Fully Degradable Polyphosphoester Cubosomes for Sustainable Agrochemical Delivery.

Microplastic pollution and the urgent need for sustainable agriculture have raised interest in developing degradable carriers for controlled agrochemical release. Porous polymeric particles are particularly promising due to their unique release profiles compared to solid or core-shell carriers. However, creating degradable, mesoporous (2-50 nm) microparticles is challenging, and their potential for agrochemical delivery is largely unexplored. A straightforward self-assembly method is demonstrated for fully degradable porous polymer cubosomes (PCs), showcasing their ability to load and release agrochemicals. Using fully degradable block copolymers (BCPs), poly(ethyl ethylene phosphate)-b-polylactide (PEEP-b-PLA), PCs are synthesized in water with high inner order and open pores averaging 19 ± 3 nm in diameter. During the self-assembly process in the presence of the hydrophobic fungicide tebuconazole, polymersomes transform into PCs by enriching the hydrophobic polymer domain and altering the BCP packing parameter. After self-assemby, highly porous and fungicide-loaded PCs are obtained. Fungicide-loaded PCs show high antimycotic activity against Botrytis cinerea (grey mold), adhere to Vitis vinifera Riesling leaves even after simulated rain, and release the fungicide continuously over several days with different release-kinetics compared to solid particles. PCs hydrolyze completely into lactic acid and phosphate derivatives, highlighting their potential as microplastic-free agrochemical delivery systems for sustainable agriculture.

Janus nanoplates, -bowls, and -cups: controlling size and curvature via terpolymer/homopolymer blending in 3D confinement.

The synthesis and properties of Janus nanoparticles with spherical, cylindrical, and disk-like shapes are nowadays rather well understood. Other topologies such as nanorings and bowl-shaped Janus nanoparticles are believed to show distinctly different solution behavior and interaction with interfaces, but limitations in their synthesis currently prevents a proper investigation of these properties. Especially the combination of shape- and surface-anisotropy of bowl-shaped Janus nanoparticles could result in enhanced selectivity in uptake of cargo and enhanced directional diffusion. We here produce bowl-shaped Janus nanoparticles without noticeable side products through evaporation-induced confinement assembly (EICA) of triblock terpolymers blended with high molecular weight homopolymer. The triblock terpolymer phase separates from the homopolymer into spherical domes, where the terpolymer adopts a hemispherical lamella-lamella morphology (ll). Selective cross-linking, removal of the homopolymer, and disassembly of the microparticles releases the bowl-shaped Janus nanoparticles. The amount of blended homopolymer determines the size of the spherical dome, allowing to control particle curvature into flat Janus nanoplates, hemispherical Janus nanobowls, and deep Janus nanocups. The use of Shirasu Porous Glass (SPG) membranes with pore sizes in the range of dpore = 0.2-2.0 µm further provides control of particle diameter. Size and shape were analyzed with electron microscopy and the Janus character through selective surface decoration. The diffusion behavior of bowl-shaped Janus nanoparticles was investigated depending on particle curvature and anisotropy using angle-dependent dynamic light scattering.

Enzymatic, skeletal, and histological ontogeny of shi drum (Umbrina cirrosa) larvae under intensive culture conditions.

This study was conducted to investigate the structural and ontogenetic development of the skeletal system and digestive tract histologically and enzymatically in larvae of shi drum (U. cirrosa) under intensive rearing conditions until 40 days after hatching (DAH). Among digestive enzymes, amylase was detected at 0.89 ± 0.12 mU mg protein-1 on the first hatching day. The specific activities of trypsin and lipase were detected simultaneously with mouth opening on 3 DAH with 28.47 ± 3.52 and 2.8 ± 0.32 mU mg protein-1, respectively. In addition, pepsin was found for the first time at 0.88 ± 0.21 mU mg protein-1 on 15 DAH in association with stomach formation and increased sharply up to 40 DAH. In the structural development of the skeletal system, the development of the caudal fin in larvae was morphologically associated with the flexion of the notochord. It was observed that the shape of the fin and spine, which reached 40 DAH, became similar to the adult shape. Histologically, 3 DAH, the mouth and anus were opened. The formation of the primitive stomach was observed at the end of the seventh day-the pyloric sphincter formed between 13 and 18 days. A functional stomach was seen on the 15th DAH. Therefore, U. cirrosa is believed to have critical aquaculture potential that can be cultured under intensive conditions. The developmental profile of skeletal, enzymatic, and histological ontogeny observed in U. cirrosa is similar to that described for other sciaenid species.

