Binary Organic Solar Cells with Exceeding 19% Efficiency via the Synergy of Polyfluoride Polymer and Fluorous Solvent.

Rational molecular design and suitable device engineering are two important strategies to boost the efficiencies in organic solar cells (OSCs). Yet these two approaches are independently developed, while their synergy is believed to be more productive. Herein, a branched polyfluoride moiety, heptafluoroisopropoxyl group, is introduced into the sidechains of conjugated polymers for the first time. Compared with the conventional alkyl chain, this polyfluoride chain can endow the resulting polymer namely PF7 with highly packing order and strong crystallinity owing to the strong polarization and fluorine-induced interactions, while good solubility and moderate miscibility are retained. As a result, PF7 comprehensively outperforms the state-of-the-art polymer PM6 in photovoltaic properties. More importantly, based on the solubility of heptafluoroisopropoxyl groups in fluorous solvents, a new post-treatment denoted as fluorous solvent vapor annealing (FSVA) is proposed to match PF7. Differing from the existing post-treatments, FSVA can selectively reorganize fluoropolymer molecules but less impact small molecules in blend films. By employing the synergy of fluoropolymer and fluorous solvent, the device achieves a remarkable efficiency of 19.09%, which is among the best efficiencies in binary OSCs. The polymer PF7 and the FSVA treatment exhibit excellent universality in various OSCs with different material combinations or device architectures. This article is protected by copyright. All rights reserved.

Effects of Selenium on the Lignin Deposition Pattern and Stem Mechanical Properties of Alfalfa (Medicago sativa L.).

Lignin provides structural support to plants; however, it reduces their utilization rate. According to our previous studies, selenium (Se) reduces lignin accumulation in alfalfa, but the specific mechanism involved remains unclear. Therefore, at the seedling stage, four root irrigation treatments using 2.5, 50, and 5 µmol/L sodium selenite (S-RI), selenomethionine (SS-RI), Se nanoparticles (SSS-RI), and deionized water (CK-RI) were performed. At the branching stage, four treatments of foliar spraying with the three Se fertilizers described above at a concentration of 0.5 mmol/L (S-FS, SS-FS, and SSS-FS) and deionized water (CK-FS) were administered. The results revealed that all Se treatments chiefly reduced the level of deposition of syringyl (S) lignin in the first internode of alfalfa stems. SS-FS and SSS-FS treatments mainly reduced the deposition of S and guaiacyl (G) lignins in the sixth internode of alfalfa stems, respectively, while S-FS treatment only slightly reduced the deposition of G lignin. S, SS, and SSS-RI treatments reduced the level of deposition of S and G lignins in the sixth internode of alfalfa stems. Se application increased plant height, stem diameter, epidermis (cortex) thickness, primary xylem vessel number (diameter), and pith diameter of alfalfa but decreased primary xylem area and pith parenchyma cell wall thickness of the first internode, and SS(SSS)-FS treatment reduced the mechanical strength of alfalfa stems. Therefore, Se application could decrease lignin accumulation by regulating the organizational structure parameters of alfalfa stems and the deposition pattern of the lignin monomers.

[Fatal Familial Insomnia With Significant Correlations Between Involuntary Movements and Postural Changes:Report of One Case].

Fatal familial insomnia,an autosomal dominant prion disease,is rare.We reported the clinical symptoms,examination results,diagnosis,treatment,and prognosis of a patient who was diagnosed with fatal familial insomnia.Furthermore,we described the unique clinical manifestations that involuntary movements and laryngeal stridor were significantly correlated with postural changes,aiming to provide reference for the clinical diagnosis,treatment,and research of the disease in the future.

Coupling between 2, 2', 4, 4'-tetrabromodiphenyl ether (BDE-47) debromination and methanogenesis in anaerobic soil microcosms.

