Intelligent materials with adaptive adhesion properties based on comb-like polymer brushes.

We investigated the adaptive adhesion properties of comb-like random copolymer brushes made of poly(ethylene glycol) (PEG)-poly(dimethylsiloxane) (PDMS) grafted on flat and rough substrates. The properties of the brush layers were investigated using ARXPS, contact angle, electrokinetics, null ellipsometry, and adhesion measurements. It was found that hydrophobic PDMS segments segregate at the brush topmost layer in the dry state. However, hydrophilic PEG chains segregate at the brush topmost layer in the wet state. The adhesion properties of fabricated materials were tested using the AFM colloid probe technique and probe tack tester. It was found that the adhesive properties depend strongly on the mechanical properties (stiff/soft) and chemical functionality (hydrophobicity/hydrophilicity) of the applied adhesion tester as well as on the chemical composition, surface roughness, and thickness of the brush. In particular, hydrophobic PDMS and hydrophilic PEG adhere more strongly to hydrophobically modified and hydrophilic native colloid probes, respectively. Thick brushes are more adhesive than thin ones, and brushes grafted to flat substrates are stickier than those grafted to rough substrates when measured with a hard AFM probe. Unlike the results of adhesion measurements performed using hard AFM probes, the PDMS surface probed by soft pressure-sensitive adhesives (PSA) is almost nonadhesive. However, PEG is strongly adhesive, and the adhesion increases with the PEG fraction in the brush when probed by both hydrophilic and hydrophobic soft adhesives. The surfaces roughness also has a considerable effect on adhesion. Contrary to the adhesion measurements performed by hard AFM colloid probes, the adhesion of rough surfaces measured with a soft PAA or SIS tack tester is greater than that on the corresponding flat one.

Water-repellent textile via decorating fibers with amphiphilic Janus particles.

We investigated morphology and wetting properties of textiles modified by chemically immobilized amphiphilic micrometer and submicrometer large Janus particles. The Janus particles bind by their reactive side to the textile surface, while their hydrophobic side faces the environment. It was found that the character of immobilization of the Janus particles on textile depends on their size: larger particles bind between fibers, while smaller ones bind to the fiber surface. In both cases, immobilization of Janus particles results in the hydrophobization of the hydrophilic textile surface. Finally, we demonstrated that submicrometer large Janus particles are very efficient for the design of water-repellent textiles.

Electrokinetic investigation of surfactant adsorption.

Fuerstenau [D.W. Fuerstenau, in: M.L. Hair (Ed.), Dekker, New York, 1971, p. 143] has already discussed the role of hydrocarbon chain of surfactants, the effect of alkyl chain length, chain structure and the pH of the solution on the adsorption process of surfactants. Later Kosmulski [M. Kosmulski, Chemical Properties of Material Surfaces, Surfactant Science Series, vol. 102, Dekker, New York, Basel, 2001] included the effect of surfactant concentration, equilibration time, temperature and electrolyte in his approaches. Certainly, the character of the head groups of the surfactant and the properties of the adsorbent surface are the basis for the adsorption process. Different surfactants and adsorbents cause different adsorption mechanisms described firstly by Rosen [M.J. Rosen, Surfactants and Interfacial Phenomena, second ed., Wiley, New York, 1989]. These adsorption mechanisms and their influencing factors were studied by electrokinetic investigations. Here only changes of the charges at the surfaces could be detected. To control the results of electrokinetic investigations they were compared with results from ellipsometric measurements. In the case of surfactant adsorption the chain length was vitally important. It could be shown by the adsorption of alkyl trimethyl ammonium bromides onto polymer films spin coated at wafer surfaces. The influence of the chain length depending on surface properties of the polymer film was studied. Streaming potential measurements were applied for these investigations. The obtained results enabled us to calculate the molar cohesive free energy per mol of CH2-group in the alkaline chain of the surfactant if all other specific adsorption effects were neglected.

Redispergation of TiO2 particles in aqueous solutions.

