Coffee-Ring Mediated Thinning and Thickness-Dependent Dewetting Modes in Printed Polymer Droplets Coupled with Assembly of Quantum Dots for Anti-Counterfeiting.

Molecular transport processes in printed polymer droplets hold enormous importance for understanding wetting phenomena and designing systems in applications such as encoding, electronics, photonics, and sensing. This paper studies thickness-dependent dewetting modes that are activated by thermal annealing and driven by interfacial interactions within microscopically confined polymeric features. The printing of poly(2-vinylpyridine) is performed in a regime where coffee-ring effects lead to strong thinning of the central region of the deposit. Thermal annealing leads to two different modes of dewetting that depend on the thickness of the central region. Mode I refers to the formation of randomly positioned small features surrounded by large hemispherical ones located along the periphery of the printed features and occurs when the central regions are thin. Observed at large central thicknesses, Mode II mediates significant molecular transport from edges toward the center of the printed droplet with thermal annealing and forms a hemispherical feature from the initial ring-like deposit. The selective adsorption of red, green, and blue emitting quantum dots over the poly(2-vinylpyridine) results in photoluminescent patterns. The selective assembly of photoluminescent quantum dots over patterned surfaces leads to deterministic and stochastic features beneficial to creating security labels for anti-counterfeiting applications.

Ultradurable Embedded Physically Unclonable Functions.

Physically unclonable functions (PUFs) have attracted growing interest for anticounterfeiting and authentication applications. The practical applications require durable PUFs made of robust materials. This study reports a practical strategy to generate extremely robust PUFs by embedding random features onto a substrate. The chaotic and low-cost electrohydrodynamic deposition process generates random polymeric features over a negative-tone photoresist film. These polymer features function as a conformal photomask, which protects the underlying photoresist from UV light, thereby enabling the generation of randomly positioned holes. Dry plasma etching of the substrate and removal of the photoresist result in the transfer of random features to the underlying silicon substrate. The matching of binary keys and features via different algorithms facilitates authentication of features. The embedded PUFs exhibit extreme levels of thermal (∼1000 °C) and mechanical stability that exceed the state of the art. The strength of this strategy emerges from the PUF generation directly on the substrate of interest, with stability that approaches the intrinsic properties of the underlying material. Benefiting from the materials and processes widely used in the semiconductor industry, this strategy shows strong promise for anticounterfeiting and device security applications.

pH Tunable Patterning of Quantum Dots.

Patterning of quantum dots (QDs) is essential for many, especially high-tech, applications. Here, pH tunable assembly of QDs over functional patterns prepared by electrohydrodynamic jet printing of poly(2-vinylpyridine) is presented. The selective adsorption of QDs from water dispersions is mediated by the electrostatic interaction between the ligand composed of 3-mercaptopropionic acid and patterned poly(2-vinylpyridine). The pH of the dispersion provides tunability at two levels. First, the adsorption density of QDs and fluorescence from the patterns can be modulated for pH > ≈4. Second, patterned features show unique type of disintegration resulting in randomly positioned features within areas defined by the printing for pH ≤ ≈4. The first capability is useful for deterministic patterning of QDs, whereas the second one enables hierarchically structured encoding of information by generating stochastic features of QDs within areas defined by the printing. This second capability is exploited for generating addressable security labels based on unclonable features. Through image analysis and feature matching algorithms, it is demonstrated that such patterns are unclonable in nature and provide a suitable platform for anti-counterfeiting applications. Collectively, the presented approach not only enables effective patterning of QDs, but also establishes key guidelines for addressable assembly of colloidal nanomaterials.

Food-Grade Physically Unclonable Functions.

Counterfeit products in the pharmaceutical and food industries have posed an overwhelmingly increasing threat to the health of individuals and societies. An effective approach to prevent counterfeiting is the attachment of security labels directly on drugs and food products. This approach requires the development of security labels composed of safely digestible materials. In this study, we present the fabrication of security labels entirely based on the use of food-grade materials. The key idea proposed in this study is the exploitation of food-grade corn starch (CS) as an encoding material based on the microscopic dimensions, particulate structure, and adsorbent characteristics. The strong adsorption of a food colorant, erythrosine B (ErB), onto CS results in fluorescent CS@ErB microparticles. Randomly positioned CS@ErB particles can be obtained simply by spin-coating from aqueous solutions of tuned concentrations followed by transfer to an edible gelatin film. The optical and fluorescence microscopy images of randomly positioned particles are then used to construct keys for a physically unclonable function (PUF)-based security label. The performance of PUFs evaluated by uniformity, uniqueness, and randomness analysis demonstrates the strong promise of this platform. The biocompatibility of the fabricated PUFs is confirmed with assays using murine fibroblast cells. The extremely low-cost and sustainable security primitives fabricated from off-the-shelf food materials offer new routes in the fight against counterfeiting.

Graphene-Based Physically Unclonable Functions with Dual Source of Randomness.