Polybrominated diphenyl ethers (PBDEs) are persistent pollutants that may undergo microbial-mediated debromination in anoxic environments, where diverse anaerobic microbes such as methanogenic archaea co-exist. However, current understanding of the relations between PBDE pollution and methanogenic process is far from complete. To address this knowledge gap, a series of anaerobic soil microcosms were established. BDE-47 (2, 2', 4, 4'-tetrabromodiphenyl ether) was selected as a model pollutant, and electron donors were supplied to stimulate the activity of anaerobes. Debromination and methane production were monitored during the 12 weeks incubation, while obligate organohalide-respiring bacteria (OHRBs), methanogenic, and the total bacterial communities were examined at week 7 and 12. The results demonstrated slow debromination of BDE-47 in all microcosms, with considerable growth of Dehalococcoides and Dehalogenimonas over the incubation observed in most BDE-47 spiked treatments. In addition, the accumulation of intermediate metabolites positively correlated with the abundance of Dehalogenimonas at week 7, suggesting potential role of these OHRBs in debromination. Methanosarcinaceae were identified as the primary methanogenic archaea, and their abundance were correlated with the production of debrominated metabolites at week 7. Furthermore, it was observed for the first time that BDE-47 considerably enhanced methane production and increased the abundance of mcrA genes, highlighting the potential effects of PBDE pollution on climate change. This might be related to the inhibition of reductive N- and S-transforming microbes, as revealed by the quantitative microbial element cycling (QMEC) analysis. Overall, our findings shed light on the intricate interactions between PBDE and methanogenic processes, and contribute to a better understanding of the environmental fate and ecological implication of PBDE under anaerobic settings.

Sedentary Behavior and Physical Frailty Among Rural Older Adults in China: The Moderating Effect of Social Isolation.

OBJECTIVES: Few studies have explored the mechanisms underlying the relationship between sedentary behavior and physical frailty. The aim of this study was to investigate the moderating effect of social isolation on the association between sedentary behavior and physical frailty among older adults in rural China. DESIGN: Cross-sectional study. SETTING AND PARTICIPANTS: Data were from 3238 individuals aged ≥60 years from rural areas in China. METHODS: Binary logistic regression was used to explore the association between sedentary behavior and physical frailty and the moderating effect of social isolation. RESULTS: The prevalence of physical frailty was 18.7% among the older adults, and 17.0% of them were sedentary for ≥8 h/d. Compared with older adults with sedentary behavior for <4 h/d, participants with sedentary behavior for ≥8 h/d were more likely to suffer from physical frailty [odds ratio (OR), 2.26; 95% CI, 1.57-3.27]. We found that social isolation may aggravate this relationship (OR, 3.31; 95% CI, 2.06-5.32), especially for rural older adults who were sedentary for ≥8 h/day. CONCLUSION AND IMPLICATIONS: More sedentary behavior was associated with higher risk of physical frailty, which was especially apparent among older adults with social isolation, suggesting that sedentary older people who experienced social isolation were more vulnerable to physical frailty. Decreasing sedentary behavior in older adults and encouraging them to participate in interactive social activities could help prevent physical frailty.

Dual Photo-/Electrochromic Pyromellitic Diimide-Based Coordination Polymer.

By the combination of N,N'-bis(carboxymethyl)-pyromellitic diimide (H2CMPMD, 1) and zinc ions, a novel PMD-based coordination polymer (CP), [Zn(CMPMD)(DMF)1.5]·0.5DMF (2) (DMF = N,N'-dimethylformamide), has been prepared and characterized. 1 and 2 exhibit completely different photochromic properties, which are mainly reflected in the photoresponsive rate (5 s for 1 vs 1 s for 2) and coloration contrast (from colorless to light green for 1 vs green for 2). This phenomenon should be attributed to the introduction of zinc ions and the consequent formation of the distinct interfacial contacts of electron donors (EDs) and electron acceptors (EAs) (dn-π = 3.404 and 3.448 Å for 1 vs dn-π = 3.343, 3.359, 3.398, and 3.495 Å for 2), suggesting a subtle modulating effect of metal ions on interfacial contacts, photoinduced intermolecular electron transfer (PIET) and photochromic behaviors. Interestingly, the photochromic performance of 2 can be enhanced after the removal of coordinated DMF, which might be ascribed to the decrease of the distance of EDs/EAs caused by lattice shrinkage, which further improves the efficiency of PIET. Meanwhile, 2 displays rapid electrochromic behavior with an obvious reversible color change from colorless to green, which can be used in an electrochromic device. This work develops a new type of EA for the construction of stimuli-responsive functional materials with excellent dual photo-/electrochromic properties.

