance to maintain glenohumeral stability. Adverse adductor muscle co-contraction is essential to preserve glenohumeral stability.

Shoulder pain and external rotation in spastic hemiplegia do not improve by injection of botulinum toxin A into the subscapular muscle.

OBJECTIVE: To study the effect of botulinum toxin A in the subscapular muscle on shoulder pain and humerus external rotation. METHODS: 22 stroke patients with spastic hemiplegia, substantial shoulder pain and reduced external rotation of the humerus participated in a randomised, double blind, placebo controlled effect study. Injections of either botulinum toxin A (Botox, 2x50 units) or placebo were applied to the subscapular muscle at two locations. Pain was scored on a 100 mm vertical Visual Analogue Scale; external rotation was recorded by means of electronic goniometry. Assessments were carried out at 0 (baseline), 6 and 12 weeks. RESULTS: 21 patients completed the study. We observed no significant changes in pain or external rotation as a result of administration of botulinum toxin A. External rotation improved significantly (p = 0.001) for both the treatment group (20.4 degrees (16.6) to 32.1 degrees (14.0)) and the control group (10.3 degrees (19.5) to 23.7 degrees (20.7)) as a function of time. CONCLUSIONS: Application of botulinum toxin A into the subscapular muscle for reduction of shoulder pain and improvement of humeral external rotation in spastic hemiplegia does not appear to be clinically efficacious.

Polyurethane scaffold formation via a combination of salt leaching and thermally induced phase separation.

Porous scaffolds have been made from two polyurethanes based on thermally induced phase separation of polymer dissolved in a DMSO/water mixture in combination with salt leaching. It is possible to obtain very porous foams with a very high interconnectivity. A major advantage of this method is that variables like porosity, pore size, and interconnectivity can be independently adjusted with the absence of toxic materials in the production process. The obtained compression moduli were between 200 kPa and 1 MPa with a variation in porosity between 76 and 84%. Currently the biological and medical aspects are under evaluation.

Pathological muscle activation patterns in patients with massive rotator cuff tears, with and without subacromial anaesthetics.

A mechanical deficit due to a massive rotator cuff tear is generally concurrent to a pain-induced decrease of maximum arm elevation and peak elevation torque. The purpose of this study was to measure shoulder muscle coordination in patients with massive cuff tears, including the effect of subacromial pain suppression. Ten patients, with MRI-proven cuff tears, performed an isometric force task in which they were asked to exert a force in 24 equidistant intervals in a plane perpendicular to the humerus. By means of bi-polar surface electromyography (EMG) the direction of the maximal muscle activation or principal action of six muscles, as well as the external force, were identified prior to, and after subacromial pain suppression. Subacromial lidocaine injection led to a significant reduction of pain and a significant increase in exerted arm force. Prior to the pain suppression, we observed an activation pattern of the arm adductors (pectoralis major pars clavicularis and/or latissimus dorsi and/or teres major) during abduction force delivery in eight patients. In these eight patients, adductor activation was different from the normal adductor activation pattern. Five out of these eight restored this aberrant activity (partly) in one or more adductor muscles after subacromial lidocaine injection. Absence of glenoid directed forces of the supraspinate muscle and compensation for the lost supraspinate abduction torque by the deltoideus leads to destabilizating forces in the glenohumeral joint, with subsequent upward translation of the humeral head and pain. In order to reduce the superior translation force, arm adductors will be co-activated at the cost of arm force and abduction torque. Pain seems to be the key factor in this (avoidance) mechanism, explaining the observed limitations in arm force and limitations in maximum arm elevation in patients suffering subacromial pathologies. Masking this pain may further deteriorate the subacromial tissues as a result of proximal migration of the humeral head and subsequent impingement of subacromial tissues.

Meniscal replacement in dogs. Tissue regeneration in two different materials with similar properties.

