Association between sickness presenteeism and depressive symptoms: a cross-sectional study using the 6th Korean working conditions survey.

PURPOSE: This study aimed to reveal the relationship of the days of experiencing sickness presentism and depressive symptoms among Korean workers. Sickness presenteeism which defined as the act of going to work despite being feeling unhealthy triggers various adverse effects on mental health, including increased risks of depression. Furthermore, Sickness presenteeism is a major social issue causing substantial socioeconomic costs. METHODS: The data of 25120 participants from sixth Korean Working Condition Survey was utilized in this cross-sectional study. Sickness presenteeism was defined using a self-reported questionnaire and depressive symptoms were assessed by WHO well-being index. Multivariate logistic regression analysis was conducted to calculate the odd ratios for depressive symptoms regarding the number of days experiencing sickness presenteeism. We calculated odds ratios (ORs) and 95% confidence interval (95% CI) for depressive symptoms after categorizing participants into three groups based on the duration of experiencing sickness presenteeism, using cut-off values of 3 and 5 days. RESULTS: Workers who have experienced sickness presenteeism for more than 5 days were at highest risk for depressive symptoms than referent group (OR 2.87; 95% CI 2.17-3.76 in male, OR 3.86; 95% CI 3.02-4.91 in female). Furthermore, there was a trend of increasing risk for depressive symptom as the duration of experiencing sickness presenteeism extended. CONCLUSION: This study presents the association between experiencing sickness presenteeism in the previous 12 months and depressive symptoms. Based on the results, we provide individual and organizational strategies of reducing sickness presenteeism. Also, screening for workers who have experienced sickness presenteeism are needed to ensure good mental health.

Development strategy of non-GMO organism for increased hemoproteins in Corynebacterium glutamicum: a growth-acceleration-targeted evolution.

Heme, found in hemoproteins, is a valuable source of iron, an essential mineral. The need for an alternative hemoprotein source has emerged due to the inherent risks of large-scale livestock farming and animal proteins. Corynebacterium glutamicum, regarded for Qualified Presumption of Safety or Generally Recognized as Safe, can biosynthesize hemoproteins. C. glutamicum single-cell protein (SCP) can be a valuable alternative hemoprotein for supplying heme iron without adversely affecting blood fat levels. We constructed the chemostat culture system to increase hemoprotein content in C. glutamicum SCP. Through adaptive evolution, hemoprotein levels could be naturally increased to address oxidative stress resulting from enhanced growth rate. In addition, we used several specific plasmids containing growth-accelerating genes and the hemA promoter to expedite the evolutionary process. Following chemostat culture for 15 days, the plasmid in selected descendants was cured. The evolved strains showed improved specific growth rates from 0.59 h-1 to 0.62 h-1, 20% enhanced resistance to oxidative stress, and increased heme concentration from 12.95 µg/g-DCW to 14.22-15.24 µg/g-DCW. Notably, the putative peptidyl-tRNA hydrolase-based evolved strain manifested the most significant increase (30%) of hemoproteins. This is the first report presenting the potential of a growth-acceleration-targeted evolution (GATE) strategy for developing non-GMO industrial strains with increased bio-product productivity.

PECI-Net: Bolus segmentation from video fluoroscopic swallowing study images using preprocessing ensemble and cascaded inference.

Bolus segmentation is crucial for the automated detection of swallowing disorders in videofluoroscopic swallowing studies (VFSS). However, it is difficult for the model to accurately segment a bolus region in a VFSS image because VFSS images are translucent, have low contrast and unclear region boundaries, and lack color information. To overcome these challenges, we propose PECI-Net, a network architecture for VFSS image analysis that combines two novel techniques: the preprocessing ensemble network (PEN) and the cascaded inference network (CIN). PEN enhances the sharpness and contrast of the VFSS image by combining multiple preprocessing algorithms in a learnable way. CIN reduces ambiguity in bolus segmentation by using context from other regions through cascaded inference. Moreover, CIN prevents undesirable side effects from unreliably segmented regions by referring to the context in an asymmetric way. In experiments, PECI-Net exhibited higher performance than four recently developed baseline models, outperforming TernausNet, the best among the baseline models, by 4.54% and the widely used UNet by 10.83%. The results of the ablation studies confirm that CIN and PEN are effective in improving bolus segmentation performance.

