Efficient Sorting of Semiconducting Single-Walled Carbon Nanotubes in Bio-Renewable Solvents Through Main-Chain Engineering of Conjugated Polymers.

Conjugated polymer sorting is recognized as an efficient and scalable method for the selective extraction of semiconducting single-walled carbon nanotubes (s-SWCNTs). However, this process typically requires the use of nonpolar and aromatic solvents as the dispersion medium, which are petroleum-based and carry significant production hazards. Moreover, there is still potential for improving the efficiency of batch purification. Here, this study presents fluorene-based conjugated polymer that integrates diamines containing ethylene glycol chains (ODA) as linkers within the main chain, to effectively extract s-SWCNTs in bio-renewable solvents. The introduction of ODA segments enhances the solubility in bio-renewable solvents, facilitating effective wrapping of s-SWCNTs in polar environments. Additionally, the ODA within the main chain enhances affinity to s-SWCNTs, thereby contributing to increased yields and purity. The polymer achieves a high sorting yield of 55% and a purity of 99.6% in dispersion of s-SWCNTs in 2-Methyltetrahydrofuran. Thin-film transistor arrays fabricated with sorted s-SWCNTs solution through slot-die coating exhibit average charge carrier mobilities of 20-23 cm2 V⁻¹ s⁻¹ and high on/off current ratios exceeding 105 together with high spatial uniformity. This study highlights the viability of bio-renewable solvents in the sorting process, paving the way for the eco-friendly approach to the purification of SWCNTs.

Chain-Kinked Design: Improving Stretchability of Polymer Semiconductors through Nonlinear Conjugated Linkers.

The manipulation of the polymer backbone structure has a profound influence on the crystalline behavior and charge transport characteristics of polymers. These strategies are commonly employed to optimize the performance of stretchable polymer semiconductors. However, a universal method that can be applied to conjugated polymers with different donor-acceptor combinations is still lacking. In this study, we propose a universal strategy to boost the stretchability of polymers by incorporating the nonlinear conjugated linker (NCL) into the main chain. Specifically, we incorporate meta-dibromobenzene (MB), characterized by its asymmetric linkage sites, as the NCL into the backbone of diketopyrrolopyrrole-thiophene-based (DPP-based) polymers. Our research demonstrates that the introduction of MB prompts chain-kinking, thereby disrupting the linearity and central symmetry of the DPP conjugated backbone. This modification reshapes the polymer conformation, decreasing the radius of gyration and broadening the free volume, which consequently adjusts the level of crystallinity, leading to a considerable increase in the stretchability of the polymer. Importantly, this method increases stretchability without compromising mobility and exhibits broad applicability across a wide range of donor-acceptor pair polymers. Leveraging this strategy, fully stretchable transistors were fabricated using a DPP polymer that incorporates 10 mol % of MB. These transistors display a mobility of approximately 0.5 cm2 V-1 s-1 and prove remarkably durable, maintaining 90% of this mobility even after enduring 1000 cycles at 25% strain. Overall, we propose a method to systematically control the main-chain conformation, thereby enhancing the stretchability of conjugated polymers in a widely applicable manner.

Reduced risk of skin cancer and internal malignancies in vitiligo patients: a retrospective population-based cohort study in Taiwan.

The relationship between cancer and vitiligo has been explored but with inconsistent results. To examine the long-term cancer risk in vitiligo patients, we conducted a retrospective nationwide cohort study. From the National Health Insurance Research Database of Taiwan, a total of 13,824 vitiligo patients were identified and matched with 55,296 reference subjects without vitiligo by age, gender, and propensity score estimated by major comorbidities from 1997 to 2013. Demographic characteristics and comorbidities were compared between these two groups. Incidence rate ratios and hazard ratios (HRs) were calculated to examine cancer risks. The 16-year incidence rates of overall cancers were 621.06 (566.56-675.55) and 726.99 (697.24-756.74) per 100,000 person-years in the vitiligo and reference groups. Patients with vitiligo showed a significantly decreased risk of overall cancers [adjusted HR, 0.85; 95% confidence interval (CI), 0.77 to 0.93, p < 0.001] compared with reference subjects without vitiligo after adjusting for age, sex, comorbidities, and treatments. The risks of basal cell carcinoma (BCC) and squamous cell carcinoma (SCC) were significantly reduced (adjusted HR 0.21, 95% CI 0.11-0.38, p < 0.001), as well as internal malignancies (adjusted HR 0.89, 95% CI 0.81-0.99, p = 0.026). The results were consistent across different subgroups of patients, including male gender, ages more than 40 years, and those receiving long-term systemic disease-modifying antirheumatic drugs and phototherapies. Information related to phenotype, disease duration, vitiligo lesion sites, family history of vitiligo or cancer, occupation, and personal lifestyle was not included in the database. Vitiligo is associated with reduced risks of BCC and SCC, as well as internal malignancies.

