CO2 doping of organic interlayers for perovskite solar cells.

In perovskite solar cells, doped organic semiconductors are often used as charge-extraction interlayers situated between the photoactive layer and the electrodes. The π-conjugated small molecule 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9-spirobifluorene (spiro-OMeTAD) is the most frequently used semiconductor in the hole-conducting layer1-6, and its electrical properties considerably affect the charge collection efficiencies of the solar cell7. To enhance the electrical conductivity of spiro-OMeTAD, lithium bis(trifluoromethane)sulfonimide (LiTFSI) is typically used in a doping process, which is conventionally initiated by exposing spiro-OMeTAD:LiTFSI blend films to air and light for several hours. This process, in which oxygen acts as the p-type dopant8-11, is time-intensive and largely depends on ambient conditions, and thus hinders the commercialization of perovskite solar cells. Here we report a fast and reproducible doping method that involves bubbling a spiro-OMeTAD:LiTFSI solution with CO2 under ultraviolet light. CO2 obtains electrons from photoexcited spiro-OMeTAD, rapidly promoting its p-type doping and resulting in the precipitation of carbonates. The CO2-treated interlayer exhibits approximately 100 times higher conductivity than a pristine film while realizing stable, high-efficiency perovskite solar cells without any post-treatments. We also show that this method can be used to dope π-conjugated polymers.

Naphthalene Diimide-Modified SnO2 Enabling Low-Temperature Processing for Efficient ITO-Free Flexible Perovskite Solar Cells.

A low-cost and indium-tin-oxide (ITO)-free electrode-based flexible perovskite solar cell (PSC) that can be fabricated by roll-to-roll processing shall be developed for successful commercialization. High processing temperatures present a challenge for the PSC fabrication on flexible substrates. The most efficient planar n-i-p PSC structures, which utilize a metal oxide as an electron transport layer (ETL), necessitate high annealing temperatures. In addition, the device performance deteriorates owing to the migration of halogen ions, which causes the oxidation of the metal electrodes. These drawbacks conflict with the development of highly efficient flexible PSCs fabricated on ITO-free transparent electrodes. Herein, an efficient ETL material that enables low-temperature processing is presented. Tin dioxide (SnO2) is modified by (sulfobetaine-N,N-dimethylamino)propyl naphthalene diimide (NDI-B) and used as an ETL. The NDI-B effectively reduces the interfacial nonradiative recombination between the ETL and perovskite and suppresses the ion migration by passivating oxygen-vacancy defects in SnO2 and strongly interacting with halogen ions, respectively. Based on the NDI-B-blended SnO2 ETL, a record PCE of 17.48% is achieved in the ITO-free flexible PSC fabricated at low temperature.

Revolutionizing Robotic Depalletizing: AI-Enhanced Parcel Detecting with Adaptive 3D Machine Vision and RGB-D Imaging for Automated Unloading.

Detecting parcels accurately and efficiently has always been a challenging task when unloading from trucks onto conveyor belts because of the diverse and complex ways in which parcels are stacked. Conventional methods struggle to quickly and accurately classify the various shapes and surface patterns of unordered parcels. In this paper, we propose a parcel-picking surface detection method based on deep learning and image processing for the efficient unloading of diverse and unordered parcels. Our goal is to develop a systematic image processing algorithm that emphasises the boundaries of parcels regardless of their shape, pattern, or layout. The core of the algorithm is the utilisation of RGB-D technology for detecting the primary boundary lines regardless of obstacles such as adhesive labels, tapes, or parcel surface patterns. For cases where detecting the boundary lines is difficult owing to narrow gaps between parcels, we propose using deep learning-based boundary line detection through the You Only Look at Coefficients (YOLACT) model. Using image segmentation techniques, the algorithm efficiently predicts boundary lines, enabling the accurate detection of irregularly sized parcels with complex surface patterns. Furthermore, even for rotated parcels, we can extract their edges through complex mathematical operations using the depth values of the specified position, enabling the detection of the wider surfaces of the rotated parcels. Finally, we validate the accuracy and real-time performance of our proposed method through various case studies, achieving mAP (50) values of 93.8% and 90.8% for randomly sized and rotationally covered boxes with diverse colours and patterns, respectively.