Relationship between long working hours and smoking behaviors: Evidence from population-based cohort studies in Korea.

OBJECTIVES: Long working hours and overwork are growing public health concerns in the Western-Pacific region. We explored the relationship between working hours and smoking behaviors of Korean workers. METHODS: This study included 284 782 observations (50 508 workers) from four nationwide cohort studies in Korea. Using generalized estimating equations, we estimated the associations of working hours with current smoking status, smoking initiation, and smoking cessation within each cohort. Cohort-specific estimates were combined through random-effect meta-analysis. Effect sizes were presented as odds ratios (OR) and 95 confidence intervals (CI). RESULTS: The overall smoking prevalence was 26.8% within the cohorts. The adjusted OR (95% CI) of the association between working hours and current smoking were 1.01 (0.94-1.08) for <35 hours/week, 1.04 (1.01-1.09) for 41-48 hours/week, 1.06 (1.01-1.10) for 49-54 hours/week, and 1.07 (1.04-1.10) for ≥55 hours/week compared with 35-40 hours/week. The adjusted OR (95% CI) of the association between working hours and smoking cessation in the follow-up were 0.93 (0.85-1.02) for <35 hours/week, 0.89 (0.83-0.96) for 41-48 hours/week, 0.87 (0.81-0.95) for 48-54 hours/week, and 0.91 (0.85-0.98) for ≥55 hours/week compared with 35-40 hours/week. No clear associations were observed between working hours and smoking initiation. CONCLUSION: Long working hours are associated with high current smoking risk and reduced likelihood of smoking cessation among Korean workers. Policy interventions are required to promote smoking cessation and reduce excess overwork for individuals experiencing long working hours.

Association between temporary employment and current smoking and change in smoking behaviors: A prospective cohort study from South Korea (2009-2018).

Background Previous studies have suggested that employment insecurity is associated with adverse health outcomes. We explored the association between temporary employment and smoking behaviors.Methods We analyzed 11,795 workers (51,867 observations) from the Korea Health Panel Study (2009-2018). Employment types were categorized as regular, fixed-term, or daily, based on the duration of labor contract. The outcomes were current smoking status and changes in smoking behavior (initiation or cessation) in the following year. Generalized estimating equations were used to estimate odds ratio (OR) and 95% confidence interval (CI).Results The proportions of fixed-term and daily workers were 41.2% and 16.4% for women and 23.6% and 12.4% for men, respectively. Temporary employment was associated with increased odds of current smoking, while also demonstrating prospective associations with changes in smoking behaviors. For instance, in prospective analyses, male workers with fixed-term and daily employments were associated with a decreased likelihood of smoking cessation (OR:0.77; 95% CI:0.65-0.91 for fixed-term employment and OR:0.66; 95% CI:0.52-0.83 for daily employment) in the following year compared to those with regular employment. Moreover, those experiencing consecutive temporary employment was most inversely associated with smoking cessation in both men (OR:0.56; 95% CI:0.44-0.71) and women (OR:0.37; 95% CI:0.16-0.85) compared to those experiencing consecutive regular employment. However, no clear association between temporary employment and smoking initiation was observed in both men and women.Conclusions Temporary employment is directly associated with current smoking and inversely associated with smoking cessation. Policies are needed to improve job insecurity among temporary employees.

Tetramic acid-motif natural products from a marine fungus Tolypocladium cylindrosporum FB06 and their anti-Parkinson activities.