The effect of conjugation degree of aromatic carboxylic acids on electronic and photo-responsive behaviors of naphthalenediimide-based coordination polymers.

Three novel naphthalenediimide-based (NDI-based) coordination polymers (CPs), namely [Cd(3-PMNDI)(2,2'-BPDC)] (1), [Cd2(3-PMNDI)1.5(4,4'-BPDC)2(H2O)3]·DMF (2) and [Cd(3-PMNDI)(4,4'-SDC)] (3) (2,2'-H2BPDC = 2,2'-biphenyldicarboxylic acid, 4,4'-H2BPDC = 4,4'-biphenyldicarboxylic acid, 4,4'-H2SDC = 4,4'-stilbenedicarboxylic acid, 3-PMNDI = N,N'-bis(3-pyridylmethyl)-1,4,5,8-naphthalenediimide, and DMF = N,N'-dimethylformamide), have been designed and synthesized here from electron-deficient PMNDI (electron acceptors, EAs) and electron-rich aromatic carboxylic acids (electron donors, EDs) in the presence of cadmium ions. The introduction of aromatic carboxylic acids with different sizes and conjugation degrees leads to the generation of a two-dimensional (2D) layer in 1, a two-fold interpenetrated three-dimensional (3D) network in 2 and an eight-fold interpenetrated 3D framework in 3. Furthermore, the use of distinct electron-donating aromatic carboxylic acids and the consequent different numbers and strengths of lone pair-π and π-π interactions in the interfacial contacts of EDs/EAs give rise to distinct intermolecular charge transfer (ICT) and initial colors of the three CPs, and consequently cause different photoinduced intermolecular electron transfer (PIET) and distinguishing photo-responsive behaviors (weak photochromic performance for 1, excellent photochromic properties for 2 and non-photochromism for 3). This study indicates that an appropriate ICT is beneficial for PIET, but too weak or too strong ICT is not conducive to PIET, which provides an effective strategy for the construction of functional CPs with distinguishing photo-responsive properties through the subtle balance of ICT and PIET.

[Characteristics of acupuncture and moxibustion therapy in Tibetan medicine based on Medical Canon in Four Sections].

By tracing to the origin of Tibetan medicine, it is known that Tibetan medicine absorbs a variety of medical ideas such as traditional Chinese medicine, Vedic medicine, Persian medicine and Byzantine medicine, and forms a unique theoretical system. The meridian-acupoint system and the characteristics and application of external therapies such as bloodletting and moxibustion in Tibetan medicine are analyzed by elaborating the relevant aspects of acupuncture and moxibustion involved in treatment of diseases listed in Medical Canon in Four Sections. The paper emphasizes the introduction of ironing moxibustion and huo'er moxibustion of fire moxibustion and the application of separation-action decoction and ghee therapy in bloodletting, as well as alternative therapy. Besides, by taking the external treatment of cirrhotic ascites and head trauma as an example, the idea of acupuncture and moxibustion therapy in Tibetan medicine embodied in the Medical Canon in Four Sections is explained so as to benefit the development of acupuncture and moxibustion therapy in Tibetan medicine.

Association of Sensory Impairment With Institutional Care Willingness Among Older Adults in Urban and Rural China: An Observational Study.