Microwave-Mediated, Catalyst-Free Synthesis of 1,2,4-Triazolo[1,5-a]pyridines from Enaminonitriles.

A catalyst-free, additive-free, and eco-friendly method for synthesizing 1,2,4-triazolo[1,5-a]pyridines under microwave conditions has been established. This tandem reaction involves the use of enaminonitriles and benzohydrazides, a transamidation mechanism followed by nucleophilic addition with nitrile, and subsequent condensation to yield the target compound in a short reaction time. The methodology demonstrates a broad substrate scope and good functional group tolerance, resulting in the formation of products in good-to-excellent yields. Furthermore, the scale-up reaction and late-stage functionalization of triazolo pyridine further demonstrate its synthetic utility. A plausible reaction pathway, based on our findings, has been proposed.

Total Synthesis of Isohericerinol A and Its Analogues to Access Their Potential Neurotrophic Effects.

The secondary metabolites from Hericium erinaceus are well-known to have neurotrophic and neuroprotective effects. Isohericerinol A (1), isolated by our colleagues from its fruiting parts has a strong ability to increase the nerve growth factor secretion in C6 glioma cells. The current work describes the total synthesis of 1 and its regioisomer 5 in a few steps. We present two different approaches to 1 and a regiodivergent approach for both 1 and 5 by utilizing easily accessible feedstocks. Interestingly, the natural product 1, regioisomer 5, and their intermediates exhibited potent neurotrophic activity in in vitro experimental systems. Thus, these synthetic strategies provide access to a systematic structure-activity relationship study of natural product 1.

Vibration-Based Loosening Detection of a Multi-Bolt Structure Using Machine Learning Algorithms.

Since artificial intelligence (AI) was introduced into engineering fields, it has made many breakthroughs. Machine learning (ML) algorithms have been very commonly used in structural health monitoring (SHM) systems in the last decade. In this study, a vibration-based early stage of bolt loosening detection and identification technique is proposed using ML algorithms, for a motor fastened with four bolts (M8 × 1.5) to a stationary support. First, several cases with fastened and loosened bolts were established, and the motor was operated in three different types of working condition (800 rpm, 1000 rpm, and 1200 rpm), in order to obtain enough vibration data. Second, for feature extraction of the dataset, the short-time Fourier transform (STFT) method was performed. Third, different types of classifier of ML were trained, and a new test dataset was applied to evaluate the performance of the classifiers. Finally, the classifier with the greatest accuracy was identified. The test results showed that the capability of the classifier was satisfactory for detecting bolt loosening and identifying which bolt or bolts started to lose their preload in each working condition. The identified classifier will be implemented for online monitoring of the early stage of bolt loosening of a multi-bolt structure in future works.

New Non-Fullerene Acceptor with Extended Conjugation of Cyclopenta [2,1-b:3,4-b'] Dithiophene for Organic Solar Cells.

Herein, we design and characterize 9-heterocyclic ring non-fullerene acceptors (NFAs) with the extended backbone of indacenodithiophene by cyclopenta [2,1-b:3,4-b'] dithiophene (CPDT). The planar conjugated CPDT donor enhances absorption by reducing vibronic transition and charge transport. Developed NFAs with different end groups shows maximum absorption at approximately 790-850 nm in film. Because of the electronegative nature of the end-group, the corresponding acceptors showed deeper LUMO energy levels and red-shifted ultraviolet absorption. We investigate the crystallinity, film morphology, surface energy, and electronic as well as photovoltaic performance. The organic photovoltaic cells using novel NFAs with the halogen end groups fluorine or chlorine demonstrate better charge collection and faster exciton dissociation than photovoltaic cells using NFAs with methyl or lacking a substituent. Photovoltaic devices constructed from m-Me-ITIC with various end groups deliver power conversion efficiencies of 3.6-11.8%.

Simultaneously Passivating Cation and Anion Defects in Metal Halide Perovskite Solar Cells Using a Zwitterionic Amino Acid Additive.