Tetramic acid-containing natural products are attracting significantly increasing attention from biologists and chemists due to their intriguing structures and biological activities. In the present study, two new tetramic acid alkaloids tolypyridone I (1) and tolypyridone J (2), together with five known ones (3-7), were isolated from cultures of a marine fungus Tolypocladium cylindrosporum FB06 isolate obtained from a marine sediment in Beaufort sea of North Alaska. Their structures were elucidated using 1D, 2D NMR, and HRESIMS. Their configurations were established on the basis of 1H coupling constants, ROESY correlations and DP4 calculations. Compound 2 was isolated as mixtures of rotational isomers with C-3 to C-7 axis between 4-hydroxy-2-pyridone and 1-ethyl-3,5-dimethylcyclohexane, hindering rotation. In our unbiased screening to discover neuroprotective compounds in an in vitro Parkinson's disease (PD) model, SH-SY5Y dopaminergic cells were treated with isolated compounds followed by treatment with 1-methyl-4-phenylpyridinium (MPP+), a parkinsonian neurotoxin. Among tested compounds, F-14329 (7) significantly protected cells from MPP+-induced cytotoxicity. MPP+-mediated cell death is known to be related to the regulation of Bcl-2 family proteins, specifically the down-regulation of anti-apoptotic Bcl-2 and the up-regulation of pro-apoptotic Bax levels. Treatment with 2 mmol/L of MPP+ for 24 h significantly reduced Bcl-2 levels compared to control treated with vehicle. However, treatment with F-14329 (7) attenuated such reduction. This study demonstrates that tetramic acid-motif compounds could be potential lead compounds for treating PD. Supplementary Information: The online version contains supplementary material available at 10.1007/s42995-023-00198-7.

Impact of Packing Geometry on Excimer Characteristics and Mobility in Perylene Bisimide Polycrystalline Films.

Efficient exciton transport is essential for high-performance optoelectronics. Considerable efforts have been focused on improving the exciton mobility in organic materials. While it is feasible to improve mobility in organic systems by forming well-ordered stacks, the formation of trap states, particularly the lower-lying states referred to as excimers, remains a significant challenge to enhancing mobility. The mobility of excimer excitons intricately depends on the strength of excitonic coupling in terms of Förster-type diffusive exciton transfer processes. Given that the formation and mobility of excimer excitons are highly sensitive to molecular arrangements (packing geometries), conducting comprehensive investigations into the structure-property relationship in organic systems is crucial. In this study, we prepared three types of polycrystalline films of perylene bisimide (PBI) by varying substituents at the imide and bay positions, which allowed us to tailor the properties of excimer excitons and their mobility based on packing geometries and excitonic coupling strengths. By utilizing femtosecond transient absorption spectroscopy, we observed ultrafast excimer formation in the higher coupling regime, while in the lower coupling regime, the transition from Frenkel to excimer excitons occurs with a time constant of 500 fs. Under high pump-fluence, exciton-exciton annihilation processes occur, indicating the diffusion of excimer excitons. Intriguingly, employing a three-dimensional diffusion model, we derived a diffusion constant that is 3000 times greater in the high coupling regime than in the low coupling regime. To investigate the optoelectronic properties in the form of a bulk system, we fabricated n-type organic field effect transistors and obtained 8000 times higher mobility in the high coupling regime. Furthermore, photocurrent measurements enable us to investigate the charge carrier transport by mobile excimer excitons, suggesting a 230-fold improvement in external quantum efficiency with tightly packing PBI molecules compared to the low coupling regime. These findings not only offer valuable insights into optimizing organic materials for optoelectronic devices but also unveil the intriguing potential of exciton migration within excimers.

Operando spectroscopic characterization of formamidinium lead iodide perovskite quantum dots for tracking electrochemical reactions.

Multidimensional ABX3 hybrid perovskites three-dimensionally confined dot-shaped structure demonstrate versatile potential to photoelectrochemical cells for water splitting, hydrogen generation, solar cells, and light-emitting diodes. To apply perovskite quantum dots (PQDs) to solar-driven chemistry and optoelectronic devices, understanding the photoinduced charge carrier dynamics of PQDs under electrochemical conditions or applied bias are important. In this study, the detailed transformation mechanism of formamidinium lead iodide perovskite quantum dots under electrochemical conditions was studied by tracking the products of the reaction through cyclic voltammetry, X-ray photoemission spectroscopy, in-situ UV-visible spectroelectrochemistry, etc. Through comprehensive characterizations, the mechanism of irreversible oxidative transformation of perovskite quantum dots was presented. This study provides deeper insight into the electrochemical behavior of PQDs for successful solar-driven chemistry and optoelectronic device applications.