Background and Objectives: An aging population has contributed to increasing rates of sensory impairment (SI) among older adults and a boom in institutional elder care. However, little is known regarding the association between SI and institutional care willingness. This study identified the association between SI and institutional care willingness among older adults living both in urban and rural China. Research Design and Methods: This was an observational study using the sixth National Health Service Survey of Shandong Province, China, in 2018. A total of 8 583 individuals aged ≥60 years were included. The primary outcome was institutional care willingness. Self-reported SI was categorized as vision impairment (VI), hearing impairment (HI), and dual sensory impairment (DSI). We used multivariable logistic regression models to estimate the association between SI and institutional care willingness, stratified by the place of residence. Results: The overall proportion of older adults with institutional care willingness was 7.8%. In fully adjusted models, older adults with HI only (odds ratio [OR] = 1.57, 95% confidence interval [CI]: 1.12-2.20) or DSI (OR = 1.68, 95% CI: 1.14-2.49) were more likely to show institutional care willingness than those without SI in urban areas, but no significant associations between VI only (OR = 0.95, 95% CI: 0.68-1.31), HI only (OR = 0.99, 95% CI: 0.73-1.34), or DSI (OR = 0.95, 95% CI: 0.68-1.31) and institutional care willingness were observed among rural older adults. Discussion and Implications: Our results underscore that the relationship between SI and institutional care willingness varied by place of residence, and provide a reference for making targeted and appropriate endowment policies. Improving the quality of institutional elder care is vital for urban older adults with SI, whereas community-based care might be more appropriate for rural older adults with SI.

Sex Difference in the Association Between Sedentary Behavior and Sleep Quality: A Longitudinal Study Among Older Adults in Rural China.

OBJECTIVES: Sleep quality plays a vital role in maintaining health in older adults. Sedentary behavior may be a risk factor for poor sleep quality in older adults. This study aimed to explore the relationship between sedentary behavior and sleep quality among older adults in rural China and determine whether there is a sex difference in this association. DESIGN: A longitudinal design. The data used in this study were obtained from the Shandong Rural Elderly Health Cohort (wave 1: 2019, wave 2: 2020). SETTING AND PARTICIPANTS: Data were from 2731 individuals aged ≥60 years from rural areas in China. METHODS: Sleep quality was assessed using the Pittsburgh Sleep Quality Index. Sedentary behavior and control variables were measured using self-reported questions. Multivariable logistic regression and generalized estimating equations were used to assess the associations. RESULTS: After full adjustment, the association between sedentary behavior and poor sleep quality was statistically significant [odds ratio (OR) 1.49, 95% CI 1.20-1.85]. Specifically, a longer sedentary time was associated with worse subjective sleep quality, less sleep latency, and lower habitual sleep efficiency (OR 1.39-1.58). A significant association was observed in women but not men. CONCLUSIONS AND IMPLICATIONS: Older adults who spend more time engaging in sedentary activities have poorer sleep quality and more sleep problems. Prolonged sedentary time is more detrimentally associated with poor sleep quality in women than men. There is a need for tailored exercise prescriptions and guidelines to stimulate older adults of different sexes to change their sedentary behavior, which may improve sleep quality in older adults.

Electrochemically Enabled Intramolecular Amino- and Oxysulfonylation of Alkenes with Sodium Sulfinates to Access Sulfonylated Saturated Heterocycles.

A practical and efficient electrochemical intramolecular amino- or oxysulfonylation of internal alkenes equipped with pendant nitrogen or oxygen-centered nucleophiles with sodium sulfinate was developed. Under undivided electrolytic cell conditions, a variety of sulfonylated N-heterocycles and O-heterocycles, such as tetrahydrofurans, tetrahydropyrans, oxepanes, tetrahydropyrroles, piperidines, δ-valerolactones, etc., were efficiently prepared from easily accessible unsaturated alcohols, carboxylic acids, and N-tosyl amines without the need for additional metal or exogenous oxidant. The robust electrochemical transformation features excellent redox economy, high diastereoselectivity, and broad substrate specificity, which provide a general and practical access to sulfone-containing heterocycles and would facilitate the related synthetic and biological studies based on this electrosynthesis.

The Commensal Anaerobe Veillonella dispar Reprograms Its Lactate Metabolism and Short-Chain Fatty Acid Production during the Stationary Phase.