Confinement Assembly of Terpolymer-Based Janus Nanoparticles.

While the confinement assembly of block copolymers into functional microparticles has been extensively studied, little is known about the behavior of Janus nanoparticles (JNPs) in spherical confinement. Here, the confinement self-assembly of JNPs in drying emulsion droplets is investigated and their behavior compared to their ABC triblock terpolymer precursors. Emulsions of both materials are prepared using Shirasu Porous Glass membranes leading to narrow size distributions of the microparticles with average hydrodynamic radii in the range of Rh  = 250-500 nm (depending on the membrane pore radius, Rpore ). The internal structure of the microparticles is verified with transmission electron microscopy (TEM) on ultrathin cross sections and compared to the corresponding bulk morphologies. While the confinement assembly of terpolymers results in microparticles with ordered inner morphologies, order for JNPs diminishes when the Janus balance deviates from parity.

Morphology and Degradation of Multicompartment Microparticles Based on Semi-Crystalline Polystyrene-block-Polybutadiene-block-Poly(L-lactide) Triblock Terpolymers.

The confinement assembly of block copolymers shows great potential regarding the formation of functional microparticles with compartmentalized structure. Although a large variety of block chemistries have already been used, less is known about microdomain degradation, which could lead to mesoporous microparticles with particularly complex morphologies for ABC triblock terpolymers. Here, we report on the formation of triblock terpolymer-based, multicompartment microparticles (MMs) and the selective degradation of domains into mesoporous microparticles. A series of polystyrene-block-polybutadiene-block-poly(L-lactide) (PS-b-PB-b-PLLA, SBL) triblock terpolymers was synthesized by a combination of anionic vinyl and ring-opening polymerization, which were transformed into microparticles through evaporation-induced confinement assembly. Despite different block compositions and the presence of a crystallizable PLLA block, we mainly identified hexagonally packed cylinders with a PLLA core and PB shell embedded in a PS matrix. Emulsions were prepared with Shirasu Porous Glass (SPG) membranes leading to a narrow size distribution of the microparticles and control of the average particle diameter, d ≈ 0.4 µm-1.8 µm. The core-shell cylinders lie parallel to the surface for particle diameters d < 0.5 µm and progressively more perpendicular for larger particles d > 0.8 µm as verified with scanning and transmission electron microscopy and particle cross-sections. Finally, the selective degradation of the PLLA cylinders under basic conditions resulted in mesoporous microparticles with a pronounced surface roughness.

The role of cyclin D1, BCL-2, p53 and Ki-67 in epithelial cells in the etiopathogenesis of pterygium.

CONTEXT: Pterygium is a degenerative disease that consists of conjunctival epithelia and fibrovascular tissue. Some studies suggest that there is a defect in the regulation of apoptosis in the epithelial cell cycle characterized by the development of the disease. But, still this matter being debated. AIMS: In this study, the clinical, histopathological data, and the expression of the cell cycle regulator Cyclin D1, anti-apoptotic BCL-2, tumor suppressor p53, and cell proliferation marker Ki-67 were searched in pterygium samples. SUBJECTS AND METHODS: The study enrolled 62 cases of primary pterygium who underwent excision between 2014 and 2017. Recurrent and pseudo-pterygium cases were excluded from series. The clinical data were obtained from the patient files and the slides were reevaluated for the histopathological data. Slides of all were stained by Cyclin D1, BCL-2, and Ki-67 by the immunohistochemical method. For each immunohistochemical marker, first the staining was determined as negative or positive. Then if there is a staining, the hot zone (the area containing more positive cells) was determined and staining percentage (SP) was assessed by counting positive cells/100 epithelial cells). RESULTS: Solar elastosis, edema, inflammation, and epithelial dysplasia were found statistically different between the control group and the patient group (P value <0.001, <0.001, <0.001 <0.001, respectively). A significant difference was found for staining percentage (SP) of Ki-67, p53, BCL-2 between the control group and the patient group (P values <0.001, 0.002, <0.001, respectively). There were no significant differences in the SP of Cyclin D1 between the two groups (p: 0,133). CONCLUSIONS: Our results indicate an abnormal expression of p53, BCL-2 and elevated proliferation measured by Ki-67 in pterygium samples when compared to normal conjunctiva. Besides the mesenchymal changes, the increased proliferation and the failure of apoptosis in the epithelial cells participate in the development of pterygium, as well.