The colloidal stability of TiO2 dispersions in aqueous solutions was studied. Aqueous solutions of ATLAS G-3300 (1.57 x 10(-3) mol/l), TRITON X-100 (5 x 10(-5) mol/l), and PMAA (4 x 10(-6) and 5.81 x 10(-3) mol/l) have been used as medium for redispergation of TiO2 particles. Stability of dispersions was investigated at different pH values by two different methods. By using analytical centrifuge the sedimentation velocity of TiO2 particles was directly measured and by means of light scattering the particle size of dispersed particles has been monitored. Combination of these two methods allowed determination of the aggregation degree of TiO2 particles as well as structure of the aggregates formed in aqueous phase. It has been found that redispergation process does not provide complete separation of virgin TiO2 particles. Even in the case of stable dispersions some aggregates were found, which consisted of 2-4 virgin TiO2 particles. With increasing colloidal stability of dispersions aggregates appear to be spherically shaped. In the system where TRITON X-100 was used, formation of secondary aggregates by fusion of primary ones was observed.

GC-IR based two-dimensional structural group analysis of petroleum products.

To characterize petroleum products, a method based on the combination of IR-spectrometric structural group analysis, GC-simulated boiling analysis and multivariate regression techniques (PLS, PCR) has been developed. The best performance was achieved by a PLS regression model with six aliphatic and aromatic structural groups. Thereby, structural group distribution related to the boiling temperature could be obtained in order to quantify product-specific distribution parameters and to control material-conversion processes caused by biodegradation.

Juvenile neuronal ceroid lipofuscinosis (Batten disease) CLN3 mutation (Chrom 16p11.2) with different phenotypes in a sibling pair and low intensity in vivo autofluorescence.

BACKGROUND: The neuronal ceroid lipofuscinoses (Batten disease) are a heterogeneous group of autosomal recessively inherited disorders causing progressive neurological failure, mental deterioration, seizures and visual loss secondary to retinal dystrophy. The juvenile type is of special interest to the ophthalmologist as visual loss is the earliest symptom of the disorder. HISTORY AND SIGNS: We present two siblings with severe retinal dystrophy due to juvenile Batten disease. Sibling A (age 10) presented with visual loss, photophobia and night blindness, starting at age 4. His vision was perception of light by the age of 10.5 years. Fundus examination revealed severe pigmentary retinopathy. Sibling B (age 7) presented with night vision difficulties. Fundus examination revealed a bull's eye maculopathy with minimal peripheral atrophic changes. In vivo autofluorescence level was found to be very low. Electroretinography (ERG) showed generalized retinal dysfunction involving both cone and rod systems, with an electronegative maximal response. In both siblings vacuolated lymphocytes were found on a peripheral blood film and on molecular genetic testing both were homozygous for the commonly reported 1.02-kb deletion of the CLN3 gene. THERAPY AND OUTCOME: Although there is no effective treatment, the early diagnosis allowed accurate genetic and social counseling. CONCLUSIONS: Juvenile Batten disease should be considered in children with a retinal dystrophy, especially where there is a bull's eye maculopathy and an abnormal full field ERG. The novel finding of very low in vivo autofluorescence is consistent with histopathological studies and may be secondary to photoreceptor cell loss.

Fundus autofluorescence imaging compared with different confocal scanning laser ophthalmoscopes.