Ionic defects (e.g., organic cations and halide anions), preferably residing along grain boundaries (GBs) and on perovskite film surfaces, are known to be a major source of the notorious environmental instability of perovskite solar cells (PeSCs). Although passivating ionic defects is desirable, previous approaches using Lewis base or acid molecules as additives suppress only the negatively or positively charged defects, thus leaving oppositely charged defects. In this work, both the cationic and anionic defects inside methyl ammonium lead tri-iodide (MAPbI3 ) are simultaneously passivated by introducing a zwitterionic form of the amino acid, L-alanine, into the precursor solution as an additive. L-alanine has both positive (NH3+ ) and negative (COO- ) functional groups at a specific solvent pH, thereby passivating both the cation and anion defects in MAPbI3 . The addition of L-alanine increases the grain size of the perovskite crystals and lengthens the charge carrier lifetime (τ > 1 µs), leading to improved power conversion efficiencies (PCEs) of 20.3% (from 18.3% without an additive) for small-area (4.64 mm2 ) devices and 15.6% (from 13.5%) for large-area submodules (9.06 cm2 ). More importantly, the authors' approach also significantly enhances the shelf storage and photoirradiation stabilities of PeSCs.

Chromosomal features revealed by comparison of genetic maps of Glycine max and Glycine soja.

Recombination is a crucial component of evolution and breeding. New combinations of variation on chromosomes are shaped by recombination. Recombination is also involved in chromosomal rearrangements. However, recombination rates vary tremendously among chromosome segments. Genome-wide genetic maps are one of the best tools to study variation of recombination. Here, we describe high density genetic maps of Glycine max and Glycine soja constructed from four segregating populations. The maps were used to identify chromosomal rearrangements and find the highly predictable pattern of cross-overs on the broad scale in soybean. Markers on these genetic maps were used to evaluate assembly quality of the current soybean reference genome sequence. We find a strong inversion candidate larger than 3 Mb based on patterns of cross-overs. We also identify quantitative trait loci (QTL) that control number of cross-overs. This study provides fundamental insights relevant to practical strategy for breeding programs and for pan-genome researches.

One-Step Sixfold Cyanation of Benzothiadiazole Acceptor Units for Air-Stable High-Performance n-Type Organic Field-Effect Transistors.

Reported here is a new high electron affinity acceptor end group for organic semiconductors, 2,1,3-benzothiadiazole-4,5,6-tricarbonitrile (TCNBT). An n-type organic semiconductor with an indacenodithiophene (IDT) core and TCNBT end groups was synthesized by a sixfold nucleophilic substitution with cyanide on a fluorinated precursor, itself prepared by a direct arylation approach. This one-step chemical modification significantly impacted the molecular properties: the fluorinated precursor, TFBT IDT, a poor ambipolar semiconductor, was converted into TCNBT IDT, a good n-type semiconductor. The electron-deficient end group TCNBT dramatically decreased the energy of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO) compared to the fluorinated analogue and improved the molecular orientation when utilized in n-type organic field-effect transistors (OFETs). Solution-processed OFETs based on TCNBT IDT exhibited a charge-carrier mobility of up to µe ≈0.15 cm2 V-1 s-1 with excellent ambient stability for 100 hours, highlighting the benefits of the cyanated end group and the synthetic approach.

Proteomic analysis of affinity-purified 26S proteasomes identifies a suite of assembly chaperones in Arabidopsis.