Prospective comparative analysis of zero-heat-flux thermometer (SpotOn®) compared with tympanic thermometer and bladder thermometer in extremely aged patients undergoing lower extremity orthopedic surgery.

Thermoregulation is important for maintaining homeostasis in the body. It can be easily broken under anesthesia. An appropriate method for measuring core body temperature is needed, especially for elderly patients, because the efficiency of thermoregulation gradually decreases with age. Zero-heat-flux (ZHF) thermometry (SpotOn) is an alternative, noninvasive method for continuous temperature monitoring at the skin surface. The aim of this study was to examine the accuracy and feasibility of using the SpotOn sensor in lower extremity orthopedic surgery in elderly patients aged over 80 years by comparing a SpotOn sensor with 2 other reliable minimally invasive methods: a tympanic membrane thermometer and a bladder thermometer. This study enrolled 45 patients aged over 80 years who were scheduled to undergo lower extremity surgery. Body temperature was measured using a SpotOn sensor, a tympanic membrane thermometer and a bladder thermometer. Agreements between the SpotOn sensor and the other 2 methods were assessed using Bland and Altman plots for repeated measures adjusted for unequal numbers of measurements per patient. Compared with bladder temperature, bias and limits of agreement for SpotOn temperature were 0.07°C ± 0.58°C. Compared with tympanic membrane temperature, bias and limits of agreement for SpotOn temperature were -0.28°C ± 0.61°C. The 3M SpotOn sensor using the ZHF method for patients aged over 80 years undergoing lower extremity surgery showed feasible measurement value and sensitivity.

Identification of Chemical and Structural Characteristics of Acrylic Paint Layer Using Terahertz Metasurfaces.

The precise investigation and monitoring of the internal structural change within complex layered systems are crucial, as the emergence of undesirable defects or formation of secondary internal structures significantly exerts a profound influence on the overall properties of the system. We demonstrate an advanced sensing platform utilizing terahertz metasurfaces, allowing chemical detection and precise identification within an acrylic paint layer with a noticeable sensitivity, reaching down to several hundreds of nanometers, in nondestructive and noncontact manners. The identification of solid and mixed paint samples was achieved by analyzing their optical properties, including the refractive index and absorption coefficient. Notably, the presence of internal pore defects within the mixed acrylic paint led to geometric distortions, affecting the state of the overall system. Intriguingly, even in cases where acrylic paint exhibited identical colors perceptible under visible light, distinct discrimination and identification of chemical compositions were successfully proposed.

3D-Printed Microcubes for Catalase Drug Delivery.

Oxidative stress, i.e., excessive production of reactive oxygen species (ROS), plays an important role in the pathogenesis of inflammatory diseases such as cardiovascular diseases, cancer, and neurodegenerative diseases. Catalase, an antioxidant enzyme, has great therapeutic potential; however, its efficacy is limited by its delivery to target cells or tissues. In order to achieve efficient delivery, consistent drug distribution, and drug activity, small and uniformly sized drug delivery vehicles are needed. Here, three-dimensional (3D) microcubes were printed by Nanoscribe Photonic Professional GT2, a high-resolution 3D printer, and the characteristics of 3D-printed microcubes as drug delivery vehicles for the delivery of catalase were investigated. The size of the 3D-printed microcubes was 800 nm in length of a square and 600 nm in height, which is suitable for targeting macrophages passively. Microcubes were also tunable in shape and size, and high-resolution 3D printing could provide microparticles with little variation in shape and size. Catalase was loaded on 3D-printed microcubes by nonspecific adsorption, and catalase on 3D-printed microcubes (CAT-MC) retained 83.1 ± 1.3% activity of intact catalase. CAT-MC also saved macrophages, RAW 264.7, from the cytotoxicity of H2O2 by 86.4 ± 4.1%. As drug delivery vehicles, 3D-printed microparticles are very promising due to their small and uniform size, which provides consistent drug distribution and drug activity. Therefore, we anticipate numerous applications of 3D-printed microparticles for delivering therapeutic proteins.