Veillonella spp. are obligate, anaerobic, Gram-negative bacteria found in the human oral cavity and gut. Recent studies have indicated that gut Veillonella promote human homeostasis by producing beneficial metabolites, specifically short-chain fatty acids (SCFAs), by lactate fermentation. The gut lumen is a dynamic environment with fluctuating nutrient levels, so the microbes present shifting growth rates and significant variations of gene expression. The current knowledge of lactate metabolism by Veillonella has focused on log phase growth. However, the gut microbes are mainly in the stationary phase. In this study, we investigated the transcriptomes and major metabolites of Veillonella dispar ATCC 17748T during growth from log to stationary phases with lactate as the main carbon source. Our results revealed that V. dispar reprogrammed its lactate metabolism during the stationary phase. Lactate catabolic activity and propionate production were significantly decreased during the early stationary phase but were partially restored during the stationary phase. The propionate/acetate production ratio was lowered from 1.5 during the log phase to 0.9 during the stationary phase. Pyruvate secretion was also greatly decreased during the stationary phase. Furthermore, we have demonstrated that the gene expression of V. dispar is reprogrammed during growth, as evidenced by the distinct transcriptomes present during the log, early stationary, and stationary phases. In particular, propionate metabolism (the propanediol pathway) was downregulated during the early stationary phase, which explains the decrease in propionate production during the stationary phase. The fluctuations in lactate fermentation during the stationary phase and the associated gene regulation expand our understanding of the metabolism of commensal anaerobes in changing environments. IMPORTANCE Short-chain fatty acids produced by gut commensal bacteria play an important role in human physiology. Gut Veillonella and the metabolites acetate and propionate, produced by lactate fermentation, are associated with human health. Most gut bacteria in humans are in the stationary phase. Lactate metabolism by Veillonella spp. during the stationary phase is poorly understood and was therefore the focus of the study. To this end, we used a commensal anaerobic bacterium and explored its short-chain fatty acid production and gene regulation in order to provide a better understanding of lactate metabolism dynamics during nutrient limitation.

Near-Infrared Acceptors with Imide-Containing End Groups for Organic Solar Cells.

Near-infrared electron acceptors for organic solar cells (OSCs) mostly contain electron-withdrawing 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IC) end groups, which can be modified by but limited to phenyl, thienyl, and naphthyl units with halogenated, methyl, and methyloxy substitution. In this work, we employed an imide-containing unit to construct a new IC end group, based on which a series of new electron acceptors were synthesized. The strong electron-deficient nature of imide units enables the new acceptors to show efficient intramolecular charge transfer and hence red-shifted absorption spectra compared to their IC counterparts. These new electron acceptors were applied to OSCs, providing efficiencies of over 17% with a low voltage loss of 0.52 eV. These results demonstrate that the new imide-containing end groups are promising fragments for the construction of near-infrared electron acceptors for high-performance OSCs.

Experimental study and kinetic model analysis on photothermal catalysis of formaldehyde by manganese and cerium based catalytic materials.