The 26S proteasome is an essential protease that selectively eliminates dysfunctional and short-lived regulatory proteins in eukaryotes. To define the composition of this proteolytic machine in plants, we tagged either the core protease (CP) or the regulatory particle (RP) sub-complexes in Arabidopsis to enable rapid affinity purification followed by mass spectrometric analysis. Studies on proteasomes enriched from whole seedlings, with or without ATP needed to maintain the holo-proteasome complex, identified all known proteasome subunits but failed to detect isoform preferences, suggesting that Arabidopsis does not construct distinct proteasome sub-types. We also detected a suite of proteasome-interacting proteins, including likely orthologs of the yeast and mammalian chaperones Pba1, Pba2, Pba3, and Pba4 that assist in CP assembly; Ump1 that helps connect CP half-barrels; Nas2, Nas6, and Hsm3 that assist in RP assembly; and Ecm29 that promotes CP-RP association. Proteasomes from seedlings exposed to the proteasome inhibitor MG132 accumulated assembly intermediates, reflecting partially built proteasome sub-complexes associated with assembly chaperones, and the CP capped with the PA200/Blm10 regulator. Genetic analyses of Arabidopsis UMP1 revealed that, unlike in yeast, this chaperone is essential, with mutants lacking the major UMP1a and UMP1b isoforms displaying a strong gametophytic defect. Single ump1 mutants were hypersensitive to conditions that induce proteotoxic, salt and osmotic stress, and also accumulated several proteasome assembly intermediates, consistent with its importance for CP construction. Insights into the chaperones reported here should enable study of the assembly events that generate the 26S holo-proteasome in Arabidopsis from the collection of 64 or more subunits.

Reversible Polymorphic Transition and Hysteresis-Driven Phase Selectivity in Single-Crystalline C8-BTBT Rods.

Organic semiconductors (OSCs) are highly susceptible to the formation of metastable polymorphs that are often transformed by external stimuli. However, thermally reversible transformations in OSCs with stability have not been achieved due to weak van der Waals forces, and poor phase homogeneity and crystallinity. Here, a polymorph of a single crystalline 2,7-dioctyl[1] benzothieno[3,2-b][1]benzothio-phene rod on a low molecular weight poly(methyl methacrylate) (≈120k) that limits crystal coarsening during solvent vapor annealing is fabricated. Molecules in the polymorph lie down slightly toward the substrate compared to the equilibrium state, inducing an order of greater resistivity. During thermal cycling, the polymorph exhibits a reversible change in resistivity by 5.5 orders with hysteresis; this transition is stable toward bias and thermal cycling. Remarkably, varying cycling temperatures leads to diverse resistivities near room temperature, important for nonvolatile multivalue memories. These trends persist in the carrier mobility and on/off ratio of the polymorph field-effect transistor. A combination of in situ grazing incident wide angle X-ray scattering analyses, visualization for electronic and structural analysis simulations, and density functional theory calculations reveals that molecular tilt governs the charge transport characteristics; the polymorph transforms as molecules tilt, and thereby, only a homogeneous single-crystalline phase appears at each temperature.

A membrane-associated NAC domain transcription factor XVP interacts with TDIF co-receptor and regulates vascular meristem activity.

Vascular stem cell maintenance is regulated by a peptide signaling involving Tracheary Element Differentiation Inhibitory Factor (TDIF) and Receptor TDR/PXY (Phloem intercalated with Xylem) and co-receptor BAK1 (BRI1-associated receptor kinase1). The regulatory mechanism of this signaling pathway is largely unknown despite its importance in stem cell maintenance in the vascular meristem. We report that activation of a NAC domain transcription factor XVP leads to precocious Xylem differentiation, disruption of Vascular Patterning, and reduced cell numbers in vascular bundles. We combined molecular and genetic studies to elucidate the biological functions of XVP. XVP is expressed in the cambium, localized on the plasma membrane and forms a complex with TDIF co-receptors PXY-BAK1. Simultaneous mutation of XVP and its close homologous NAC048 enhances TDIF signaling. In addition, genetics analysis indicated that XVP promotes xylem differentiation through a known master regulator VASCULAR-RELATED NAC-DOMAIN6 (VND6). Expression analyses indicate that XVP activates CLAVATA3/ESR (CLE)-related protein 44 (CLE44), the coding gene of TDIF, whereas TDIF represses XVP expression, suggesting a feedback mechanism. Therefore, XVP functions as a negative regulator of the TDIF-PXY module and fine-tunes TDIF signaling in vascular development. These results shed new light on the mechanism of vascular stem cell maintenance.

LBD29-Involved Auxin Signaling Represses NAC Master Regulators and Fiber Wall Biosynthesis.

