Charge Management Enables Efficient Spontaneous Chromatic Adaptation Bipolar Photodetector.

Solution-processed photodetectors have emerged as promising candidates for next-generation of visible-near infrared (vis-NIR) photodetectors. This is attributed to their ease of processing, compatibility with flexible substrates, and the ability to tune their detection properties by integrating complementary photoresponsive semiconductors. However, the limited performance continues to hinder their further development, primarily influenced by the difference of charge transport properties between perovskite and organic semiconductors. In this work, a perovskite-organic bipolar photodetectors (PDs) is introduced with multispectral responsivity, achieved by effectively managing charges in perovskite and a ternary organic heterojunction. The ternary heterojunction, incorporating a designed NIR guest acceptor, exhibits a faster charge transfer rate and longer carrier diffusion length than the binary heterojunction. By achieving a more balanced carrier dynamic between the perovskite and organic components, the PD achieves a low dark current of 3.74 nA cm-2 at -0.2 V, a fast response speed of <10 µs, and a detectivity of exceeding 1012 Jones. Furthermore, a bioinspired retinotopic system for spontaneous chromatic adaptation is achieved without any optical filter. This charge management strategy opens up possibilities for surpassing the limitations of photodetection and enables the realization of high-purity, compact image sensors with exceptional spatial resolution and accurate color reproduction.

Green-solvent Processable Dopant-free Hole Transporting Materials for Inverted Perovskite Solar Cells.

The commercialization of perovskite solar cells (PVSCs) urgently requires the development of green-solvent processable dopant-free hole transporting materials (HTMs). However, strong intermolecular interactions that ensure high hole mobility always compromise the solubility and film-forming ability in green solvents. Herein, we show a simple but effective design strategy to solve this trade-off, that is, constructing star-shaped D-A-D structure. The resulting HTMs (BTP1-2) can be processed by green solvent of 2-methylanisole (2MA), a kind of food additive, and show high hole mobility and multiple defect passivation effects. An impressive efficiency of 24.34 % has been achieved for 2MA-processed BTP1 based inverted PVSCs, the highest value for green-solvent processable HTMs so far. Moreover, it is manifested that the charge separation of D-A type HTMs at the photoinduced excited state can help to passivate the defects of perovskites, indicating a new HTM design insight.

Naphthyl Substituted Impurities Induce Efficient Room Temperature Phosphorescence.

Accidentally, it was found that triphenylamine (TPA) from commercial sources shows ultralong yellow-green room temperature phosphorescence (RTP) like commercial carbazole, which however disappears for lab-synthesized TPA with high purity. Herein, we for the first time identify the impurity types that cause RTP of commercial TPA, which are two N, N-diphenyl-naphthylamine isomers. Due to similar molecular polarity and very trace amount (≈0.8 ‰, molar ratio), these naphthyl substituted impurities can be easily overlooked. We further show that even at an extremely low amount (1000000 : 1, mass ratio) of impurities, RTP emission is still generated, attributed to the triplet-to-triplet energy transfer mechanism. Notably, this doping strategy is also applicable to the triphenylphosphine and benzophenone host systems, of which strong RTP emission can be activated by simply doping the corresponding naphthyl substituted analogues into them. This work therefore provides a general and efficient host/guest strategy toward high performance and diverse organic RTP materials.

Whole-exome sequencing of a large Chinese azoospermia and severe oligospermia cohort identifies novel infertility causative variants and genes.

Rare coding variants have been proven to be one of the significant factors contributing to spermatogenic failure in patients with non-obstructive azoospermia (NOA) and severe oligospermia (SO). To delineate the molecular characteristics of idiopathic NOA and SO, we performed whole-exome sequencing of 314 unrelated patients of Chinese Han origin and verified our findings by comparing to 400 fertile controls. We detected six pathogenic/likely pathogenic variants and four variants of unknown significance, in genes known to cause NOA/SO, and 9 of which had not been earlier reported. Additionally, we identified 20 novel NOA candidate genes affecting 25 patients. Among them, five (BRDT, CHD5, MCM9, MLH3 and ZFX) were considered as strong candidates based on the evidence obtained from murine functional studies and human single-cell (sc)RNA-sequencing data. These genetic findings provide insight into the aetiology of human NOA/SO and pave the way for further functional analysis and molecular diagnosis of male infertility.

