Mechanism of the biomolecular synthesis of PEDOT:PSS: importance of heme degradation by hydrogen peroxide.

The use of biomolecules as oxidants for the synthesis of conducting polymers provides an important tool for the control of polymer properties. Using PEDOT: PSS as a representative conducting polymer, we compare a set of heme proteins (soybean peroxidase, cytochrome c, and horseradish peroxidase) used as oxidants. The resulting PEDOT: PSS was characterized with visible and near IR spectroscopy, Fourier transform infrared spectroscopy, electron spin resonance spectroscopy, and four point probe conductivity measurements. We find that the relative concentrations of bipolarons and polarons vary as a function of the protein used for polymerization. We then show that heme degradation by hydrogen peroxide plays a critical role in determining polymer properties.

Hemoglobin-mediated synthesis of PEDOT:PSS: enhancing conductivity through biological oxidants.

Hemoglobin- and catalase-polymerized PEDOT: PSS were characterized by X-ray photoelectron spectroscopy, visible and near-IR spectroscopy, FTIR, and ESR. Hemoglobin-polymerized PEDOT: PSS possesses bipolarons, while catalase-polymerized PEDOT: PSS is dominated by polarons. Use of heme-bound iron as an oxidant yields PEDOT: PSS with conductivity of 19.5 S cm(-1) in a single-step aqueous reaction.

Randomized multicenter clinical trial of myofascial physical therapy in women with interstitial cystitis/painful bladder syndrome and pelvic floor tenderness.

PURPOSE: We determined the efficacy and safety of pelvic floor myofascial physical therapy compared to global therapeutic massage in women with newly symptomatic interstitial cystitis/painful bladder syndrome. MATERIALS AND METHODS: A randomized controlled trial of 10 scheduled treatments of myofascial physical therapy vs global therapeutic massage was performed at 11 clinical centers in North America. We recruited women with interstitial cystitis/painful bladder syndrome with demonstrable pelvic floor tenderness on physical examination and a limitation of no more than 3 years' symptom duration. The primary outcome was the proportion of responders defined as moderately improved or markedly improved in overall symptoms compared to baseline on a 7-point global response assessment scale. Secondary outcomes included ratings for pain, urgency and frequency, the O'Leary-Sant IC Symptom and Problem Index, and reports of adverse events. We compared response rates between treatment arms using the exact conditional version of the Mantel-Haenszel test to control for clustering by clinical center. For secondary efficacy outcomes cross-sectional descriptive statistics and changes from baseline were calculated. RESULTS: A total of 81 women randomized to the 2 treatment groups had similar symptoms at baseline. The global response assessment response rate was 26% in the global therapeutic massage group and 59% in the myofascial physical therapy group (p=0.0012). Pain, urgency and frequency ratings, and O'Leary-Sant IC Symptom and Problem Index decreased in both groups during followup, and were not significantly different between the groups. Pain was the most common adverse event, occurring at similar rates in both groups. No serious adverse events were reported. CONCLUSIONS: A significantly higher proportion of women with interstitial cystitis/painful bladder syndrome responded to treatment with myofascial physical therapy than to global therapeutic massage. Myofascial physical therapy may be a beneficial therapy in women with this syndrome.

Triplet organometallic reactivity under ambient conditions: an ultrafast UV pump/IR probe study.

The reactivity of triplet 16-electron organometallic species has been studied in room-temperature solution using femtosecond UV pump IR probe spectroscopy. Specifically, the Si-H bond-activation reaction of photogenerated triplet Fe(CO)(4) and triplet CpCo(CO) with triethylsilane has been characterized and compared to the known singlet species CpRh(CO). The intermediates observed were studied using density functional theory (DFT) as well as ab initio quantum chemical calculations. The triplet organometallics have a greater overall reactivity than singlet species due to a change in the Si-H activation mechanism, which is due to the fact that triplet intermediates coordinate weakly at best with the ethyl groups of triethylsilane. Consequently, the triplet species do not become trapped in alkyl-solvated intermediate states. The experimental results are compared to the theoretical calculations, which qualitatively reproduce the trends in the data.