NAM, ATAF1/2 and CUC2 (NAC) domain transcription factors function as master switches in regulating secondary cell wall (SCW) biosynthesis in Arabidopsis (Arabidopsis thaliana) stems. Despite the importance of these NACs in fiber development, the upstream signal is still elusive. Using a large-scale mutant screening, we identified a dominant activation-tagging mutant, fiberless-d (fls-d), showing defective SCW development in stem fibers, similar to that of the nac secondary wall thickening promoting factor1-1 (nst1-1)nst3-3 double mutant. Overexpression of LATERAL ORGAN BOUNDARIES DOMAIN29 (LBD29) is responsible for the fls-d mutant phenotypes. By contrast, loss-of-function of LBD29, either in the dominant repression transgenic lines or in the transfer-DNA (T-DNA) insertion mutant lbd29-1, enhanced SCW development in fibers. Genetic analysis and transgenic studies demonstrated LBD29 depends on master regulators in mediating SCW biosynthesis, specifically NAC SECONDARY WALL THICKENING PROMOTING FACTOR1 (NST1), NST2, and NST3. Increasing indole-3-acetic acid (IAA) levels, either in stem tissues above a N-1-naphthylphthalamic acid-treated region or in plants directly sprayed with IAA, inhibits fiber wall thickening. The inhibition effect of naphthylphthalamic acid treatment and exogenous IAA application depends on a known auxin signaling pathway involving AUXIN RESPONSE FACTOR7 (ARF7)/ARF19 and LBD29. These results demonstrate auxin is upstream of LBD29 in repressing NAC master regulators, and therefore shed new light on the regulation of SCW biosynthesis in Arabidopsis.

Maize w3 disrupts homogentisate solanesyl transferase (ZmHst) and reveals a plastoquinone-9 independent path for phytoene desaturation and tocopherol accumulation in kernels.

Maize white seedling 3 (w3) has been used to study carotenoid deficiency for almost 100 years, although the molecular basis of the mutation has remained unknown. Here we show that the w3 phenotype is caused by disruption of the maize gene for homogentisate solanesyl transferase (HST), which catalyzes the first and committed step in plastoquinone-9 (PQ-9) biosynthesis in the plastid. The resulting PQ-9 deficiency prohibits photosynthetic electron transfer and eliminates PQ-9 as an oxidant in the enzymatic desaturation of phytoene during carotenoid synthesis. As a result, light-grown w3 seedlings are albino, deficient in colored carotenoids and accumulate high levels of phytoene. However, despite the absence of PQ-9 for phytoene desaturation, dark-grown w3 seedlings can produce abscisic acid (ABA) and homozygous w3 kernels accumulate sufficient carotenoids to generate ABA needed for seed maturation. The presence of ABA and low levels of carotenoids in w3 nulls indicates that phytoene desaturase is able to use an alternate oxidant cofactor, albeit less efficiently than PQ-9. The observation that tocopherols and tocotrienols are modestly affected in w3 embryos and unaffected in w3 endosperm indicates that, unlike leaves, grain tissues deficient in PQ-9 are not subject to severe photo-oxidative stress. In addition to identifying the molecular basis for the maize w3 mutant, we: (1) show that low levels of phytoene desaturation can occur in w3 seedlings in the absence of PQ-9; and (2) demonstrate that PQ-9 and carotenoids are not required for vitamin E accumulation.

The α-Aurora Kinases Function in Vascular Development in Arabidopsis.

The Aurora kinases are serine/threonine kinases with conserved functions in mitotic cell division in eukaryotes. In Arabidopsis, Aurora kinases play important roles in primary meristem maintenance, but their functions in vascular development are still elusive. We report a dominant xdi-d mutant showing the xylem development inhibition (XDI) phenotype. Gene identification and transgenic overexpression experiments indicated that the activation of the Arabidopsis Aurora 2 (AtAUR2) gene is responsible for the XDI phenotype. In contrast, the aur1-2 aur2-2 double mutant plants showed enhanced differentiation of phloem and xylem cells, indicating that the Aurora kinases negatively affect xylem differentiation. The transcript levels of key regulatory genes in vascular cell differentiation, i.e. ALTERED PHLOEM DEVELOPMENT (APL), VASCULAR-RELATED NAC-DOMAIN 6 (VND6) and VND7, were higher in the aur1-2 aur2-2 double mutant and lower in xdi-d mutants compared with the wild-type plants, further supporting the functions of α-Aurora kinases in vascular development. Gene mutagenesis and transgenic studies showed that protein phosphorylation and substrate binding, but not protein dimerization and ubiquitination, are critical for the biological function of AtAUR2. These results indicate that α-Aurora kinases play key roles in vascular cell differentiation in Arabidopsis.