Morphological Transformation and In Situ Polymerization of Caspase-3 Responsive Diacetylene-Containing Lipidated Peptide Amphiphile for Self-Amplified Cooperative Antitumor Therapy.

In order to artificially regulate cell behaviors, intracellular polymerization as an emerging chemical technique has attracted much attention. Yet, it is still a challenge to achieve effective intracellular polymerization to conquer tumors in the complex cellular environment. Herein, this work develops a tumor-targeting and caspase-3 responsive nanoparticle composed of a diacetylene-containing lipidated peptide amphiphile and mitochondria-targeting photosensitizer (C3), which undergoes nanoparticle-to-nanofiber transformation and efficient in situ polymerization triggered by photodynamic treatment and activation of caspase-3. The locational nanofibers on the mitochondria membranes lead to mitochondrial reactive oxygen species (mtROS) burst and self-amplified circulation, offering persistent high oxidative stress to induce cell apoptosis. This study provides a strategy for greatly enhanced antitumor therapeutic efficacy through mtROS burst and self-amplified circulation induced by intracellular transformation and in situ polymerization.

Molecular Insights of Non-fused Ring Acceptors for High-Performance Non-fullerene Organic Solar Cells.

Non-fullerene acceptors with fused-ring structures have rapidly improved the performance of organic solar cells over the past five years, but they still suffer from synthetic complexity and thus high material costs, one of the major obstacles of hindering their commercialization process. The construction of non-fused ring acceptors (NFRAs) has recently been regarded as a feasible solution due to their facile synthesis and satisfactory device performances. Thus in this concept, we highlight the important progress of NFRAs in recent years, and discuss the key relationship between molecular design strategies and device performance. Finally, we provide some potential molecular insights for the future design of high-performance NFRAs.

Deep-Red Emissive Squaraine-AIEgen in Elastomer Enabling High Contrast and Fast Thermoresponse for Anti-Counterfeiting and Temperature Sensing.

Two challenges remain for organic thermoresponsive materials; one is to develop high-performance red-emissive thermoresponsive materials, while another is to simultaneously achieve high contrast ratio (CR), fast and reversible thermoresponse in a single element. Herein, we not only develop a new deep-red emissive squaraine-based AIEgen (TPE-SQ12) based on a pyrylium end group, which is suitable for fabricating high-performance thermoresponsive materials, but also show an effective approach to improve both CR (∼ten times increase) and response time (less than 3 seconds), that is, molecularly dispersing AIEgen into an elastomer, attributed to the significantly expanded free volume of elastomer upon increasing the temperature that can activate the AIEgen intramolecular movements more pronouncedly. Double encryption and temperature mapping systems have been separately established by using our designed elastomer/TPE-SQ12 film, showing the great potential for anti-counterfeiting and temperature sensing. Finally, white emission is further achieved by co-doping TPE-SQ12 with cyan dye into elastomer, which enables fluorescent thermochromism for improving the temperature mapping ability.

Tetracyanobutadienyl-Based Nonlinear Optical Dendronized Hyperbranched Polymer Synthesized via [2+2] Cycloaddition Polymer Postfunctionalization.

Dendronized hyperbranched polymers (DHPs) can provide advantages for both hyperbranched polymers and dendrimers, making them a promising structure platform for high-performance second-order nonlinear optical (NLO) materials. Herein, a new A3 +B2 -type DHP (HP2) is reported through facile and efficient [2+2] cycloaddition polymer postfunctionalization, in which tetracyanobutadienyl-based moieties are introduced as the main chromophores while isophorone-bridged moieties serve as the isolation chromophores. Benefiting from this unique hyperbranched structure design, the measured second-harmonic generation coefficient of HP2 can reach up to 96.6 pm V-1 with high thermal stability, making it a good material candidate for second-order NLO applications.

A New Diazabenzo[k]fluoranthene-Based D-A Conjugated Polymer Donor for Efficient Organic Solar Cells.