Recent Advances in the Synthesis and Application of Polymer Compartments for Catalysis.

Catalysis is one of the most important processes in nature, science, and technology, that enables the energy efficient synthesis of essential organic compounds, pharmaceutically active substances, and molecular energy sources. In nature, catalytic reactions typically occur in aqueous environments involving multiple catalytic sites. To prevent the deactivation of catalysts in water or avoid unwanted cross-reactions, catalysts are often site-isolated in nanopockets or separately stored in compartments. These concepts have inspired the design of a range of synthetic nanoreactors that allow otherwise unfeasible catalytic reactions in aqueous environments. Since the field of nanoreactors is evolving rapidly, we here summarize-from a personal perspective-prominent and recent examples for polymer nanoreactors with emphasis on their synthesis and their ability to catalyze reactions in dispersion. Examples comprise the incorporation of catalytic sites into hydrophobic nanodomains of single chain polymer nanoparticles, molecular polymer nanoparticles, and block copolymer micelles and vesicles. We focus on catalytic reactions mediated by transition metal and organocatalysts, and the separate storage of multiple catalysts for one-pot cascade reactions. Efforts devoted to the field of nanoreactors are relevant for catalytic chemistry and nanotechnology, as well as the synthesis of pharmaceutical and natural compounds. Optimized nanoreactors will aid in the development of more potent catalytic systems for green and fast reaction sequences contributing to sustainable chemistry by reducing waste of solvents, reagents, and energy.

Evaluation of Visual Field and Balance Function Alterations in Patients Who Underwent Dermatochalasis Surgery.

PURPOSE: To compare perioperative visual field (VF), balance functions (BF), and changes in the other ocular parameters in patients undergoing upper eyelid dermatochalasis (DC) surgery. METHODS: One hundred and fifty-eight eyes of 79 patients who underwent DC surgery were included in the study. The VF, BF, intraocular pressure (IOP), pachymetry (PM), macular, and optic nerve measurements were recorded. Measurements were repeated at postoperative month 1. The preoperative and postoperative ocular measurements and the balance data were compared. RESULTS: Nineteen of 79 (24.05%) patients were male and 60 of 79 (75.95%) were female, while the mean age of the patients was 58.65 ± 7.38 years. There were statistically significant differences in terms of VF and macular thickness between the preoperative and postoperative values. The improvements in mean defect, standard loss variance, and mean sensitivity values of global VF parameters in both eyes were statistically significant after surgery. Central macular thickness, mean macular thickness, and macular volume decreased significantly in all eyes after surgery (p < 0.05). CONCLUSIONS: Although a marked improvement was observed in VF and peripheral vision after surgery, no significant change was found in BF parameters including primarily falling risk. The significant change in the macular parameters was only remarkable, and we think that the decrease was due to subtle vasospasm. There is a need for further comprehensive studies including especially patients older than 65 with a view to understanding the effect of DC surgery on BF.

Investigation of relationship between colour discrimination ability and stereoscopic acuity using Farnsworth Munsell 100 hue test and stereo tests.

