Synthesis and hygrothermal aging of polycarbonates containing a bisphenol fluorene moiety.

This study aims to synthesize a specific type of polycarbonate with high refractive index, low birefringence, and resistance to hygrothermal aging by copolymerizing 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE) with 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF). Comparative analysis revealed that the copolymer synthesized from BNE and BPEF demonstrated superior hydrolytic stability relative to the bisphenol A-based polycarbonate. This augmented stability can be attributed to the monomers' higher pKa values, rendering acidic substances less capable of dissociating and thereby mitigating ester hydrolysis under hygrothermal conditions. Furthermore, the investigation probed into the phenomenon of physical aging in copolymerized polycarbonate when exposed to hygrothermal environments. It was discerned that the enthalpy loss, observable under both dry and hygrothermal conditions, could be linearly correlated with the difference between the aging temperature and the glass transition temperature (Tg), signifying a close correlation between the magnitude of physical aging and Tg. A lower Tg in the copolymerized polycarbonate led to more pronounced physical aging within the same timeframe, resulting in an augmentation of tensile strength and modulus, while higher Tg effectively mitigated the physical aging phenomenon.

Mechanochemical dynamics of collective cells and hierarchical topological defects in multicellular lumens.

Collective cell dynamics is essential for tissue morphogenesis and various biological functions. However, it remains incompletely understood how mechanical forces and chemical signaling are integrated to direct collective cell behaviors underlying tissue morphogenesis. Here, we propose a three-dimensional (3D) mechanochemical theory accounting for biochemical reaction-diffusion and cellular mechanotransduction to investigate the dynamics of multicellular lumens. We show that the interplay between biochemical signaling and mechanics can trigger either pitchfork or Hopf bifurcation to induce diverse static mechanochemical patterns or generate oscillations with multiple modes both involving marked mechanical deformations in lumens. We uncover the crucial role of mechanochemical feedback in emerging morphodynamics and identify the evolution and morphogenetic functions of hierarchical topological defects including cell-level hexatic defects and tissue-level orientational defects. Our theory captures the common mechanochemical traits of collective dynamics observed in experiments and could provide a mechanistic context for understanding morphological symmetry breaking in 3D lumen-like tissues.

Preparation of NIR-II Polymer Nanoprobe Through Twisted Intramolecular Charge Transfer and Förster Resonance Energy Transfer of NIR-I Dye.

Near-infrared-II (NIR-II) fluorescence imaging is pivotal in biomedical research. Organic probes exhibit high potential in clinical translation, due to advantages such as precise structure design, low toxicity, and post-modifications convenience. In related preparation, enhancement of NIR-II tail emission from NIR-I dyes is an efficient method. In particular, the promotion of twisted intramolecular charge transfer (TICT) of relevant NIR-I dyes is a convenient protocol. However, present TICT-type probes still show disadvantages in relatively low emission, large particle sizes, or limited choice of NIR-I dyes, etc. Herein, the synthesis of stable small-sized polymer NIR-II fluoroprobes (e.g., 7.2 nm), integrating TICT and Förster resonance energy transfer process to synergistically enhance the NIR-II emission is reported. Strong enhanced emissions can be obtained from various NIR-I dyes and lanthanide elements (e.g., twelvefold at 1250 nm from Nd-DTPA/IR-808 sample). The fluorophore provides high-resolution angiography, with high-contrast imaging on middle cerebral artery occlusion model mice for distinguishing occlusion. The fluorophore can be rapidly excreted from the kidney (urine ≈65% within 4 h) in normal mice and exhibits long-term renal retention on acute kidney injury mice, showing potential applications in the prognosis of kidney diseases. This development provides an effective strategy to design and synthesize effective NIR-II fluoroprobes.

Altered development of face recognition among infants born amid the COVID-19 pandemic.

To effectively contain the spread of COVID-19, public health agencies mandated special regulations. Although they protected us from COVID-19, these restrictions have inevitably changed the environment around us. It remains unclear how these changes may have affected early cognitive development among infants born during the pandemic. Thus, this study examined how the COVID-19 restrictions have affected infants' face recognition ability, a hallmark of their cognitive capacities. Specifically, we used the familiarization and visual pair comparison paradigm to examine face recognition performance among infants aged 6 to 14 months amid the second wave of the pandemic (February to July 2021). Experiment 1 investigated the recognition of unmasked faces and found that only younger infants, but not older infants, recognized faces by showing a novelty preference. Experiment 2 examined the recognition of faces wearing masks and found that only older infants, but not younger ones, recognized faces by exhibiting a familiarity preference. These results suggest that with limited interactions during the pandemic, infants could have developed an overly specialized face processing ability that failed to recognize the faces of strangers. Moreover, infants could have obtained more information on masked faces during the pandemic and adapted to the current situation. In Expreiment 3, we further confirmed the restriction on infants' interpersonal experiences with a survey conducted both before and during the pandemic. Overall, these findings demonstrated how the pandemic altered early perceptual development and further confirmed that interpersonal experiences during infancy are critical in their cognitive development.