In earlier studies, meniscal replacement with a porous polymer implant led to regeneration of neo-meniscal tissue. To evaluate the influence of the chemical properties on the tissue regeneration in the implant, in the present study, the meniscus in the dog's knee was replaced with either an aromatic 4,4-diphenylmethanediisocyanate based polyesterurethane implant (Estane) (n = 6) or with an aliphatic 1,4-butanediisocyanate based polyesterurethane implant (PCLPU) (n = 6). After 6 months, the knee joints were resected and the tissue behavior in the two different prostheses was evaluated microscopically. In both prostheses, a meniscus-like distribution of the tissue phenotype was found with collagen type I in the peripheral fibrous zones and collagen type II in the central, more cartilaginous zones. The compression-stress behavior of the implant-tissue construct remained in between the stiffness of the polymer material and that of the native meniscus. The PCLPU implant seemed to provoke less synovial tissue reaction. After meniscectomy solely, in 5 out of 6 cases, a meniscus-like regenerate was formed. Furthermore, the articular cartilage degeneration after placing a PCLPU implant did also not exceed the degeneration after the Estane implant or after meniscectomy. The differences between these two implants did not seem to influence the tissue regeneration in the implant. However, PCLPU seemed to evoke less tissue reaction and, therefore, is thought to be less or even nontoxic as compared with the Estane implant. Therefore, for studies in the future, the authors prefer the PCLPU prostheses for replacement of the meniscus.

Pathological Teres Major activation in patients with massive rotator cuff tears alters with pain relief and/or salvage surgery transfer.

BACKGROUND: Massive rotator cuff tears impose restraints on overhand arm functionality and are often accompanied by pain. After musculotendinous Teres Major transfer, overhand arm function is generally restored and pain is reduced. The assumed mechanical abduction insufficiency and Teres Major muscle function adaptation will be experimentally verified. METHODS: Principal Teres Major muscle activation (surface IEMG averaged over 3s) is recorded for 12-24 isometric and isotonic force directions perpendicular to the 60 degrees forward flexed humerus in three conditions: prior to surgery (n = 6 patients), prior to surgery and after subacromial anaesthetic (n = 6) and post-surgery (n = 3). Principal direction and on-, offset directions were estimated. FINDINGS: Teres Major activation adapts both to pathological and post surgery conditions: the normal activation during adduction changes into activation during forward flexion or abduction. Glenohumeral stabilisation, not abduction torque, seems to be the explanation for post surgery Teres Major transfer success. INTERPRETATIONS: The pathological absence of Supraspinatus and Infraspinatus forces during forward flexion result in increased upward glenohumeral instability. The superior translations are compensated for by Teres Major activity during forward flexion. This translation-'force' function conflicts with the adduction-generating rotation-'torque' function. This may explain the pain-induced reduction of arm elevation in these patients. Musculotendinous transfer solves the force-torque conflict by changing the moment arm of the Teres Major from adduction to abduction. Teres Major can now both compensate for the loss of Supraspinatus and Infraspinatus forces needed for glenohumeral stabilisation and contribute to forward flexion of the arm.

Design, synthesis and properties of a degradable polyurethane scaffold for meniscus regeneration.

Longitudinal lesions in menisci are among the most frequent orthopedic problems of the knee. Repair by simple techniques is only limited to the vascular part of the meniscus. For repair of the avascular part of the meniscus a scaffold, which will assist the body in the formation of new meniscus cell tissue, might be applicable. In this study a biomedical segmented polyurethane with poly(epsilon-caprolactone) as soft segment and 1,4-butanediisocyanate and 1,4-butanediol as uniform hard segments has been synthesised. The material has a micro phase separated morphology and excellent mechanical properties. A porous scaffold was prepared via a combination of liquid-liquid phase separation and salt leaching. The foams prepared combined a very high interconnectivity and porosity with the desired compression modulus. After six months of implantation in the knees of beagles full ingrowth with cells was obtained and it was found that meniscus like tissue had been formed in the scaffold. Moreover, compression behaviour appeared to be comparable to native meniscus tissue.

A porous polymer scaffold for meniscal lesion repair--a study in dogs.