Atopic dermatitis does not increase the risk of inflammatory bowel disease: A nationwide cohort study.

Coexistence of inflammatory bowel disease (IBD) in atopic dermatitis (AD) patients has been reported. The long-term risk of IBD in AD patients remains unclear. Our aim for the study is to examine the long-term risk of IBD in AD patients. This is a nationwide cohort study. From the National Health Insurance Research Database of Taiwan (1997-2013), a total of 36 400 AD patients were identified and matched with 364 000 reference subjects without AD by age, sex and number of hospital visits. Demographic characteristics and comorbidities were compared. Cox proportional hazards regression analysis was conducted to examine the risk of IBD. The 16-year cumulative incidences of IBD were 0.047% (95% confidence interval [CI], 0.040-0.054) and 0.047% (95% CI, 0.025-0.096) in non-AD and AD cohorts, respectively (P = 0.973). There were 17 cases of IBD (0.05%), including 10 ulcerative colitis and seven Crohn's disease, among AD patients compared with 169 IBD cases (0.05%) among controls (P > 0.999). Infections (adjusted hazard ratio [HR], 2.71; 95% CI, 1.96-3.95; P < 0.001) and age (adjusted HR, 1.03; 95% CI, 1.02-1.03; P < 0.001) were independently associated with IBD, after adjusting for major comorbidities and conducting multivariate analyses. AD was not associated with IBD development. In conclusion, AD is not independently associated with IBD development.

Characterization and Optimization of Silver-Modified In0.2Cd0.8S-Based Photocatalysts.

In this research, we performed scanning electrochemical microscopy to screen M x (In0.2Cd0.8)1-x S (M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Ag, W, Ir, Pt, and Te) photocatalyst arrays for efficient photoelectrochemical reaction. Doping 30% Ag to form the Ag0.3(In0.2Cd0.8)0.7S electrode could result in the highest photocurrent, and also, the anode photocurrents were found to be 1 and 0.53 mA/cm2 under UV-visible and visible light, respectively, comparatively higher than that of the In0.2Cd0.8S electrode (0.45 and 0.25 mA/cm2). The highest incident photo-to-current conversion efficiency of the Ag0.3(In0.2Cd0.8)0.7S photocatalyst and In0.2Cd0.8S were found to be 64% (λ = 450 nm) and 57% (λ = 400 nm), respectively. The Mott-Schottky plots showed that In0.2Cd0.8S and Ag0.3(In0.2Cd0.8)0.7S photoelectrodes could exhibit a flat-band potential of -0.85 and -0.55 V versus Ag/AgCl, respectively. Based on these findings, the superior photocatalytic activity of the Ag0.3(In0.2Cd0.8)0.7S photoelectrode was mainly attributed to its high crystalline structure for efficient charge separation and reduction of charge recombination in the heterojunction of Ag0.3(In0.2Cd0.8)0.7S and Ag2S.

Pityriasis Lichenoid-like Mycosis Fungoides in a 9-year-old Boy: A Case Report.