The development of wide-bandgap polymer donors having complementary absorption and compatible energy levels with near-infrared (NIR) absorbing nonfullerene acceptors is highly important for realizing high-performance organic solar cells (OSCs). Herein, a new thiophene-fused diazabenzo[k]fluoranthene derivative is successfully synthesized as the electron-deficient unit to construct an efficient donor-acceptor (D-A) type alternating copolymer donor, namely, PABF-Cl, using the chlorinated benzo[1,2-b:4,5-b']dithiophene as the copolymerization unit. PABF-Cl exhibits a wide optical bandgap of 1.93 eV, a deep highest occupied molecular level of -5.36 eV, and efficient hole transport. As a result, OSCs with the best power conversion efficiency of 11.8% are successfully obtained by using PABF-Cl as the donor to blend with a NIR absorbing BTP-eC9 acceptor. This work provides a new design of electron-deficient unit for constructing high-performance D-A type polymer donors.

Randomised controlled trial: effect of metformin add-on therapy on functional cure in entecavir-treated patients with chronic hepatitis B.

INTRODUCTION AND OBJECTIVES: Hepatitis B surface antigen (HBsAg) clearance, indicating functional cure or resolved chronic hepatitis B (CHB), remains difficult to achieve via nucleos(t)ide analogue monotherapy. We investigated whether metformin add-on therapy could help achieve this goal in entecavir-treated patients with hepatitis B e antigen (HBeAg)-negative CHB. PATIENTS AND METHODS: Patients with HBeAg-negative CHB who met eligibility criteria (entecavir treatment for > 12 months, HBsAg < 1000 IU/mL) were randomly assigned (1:1) to receive 24 weeks of either metformin (1000 mg, oral, once a day) or placebo (oral, once a day) add-on therapy. The group allocation was blinded for both patients and investigators. Efficacy and safety analyses were based on the intention-to-treat set. The primary outcome, serum HBsAg level (IU/mL) at weeks 24 and 36, was analysed using mixed models. RESULTS: Sixty eligible patients were randomly assigned to the metformin (n = 29) and placebo (n = 31) groups. There was no substantial between-group difference in the HBsAg level at week 24 (adjusted mean difference 0.05, 95% confidence interval -0.04 to 0.13, p = 0.278) or week 36 (0.06, -0.03 to 0.15, p = 0.187), and no significant effect of group-by-time interaction on the HBsAg level throughout the trial (p = 0.814). The occurrence of total adverse events between the two groups was comparable (9 [31.0%] of 29 vs. 5 [16.1%] of 31, p = 0.227) and no patient experienced serious adverse events during the study. CONCLUSION: Although it was safe, metformin add-on therapy did not accelerate HBsAg clearance in entecavir-treated patients with HBeAg-negative CHB.

Anionic Cyanine J-Type Aggregate Nanoparticles with Enhanced Photosensitization for Mitochondria-Targeting Tumor Phototherapy.

Cyanines have been widely used as the photosensitizers (PSs) in the biomedical field, but controlling their molecular aggregates in nanoparticles (NPs) remains a major challenge. Moreover, the impact of aggregate behaviors of cyanines on the photosensitization is still unclear. Herein, the first anionic cyanine PSs based on a tricyanofuran end group have been designed by achieving supramolecular J-type aggregates in NPs via counterion engineering. Our results indicate that J-type aggregates in NPs can not only bring significantly red-shifted emission, negatively charged surface, and high photostability, but also enable a significant 5-fold increase in singlet oxygen generation efficiency compared to that in the nonaggregate state, providing strong experimental evidence for the superiority of J-aggregates in enhancing photosensitization. Thus, combined with the mitochondria-targeting ability, the J-type aggregate NPs show remarkable in vivo antitumor phototheranostic efficacy, making them have a potential for clinical use.

Unfused Nonfullerene Acceptors Based on Simple Dipolar Merocyanines.

Merocyanine (MC) dyes exhibit facile synthesis and attractive optical properties, making them widely studied as the donor materials in organic solar cells (OSCs). In this study, for the first time, simple indole-based MCs are successfully designed as unfused nonfullerene acceptors (NFAs) for OSCs by forming dimers with A-D-π-D-A structure, which possess enhanced photostability compared to the well-known ITIC acceptor and high electron mobility in blend films. When blended with P3HT donor, one of the dimers, i. e. Z2, shows a good cell efficiency of 3.53 %, which outperforms the performance of most of P3HT/NFA blends, particularly for unfused systems, and thus indicates good potential of simple MCs as NFAs.