OBJECTIVE: To evaluate the effect of colour discrimination ability on the stereoscopic acuity by comparing individuals having congenital colour vision deficiency (CCVD) with healthy individuals. DESIGN: A comparative study. PARTICIPANTS: The study included 53 binocular males, of whom 26 (mean age, 36.04 ± 9.30 years) were in the healthy group and 27 (mean age, 33.04 ± 9.81 years) were in the CCVD group. METHODS: The following tests were used: the Ishihara pseudo-isochromatic plate test for detecting CCVD, the Farnsworth Munsell 100 (FM100) hue test for colour discrimination ability, the TNO and Titmus stereo tests for stereoscopic acuity. RESULTS: In the CCVD group, 20 males were deutan and 7 males were protan. According to the FM100 hue test, total error score (TES), blue/yellow (b/y) local error score (LES), and red/green LES were significantly lower in the healthy group (30.23 ± 18.78, 15.15 ± 10.38, and 13.88 ± 11.93, respectively) than in the CCVD group (133.59 ± 67.45, 41.15 ± 22.03, and 89.15 ± 52.16, respectively) (p < 0.01 for each). The stereo test scores revealed significantly higher stereoscopic acuity in the healthy group (43.85 ± 33.92 arcsec for the TNO test and 40.00 ± 0.00 arcsec for the Titmus test) than in the CCVD group (93.33 ± 90.51 arcsec for TNO stereo test and 52.96 ± 24.62 arcsec for the Titmus test) (p < 0.05 for each). The TNO test score was significantly and positively correlated with the TES (r = 0.390, p = 0.049) and b/y LES (r = 0.490, p = 0.011) in the healthy group. CONCLUSIONS: Colour discrimination ability affected stereoscopic acuity. Moreover, stereoscopic acuity increased with increasing colour discrimination ability, which could be originated from the b/y colour region.

Is age-related macular degeneration a local manifestation of systemic disorder? Changes in nailfold capillaries at age-related macular degeneration.

AIMS: Determining whether nailfold capillary involvement is present in patients with Age-related macular degeneration (AMD) and whether there are different nailfold capillaroscopy findings between wet and dry types. METHODS: From January 2016 to December 2017, with an initial diagnosis of AMD, 53 consecutive adult patients (AMD group) and 91 age- and sex-matched healthy individuals were studied prospectively. There was no history of any other ocular disease and other disease affecting nailfold capillaries. All subjects underwent a complete ophthalmic examination. The classified and advanced stages of wet and dry types were not included. All nailfold capillaroscopy examinations were performed by the same rheumatologist. RESULTS: It was found that the frequency of major capillaroscopic findings such as capillary ectasia, micro-hemorrhage, tortuosity, neo-formation, bizarre capillary, and bushy capillaries increased in the AMD group according to the normal group, but no significant relationship was found for capillary aneurysm. In dry or wet type of AMD in terms of ectasia, micro-hemorrhage, tortuosity, neo-formation, bizarre structure, bushy structure, or aneurism of nailfold capillaries, no significant correlation was found. CONCLUSIONS: Nailfold capillaroscopy can detect microvascular changes in the nailfold capillary, in early and late stages of AMD. There were morphological changes in the nailfold capillaries of AMD patients, suggesting that there are systemic superficial microvascular changes that may be due to the systemic nature of the disease.

Optical coherence tomography angiography findings in malignant hypertensive retinopathy / Achados da angiografia por tomografia de coerência óptica na retinopatia hipertensiva maligna

ABSTRACT A 33-year-old male presented to our clinic with low vision in both eyes that started during the previous week. Visual acuity was 20/63 in the right eye and 20/50 in the left eye. Fundus examination revealed signs of hypertensive retinopathy; thus, a multidisciplinary approach was adopted for the diagnosis and treatment of this patient. We consulted the nephrology and cardiology departments on this case. Upon diagnosing malignant hypertension and renal failure, the patient was put on hemodialysis. His visual acuity was 20/20 at 6 months, whereas foveal assessment on optical coherence tomography angiography revealed neither marked superficial and deep capillary density loss and foveal avascular zone enlargement nor a decrease in disc flow and radial peripapillary capillary density. Early diagnosis and treatment of malignant hypertension are critical in preventing progression of end-organ damage including the eyes. Optical coherence tomography angiography may be useful in cases when fundus fluorescein angiography is relatively contraindicated (e.g., renal failure).

RESUMO Um homem de 33 anos apresentou-se à nossa clínica com baixa visão em ambos os olhos que começou uma semana antes. A acuidade visual foi de 20/63 no olho direito e 20/50 no olho esquerdo. O exame de fundo de olho revelou sinais de retinopatia hipertensiva; então, adotou-se uma abordagem multidisciplinar para o diagnóstico e tratamento desse paciente. Consultamos os departamentos de nefrologia e cardiologia neste caso. Ao diagnosticar hipertensão maligna e insuficiência renal, o paciente foi colocado em hemodiálise. Sua acuidade visual era 20/20 aos 6 meses, enquanto a avaliação foveal com angiotomografia de coerência óptica não revelou perda de densidade capilar superficial e profunda acentuada e aumento da zona avascular foveal nem uma diminuição no fluxo de disco e na densidade capilar peripapilar radial. O diagnóstico precoce e o tratamento da hipertensão maligna são fundamentais na preveção da progressão de danos nos órgãos-alvo, incluindo os olhos. A Angiografia por tomografia de coerência óptica pode ser útil nos casos em que a angiografia com fluoresceína do fundo de olho é relativamente contraindicada (por exemplo, insuficiência renal).