Dear Editors, Pityriasis lichenoides (PL)-like mycosis fungoides (MF) is a rare variant of MF, presenting clinical findings of PL but histological features of MF. It was first reported by Ko et al. (1) and only a few cases have been reported since (2-5). Herein we report the case of a boy with PL-like MF and review the related literature. A 9-year-old boy presented with a 1-year history of multiple pruritic crusted erythematous papules and scaly pink maculopatches on the face, trunk, and extremities (Figure 1, a and b). Histologic examination of a papule revealed lymphocytic epidermotropism and lymphocytes tagging the dermoepidermal junction. The nuclei of the lymphocytes were hyperchromatic and irregular (Figure 1, c and d). Immunohistochemically, the infiltrating lymphocytes revealed positivity for CD2, CD3, CD5, CD7, and CD8, but were negative for CD4, CD20, CD30, CD68, and CD163 (Figure 1, e-g). T-cell receptor gene rearrangement analysis (TCR-GRA) demonstrated the rearrangement of the gamma chain (Figure 1, h). PL-like MF was diagnosed. The patient was started on narrowband ultraviolet B (NBUVB) phototherapy. The skin lesions markedly improved after 6 months of treatment. There was no recurrence during the 2 years of follow-up. There has long been a controversy regarding whether PL is just an inflammatory dermatosis or a genuine T-cell lymphoproliferative disease. Wang et al. (2) proposed three categories for the relationship between PL and MF: (A) PL with a dominant T-cell clone, (B) PL subsequently progressing into MF, and (C) PL-like MF. In the first category, PL is a monoclonal T-cell-mediated inflammatory disorder, in which T-cell clones were found in about 50% of patients (6,7). The second category involves progression from long-term PL to MF (8,9). The average time-to-progression is about 8 years. It has been speculated that the PL-related immunologic microenvironment is favorable for developing a tumoral clone. Our patient presented with PL-like lesions clinically, while biopsy findings, results of immunohistochemistry, and TCR-GRA all suggested that this case was MF. Due to the short duration (only one year) of his lesions, we established the diagnosis of PL-like MF de novo, rather than evolution from PL to MF. The features of previously reported cases of PL-like MF and those of our patient are summarized in Table 1 (1-5). Men were predominant (18:7) among the total of 25 patients. Most patients were children or young adults (mean age of 23.4 years).The interval between presence of lesions and diagnosis varied from 1 month to 10 years. The cutaneous eruptions were all PL in appearance and almost all involved both the trunk and extremities. Pruritus was reported by approximately half of the patients. Histologically, the scaly papules were usually indistinguishable from classical MF, showing epidermotropism, haloed lymphocytes, lymphocytes aligning along the dermoepidermal junction, and Pautrier's microabscesses. Immunohistochemically, all tested cases demonstrated positivity for CD3 but were negative for CD20 and CD30. Cases with predominantly CD8-positive cells were twice as prevalent as cases with predominantly CD4-positive cells. TCR-GRA was performed in 20 cases, 15 of which revealed monoclonality. Most patients received psoralen combined with ultraviolet A or NBUVB phototherapy, and demonstrated either a complete or partial response. Recurrence was reported in only 2 cases (5). In summary, PL-like MF is a rare variant of MF. It has some features distinct from classic MF, such as a higher incidence in young men and predominantly CD8-positive T-cells infiltration. Phototherapy can be used as the first line of treatment. A good response and a favorable prognosis can be expected.

Ascorbic acid sensor using a PVA/laccase-Au-NPs/Pt electrode.

A surface-modified electrode, PVA/laccase-Au-NPs/Pt, was prepared to sense ascorbic acid (H2A) in this study. An amount of the following composite, PVA/laccase-Au-NPs/Pt, the polyvinyl acetate (PVA) was employed as a surfactant to adhere the substrate, Pt; then the laccase peptides were spun inside the PVA fiber to wind around the immobilized Au-NPs and construct a hierarchical structure. The PVA shell layer was in charge of sensing H2A and transmitting electrical signals, i.e. transducing redox reaction of H2A. Inside the core region, laccase peptides were responsible for transducing electrons and the Au-NPs collected and relayed them to the substrate of the Pt electrode. It was found that the sensing mechanism for the transducing laccase molecules involved a long-chain electron transmission and peroxide bridging, and for the sensed object, H2A, is related to a sequential discharge of two electrons. According to a test of the catalytic activity, the sensitivity increased with the increase of the doped Au-NPs up to a maximum amount and then decreased because excess Au-NPs tended to agglomerate and obstruct the relaying electrons. The response time and sensitivity were measured to be ca. 40 s and 1.8 µA cm-2 ppm. The surface-modified electrode, PVA/laccase-Au-NPs/Pt, was found to show good selectivity among several disturbing reagents and good stability for 76 days.

Ruthenium oxide modified nickel electrode for ascorbic acid detection.

Electrodes of ruthenium oxide modified nickel were prepared by a thermal decomposition method. The stoichiometry of the modifier, RuOx, was quantitatively determined to be a meta-stable phase, RuO5. The electrodes were employed to sense ascorbic acid in alkaline solution with a high sensitivity, 296 µAcm-2 mM-1, and good selectivity for eight kinds of disturbing reagents. We found that the ascorbic acid was oxidized irreversibly in solution. To match with the variation of the morphology, the sensitivity reached a maximum when the RuOx segregated with a nano-crystalline feature. We find that the substrate oxidized as the deposited RuOx grew thicker. The feature of the deposited RuOx changed from nano-particles to small islands resulting from the wetting effect of the substrate oxide, NiO; meanwhile the sensitivity decreased dramatically. The endurance of the RuOx/Ni electrode also showed a good performance after 38 days of successive test.