[L-carnitine-astaxanthin compound nutrients for the treatment of idiopathic oligospermia and asthenozoospermia: A multicenter clinical observation].

OBJECTIVE: To investigate the clinical effects of the L-carnitine-astaxanthin compound nutrients Menglankang (MLK) on idiopathic oligospermia (OS) and asthenospermia (AS). METHODS: This study included 73 cases of OS and 220 cases of AS treated with MLK once a bag, bid, for 3 successive months. Before and at 1, 2 and 3 months after treatment, we obtained and analyzed the semen parameters and sperm DNA fragmentation index (DFI) of the patients. RESULTS: Compared with the baseline, the OS patients showed remarkable increases after 1 and 2 months of treatment in the semen volume (ï¼»3.07 ± 1.47ï¼½ vs ï¼»3.26 ± 1.26ï¼½ and ï¼»3.30 ± 1.28ï¼½ ml), sperm concentration (ï¼»10.96 ± 6.09ï¼½ vs ï¼»16.74 ± 11.15ï¼½ and ï¼»17.56 ± 9.92ï¼½ ×106/ml, P < 0.05), total sperm count (ï¼»29.78 ± 17.48ï¼½ vs ï¼»52.98 ± 32.07ï¼½ and ï¼»57.67 ± 36.98ï¼½ ×106, P < 0.05) and the percentages of progressively motile sperm (PMS) (ï¼»39.8 ± 11.66ï¼½% vs ï¼»45.3 ± 14.03ï¼½% and ï¼»46.42 ± 10.69ï¼½%, P < 0.05) and morphologically normal sperm (MNS) (ï¼»1.71 ± 1.07ï¼½% vs ï¼»1.79 ± 0.91ï¼½% and ï¼»1.84 ± 0.96ï¼½%), and so did the AS patients in PMS (ï¼»19.23 ± 8.32ï¼½% vs ï¼»25.46 ± 13.86ï¼½% and ï¼»27.33 ± 12.88ï¼½%, P < 0.05). After 3 months of medication, the OS patients exhibited even more significant increases in the semen volume (ï¼»3.63 ± 1.39ï¼½ ml) (P < 0.05), sperm concentration (ï¼»20.56 ± 14.7ï¼½ ×106/ml) (P < 0.05), total sperm count (ï¼»66.35 ± 55.91ï¼½ ×106) (P < 0.05), PMS (ï¼»49.24 ± 13.45ï¼½%) (P < 0.05) and MNS (ï¼»2.59 ± 0.93ï¼½%) (P < 0.05), and so did the AS patients in the semen volume (ï¼»3.27 ± 1.42ï¼½ vs ï¼»3.85 ± 1.59ï¼½ ml, P < 0.05), PMS (ï¼»29.11 ± 13.58ï¼½%) (P < 0.05) and NMS (ï¼»2.01 ± 1.14ï¼½% vs ï¼»2.57 ± 1.15ï¼½%, P < 0.05). In comparison with the baseline, the sperm DFI was not significantly improved at 1 month after treatment, but remarkably decreased at 2 and 3 months in the OS patients (ï¼»25.87 ± 13.76ï¼½% vs ï¼»18.66 ± 10.83ï¼½% and ï¼»16.48 ± 11.46ï¼½%, P < 0.05) and the AS patients as well (ï¼»26.40 ± 12.28ï¼½% vs ï¼»19.35 ± 11.54ï¼½% and ï¼»15.32 ± 10.89ï¼½%, P < 0.05). CONCLUSIONS: The L-carnitine-astaxanthin compound nutrients Menglankang can significantly improve the semen quality of the patients with idiopathic oligospermia or asthenospermia.

Efficient Inverted Perovskite Solar Cells with Low Voltage Loss Achieved by a Pyridine-Based Dopant-Free Polymer Semiconductor.