BACKGROUND: With the advent of confocal scanning laser ophthalmoscopes (cSLO), fundus autofluorescence (FAF) resulting mainly from lipofuscin accumulation on the level of the retinal pigment epithelium can be visualised in vivo. Various cSLOs are available to document FAF. The authors analysed and compared results of FAF using three different instruments. METHODS: Eight eyes of eight normal volunteers and 18 eyes of 12 patients with different retinal diseases (age related macular degeneration, macular dystrophy, central serous retinopathy) were examined. FAF images were recorded from each subject with the Heidelberg retina angiograph (HRA), the Rodenstock cSLO (RcSLO) and the Zeiss Prototype SM 30-4024 (ZcSLO). For excitation an argon laser (488 nm) was used (barrier filter: HRA 500 nm; RcSLO 515 nm; ZcSLO 521 nm). 32 FAF images were aligned and averaged using the same software for all cSLOs. FAF distribution was measured and grey scale values as well as root mean square (RMS) contrast were compared. RESULTS: Mean age of all subjects was 55.5 (SD 21.4) years. The maximum grey scale value averaged across all eyes was 76.19 (39.34) for the HRA, 61.44 (22.12) for the ZcSLO and 37.0 (9.97) for the RcSLO. The RMS contrast was 0.46 (0.20) for the ZcSLO, 0.40 (0.12) for the HRA, and 0.13 (0.05) for the RcSLO. The differences between the cSLOs were statistically significant with higher grey scale levels and more contrast for the HRA and ZcSLO than the RcSLO (repeated measures ANOVA; p<0.0001). The differences between the HRA and the ZcSLO were not significant (post hoc comparisons; p<0.05). CONCLUSIONS: All cSLOs allow clinically useful FAF imaging in retinal diseases. However, grey scale levels and contrast were much lower on the RcSLO. Therefore, RcSLO images appear much darker than HRA or ZcSLO images. Furthermore, not all cSLOs have a fixed photodetector gain and a standardised value for the argon laser amplification, which is mandatory for an absolute comparison of FAF imaging results.

Digital analysis of choroidal neovascularisation in consecutive fluorescein angiograms for use in longitudinal clinical trials.

BACKGROUND/AIMS: To document the natural history and to assess the efficacy of interventional therapies in neovascular age related macular degeneration (AMD), an accurate and reproducible method is required for analysis of consecutive fluorescence angiograms. The development and evaluation of an image analysis software for this purpose is described here. It allows for the quantitative analysis of changes in CNV and/or leakage area over time. METHODS: In digitised angiograms, a mouse driven arrow was used to delineate the CNV border. The ratio of the CNV area to the square of the distance between two vessels was automatically calculated by pixel count to compensate for variation in image sizes at different examination times. These results were directly transferred and stored in a database. To assess reproducibility, CNV areas in 20 patients with occult and 20 patients with classic CNV were determined independently by two readers. RESULTS: There was only marginal variability between observers with this method: the mean deviation was 0.01 pixels for classic CNV (95% CI -0.17 to +0.15, SD 0.35) and 0.55 pixels for occult CNV (95% CI -1.06 to -0.04, SD 1.14). CONCLUSIONS: This practical PC based method allows for quantification of angiographic features such as CNV size in early frames and area of leakage in late frames. Limitations include non-readily defined borders in angiograms of poor image quality or indistinct borders of the hyperfluorescent areas of interest. The software is applicable to future clinical trials where the analysis of neovascular complex changes is required, for example, following therapeutic intervention.

Stereotactic radiation therapy for malignant choroidal tumors: preliminary, short-term results.

PURPOSE: To evaluate the role of stereotactic radiation therapy (SRT) in the treatment of malignant choroidal tumors. DESIGN: Prospective, noncomparative case series. PARTICIPANTS: Ten patients with unifocal choroidal metastasis (three lung carcinoma, three breast carcinoma, three colon carcinoma, one cutaneous melanoma) and five patients with primary choroidal melanoma underwent single-dose or fractionated SRT. METHODS: Before treatment, computed tomography (CT) scans of the orbit were obtained with the patient wearing an individualized immobilization mask. An integrated macro-CCD-camera system viewed the eye for detection of movements. Three-dimensional computer-based treatment planning was carried out. Dose distribution was calculated and displayed in isodose lines on the CT data set. For SRT, a dedicated stereotactic linear accelerator (6 MV) was used. Total doses for choroidal metastases were 12 to 20 Gy in a single dose or 30 Gy over 10 days (3 Gy each session), and total doses for choroidal melanoma were 50 Gy over 5 or 10 days (10 or 5 Gy each session). MAIN OUTCOME MEASURES: Best corrected visual acuity (ETDRS-chart), biomicroscopy, ultrasound examination, fluorescein angiography, and magnetic resonance imaging (MRI) were performed before treatment and at regular intervals after completion of SRT. RESULTS: During a follow-up period from 1 to 34 months (median, 6.5 months), local tumor control was achieved in all eyes. A decrease in tumor size on ultrasonography or MRI was noted in eight patients. No persistent side effects were observed during follow-up. CONCLUSIONS: Stereotactic radiation therapy allows steep dose gradients outside the target volume by minimizing the field of exposure. Thus only low radiation doses affect surrounding radiosensitive ocular structures. Our initial findings suggest that this technique may be effective in controlling tumor growth. Further studies are needed to compare treatment efficacy and safety with conventional treatment methods.