Multidimensional employment precariousness mediates the association between low educational attainment and poor subjective well-being: results from a nationwide cross-sectional study in South Korea.

OBJECTIVE: This paper explored how multidimensional employment precariousness (MEP) mediates the relationship between educational attainment and subjective well-being. METHODS: A nationwide sample of 46 919 Korean workers participated in surveys between 2017 and 2020. Educational attainment was divided into four categories: elementary school, middle school, high school, and college. Subjective well-being was assessed using the 5-item World Health Organization Well-Being Index, and MEP was evaluated using a modified version of the Employment Precariousness Scale (ERPES-E), with scores ranging from 0 to 100 and higher scores indicating worse employment precariousness. A counterfactual-based logistic mediation analyses were used to estimation. RESULTS: The mean MEP score was 36.0 [standard deviation (SD) 12.1] for college education, 44.3 (SD 11.5) for high school, 49.5 (SD 10.1) for middle school, and 51.1 (SD 10.0) for elementary school. The prevalence of poor subjective well-being was 24.0% for college education, 31.3% for high school, 40.6% for middle school, and 44.8% for elementary school. Odds ratios (OR) for the total effect of education on the poor subjective well-being were 1.44 [95% confidence interval (CI) 1.37-1.53] for high school, 2.19 (95% CI 1.98-2.24) for middle school, and 2.40 (95% CI 2.04-2.82) for elementary school when compared to college education. The OR for the indirect effect mediated through MEP were 1.27 (95% CI 1.25-1.29) for high school, 1.46 (95% CI 1.42-1.51) for middle school, and 1.53 (95% CI 1.48-1.59) for elementary school, accounting for 63.9%, 48.5%, and 48.6% of the total effect, respectively. CONCLUSION: Our study suggests that MEP is an important contributor to the disparities in subjective well-being resulting from educational gradients.

Clearance of defective muscle stem cells by senolytics restores myogenesis in myotonic dystrophy type 1.

Muscle stem cells, the engine of muscle repair, are affected in myotonic dystrophy type 1 (DM1); however, the underlying molecular mechanism and the impact on the disease severity are still elusive. Here, we show using patients' samples that muscle stem cells/myoblasts exhibit signs of cellular senescence in vitro and in situ. Single cell RNAseq uncovers a subset of senescent myoblasts expressing high levels of genes related to the senescence-associated secretory phenotype (SASP). We show that the levels of interleukin-6, a prominent SASP cytokine, in the serum of DM1 patients correlate with muscle weakness and functional capacity limitations. Drug screening revealed that the senolytic BCL-XL inhibitor (A1155463) can specifically remove senescent DM1 myoblasts by inducing their apoptosis. Clearance of senescent cells reduced the expression of SASP, which rescued the proliferation and differentiation capacity of DM1 myoblasts in vitro and enhanced their engraftment following transplantation in vivo. Altogether, this study identifies the pathogenic mechanism associated with muscle stem cell defects in DM1 and opens a therapeutic avenue that targets these defective cells to restore myogenesis.

Working hours and the onset of suicidal ideation and depressive symptoms: A 10-year nationwide longitudinal study in South Korea (2012-2022).

Long working hours are associated with adverse health outcomes. We investigated the association between working hours and suicidal ideation and depressive symptoms. We analyzed a nationally representative sample of 11,116 Korean workers, comprising 64,661 observations from 2012 to 2022, to investigate how working hours were associated with mental health problems. To account for repeated measurements in each participant, we employed a generalized estimating equation to estimate risk ratios (RRs) and 95% confidence intervals (CIs). Of the total observations, 13.1% reported working ≥55 h/week. The RR (95% CI) of the association between long working hours and onset of suicidal ideation in the subsequent year was 1.20 (0.95-1.53) for 41-48 h, 1.35 (1.02-1.78) for 49-54 h, and 1.56 (1.23-1.98) for ≥55 h/week, compared to 35-40 h/week. The RR (95% CI) of the association between long working hours and onset of depressive symptoms in the subsequent year was 1.19 (1.07-1.34) for 41-48 h, 1.11 (0.97-1.28) for 49-54 h, and 1.24 (1.10-1.40) for ≥55 h per week, compared to 35-40 h/week. Those working fewer than 35 h/week also had an increased risk of suicidal ideation and depressive symptoms. Policy interventions are needed to reduce excess working hours and protect workers' mental health.