Meniscal lesions often occur in the avascular area of the meniscus with little chance of spontaneous repair. An access channel in the meniscal tissue can function as an entrance for ingrowing repair tissue from the vascular periphery of the meniscus to the lesion in the avascular zone which again induced healing of the lesion. Implantation of a porous polymer in a full-thickness access channel induced healing. However, a better integration between meniscal tissue and the implant might be achieved with the combination of the newly developed porous polymers and a modified surgical technique. This might improve meniscal lesion healing and the repair of the access channel with neo-meniscal tissue. Longitudinal lesions were created in the avascular part of 24 canine lateral menisci and a partial-thickness access channel was formed to connect the lesion with the meniscal periphery. In 12 menisci, the access channel was left empty (control group), while in the remaining 12 menisci the polymer implant was sutured into the access channel. Repair of the longitudinal lesions was achieved with and without polymer implantation in the partial-thickness access channel. Polymer implants induced fibrous ingrowth with cartilaginous areas, which resembled neo-meniscal tissue. Implantation did not prevent articular cartilage degeneration.

Presence and mechanism of knee articular cartilage degeneration after meniscal reconstruction in dogs.

OBJECTIVE: Partial meniscectomy is the golden standard for treating a bucket-handle tear in the meniscus of the knee, but it inevitably leads to articular cartilage degeneration. Surgical creation of an access channel between the lesion and the vascularized synovial lining is intended to induce ingrowth of repair tissue and thus avoid degeneration of articular cartilage. DESIGN: The presence and mechanism of cartilage degeneration were evaluated in 24 canine menisci after a longitudinal lesion and access channel had been created in the avascular part of the meniscus. In 12 menisci the channel was implanted with a porous polymer scaffold, while the remaining 12 were left empty. Evaluation was performed using routine histology and antibodies directed against denatured type II collagen (Col2-3/4M). RESULTS: Articular degeneration was apparent in the polymer implant group and the empty channel group. This consisted of fibrillation, loss of chondrocytes and decreased proteoglycan content. Areas of fibrillated cartilage always showed positive labeling with the collagen degradation antibody Col2-3/4M. Collagen degradation was also visible in non-fibrillated areas. The upper zone of the cartilage showed swelling especially in the implant group, with empty cell lacunae and moderate levels of Col2-3/4M antibody labeling. DISCUSSION: This reconstruction technique cannot be considered superior to partial meniscectomy. We propose that degradation of the collagen type II network is a result of cartilage fibrillation and vice versa.

Injectable intraocular lens materials based upon hydrogels.

The possibilities to develop an injectable hydrogel lens were investigated. Aqueous solutions of reactive polymers in combination with a water-soluble blue light photoinitiator were transformed into hydrogels by irradiation with blue light. Poly(ethylene glycol) diacrylates (PEGDA) with low molecular weights and an acrylate modified copolymer of N-vinylpyrrolidone and vinyl alcohol with a high molecular weight were used as reactive polymers. A copolymer of (4-vinyl-2,6-dimethylbenzoyl)diphenylphosphine oxide and dimethylacrylamide was used as a water-soluble blue light photoinitiator. PEGDA showed high reactivity and the hydrogels were more transparent than the natural lens. The mass loss and the additional swelling of the hydrogel were 1.0 and 4.0%, respectively. The refractive index of these hydrogels was 1.40, lower than that of natural lens. The viscosity of the solutions before cross-linking was too low for injection into the capsular bag. Hydrogels based upon the copolymer had a transmission comparable to a 25-year-old natural lens. The materials showed no mass loss and the additional swelling after curing was less than 1%. The refractive index was comparable to that of the natural lens (1.42). The viscosity of the polymer solutions was sufficient for injection into the capsular bag without leakage.

A three-dimensional regression model of the shoulder rhythm.