[Bilateral acute syphilitic posterior placoid chorioretinopathy--angiographic and autofluorescence characteristics]. / Bilaterale akute syphilitische posteriore plakoide Chorioretinopathie (ASPPC). Angiographie- und Autofluoreszenz-Merkmale.

UNLABELLED: Acute syphilitic posterior placoid chorioretinitis (ASPPC) has been described as a rare chorioretinal manifestation in patients with secondary syphilis. The fundus changes may simulate other chorioretinal disorders and thus delay an accurate diagnosis and initiation of appropriate pharmacological therapy. PATIENT: A 54-year-old male patient presented with severely impaired visual acuity in both eyes. Yellowish geographic lesions were noted at the posterior pole. Scanning laser ophthalmoscopy showed corresponding areas of increased fundus autofluorescence. On fluorescein angiography hypofluorescent lesions were noted in the early phase, which became hyperfluorescent in later frames. Indocyanine green agiography demonstrated hypofluorescent lesions both during the early and late frames. Serological examinations were positive for secondary lues (TPHA, FTA-IgM, cardiolipin antibody). Treatment with penicillin was introduced, resulting in complete functional and morphological recovery. CONCLUSION: Fundus and angiographic changes in ASPPC may mimic other chorioretinal diseases, including acute posterior multifocal placoid pigmentepitheliopathy (APMPPE). The angiographic findings suggest that inflammation-associated perfusion abnormalities of the choriocapillaris contribute to the pathophysiological process. Accurate diagnosis of ASPPC as a presenting sign of secondary lues is especially important for the prompt initiation of systemic antibiotic treatment.

Patterns of increased in vivo fundus autofluorescence in the junctional zone of geographic atrophy of the retinal pigment epithelium associated with age-related macular degeneration.

PURPOSE: To determine in vivo lipofuscin (LF)-induced topographic variations of fundus autofluorescence in eyes with geographic atrophy (GA) of the retinal pigment epithelium (RPE) associated with age-related macular degeneration (ARMD). METHODS: Fundus autofluorescence was examined with a confocal scanning laser ophthalmoscope (Heidelberg Retina Angiograph) after excitation with an argon laser (488 nm) and detection of the emitted light above 500 nm. Fifty-seven eyes of 38 patients with uni- or multifocal GA associated with ARMD were studied. The findings were compared with 43 eyes with GA secondary to other etiologies, including juvenile macular dystrophies. RESULTS: An increased autofluorescence outside the GA was observed in 47 (82.5%) of 57 eyes with GA associated with ARMD in contrast to 4 (9.3%) of 43 eyes with GA of other causes (P < 0.001). Three different patterns were noted: a continuous band at the margin with variable peripheral extension in 36 eyes (76.6%), a diffusely increased autofluorescence at the entire posterior pole in 6 eyes (12.8%), and small focal spots of increased autofluorescence in the junctional zone in 3 eyes (6.4%). Of 19 patients with bilateral GA, 17 (89.5%) had an identical pattern in both eyes. CONCLUSIONS: The different patterns of autofluorescence in the presence of GA associated with ARMD may reflect variable forms of reactive changes in the surrounding RPE cells, and may indicate the extend of compromised RPE secondary to ageing changes in the outer retina, Bruch's membrane and choriocapillaris. Since GA spreads over time, increased LF accumulation in the junctional zone may precede cell death and may, therefore, be of prognostic value. Knowledge of the topographic variation in LF accumulation is important because heterogeneity may reflect underlying differences in cell kinetics, metabolism and biochemistry.