Spike-based dynamic computing with asynchronous sensing-computing neuromorphic chip.

By mimicking the neurons and synapses of the human brain and employing spiking neural networks on neuromorphic chips, neuromorphic computing offers a promising energy-efficient machine intelligence. How to borrow high-level brain dynamic mechanisms to help neuromorphic computing achieve energy advantages is a fundamental issue. This work presents an application-oriented algorithm-software-hardware co-designed neuromorphic system for this issue. First, we design and fabricate an asynchronous chip called "Speck", a sensing-computing neuromorphic system on chip. With the low processor resting power of 0.42mW, Speck can satisfy the hardware requirements of dynamic computing: no-input consumes no energy. Second, we uncover the "dynamic imbalance" in spiking neural networks and develop an attention-based framework for achieving the algorithmic requirements of dynamic computing: varied inputs consume energy with large variance. Together, we demonstrate a neuromorphic system with real-time power as low as 0.70mW. This work exhibits the promising potentials of neuromorphic computing with its asynchronous event-driven, sparse, and dynamic nature.

Discovery of Methylenetetrahydrofolate Reductase (MTHFR) Deficiency in Individuals With Common Psychiatric Comorbidities: A Retrospective Case Review.

INTRODUCTION: A retrospective analysis was conducted of a data set collected in an outpatient behavioral health clinic to assess medication metabolism and methylenetetrahydrofolate reductase (MTHFR) and to see if there was a correlation with certain diagnoses and/or gender. METHOD: The outpatient routine completed genetic testing on their patients and the test results were later collected through a third-party company, which completed the pharmacogenomic test analyzing genetic variations in DNA, medication metabolism, and an MTHFR deficiency. RESULTS: This study reviewed 186 patients seen in an outpatient setting who were tested for an MTHFR deficiency and compared their psychiatric diagnoses and the number of failed medication attempts. Of those 186 patients, 77 had normal MTHFR enzyme function, 85 were found to have a moderate MTHFR deficiency, and 24 had a severe MTHFR deficiency. Those with a severe MTHFR deficiency had a higher number of medication trials as compared to those without the deficiency and there were overall more patients with a moderate MTHFR deficiency in this data set. CONCLUSION: Currently, MTHFR deficiency is not commonly tested due to lack of insurance coverage and provider knowledge, and due to the cost of the test itself. Thus, the diagnosis can often be missed.

Design principles as minimal models.

In this essay I suggest that we view design principles in systems biology as minimal models, for a design principle usually exhibits universal behaviors that are common to a whole range of heterogeneous (living and nonliving) systems with different underlying mechanisms. A well-known design principle in systems biology, integral feedback control, is discussed, showing that it satisfies all the conditions for a model to be a minimal model. This approach has significant philosophical implications: it not only accounts for how design principles explain, but also helps clarify one dispute over design principles, e.g., whether design principles provide mechanistic explanations or a distinct kind of explanations called design explanations.

Electrical aligned polyurethane nerve guidance conduit modulates macrophage polarization and facilitates immunoregulatory peripheral nerve regeneration.

Biomaterials can modulate the local immune microenvironments to promote peripheral nerve regeneration. Inspired by the spatial orderly distribution and endogenous electric field of nerve fibers, we aimed to investigate the synergistic effects of electrical and topological cues on immune microenvironments of peripheral nerve regeneration. Nerve guidance conduits (NGCs) with aligned electrospun nanofibers were fabricated using a polyurethane copolymer containing a conductive aniline trimer and degradable L-lysine (PUAT). In vitro experiments showed that the aligned PUAT (A-PUAT) membranes promoted the recruitment of macrophages and induced their polarization towards the pro-healing M2 phenotype, which subsequently facilitated the migration and myelination of Schwann cells. Furthermore, NGCs fabricated from A-PUAT increased the proportion of pro-healing macrophages and improved peripheral nerve regeneration in a rat model of sciatic nerve injury. In conclusion, this study demonstrated the potential application of NGCs in peripheral nerve regeneration from an immunomodulatory perspective and revealed A-PUAT as a clinically-actionable strategy for peripheral nerve injury.

Robust Gaussian Process Regression Method for Efficient Tunneling Pathway Optimization: Application to Surface Processes.