Currently, the performance improvement for inverted perovskite solar cells (PVSCs) is mainly limited by the high open circuit voltage (VOC ) loss caused by detrimental non-radiative recombination (NRR) processes. Herein, we report a simple and efficient way to simultaneously reduce the NRR processes inside perovskites and at the interface by rationally designing a new pyridine-based polymer hole-transporting material (HTM), PPY2, which exhibits suitable energy levels with perovskites, high hole mobility, effective passivation of the uncoordinated Pb2+ and iodide defects, as well as the capability of promoting the formation of high-quality polycrystalline perovskite films. In absence of any dopants, the inverted PVSCs using PPY2 as the HTM deliver an encouraging PCE up to 22.41 % with a small VOC loss (0.40 V), among the best device performances for inverted PVSCs reported so far. Furthermore, PPY2-based unencapsulated devices show an excellent long-term photostability, and over 97 % of its initial PCE can be maintained after one sun constant illumination for 500 h.

Effects of Trough Concentration and Solute Carrier Polymorphisms on Imatinib Efficacy in Chinese Patients with Chronic Myeloid Leukemia.

PURPOSE: We investigated the relationship between imatinib trough concentrations and genetic polymorphisms with efficacy of imatinib in Chinese patients with chronic myeloid leukemia (CML). METHODS: There were 171 eligible patients. Peripheral blood samples were collected from 171 eligible patients between 21 and 27 hours after the last imatinib administration. Complete cytogenetic response (CCyR), major molecular response (MMR) and complete molecular response (CMR) were used as metrics for efficacy. Nine single nucleotide polymorphisms in 5 genes, SLC22A4 (917 T>C, -248 C>G and -538 C>G), SLC22A5 (-945 T>G and -1889 T>C), SLCO1A2 (-361 G>A), SLCO1B3 (334 T>G and 699 G>A) and ABCG2 (421C>A) were selected for genotyping. RESULTS: Patients with CCyR achieve higher trough concentrations than those without CCyR (1478.18±659.83 vs 984.89±454.06 ng mL-1, p<0.001). Patients with MMR and CMR achieve higher trough concentrations than those without MMR and CMR, respectively (1486.40±703.38 vs 1121.17±527.14 ng mL-1, p=0.007; 1528.00±709.98 vs 1112.67±518.35 ng mL-1, p=0.003, respectively). Carriers of A allele in SLCO1A2 -361G>A achieve higher CCyR and MMR rates (p=0.047, OR=4.320, 95% CI: 0.924-20.206; p=0.042, OR=2.825, 95% CI: 1.016-7.853, respectively). Both trough concentrations and SLCO1A2 -361G>A genotypes are independent factors affecting imatinib efficacy. The positive and negative predictive values for CCyR are 71.01% and 68.75%, respectively. The positive and negative predictive values for MMR are 62.86% and 69.70%, respectively. CONCLUSION: Imatinib trough concentrations and SLCO1A2 -361G>A genotypes are associated with imatinib efficacy in Chinese patients with CML.

Crosstalk-Free Patterning of Cooperative-Thermoresponse Images by the Synergy of the AIEgen with the Liquid Crystal.

Patterning multiple images within a single element without crosstalk can significantly increase the information capacity and security, but it is challenging to enable the response capability in each image. Now, the patterning of crosstalk-free yet cooperative-thermoresponse images (holographic and fluorescent images) is successfully achieved by designing a liquid crystal (LC)/AIEgen system with a unique synergy. The AIEgen's fluorescence intensity is controlled by the LC, while the LC's phase transition is in turn promoted by the AIEgen. The fluorescent image contrast is significantly boosted by efficient energy transfer (ΦET : 96 %) from the LC to the AIEgen. The AIEgen's photocyclization for fluorescent patterning occurs in a zero-order kinetic manner and can be completed within several minutes when assisted by the LC. The photocyclization conversion is quantitatively dependent on the aggregation size: α∼exp(-d), and able to reach as high as 98 %.

Cationic Polyelectrolyte for Anionic Cyanines: An Efficient Way To Translate Molecular Properties into Material Properties.

In this work, a new phosphonium-containing cationic polyelectrolyte (PE1) has been rationally designed and developed via a facile click-chemistry type postfunctionalization, which can form complexes with highly polarizable anionic cyanines to significantly reduce the strong and random cyanine-cyanine interactions (i.e., aggregation) in the solid-state. This material design strategy enables an efficient translation of the favorable molecular properties of cyanines into macroscopic material properties. One of such complexes exhibits a very large third-order susceptibility over 10-10 esu with low nonlinear optical loss suitable for all optical signal processing.