Simultaneous confocal scanning laser fluorescein and indocyanine green angiography.

PURPOSE: To evaluate clinically a recently developed confocal scanning laser ophthalmoscope for simultaneous fluorescein and indocyanine green angiography. METHODS: After comprehensive ophthalmic examination, including stereoscopic biomicroscopy, and after color fundus photographs, simultaneous confocal scanning laser fluorescein and indocyanine green angiography was performed after injection of 500 mg of fluorescein and 25 mg of indocyanine green mixed in one syringe using the Heidelberg Retina Angiograph. An argon laser beam (488 nm) and a diode laser beam (795 nm) from an external source were delivered by single-mode fibers. Emission was recorded between 500 and 700 nm and above 810 nm, respectively. Digital images were displayed simultaneously on a monitor during angiography. RESULTS: Two hundred twenty simultaneous fluorescein and indocyanine green angiograms were obtained in 193 consecutive patients with various diagnoses, including exudative age-related macular degeneration with occult and classic choroidal neovascularization. Simultaneous angiography with both dyes gave high-contrast images during all phases of the angiography, which allowed for accurate correlation of fluorescein and indocyanine green angiographic findings and correct comparison of the transit of both dyes through the retinal and choroidal circulation. Corresponding display of quasisimultaneous frames facilitated interpretation of the angiograms. CONCLUSIONS: Confocal laser scanning angiography allows for quasisimultaneous fluorescein and indocyanine green angiography. The investigation is possible at low retinal irradiance and offers high-contrast digital images. Compared with consecutive angiographic investigations using both dyes, simultaneous angiography is less time consuming, requires only one injection, and, because quasisimultaneous frames are obtained, facilitates interpretation of the angiograms.

[Topography of fundus autofluorescence with a new confocal scanning laser ophthalmoscope]. / Topographie der Fundusautofluoreszenz mit einem neuen konfokalen Scanning-Laser-Ophthalmoskop.

BACKGROUND: We investigated fundus autofluorescence in vivo using a novel scanning laser ophthalmoscope. MATERIALS AND METHODS: A total of 550 patients with various retinal diseases were examined and compared with normal eyes. Autofluorescence was detected after excitation with an argon blue laser (488 nm), and emission was recorded with a short wavelength cut off above 500 nm. RESULTS: Reduced autofluorescence was observed in the foveal and parafoveal region due to retinal xanthophyll, along the retinal vessels, at the optic nerve head and in areas with atrophy of the retinal pigment epithelium (RPE). Autofluorescence intensity was increased either focally or diffusely in certain degenerative (AMD) or genetically determined retinal diseases (e.g., Stargardt's disease, Best's disease). CONCLUSIONS: These findings are in accordance with the view that in vivo fundus autofluorescence originates at the level of the RPE and suggest that it is derived from lipofuscin.

[Carcinoma-associated retinopathy in breast carcinoma and carcinoid tumor]. / Karzinomassoziierte Retinopathie (CAR) bei Mammakarzinom und Karzinoid.