Femtosecond infrared study of the dynamics of solvation and solvent caging.

The ultrafast reaction dynamics following 295-nm photodissociation of Re2CO10 were studied experimentally with 300-fs time resolution in the reactive, strongly coordinating CCl4 solution and in the inert, weakly coordinating hexane solution. Density-functional theoretical (DFT) and ab initio calculations were used to further characterize the transient intermediates seen in the experiments. It was found that the quantum yield of the Re-Re bond dissociation is governed by geminate recombination on two time scales in CCl4, approximately 50 and approximately 500 ps. The recombination dynamics are discussed in terms of solvent caging in which the geminate Re(CO)5 pair has a low probability to escape the first solvent shell in the first few picoseconds after femtosecond photolysis. The other photofragmentation channel resulted in the equatorially solvated dirhenium nonacarbonyl eq-Re2(CO)9(solvent). Theoretical calculations indicated that a structural reorganization energy cost on the order of 6-7 kcal/mol might be required for the unsolvated nonacarbonyl to coordinate to a solvent molecule. These results suggest that for Re(CO)5 the solvent can be treated as a viscous continuum, whereas for the Re2(CO)9 the solvent is best described in molecular terms.

Behavioral therapy for overactive bladder.

What is behavioral therapy? On the one hand there is no consensus in the literature as to the definition of the treatment or the optimal mode of delivery. On the other hand, it is possibly the "best" single treatment for urinary incontinence when viewed from a risk:benefit analysis. There is general agreement that within this framework wide variations exist in intensity of treatment, expertise required to deliver the treatment, and the subsequent cost of therapy. A definition of behavioral therapy should include at least the following techniques: first, education and explanation of normal lower urinary tract function; second, micturition charts and diaries; and finally, timed voiding/bladder training regimens. All of the behavioral methods are demonstrably effective, with improvement rates in incontinence episodes uniformly in excess of 50%. Our challenge is to define the critical parts of behavioral therapy and develop algorithms that can be delivered to the incontinent population in the most cost-effective manner.

A transvaginal sling procedure with bone anchor fixation.

Urethral sling procedures have become increasingly popular in the treatment of female stress incontinence. Until recently, the use of this procedure in the urologic community has been limited by technical difficulties and complications (e.g., urinary retention, urethral injury, urge frequency). Many modifications of the original sling procedure recently have been described to decrease surgical morbidity. This article describes a minimally invasive sling procedure performed completely through the vagina, with the aid of bone anchor fixation. The potential advantages of this operation include a rapid return to full activity and normal voiding. It should be noted that neither the long-term safety nor the efficacy has been established.

Epidemiology, pathophysiology, and evaluation of urinary incontinence and overactive bladder.

OBJECTIVES: To present an overview of current knowledge regarding the epidemiology, pathophysiology, and evaluation of urinary incontinence (UI) with a focus on the problem of the overactive bladder. METHODS: The most recent data on the epidemiology of UI are presented. The literature on the pathophysiology of urinary urge incontinence (UUI) is reviewed, and key concepts related to patient evaluation are summarized. RESULTS: The prevalence of UI depends on the population being surveyed. The overactive bladder constitutes a substantial percentage of the overall problem, ranging from > 50% of incontinent men to only 10% to 15% of incontinent younger women. Few data are available on the incidence of the disorder or on racial/ethnic trends. Overactive bladder or urge incontinence is called detrusor hyperreflexia when a neurologic cause is known and detrusor instability when there is no neurologic abnormality. Although the pathophysiology of idiopathic instability is not well understood, some evidence suggests that this condition may result from subclinical neurologic disease or primary smooth muscle disease. Most patients with UUI can be adequately evaluated with a history, physical examination, determination of postvoid residual volume, and urinalysis. When neurologic disease or other complicating factors are present, or if initial treatment fails, sophisticated urodynamic testing is appropriate. CONCLUSIONS: Urinary incontinence is prevalent in all strata of the population, although it affects women and the elderly disproportionately. With the exception of cases in which a neurologic lesion can be demonstrated, the etiology of UUI remains elusive. A thorough history, physical examination, determination of postvoid residual, and urinalysis will be adequate to classify and treat the majority of patients.