Optical coherence tomography angiography findings in malignant hypertensive retinopathy.

A 33-year-old male presented to our clinic with low vision in both eyes that started during the previous week. Visual acuity was 20/63 in the right eye and 20/50 in the left eye. Fundus examination revealed signs of hypertensive retinopathy; thus, a multidisciplinary approach was adopted for the diagnosis and treatment of this patient. We consulted the nephrology and cardiology departments on this case. Upon diagnosing malignant hypertension and renal failure, the patient was put on hemodialysis. His visual acuity was 20/20 at 6 months, whereas foveal assessment on optical coherence tomography angiography revealed neither marked superficial and deep capillary density loss and foveal avascular zone enlargement nor a decrease in disc flow and radial peripapillary capillary density. Early diagnosis and treatment of malignant hypertension are critical in preventing progression of end-organ damage including the eyes. Optical coherence tomography angiography may be useful in cases when fundus fluorescein angiography is relatively contraindicated (e.g., renal failure).

Electroneuromyographic findings in pseudoexfoliation syndrome.

PURPOSE: To examine peripheral electroneuromyographic findings in patients with ocular pseudoexfoliation syndrome (PEX) and to compare them controls without PEX. METHODS: A case-control study design was used to examine 31 patients with PEX and compare the findings with those of 31 age- and sex-matched healthy controls. All patients underwent complete ophthalmologic examination that included peripheral electroneuromyography examination. Motor and sensorial nerve conduction of the median, ulnar, tibial, peroneal, and sural nerve and the sympathetic skin response were measured. RESULTS: The average sensorial nerve latency of the ulnar and sural nerve was significantly longer in the PEX group compared to the control group (p < 0.05). The average sensorial nerve conduction amplitude and the velocity of the ulnar and sural nerve were significantly lower in the PEX group (p < 0.05). DISCUSSION: Peripheral nerves, especially sensorial fibers, appear to be affected in PEX patients. These finding may indicate that PEX is a systemic disease.

The Frequency of Primary Sjogren's Syndrome and Fibromyalgia in Irritable Bowel Syndrome.

OBJECTIVE: To determine the frequency of sicca complex, Sjogren's Syndrome (SS) and Fibromyalgia (FM) in patients with Irritable Bowel Syndrome (IBS). METHODS: Seventy seven IBS patients who fulfilled the Rome-III criteria were included in the study. All patients were assessed for FM according to the American College of Rheumatology (ACR) 2010 criteria. After examination for objective evidence of sicca complex by Schirmer test, TBUT and Ocular Staining Score (OSS), serological tests were performed. And the diagnosis of SS was made according to the American College of Rheumatology (ACR) classification criteria for SS - 2012. RESULTS: Thirteen (16.9%) of IBS patients had FM. Dry eye was detected in 20(26.0%), 7(9.1%) and 29(37.7%) patients by OSS, Schirmer test and TBUT, respectively. Of 77 patients with IBS, the diagnosis of SS was established in two patients (2.6%). CONCLUSION: The frequency of Sjogren's Syndrome among patients with IBS is relatively higher than the general population. All IBS patients should be questioned for dryness of the mouth and eyes, and if necessary, should be evaluated for SS.

Primary Sjögren's syndrome in patients with celiac disease.

BACKGROUND/AIM: Many autoimmune diseases occur concomitantly with celiac disease (CD). We aimed to determine the frequency of Sjögren's syndrome (SS) in CD patients based on SS-specific serology verified by minor labial salivary biopsy. MATERIALS AND METHODS: Eight-two patients with CD were included in the study. After examination for objective evidence of sicca complex, all patients were tested for serological presence of rheumatoid factor (RF) and antinuclear antibodies (ANAs) and for ANA profile. Minor labial salivary biopsy was performed for patients with positive serology and/or clinical signs of SS. RESULTS: Of the patients included, 24 (29.3%) had dry eye symptoms while 20 (24.4%) had dry mouth symptoms. Dry eye was detected by Schirmer test in 10 patients (12.2%) and by ocular staining score in only 2 patients (2.4%). All samples were negative for RF while 12 (14.6%) samples were positive for ANAs. Of 82 patients with CD, the diagnosis of SS was established in only one patient (1.2%), while one patient (1.2%) was diagnosed with morphea and 4 patients (4.9%) were classified as having undifferentiated connective tissue disease. CONCLUSION: The prevalence of SS in CD is low, so there is no need for serologic screening of all patients with CD for SS.