OBJECTIVE: The development of a thorax-fixed regression model for the shoulder which statistically predicts the orientation of the clavicle and the scapula from the humerus orientation. BACKGROUND: The application of three-dimensional position recording systems to the shoulder mechanism is limited to laboratory conditions. Studies in the field of ergonomics and sports require a method that can be applied in situ. It was found that the relation between the scapular and the humeral motions is consistent. In order to facilitate the biomechanical research on the shoulder a descriptive statistical model of the shoulder rhythm was developed. METHODS: The orientation of the shoulder bones of 10 subjects was determined in a large range of 23 humerus positions. The elbow was flexed in a splint and the arm was fully supported. The subjects exerted a 20 N external abduction and adduction force at the elbow in a plane perpendicular to the humerus. Other forces and moments were mechanically minimized. During the task the postures of the shoulder were recorded. The linear regression equations for the clavicular and scapular orientations were determined by means of a repeated measurements multi-variate analysis of variance for the co-variates: humerus orientation, initial orientation of the clavicle and the scapula, external force direction, gender and morphological characteristics of the subjects. RESULTS: The orientation of the clavicle and the scapula was predicted by five linear regression equations, including the co-variates: humerus orientation, external force direction and initial position. Morphology and gender did not significantly contribute to the clavicular and scapular orientation predictions. CONCLUSIONS: A statistical model is developed for the prediction of clavicular and scapular orientations, based on the humerus position, the initial posture and the direction of the external force. The model fitted well on an independent set of recorded position data for a different group of subjects. RELEVANCE: Morphological data of the shoulder girdle and gender did not significantly contribute to the model structure.

Localized immediate early gene expression related to the strength of song learning in socially reared zebra finches.

Recent evidence showed that exposure of tape-tutored zebra finch (Taeniopygia guttata castanotis) males to the tutor song involves neuronal activation in brain regions outside the conventional 'song control pathways', particularly the caudal part of the neostriatum (NCM) and of the hyperstriatum ventrale (CMHV). Zebra finch males were reared with a live tutor during the sensitive period for song learning. When, as adults, they were re-exposed to the tutor song, the males showed increased expression of Fos, the protein product of the immediate early gene c-fos, in the NCM and CMHV, compared with expression in two conventional 'song control nuclei', high vocal centre (HVC) and Area X. The strength of the Fos response (which is a reflection of neuronal activation) in the NCM (but not in the other three regions) correlated significantly and positively with the number of song elements that the birds had copied from the tutor song. Thus, socially tutored zebra finch males show localized neural activation in response to tutor song exposure, which correlates with the strength of song learning.

Hydrophilic polymeric acylphospine oxide photoinitiators/crosslinkers for in vivo blue-light photopolymerization.

Three vinyl-functionalized phosphine oxide photoinitiating monomers have been synthesized: 4-vinylbenzoyldiphenylphosphine oxide (VBPO), 2,6-dimethyl-4-vinylbenzoyldiphenylphosphine oxide (DMVBPO), and 2,4,6-trimethylbenzoylphenyl-4-vinylphenylphosphine oxide (TMBVPO). VBPO was copolymerized with vinylpyrrolidone or vinyl acetate (PPI-1a) and dimethylacrylamide (PPI-1b). DMVBPO and TMBVPO were both copolymerized with dimethylacrylamide (PPI-2 and PPI-3, respectively). The choice of vinylphosphine oxide and comonomer(s) had a significant influence on the properties of the resulting PPI. PPI-1a was not stable in solution in 2-hydroxyethyl methacrylate (HEMA), whereas the VBPO-dimethylacrylamide (DMA) copolymer (PPI-1b) was stable in HEMA but not stable in aqueous solutions. PPI-2 was both soluble and stable in water up to 22 months. PPI-1a was as effective as trimethylbenzoyldiphenylphosphine oxide (TPO, BASF Lucirin). PPI-2 was more effective in the polymerization of HEMA/water mixtures than PPI-3. PPI-2 and PPI-3 acted as self-cross-linking species, resulting in the formation of hydrogels; PPI 3 was more effective in this. PPI-2 was very effective in forming hydrogels based on poly(ethylene glycol) diacrylate.