Biofeedback for community-dwelling individuals with urinary incontinence.

OBJECTIVES: To review the role of biofeedback in the management of community-dwelling individuals with urge urinary incontinence (UUI), and to present a practical approach to patient evaluation and treatment selection. METHODS: In view of a lack of objective published information, perspectives on the use of biofeedback in UUI are derived from extrapolation of studies in patients with stress incontinence as well as from the author's personal experience. RESULTS: Through the use of careful baseline evaluations, appropriate exercise and biofeedback treatment for UUI can be selected for specific patients. Office-based biofeedback is preferred for patients who have no or minimal ability to isolate and contract the levator muscles at baseline. Such individuals cannot be expected to exercise effectively without instruction but can be converted to home-based treatment once responses have been achieved. Patients with weak contractions but appropriate muscle isolation are appropriate candidates for Kegel exercises; biofeedback has not been conclusively demonstrated to be superior to exercise therapy alone in this group. Vaginal cones or simple home biofeedback units may be useful adjuncts in these cases. Patients who have good muscle isolation and strong pelvic contractions at baseline generally have more severe bladder dysfunction and require aggressive treatment aimed at the detrusor. Instruction in "quick flicks" may assist in inhibiting urgency, and motivated patients may be offered vaginal cones. CONCLUSIONS: Pelvic floor muscle dysfunction is an important but often-overlooked component of UUI. The algorithm presented here can assist in tailoring exercise and biofeedback therapy to the individual patient. However, more research is needed to help stratify patients according to the degree of detrusor dysfunction and status of pelvic floor muscles before intervention.

Genitourinary problems in the elderly patient.

Dramatic advances across several fronts have provided a marked improvement in the quality of life for the elderly urologic patient. Radical surgery for cancer is much safer than in the past, and our focus is on preservation of function or complete functional reconstruction. In other areas we strive to continue to deliver excellent treatment while minimizing patient morbidity. This is seen most dramatically in the treatment of urinary stone disease. Ongoing work in patients with BPH promises to provide similar benefits to this population in the coming years. At the same time, we must remember that our abundance of therapeutic options imposes a responsibility to individualize treatment so as to best serve each patient.

Gastrocystoplasty without opening the stomach.

We describe a modification of gastrocystoplasty using the GIA stapler to harvest the segment for augmentation without opening the stomach. This simplification reduces operative time and blood loss without introducing complication specific to it and has been successfully used in our first 5 patients.

Contributions of a supportive work environment to parents' well-being and orientation to work.

Examined the joint and unique contributions of informal social support in the workplace and formal, family-responsive benefits and policies provided by employers to the job-related attitudes and personal well-being of employed parents with a young child. Eighty married men, 169 married women, and 72 single women with a preschool child completed a survey concerning social support from co-workers and supervisor, utilization of family-responsive benefits and policies, readiness to leave the employer for additional benefits, job satisfaction, organizational commitment, role strain, and health symptoms. Among the findings: (a) Fathers and mothers expressed equal levels of job satisfaction and organizational commitment, but mothers reported more role strain and health symptoms; (b) nearly 48% of married women's organizational commitment was accounted for by measures of support in the workplace; (c) informal social support at work was significantly more important to men's well-being than that of women; and (d) formal, family-responsive policies appeared more consequential for the prediction of women's role strain, perhaps because of women's greater responsibility for adjusting work life to meet the demands of family roles.