BACKGROUND: Carcinoma-associated retinopathy (CAR) is a rare paraneoplastic syndrome characterized by diffuse retinal photoreceptor degeneration in the presence of an epithelial tumor. We report on three patients, who developed paraneoplastic retinopathy in the presence of breast carcinoma and a cervical carcinoid tumor. MATERIALS AND METHODS: In addition to biomicroscopic, psychophysical, electrophysiological and angiographic examinations, serum samples were obtained for immunohistochemical staining of human retina. RESULTS: Ring-shaped visual field defects with statokinetic dissociation and abnormal rod and cone responses were found. Immunohistochemical findings included reactions at the level of the inner segments of the photoreceptors, the outer nuclear layer and the outer plexiform layer in absence of anti-recoverin antibodies. CONCLUSIONS: CAR should be considered in the differential diagnosis of visual loss in presence of tumors other than small-cell carcinoma of the lung. The presence of antiretinal antibodies is compatible with a tumor-induced immune response to epitopes shared by both the tumor and retinal tissue. Apparently, various retinal proteins may function as autoantigens.

[Confocal scanning laser indocyanine green angiography of classical choroid neovascularization]. / Konfokale Scanning-Laser-Indozyaningrünangiographie klassischer choroidaler Neovaskularisationen.

"Classic" choroidal neovascularization (CNV) has a relatively uniform appearance in fluorescein angiography. In contrast, indocyanine green (ICG) angiography shows variable features of well-defined CNV. We examined 31 classic CNV patients secondary to age-related macular degeneration using a confocal laser scanning ophthalmoscope (Heidelberg Retina Angiograph) in order to determine ICG characteristics of classic CNV. Vascular patterns (97%), a hypofluorescent rim (84%), a hyperfluorescent margin (42%), late ICG leakage (32%) and "feeder vessels" were identified in variable frequency. Some of the ICG characteristics may correlate with histological features of the membrane and reflect proliferative activity. Extrafoveal "feeder vessels" may be amenable to laser photocoagulation in the presence of subfoveal CNV.

[Simultaneous fluorescein and indocyanine green angiography with a confocal laser ophthalmoscope]. / Simultane Fluorescein- und Indozyaningrünangiographie mit einem konfokalen Scanning-Laser-Ophthalmoskop.

BACKGROUND: We report on our clinical experience with a recently developed confocal scanning laser ophthalmoscope for simultaneous fluorescein and indocyanine-green (ICG) angiography. MATERIALS AND METHODS: Following injection of fluorescein and ICG mixed in one syringe simultaneous confocal scanning laser fluorescein and ICG angiography were carried out using the Heidelberg Retina Angiograph (HRA). An argon laser (488 nm) and a diode laser beam (795 nm) from an external source were delivered via single-mode fibers. Emission was recorded between 500 and 650 nm and above 810 nm, respectively. Digital images were displayed simultaneously on a monitor during angiography. RESULTS: A total of 295 simultaneous angiograms in 268 patients with various retinal and choroidal diseases, including exudative age-related macular degeneration with occult and classic choroidal neovascularization, were obtained. High-contrast images during all phases of the angiography were obtained. Besides mild side effects in similar frequency known from individual injections, no additional toxic or allergic reactions from simultaneous injections of the two dyes were observed. CONCLUSIONS: Confocal laser scanning angiography allows for simultaneous fluorescein and ICG angiography. Compared with consecutive investigations using both dyes, simultaneous angiography requires only one injection, and offers identical digital frames. Simultaneous injection is not associated with additional side effects.

[Paraneoplastic retinopathy in 2 patients with breast carcinoma]. / Paraneoplastische Retinopathie bei zwei Patientinnen mit Mammakarzinom.

Paraneoplastic retinopathies are rare paraneoplastic phenomena resulting in retinal degeneration. They occur in association with different tumor types, yet most frequently encountered in small cell carcinoma of the lung. Clinical symptoms may be present before the diagnosis of the underlying malignancy. They are characterized clinically by progressive visual loss with ring scotomas, photopsia and night-blindness. An autoimmune disorder is suggested. In the sera of patients antiretinal antibodies may be detected that are sometimes reactive with the 23 kD retinal antigen recoverin, a photoreceptorprotein. We report on two patients with breast cancer who developed paraneoplastic retinopathy during the course of disease. Immunologic tests showed antiretinal antibodies that were not reactive with the 23 kD retinal antigen recoverin.