Peptide Assembly of Different Dimensions and Their Effect on Myoblast Proliferation.

Variations in the functionalities of materials of different dimensions containing the same functional groups can be attributed to the structural stability and morphology of the materials. The morphology of peptide assemblies can influence their interactions with biological systems and ultimately modulate their bioactivity. Among reported Arg-Gly-Asp (RGD)-based supramolecular materials, two-dimensional (2-D) peptide assembly has been rarely studied. Herein, we report the fabrication of RGD-based supramolecular one-dimensional (1-D) and 2-D assemblies as peptide-based myoblast growth accelerators. The 2-D assembly was more effective in proliferating C2C12 cells than the 1-D assembly. These findings provide insights into the construction of optimal RGD-based supramolecular functional materials of different dimensions.

Enhanced catalytic oxidation of naproxen via activation of peroxymonosulfate by Fe-based metal-organic framework aerogels functionalized with Ag nanoparticles.

In this study, Ag3PO4 and Fe-based metal-organic frameworks (MOFs)-functionalized three-dimensional (3D) porous gelatin aerogels (Ag/Fe@GMA) were fabricated and used as adsorbents and catalysts for the activation of peroxymonosulfate (PMS) for naproxen (NPX) removal from water. The morphology, crystallinity, surface functional groups, and surface chemical element compositions of the fabricated Ag/Fe@GMA was evaluated using various analytical techniques. Our results showed that as an adsorbent, Ag/Fe@GMA showed a 18.0 % higher NPX adsorption capacity compared with the pristine aerogels. This can be attributed to the well-embedded Ag3PO4 and MOFs, indicating a stronger interaction between functionalized aerogels and NPX. After adsorption, 99.9 % of total NPX removal was achieved within 15 min by activating PMS and effectively generating •OH and •SO4- in water. The PMS/Ag/Fe@GMA aerogel system also showed high removal performance for rhodamine B (99.5 %) and tetracycline (93.7 %). Moreover, the Ag/Fe@GMA aerogels showed excellent reusability to achieve 95.7 % NPX removal efficiency after six times of recycling. This study revealed that the Ag/Fe@GMA aerogels had good potential for PMS activation and NPX removal. In particular, as an alternative to powdery materials, 3D shape of Ag/Fe@GMA with excellent reusability facilitates its application in the treatment of water contaminated with organic contaminants.

New secondary metabolites produced by Paraphoma radicina FB55 as potential antifungal agents.

Microorganisms in specific environments are rich sources of bioactive natural products as they produce compounds that can aid their survival in harsh environments. In an effort to investigate antifungal compounds produced by microorganisms, the fungal strain Paraphoma radicia FB55, isolated from a marine sediment of the Beaufort Sea, north of Alaska, was subjected to chemical investigation. Chromatography of the culture extracts yielded two new compounds (1 and 2) and eight known compounds (3-10). Their structures were determined using spectroscopic and chemical methods. Compound 1 was a new analog of the known compound (3) with an isobenzofuranone skeleton. The absolute configuration of the chiral center in 1 was established by comparison of its ECD and specific rotation values with those for a known analogue. Compound 2 is a polyketide-amino acid hybrid. Comprehensive Nuclear Magnetic Resonance (NMR) analysis indicated that 2 consisted of two substructures:5-methyl-6-oxo-2,4-heptadienoic acid and isoleucinol. The absolute configuration of the isoleucinol moiety in 2 was determined to be D using Marfey's method. All the isolated compounds were evaluated for antifungal activities. Although the antifungal activity of the isolated compounds was not potent, co-treatment of compounds 7 and 8 with a clinically available amphotericin B (AmB) lowered the IC50 values of AmB by synergism against human pathogenic yeast.