Simulation of surface processes is a key part of computational chemistry that offers atomic-scale insights into mechanisms of heterogeneous catalysis, diffusion dynamics, and quantum tunneling phenomena. The most common theoretical approaches involve optimization of reaction pathways, including semiclassical tunneling pathways (called instantons). The computational effort can be demanding, especially for instanton optimizations with an ab initio electronic structure. Recently, machine learning has been applied to accelerate reaction-pathway optimization, showing great potential for a wide range of applications. However, previous methods still suffer from numerical and efficiency issues and were not designed for condensed-phase reactions. We propose an improved framework based on Gaussian process regression for general transformed coordinates, which has improved efficiency and numerical stability, and we propose a descriptor that combines internal and Cartesian coordinates suitable for modeling surface processes. We demonstrate with 11 instanton optimizations in three representative systems that the improved approach makes ab initio instanton optimization significantly cheaper, such that it becomes not much more expensive than a classical transition-state theory rate calculation.

Inhibition of STAT3 by S3I-201 suppress peritoneal fibroblast phenotype conversion and alleviate peritoneal fibrosis.

Peritoneal fibrosis is a common pathological response to long-term peritoneal dialysis (PD) and a major cause for PD discontinuation. Understanding the cellular and molecular mechanisms underlying the induction and progression of peritoneal fibrosis is of great interest. In our study, in vitro study revealed that signal transducer and activator of transcription 3 (STAT3) is a key factor in fibroblast activation and extracellular matrix (ECM) synthesis. Furthermore, STAT3 induced by IL-6 trans-signalling pathway mediate the fibroblasts of the peritoneal stroma contributed to peritoneal fibrosis. Inhibition of STAT3 exerts an antifibrotic effect by attenuating fibroblast activation and ECM production with an in vitro co-culture model. Moreover, STAT3 plays an important role in the peritoneal fibrosis in an animal model of peritoneal fibrosis developed in mice. Blocking STAT3 can reduce the peritoneal morphological changes induced by chlorhexidine gluconate. In conclusion, our findings suggested STAT3 signalling played an important role in peritoneal fibrosis. Therefore, blocking STAT3 might become a potential treatment strategy in peritoneal fibrosis.

Multi-fidelity machine learning for predicting bandgaps of nonlinear optical crystals.

Nonlinear optical (NLO) materials are of great importance in modern optics and industry because of their intrinsic capability of wavelength conversion. Bandgap is a key property of NLO crystals. In recent years, machine learning (ML) has become a powerful tool to predict the bandgaps of compounds before synthesis. However, the shortage of available experimental data of NLO crystals poses a significant challenge for the exploration of new NLO materials using ML. In this work, we proposed a new multi-fidelity ML approach based on the multilevel descriptors developed by us (Z.-Y. Zhang, X. Liu, L. Shen, L. Chen and W.-H. Fang, J. Phys. Chem. C, 2021, 125, 25175-25188) and the gradient boosting regression tree algorithm. The calculated and experimental bandgaps of NLO crystals were collected as the low- and high-fidelity labels, respectively. The experimental values were predicted based on chemical compositions of crystals without prior knowledge about crystal structures. The multi-fidelity ML model overcame the performance of single-fidelity predictor. Furthermore, it was observed that less accurate predictions on the low-fidelity label may result in more accurate prediction on the high-fidelity label, at least in the present case. Using the multi-fidelity ML model with the best performance in this work, the mean absolute error on the test set of experimental bandgaps was 0.293 eV, which is smaller than that using the single-fidelity model (0.355 eV). It is far from perfect but accurate enough as an effective computational tool in the first step to discover novel NLO materials.

Effects of theacrine on the astringency of EGCG by affecting salivary protein - EGCG interactions through different molecular mechanisms.

(-)-Epigallocatechin gallate (EGCG) and theacrine are involved in imparting tea with its astringent and bitter tastes. This study investigated the effect of theacrine on the astringency of EGCG and its molecular mechanism. Sensory evaluation was used to study the astringent intensities of EGCG solutions in the presence and absence of various concentrations of theacrine. The results indicated a considerable increase in the astringency values of EGCG-theacrine solutions compared with those of EGCG solutions alone. Furthermore, dynamic light scattering (DLS) and molecular dynamics simulations (MD) were to explore the interaction mechanisms. The results revealed that theacrine increased the particle size of EGCG-proline-rich proteins (PRPs) aggregates with that of EGCG and PRPs alone. MD revealed that theacrine potentially acted as a bridge between EGCG and PRPs, promoting their interaction and intensifying the EGCG's astringency. However, theacrine could not bridge two or more mucins owing to the substantial spatial structure of mucin.

Progress in Rice Breeding Based on Genomic Research.

The role of rice genomics in breeding progress is becoming increasingly important. Deeper research into the rice genome will contribute to the identification and utilization of outstanding functional genes, enriching the diversity and genetic basis of breeding materials and meeting the diverse demands for various improvements. Here, we review the significant contributions of rice genomics research to breeding progress over the last 25 years, discussing the profound impact of genomics on rice genome sequencing, functional gene exploration, and novel breeding methods, and we provide valuable insights for future research and breeding practices.