Combinatorial biomimetics. optimization of a composition of copper(II) poly-L-histidine complex as an electrocatalyst for O2 reduction by scanning electrochemical microscopy.

A simple approach to prepare and characterize biomaterial-based electrocatalysts for oxygen reduction was carried out. Poly-l-histidine was used as a matrix and ligand to complex Cu2+ to mimic the active sites of laccases. A modified glassy carbon (GC) electrode with Cu2+-poly-l-histidine complex decreases the oxygen reduction overpotential as compared with the bare GC electrode. An array of Cu2+-poly-l-histidine spots with different compositions was deposited on a GC substrate, and their catalytic activity for oxygen reduction was evaluated by a scanning electrochemical microscopy-based screening technique. The electrocatalytic activities of complexes for oxygen reduction strongly depended on the mole ratio of Cu2+ to poly-l-histidine and the applied potential of the substrate.

CT60 single nucleotide polymorphism of the CTLA-4 gene is associated with susceptibility to Graves' disease in the Taiwanese population.

Graves' disease (GD) is an autoimmune disease but the underlying etiology has not been completely elucidated. Genetic susceptibility has been believed to play a major role. Recent studies showed that the CT60 single nucleotide polymorphism (SNP), which is in the 3'-noncoding region of the CTLA-4 gene, is strongly associated with some immune-mediated diseases. The aim of this study was to test for association between GD susceptibility and polymorphisms of CTLA-4 (ie, the CT60 SNP and the exon 1 +49 SNP) in the Taiwanese population. Our results demonstrate significant differences in the frequencies of the genotypes and alleles between 107 GD patients and 101 control subjects in the CT60 and exon 1 +49 SNPs (p <0.05). Significant differences in phenotypes were only found for CT60 SNP (78.4% vs 67.8% between patients and controls; chi2 = 3.93, p = 0.047). Furthermore, we found that the G/G genotype of both CT60 and exon 1 +49 was associated with increased risk for GD (p = 0.022, OR = 1.97). Significant linkage disequilibrium was found between the CT60 SNP and the exon 1 +49 SNP in both GD patients and control subjects (D' = 1.00). Because of tight linkage disequilibrium, a combination of these SNPs enhanced the role of the CTLA-4 gene in GD. The frequency of the disease-susceptible G allele of CT60 was comparable to that in Japanese and higher than in Caucasians. In conclusion, we provide evidence that CT60 SNP is associated with susceptibility to GD in the Taiwanese population.

Telemetric electrochemical sensor.

A telemetric system was designed and constructed to sense pH and ethanol variation in aqueous solutions. The measured signals were transferred by software digitally and transmitted wirelessly by the telemeter, personal digital assistant (PDA), through the General Packet Radio Service (GPRS) protocol. The pH sensing electrode was designed to measure a chemical potential induced by a proton concentration gradient on the electrode's surface which exhibits internal Donnon diffusion behavior, and a linear relationship between the electrical potential and pH was found. The result shows that the wireless sensing system allowed not only long-term usage and long-distance transmission but also with high accuracy (e.g. S.D. less than +/-2%). The telemetric system can also be modified to measure ethanol concentration in aqueous solution amperometrically. It was found that the sensitivity of that ex situ measurements matched those of in field measurements with negligible deviation, less than 4%.

A sputtered thin film of nanostructured Ni/Pt/Ti on Al2O3 substrate for ethanol sensing.

A novel thin film ethanol sensor using sputtered Ni/Pt/Ti on an Al2O3 substrate as the working electrode in an alkaline solution was developed. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to characterize the nanostructure of nickel films. Sputtering deposition conditions for maximum catalytic efficiency, electrode selectivity, and reproducibility were discussed. The results showed that ethanol oxidation was more efficient on the sputtered Ni/Pt/Ti on an Al2O3 substrate electrode than that on the conventional nickel electrode. The optimal operating conditions to generate the sputtered Ni/Pt/Ti on the Al2O3 substrate electrode were: 45 min of Ni sputtering deposition time, and 50 W of Ni sputtering power. The results also indicated that the response time of the prepared ethanol sensor is 27 s and the best sensitivity is 3.08 microA microM(-1) cm(-2).