Modern people spend more and more time in cars in their daily lives, and the pollution of formaldehyde in the car may directly affect people's health. Thermal catalytic oxidation technology by solar light is a potential way to purify formaldehyde in cars. MnOx-CeO2 was prepared by the modified co-precipitation method as the main catalyst, and the basic characteristic (SEM, N2 adsorption, H2-TPR, UV-visible absorbance) were also analyzed in detail. The experimental study was set up to simulate the solar photothermal catalysis of formaldehyde in-car environment. The results showed that the higher the temperature in the experimental box (56.7 ± 0.2°C, 62.6 ± 0.2°C, 68.2 ± 0.2°C), the better the formaldehyde degradation by catalytic effect (formaldehyde degradation percentage: 76.2%, 78.3%, 82.1%). With increase of the initial formaldehyde concentration (200 ppb, 500 ppb, 1000 ppb), the catalytic effect first increased and then decreased (formaldehyde degradation percentage: 63%, 78.3%, 70.6%). The catalytic effect risen gradually with the increase of load ratio (10g/m2, 20g/m2, and 40g/m2), and the formaldehyde degradation percentages were 62.8%, 78.3%, and 81.1%, respectively. According to the expressions of the Eley-Rideal (ER) model, the Langmuir-Hinshelwood (LH) model, and the Mars-Van Krevelen (MVK) model, the experimental results were fitted and verified, and it was found that the ER model had a high degree of fit. It is more suitable to explain the catalytic mechanism of formaldehyde by MnOx-CeO2 catalyst in the experimental cabin, where formaldehyde is in the adsorption state and oxygen is in the gas phase.Implications: Judging from the current research status, vehicles have become an indispensable mode of travel for people, and the air quality in the vehicle is not optimistic. Most vehicles generally have the phenomenon of excessive formaldehyde. The characteristic of formaldehyde in the car is the continuous release, especially in the hot summer, the temperature inside the car rises sharply under the sun radiation. At this time, the formaldehyde concentration exceeds the standard by 4 to 5 times, which can cause great damage to the health of the passengers. In order to improve the air quality in the car, it is necessary to adopt the correct purification technology to degrade formaldehyde. The problem brought by this situation is how to effectively use solar radiation and high temperature in the car to degrade formaldehyde in the car. Therefore, this study uses the thermal catalytic oxidation technology to catalyze the degradation of formaldehyde in the high temperature environment of the car in summer. The selected catalyst is MnOx-CeO2, mainly because manganese oxide (MnOx) itself is the most effective catalyst for volatile organic compounds (TCO) among transition metal oxides, and CeO2 has excellent oxygen storage and release capacity and Oxidation activity, which helps to improve the activity of MnOx. Finally, the effects of temperature, initial concentration of formaldehyde and catalyst loading on the experiment were explored, and the kinetic model of thermal catalytic oxidation of formaldehyde with MnOx-CeO2 catalyst was analyzed to provide technical support for the future application of this research in practice.

Contrasting responses of bacterial community to 4,4'-dibromodiphenyl ether (BDE-15) contamination in soil microcosms at different temperatures.

Polybrominated diphenyl ethers (PBDEs) are biodegradable organic pollutants and pose potential risks to microorganisms exposed to the contamination, which are also affected by a variety of factors, such as temperature, in real environmental settings. A better understanding of the microbial community responses to PBDEs at different temperatures has practical significance for assessing ecological risks or possible degraders of these widely used flame retardants. In this study, soil microcosms spiked with or without 100 mg kg-1 4,4'-dibromodiphenyl ether (BDE-15) were established and incubated at four different temperatures (4 °C, 20 °C, 37 °C, and varying ambient temperature) for up to 180 days. Concentration and carbon isotope analyses were used to verify the transformation of BDE-15. Bacterial communities were monitored during the incubation to evaluate the community succession under the PBDE stress. The results showed the majority of added BDE-15 remained after the incubation period, with limited degradation occurred at all four temperatures. Temperature significantly shaped the richness, diversity, composition and co-occurrence network of soil bacterial community, while the impacts of PBDE on soil bacteria were temperature dependent. When incubated at 4 °C, BDE-15 substantially reduced the network complexity and changed the ratio of negative to positive interactions between taxa (nodes), highlighting the PBDE-associated risks at low temperature. At higher temperatures, BDE-15 had negligible influence on the community characteristics and network. Random forest model identified distinct taxa that might be related to PBDE degradation at different incubation temperatures. These findings demonstrate contrasting bacterial community effects of PBDE at different temperatures, thus attention should be paid to the ecological impacts of soil pollution under real environmental conditions.

[Percutaneous foraminal endoscopy for the treatment of lumbar lateral recess stenosis in elderly].