Nonlinear refraction and absorption measurements of thin films by the dual-arm Z-scan method.

We extend the recently developed dual-arm Z-scan to increase the signal-to-noise ratio (SNR) for measuring the nonlinear refraction (NLR) of thin films on thick substrates. Similar to the case of solutes in solution, the phase shift due to NLR in a thin film can often be dominated by the phase shift due to NLR in the much thicker substrate. SNR enhancement is accomplished by simultaneously scanning a bare substrate and the film plus substrate in two separate but identical Z-scan arms. The subtraction of these signals taken simultaneously effectively cancels the nonlinear signal from the substrate, leaving only the signal from the film. More importantly, the SNR is increased since the correlated noise from effects such as beam-pointing instabilities cancels. To show the versatility of the dual-arm Z-scan method, we perform measurements on semiconductor and organic thin films, some less than 100 nm thick and with thicknesses up to 4 orders of magnitude less than the substrate.

Resveratrol protects BV2 mouse microglial cells against LPS-induced inflammatory injury by altering the miR-146a-5p/TRAF6/NF-κB axis.

Objective: To investigate the role of miR-146a-5p in the effects of resveratrol (RSV) on inflammatory response in BV2 mouse microglial cells. Materials and methods: BV2 cells were pretreated by RSV and stimulated with lipopolysaccharide (LPS). Cell Viability was checked using a MTT assay. Real-Time PCR was performed to detect the levels of pro-inflammatory cytokines (tumor necrosisfactor-α－TNF-α, interleukin-1ß－IL-1ß and interleukin-6 － IL-6) and miR-146a-5p expression. Western blot was used to analyze the protein expression of TNF receptor associated factor 6 (TRAF6) and phospho-nuclear factor kappa B (pNF-κB). Gain-of-function and loss-of-function analysis of miR-146a-5p was performed using transfection of miR-146a-5p mimic and miR-146a-5p inhibitor, respectively. Results: Pretreatment with RSV significantly and dose dependently inhibited LPS-induced production of TNF-α, IL-1ß and IL-6 in BV2 cells. MiR-146a-5p was significantly upregulated after LPS treatment, and further increased in RSV and LPS-co-treated cells. MiR-146a-5p overexpression via miR-146a-5p mimic transfection downregulated the mRNA level of TNF-α, IL-1ß and IL-6, as well as abrogated the protein expression of TRAF6 and pNF-κB in BV2 cells exposed to LPS. More importantly, the reducion of TNF-α, IL-1ß and IL-6 level by RSV were reversed by miR-146a-5p silence via miR-146a-5p inhibitor transfection. Furthermore, silencing miR-146a-5p attenuated the inhibitory effect of RSV on the TRAF6/NF-κB pathway which was activated after induction with LPS. Conclusions: RSV can suppress LPS-induced inflammatory injury via modulating the miR-146a-5p/TRAF6/NF-κB axis in BV2 mouse microglial cells.

Dopant-Free Squaraine-Based Polymeric Hole-Transporting Materials with Comprehensive Passivation Effects for Efficient All-Inorganic Perovskite Solar Cells.

Development of high-performance dopant-free hole-transporting materials (HTMs) with comprehensive passivation effects is highly desirable for all-inorganic perovskite solar cells (PVSCs). Squaraines (SQs) could be a candidate for dopant-free HTMs as they are natural passivators for perovskites. One major limitation of SQs is their relatively low hole mobility. Herein we demonstrate that polymerizing SQs into pseudo two dimensional (2D) p-π conjugated polymers could overcome this problem. By rationally using N,N-diarylanilinosquaraines as the comonomers, the resulting polysquaraine HTMs not only exhibit suitable energy levels and efficient passivation effects, but also achieve very high hole mobility close to 0.01 cm-2 V-1 s-1 . Thus as dopant-free HTMs for α-CsPbI2 Br-based all-inorganic PVSCs, the best PCE reached is 15.5 %, outperforming those of the doped-Spiro-OMeTAD (14.4 %) based control devices and among the best for all-inorganic PVSCs.