Compression of Organic Molecules Coupled with Hydrogen Bonding Extends the Charge Carrier Lifetime in BA2SnI4.

Two-dimensional (2D) metal halide perovskites, such as BA2SnI4 (BA═CH3(CH2)3NH3), exhibit an enhanced charge carrier lifetime in experiments under strain. Experiments suggest that significant compression of the BA molecule, rather than of the inorganic lattice, contributes to this enhancement. To elucidate the underlying physical mechanism, we apply a moderate compressive strain to the entire system and subsequently introduce significant compression to the BA molecules. We then perform ab initio nonadiabatic molecular dynamics simulations of nonradiative electron-hole recombination. We observe that the overall lattice compression reduces atomic motions and decreases nonadiabatic coupling, thereby delaying electron-hole recombination. Additionally, compression of the BA molecules enhances hydrogen bonding between the BA molecules and iodine atoms, which lengthens the Sn-I bonds, distorts the [SnI6]4- octahedra, and suppresses atomic motions further, thus reducing nonadiabatic coupling. Also, the elongated Sn-I bonds and weakened antibonding interactions increase the band gap. Altogether, the compression delays the nonradiative electron-hole recombination by more than a factor of 3. Our simulations provide new and valuable physical insights into how compressive strain, accommodated primarily by the organic ligands, positively influences the optoelectronic properties of 2D layered halide perovskites, offering a promising pathway for further performance improvements.

Development of soy protein isolate gels added with Tremella polysaccharides and psyllium husk powder as 3D printing inks for people with dysphagia.

The aim of this study was to investigate the feasibility of soy protein isolate (SPI) gels added with Tremella polysaccharides (TPs) and psyllium husk powder (PHP) as 3D printing inks for developing dysphagia-friendly food and elucidate the potential mechanism of TPs and PHP in enhancing the printing and swallowing performance of SPI gels. The results indicated that the SPI gels with a TP : PHP ratio of 3 : 7 could be effectively used as printing inks to manufacture dysphagia-friendly food. The addition of TPs increased the free water content, resulting in a decrease in the viscosity of the SPI gels, which, in turn, reduced the line width of the 3D-printed product and structural strength of the gel system. The addition of PHP increased disulfide bond interactions and excluded volume interactions, which determined the mechanical strength of SPI gels and increased the line width of the printed product. The synergistic effects between TPs and PHP improved the printing precision and structural stability. This study presents meaningful insights for the utilization of 3D printing in the creation of dysphagia-friendly food using protein-polysaccharide complexes.

Synthesis and Properties of Bio-Based Polycarbonates Containing Silicone Blocks.

This study aims to investigate the effects of different hydroxy-terminated silicones on the properties of polycarbonate-silicone copolymers (ICS-PC) by introducing flexible and hydrophobic silicone into isosorbide-based polycarbonate through melt transesterification- polycondensation method. Through compatibility and transesterification experiments, it is confirmed that the alcohol-hydroxyl polydimethylsiloxane (a-PDMS) has higher reactivity and silicone conversion than the phenol-hydroxyl polydimethylsiloxane (p-PDMS), but the conversion does not exceed 81%. Polyether-modified silicone (PEMS) exhibits better compatibility and higher reactivity, thus resulting in higher conversion that can reach 86%. Effects of the type and content of silicone on the glass transition temperature (Tg), optical transparency, saturated water absorption, and mechanical strength of ICS-PCs were also discussed. It is found that p-PDMS has higher Tg, hydrophobicity, and mechanical strength with similar silicone content, but the total transmittance does not exceed 60%. In contrast, the PEMS system exhibits better optical transparency due to its improved compatibility with the PC matrix, with a total transmittance of up to 73%, Tg exceeding 150 °C while maintaining excellent flexibility and hydrophobicity. These results are helpful to further improve the comprehensive properties of bio-based polycarbonates.

Oxidative Addition of E-H (E = C, N) Bonds to Transient Uranium(II) Centers.

Two-electron oxidative addition is one of the most important elementary reactions for d-block transition metals but it is uncommon for f-block elements. Here, we report the first examples of intermolecular oxidative addition of E-H (E = C, N) bonds to uranium(II) centers. The transient U(II) species was formed in-situ by reducing a heterometallic cluster featuring U(IV)-Pd(0) bonds with potassium-graphite (KC8). Oxidative addition of C-H or N-H bonds to the U(II) centers was observed when this transient U(II) species was treated with benzene, carbazole or 1-adamantylamine, respectively. The U(II) centers could also react with tetracene, biphenylene or N2O, leading to the formation of arene reduced U(IV) products and uranyl(VI) species via two- or four-electron processes. This study demonstrates that the intermolecular two-electron oxidative addition reactions are viable for actinide elements.