Green-light-selective organic photodiodes for full-color imaging.

In this work, organic photodiodes (OPDs) based on two newly synthesized p-type dipolar small molecules are reported for application to green-light-selective OPDs. In order to reduce the blue-color absorption induced by the use of C60 as the n-type material in a bulk heterojunction (BHJ), the electron donor:electron acceptor composition ratio is tuned in the BHJ. With this light manipulation approach, the blue-wavelength external quantum efficiency (EQE) is minimized to 18% after reducing the C60 concentration in the center part of the BHJ. The two p-type molecules get a cyanine-like character with intense and sharp absorption in the green color by adjusting the strength of their donating and accepting parts and by choosing a selenophene unit as a π-linker. When combined to C60, the green-wavelength EQE reaches 70% in a complete device composed of two transparent electrodes. Finally, the optical simulation shows the good color-balance performance of hybrid full-color image sensor without an additional filter by using the developed green OPD as the top-layer in stacked device architecture.

The Proteasome Stress Regulon Is Controlled by a Pair of NAC Transcription Factors in Arabidopsis.

Proteotoxic stress, which is generated by the accumulation of unfolded or aberrant proteins due to environmental or cellular perturbations, can be mitigated by several mechanisms, including activation of the unfolded protein response and coordinated increases in protein chaperones and activities that direct proteolysis, such as the 26S proteasome. Using RNA-seq analyses combined with chemical inhibitors or mutants that induce proteotoxic stress by impairing 26S proteasome capacity, we defined the transcriptional network that responds to this stress in Arabidopsis thaliana This network includes genes encoding core and assembly factors needed to build the complete 26S particle, alternative proteasome capping factors, enzymes involved in protein ubiquitylation/deubiquitylation and cellular detoxification, protein chaperones, autophagy components, and various transcriptional regulators. Many loci in this proteasome-stress regulon contain a consensus cis-element upstream of the transcription start site, which was previously identified as a binding site for the NAM/ATAF1/CUC2 78 (NAC78) transcription factor. Double mutants disrupting NAC78 and its closest relative NAC53 are compromised in the activation of this regulon and notably are strongly hypersensitive to the proteasome inhibitors MG132 and bortezomib. Given that NAC53 and NAC78 homo- and heterodimerize, we propose that they work as a pair in activating the expression of numerous factors that help plants survive proteotoxic stress and thus play a central regulatory role in maintaining protein homeostasis.

Genetic diversity patterns and domestication origin of soybean.

KEY MESSAGE: Genotyping data of a comprehensive Korean soybean collection obtained using a large SNP array were used to clarify global distribution patterns of soybean and address the evolutionary history of soybean. Understanding diversity and evolution of a crop is an essential step to implement a strategy to expand its germplasm base for crop improvement research. Accessions intensively collected from Korea, which is a small but central region in the distribution geography of soybean, were genotyped to provide sufficient data to underpin population genetic questions. After removing natural hybrids and duplicated or redundant accessions, we obtained a non-redundant set comprising 1957 domesticated and 1079 wild accessions to perform population structure analyses. Our analysis demonstrates that while wild soybean germplasm will require additional sampling from diverse indigenous areas to expand the germplasm base, the current domesticated soybean germplasm is saturated in terms of genetic diversity. We then showed that our genome-wide polymorphism map enabled us to detect genetic loci underlying flower color, seed-coat color, and domestication syndrome. A representative soybean set consisting of 194 accessions was divided into one domesticated subpopulation and four wild subpopulations that could be traced back to their geographic collection areas. Population genomics analyses suggested that the monophyletic group of domesticated soybeans was likely originated at a Japanese region. The results were further substantiated by a phylogenetic tree constructed from domestication-associated single nucleotide polymorphisms identified in this study.