Particulate matter in school buildings: Influence of influx control of outdoor PM particles and building renovation in summer.

The hazardous effects of air pollution on the human body are of grave concern, particularly the rising levels of 2.5 µm-particulate matter. Children are more susceptible to the lethal effects of particulate matter (PM) than adults. In this study, a case study of architectural renovation (ARCH-R) and facility renovation (FAC-R) was conducted in a school by focusing on the exit and entrance gates. In addition, the PM influx rate was evaluated. To evaluate the influx rate of PM, opening/closing recognition equipment and particle sensors were utilized. Following the renovation, the result was evaluated. During the daytime, the air curtain led to a reduction in the influx rate of PM of approximately 8% when the door was open. During the nighttime, it was confirmed that the fine dust influx rate was reduced through reinforcement of the door. However, regarding using these two measures in combination, it was confirmed that the concentration of PM increased in the corridor when the air curtain was operated while the door was closed. It was confirmed that both ARCH-R and FAC-R are necessary for controlling the influx of fine dust from the outdoor air. Appropriate operating guidelines should be provided for school operators.

Coherent Vibronic Wavepackets Show Structure-Directed Charge Flow in Host-Guest Donor-Acceptor Complexes.

Designing and controlling charge transfer (CT) pathways in organic semiconductors are important for solar energy applications. To be useful, a photogenerated, Coulombically bound CT exciton must further separate into free charge carriers; direct observations of the detailed CT relaxation pathways, however, are lacking. Here, photoinduced CT and relaxation dynamics in three host-guest complexes, where a perylene (Per) electron donor guest is incorporated into two symmetric and one asymmetric extended viologen cyclophane acceptor hosts, are presented. The central ring in the extended viologen is either p-phenylene (ExV2+) or electron-rich 2,5-dimethoxy-p-phenylene (ExMeOV2+), resulting in two symmetric cyclophanes with unsubstituted or methoxy-substituted central rings, ExBox4+ and ExMeOBox4+, respectively, and an asymmetric cyclophane with one of the central viologen rings being methoxylated ExMeOVBox4+. Upon photoexcitation, the asymmetric host-guest ExMeOVBox4+ ⊃ Per complex exhibits directional CT toward the energetically unfavorable methoxylated side due to structural restrictions that facilitate strong interactions between the Per donor and the ExMeOV2+ side. The CT state relaxation pathways are probed using ultrafast optical spectroscopy by focusing on coherent vibronic wavepackets, which are used to identify CT relaxations along charge localization and vibronic decoherence coordinates. Specific low- and high-frequency nuclear motions are direct indicators of a delocalized CT state and the degree of CT character. Our results show that the CT pathway can be controlled by subtle chemical modifications of the acceptor host in addition to illustrating how coherent vibronic wavepackets can be used to probe the nature and time evolution of the CT states.

Quantitative comparison of EGFR expression levels of optically trapped individual cells using a capacitance biosensor.

Cellular endocytosis is an essential phenomenon which induces cellular reactions, such as waste removal, nutrient absorption, and drug delivery, in the process of cell growth, division, and proliferation. To observe capacitance responses upon endocytosis on a single-cell scale, this study combined an optical tweezer that can optically place a single cell on a desired location with a capacitance sensor and a cell incubation chamber. Single HeLa cancer cell was captured and moved to a desired location through optical trapping, and the single-cell capacitance change generated during the epidermal growth factor (EGF) molecule endocytosis was measured in real time. It was found that single HeLa cells showed a larger increase in capacitance values compared to that of the single NIH3T3 cells when exposed to varying EGF concentrations. In addition, the capacitance change was in proportion to the cell's EGF receptor (EGFR) level when cells of different levels of EGFR expression were tested. An equation derived from these results was able to estimate the EGFR expression level of a blind-tested cell. The biosensor developed in this research can not only quickly move a single cell to a desired location in a non-invasive manner but also distinguish specific responses between cancer and normal cells by continuous measurement of real-time interactions of a single cell in culture to the external ligands.