Cognitive performance of primary open-angle glaucoma and normal-tension glaucoma patients.

PURPOSE: To assess cognitive performance differences among primary open-angle glaucoma (POAG) patients, normal-tension glaucoma (NTG) patients, and healthy control (C) subjects. METHODS: A total of 60 participants (20 POAG, 20 NTG, and 20 C subjects) were included in this study. A detailed ophthalmologic examination was performed on all participants. A spectral domain-optical coherence tomography (SD-OCT) system was used to measure the ganglion cell-inner plexiform layer (GC-IPL) and retinal nerve fiber layer (RNFL) thicknesses. To assess the cognitive performance of all participants, detailed neurological examinations, including the mini-mental state examination (MMSE), were performed by the same neurologist. RESULTS: There were no significant differences among the groups in terms of age (p =0.348) or gender (p =0.935). The mean RNFL thicknesses were significantly different among the groups (85.2 ± 14.7, 76.8 ± 10.3, and 91.4 ± 7.7 µm in the POAG, NTG, and C subjects, respectively; p <0.001). The mean GC-IPL thicknesses were 77.5 ± 9.7 µm in the POAG group, 73.4 ± 7.8 µm in the NTG group, and 78.8 ± 3.8 µm in the C group. Differences among the groups were not statistically significant (p =0.085). MMSE scores were 26.1 ± 1.4, 25.7 ± 2.3, and 28.8 ± 0.9 in the POAG, NTG, and C groups, respectively. There were significant differences among the three groups (p <0.001). Specifically, there were significant differences between the NTG and C groups (p <0.001), and between the POAG and C groups (p =0.001). There was no significant difference between the POAG and NTG groups (p =0.595). CONCLUSIONS: There appear to be similar risk factors in glaucoma and neurodegenerative disorders that cause deterioration in cognitive performance. Comparing the low MMSE scores of the POAG and NTG patients with the scores of healthy C participants supports our hypothesis. Consequently, it is recommended that a neurologist should also examine glaucoma patients.

Is there a correlation between the clinical findings and the radiological findings in chronic maxillary sinus atelectasis?

OBJECTIVE: Silent sinus syndrome (SSS) is a clinical syndrome that occurs as a result of chronic maxillary sinus atelectasis (CMA) and is seen with progressive enophthalmos and hypoglobus. The aim of this study was to investigate the correlation between radiological findings and clinical findings in patients with radiologically asymmetrical reduced maxillary sinus volume. MATERIAL AND METHOD: A comparison was made of patients with CMA through evaluation of paranasal sinus computed tomography, magnetic resonance imaging examination of maxillary sinus volume of the CMA side and the contralateral side, thickness of the retroantral fat tissue, infraorbital bone curve, uncinate process lateralisation measurement, middle concha diameter, and calculation of the change in location of the inferior rectus muscle. RESULTS: The study included 16 patients. Although a statistically significant difference was determined between the healthy and the pathological sides in respect to maxillary sinus volume, thickness of the retroantral fat tissue, infraorbital bone curve, uncinate process lateralisation measurement, and middle concha diameter (p = 0.00, p = 0.002, p = 0.020, p = 0.020, p = 0.007), no significant difference was determined in respect to the change in location of the inferior rectus muscle (p = 0.154). A positive correlation was determined between the increase in sulcus depth and maxillary sinus volume and inferior orbital bone curve (p < 0.05). CONCLUSION: In CMA patients suspected of having SSS, radiological maxillary sinus volume analysis, determination of retroantral fat thickness, measurement of the infraorbital bone curve, and measurement of the uncinate process lateralisation can be used as objective tests. However, it should be kept in mind that radiological findings may not always be compatible with the ophthalmological examination findings.