OBJECTIVE: To investigate the clinical efficacy and safety of percutaneous foraminal endoscopy in the treatment of lumbar lateral recess stenosis in elderly. METHODS: The clinical data of 31 elderly patients with lumbar lateral recess stenosis treated by percutaneous foraminal endoscopic decompression from March 2018 to August 2019 were retrospectively analyzed. Including 16 males and 15 females, aged from 65 to 81 years with an average of (71.13±5.20) years, the course of disease ranged from 3 months to 7 years with an average of (14.36±6.52) months. Visual analogue scale (VAS) and Oswestry disability index (ODI) were used to assess clinical symptom and functional status before operation and 1, 6, 12 months after operation. At the final follow-up, the modified Macnab standard was used to evaluate clinical efficacy. RESULTS: All patients were completed the operation successfully. The operation time was from 75 to 120 min with an average of (97.84±11.22 ) min. All 31 patients were followed up from 12 to 28 months with an average of (17.29±5.56) months. Postoperative lumbago-leg pain VAS and ODI were significantly improved at 1, 6, and 12 months(P<0.01). At the final follow-up, according to the modified Macnab standard to evaluate the effect, 23 got excellent results, 5 good, 3 fair. One patient had severe adhesions between peripheral tissues and nerve root, and postoperative sensory abnormalities in the lower extremities were treated conservatively with traditional Chinese medicine and neurotrophic drugs, which recovered at 2 weeks after surgery. No complications such as nerve root injury and infection occurred. CONCLUSION: The intervertebral foraminal endoscopy technique, which is performed under local anesthesia for a short period of operation, ensures adequate decompression while minimizing complications, and is a safe and effective surgical procedure for elderly patients with lumbar lateral recess stenosis.

New approaches for developing biomarkers of hormonal contraceptive use.

To identify biomarkers of hormonal contraceptive (HC) use in urine and saliva, we conducted a pilot study with 30 women initiating levonorgestrel (LNG) containing combined oral contraceptives (COCs) or depot medroxyprogesterone acetate (DMPA) (15/group). Based on established COC pharmacokinetics, we collected serum and urine samples before COC ingestion and during Days one and three of use, or before DMPA injection and on Days 21 and 60 post-injection. We used liquid chromatography-tandem mass spectrometry (LC-MS/MS) to measure serum/urine LNG and MPA. LNG was undetectable at baseline (specificity 100%); post ingestion, most urine samples had detectable LNG levels (sensitivity: 80% 6 h post Dose one, 93% 6 h post Dose three). We used a DetectX LNG immunoassay kit and showed 100% sensitivity measuring urine LNG. Urine MPA levels were undetectable in 14/15 women at baseline (specificity 91%); post-injection all urine samples had detectable MPA levels (sensitivity: 100% days 21 and 60). Results suggest urine sampling can be used to identify a biomarker of LNG and MPA use. Based on evidence from other steroidal hormonal studies showing changes affecting the transcriptome profile of saliva at 24 h, we used the same (COC, DMPA) timepoints to collect saliva. We performed transcriptome analysis and detected several differentially expressed genes in DMPA users' saliva on Days 21 and 60 compared to baseline; none among COC users. We plan further research of differential gene expression in saliva as a HC biomarker of DMPA use, and will explore longer periods of COC use and saliva collection times, and application of microRNA sequencing to support using saliva as a COC biomarker.

The modulation effect of auxiliary ligands on photochromic properties of 3D naphthalene diimide coordination polymers.

Two novel naphthalene diimide (NDI) coordination polymers (CPs), [Cd(NicNDI)(4,4'-SBC)] (1) and [Cd(NicNDI)(2,2'-BPC)] (2) (NicNDI = (3-pyridylacylamino)-1,4,5,8-naphthalene diimide, 4,4'-SBC = 4,4'-stilbene dicarboxylic acid, 2,2'-BPC = 2,2'-biphenyl dicarboxylic acid), were designed and prepared by the combination of electron-deficient NicNDI and electron-rich aromatic carboxylic acid ligands in the presence of cadmium ions. The usage of aromatic carboxylic acid ligands with different conjugation degrees, sizes, shapes and charge densities leads to the generation of distinct interpenetrated three-dimensional (3D) frameworks. Interestingly, photochromism of 1 and weak photoactivity of 2 should be attributed to the introduction of different auxiliary ligands and consequently the formation of distinct interfacial contacts of electron donors (EDs)/electron acceptors (EAs) (dπ-π = 3.427 Å, infinite -ED-EA-ED-EA- for 1vs. dπ-π = 3.634 Å, discrete ED-EA-ED for 2), suggesting a subtle modulating effect of auxiliary ligands on interfacial contacts, photoinduced intermolecular electron transfer (PIET) and photoresponsive behaviors.