There is growing interest in systems with randomized responses for generating physically unclonable functions (PUFs) in anticounterfeiting and authentication applications. Atomic-level control over its thickness and unique Raman spectrum make graphene an attractive material for PUF applications. Herein, we report graphene PUFs that emerge from two independent stochastic processes. Randomized variations in the shape and number of graphene adlayers were achieved by exploiting and improving the mechanistic understanding of the chemical vapor deposition of graphene. The randomized positioning of the graphene domains was then facilitated by dewetting the polymer film, followed by oxygen plasma etching. This approach yielded surfaces with randomly positioned and shaped graphene islands with varied numbers of layers and, therefore, Raman spectra. Raman mapping of surfaces resulted in multicolor images with a high encoding capacity. Advanced feature-matching algorithms were employed for the authentication of multicolor images. The use of two independent stochastic processes on a two-dimensional nanomaterial platform enables the creation of unique and complex surfaces that excessively challenge clonability.

Physically Unclonable Surfaces via Dewetting of Polymer Thin Films.

From anti-counterfeiting to biotechnology applications, there is a strong demand for encoded surfaces with multiple security layers that are prepared by stochastic processes and are adaptable to deterministic fabrication approaches. Here, we present dewetting instabilities in nanoscopic (thickness <100 nm) polymer films as a form of physically unclonable function (PUF). The inherent randomness involved in the dewetting process presents a highly suitable platform for fabricating unclonable surfaces. The thermal annealing-induced dewetting of poly(2-vinyl pyridine) (P2VP) on polystyrene-grafted substrates enables fabrication of randomly positioned functional features that are separated at a microscopic length scale, a requirement set by optical authentication systems. At a first level, PUFs can be simply and readily verified via reflection of visible light. Area-specific electrostatic interactions between P2VP and citrate-stabilized gold nanoparticles allow for fabrication of plasmonic PUFs. The strong surface-enhanced Raman scattering by plasmonic nanoparticles together with incorporation of taggants facilitates a molecular vibration-based security layer. The patterning of P2VP films presents opportunities for fabricating hybrid security labels, which can be resolved through both stochastic and deterministic pathways. The adaptability to a broad range of nanoscale materials, simplicity, versatility, compatibility with conventional fabrication approaches, and high levels of stability offer key opportunities in encoding applications.

Assessment of biological effects of environmental pollution in Mersin Bay (Turkey, northeastern Mediterranean Sea) using Mullus barbatus and Liza ramada as target organisms.

The increasing emphasis on the assessment and monitoring of marine ecosystems has revealed the need to use appropriate biological indicators for these areas. Enzyme activities and histopathology are increasingly being used as indicators of environmental stress since they provide a definite biological end-point of pollutant exposure. As part of an ecotoxicological assessment of Mersin Bay, EROD enzyme activity and histopathological response in selected organs and tissues of two species of fish, Mullus barbatus (red mullet) and Liza ramada (thinlip grey mullet), captured from area were examined. Pollutant (Organochlorines (OC), alkylphenols (APs) and BPA) levels and biomarker responses in tissue samples were evaluated together for their potential to alter the metabolism and cellular aspects in liver and gonad. Elevated induction of EROD activity and histopathological alterations in contaminated samples from Mersin Bay was observed compared to reference site indicating the exposure to potential pollutants.

Efficacy of citalopram on climacteric symptoms.

OBJECTIVE: The aim of this study was to evaluate the efficacy of citalopram for climacteric symptoms and to assess the combined effect of citalopram and hormone therapy (HT) on climacteric symptoms in women inadequately responsive to HT alone. DESIGN: The study included 100 postmenopausal women who were allocated into one of four groups: (1) citalopram, (2) placebo, (3) citalopram+HT, or (4) placebo+HT. The women who were unable or unwilling to take HT were randomly placed in groups 1 and 2. The women who were inadequately responsive to HT were randomly placed in groups 3 and 4. The initial dose of citalopram was 10 mg/day in groups 1 and 3. After 1 week, the dose was increased to 20 mg/day. After starting the medication, follow-up visits took place during the fourth and eighth weeks of treatment. During the first and eighth weeks, women completed two questionnaires: a modified Kupperman index and the Menopause-Specific Quality of Life Questionnaire. RESULTS: Mean hot flash scores significantly improved in all groups (P<0.05). The reduction rates were 37% in group 1, 13% in group 2, 50% in group 3, and 14% in group 4. Psychosocial complaints and mean values on the Kupperman index significantly decreased in all groups (P<0.05). Physical well-being significantly improved in groups 1, 3, and 4 (P<0.05). The decrease in all scores was significantly greater in groups 1 and 3 compared to groups 2 and 4 (P<0.01). CONCLUSION: Citalopram is an effective alternative treatment option for patients who do not want to take HT for the alleviation of climacteric symptoms. Adjuvant treatment with a selective serotonin reuptake inhibitor increases the effectiveness of HT for the treatment of climacteric symptoms in women who had responded inadequately to HT.

Incidence of depression related to isotretinoin treatment in 100 acne vulgaris patients.

The incidence of depression in acne patients using isotretinoin was assessed in 100 patients with moderate and nodulocystic acne. All patients received 0.75-1.00 mg/kg/day of isotretinoin for 20-28 weeks after acne was assessed. All patients' acne lesions were improved at the end of the treatment period. Psychological state was evaluated at baseline, at Month 3, and Month 6 by a psychiatrist using a Turkish version of the Hamilton Depression Rating Scale. Only one patient's score increased to the clinical level of depression at Month 3 of treatment and declined to subclinical levels at Month 6. Although Hamilton scores increased at Month 3 over baseline scores, except for one patient, others' scores remained below the subclinical level for depression. At the end of Month 6, the mean score decreased below that at Month 3. These changes in means might be related to the onset of clinical effect of isotretinoin.