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Large Stokes shift red fluorescent proteins (LSS-RFPs) are of growing interest for multicolor bioimaging applications. However, their photochemical mechanisms are not fully understood. Here, we employed the QM(XDW-CASPT2//CASSCF)/MM method to investigate the excited-state proton transfer and photoisomerization processes of the LSS-RFP mKeima starting from its cis neutral isomer. Upon excitation to the bright S1state in the Franck–Condon region, mKeima relaxes to a metastable minimum-energy state. From this short-lived species, two competing deactivation pathways are available: the excited-state proton transfer in the S1state, and the S1decay via the S1/S0conical intersection as a result of the cis–trans photoisomerization. In comparison, the former is a dominant excited-state relaxation pathway, leading to the cis anionic isomer of mKeima in the S1state. This anionic intermediate then undergoes cis–trans photoisomerization after overcoming a barrier of approximately 10 kcal/mol in the S1state, which is followed by an excited-state decay via the S1/S0conical intersection region. The efficient nonadiabatic decay of the cis anionic isomer of mKeima in the S1state inhibits the radiative process, leading to a weak emission around 520 nm observed experimentally. These findings shed important mechanistic light on the experimental observations and provide valuable insights that could help in the design of LSS-RFPs with superior fluorescence properties.

The phosphoinositide 3-kinase (PI3K)–Akt axis is one of the most frequently activated pathways and is demonstrated as a therapeutic target in Kirsten rat sarcoma viral oncogene homolog (KRAS)-mutated colorectal cancer (CRC). Targeting the PI3K–Akt pathway has been a challenging undertaking through the decades. Here we unveiled an essential role of E3 ligase SMAD ubiquitylation regulatory factor 1 (Smurf1)-mediated phosphoinositide-dependent protein kinase 1 (PDK1) neddylation in PI3K–Akt signaling and tumorigenesis. Upon growth factor stimulation, Smurf1 immediately triggers PDK1 neddylation and the poly-neural precursor cell expressed developmentally downregulated protein 8 (poly-Nedd8) chains recruit methyltransferase SET domain bifurcated histone lysine methyltransferase 1 (SETDB1). The cytoplasmic complex of PDK1 assembled with Smurf1 and SETDB1 (cCOMPASS) consisting of PDK1, Smurf1 and SETDB1 directs Akt membrane attachment and T308 phosphorylation. Smurf1 deficiency dramatically reduces CRC tumorigenesis in a genetic mouse model. Furthermore, we developed a highly selective Smurf1 degrader, Smurf1-antagonizing repressor of tumor 1, which exhibits efficient PDK1–Akt blockade and potent tumor suppression alone or combined with PDK1 inhibitor in KRAS-mutated CRC. The findings presented here unveil previously unrecognized roles of PDK1 neddylation and offer a potential strategy for targeting the PI3K–Akt pathway and KRAS mutant cancer therapy.

The release control of organic dye pollutants has become a global issue, and improper disposal of red mud(RM) can also cause environmental pollution. In this paper, a novel composite material, RM-SC-HA, was prepared to adsorb MB (methylene blue) from dye wastewater by co-hydrothermal treatment using RM, sucrose, and humic acid as raw materials. RM-SC-HA is simple to prepare and has better adsorption of MB in dye wastewater. The results supported the proposed secondary (R2= 0.99) kinetic model, which states that chemisorption is the primary form of adsorption. The maximum amount of adsorption, which was achieved by Langmuir's isothermal model, was 417.12 mg/g. In addition, the adsorption mechanism can be attributed to the role of electrostatic interactions, hydrogen bonding, π-π stacking and void diffusion. When RM-SC-HA was used to treat simulated industrial wastewater samples, the removal rate was also maintained at a high level(About 90 %). In addition, RM-SC-HA has good magnetic properties and reusability. Its magnetic properties (saturation magnetization value of 2.49 emu/g) make it easy to separate from water under an applied magnetic field. The present study provides an efficient novel MB adsorbent and promotes the practical application of modified RM composites in water purification.

Based on the financial data of A-share listed companies in China from 2016 to 2020, this study examines the impact of market integration on corporate participation in rural revitalization and its mechanisms. The findings indicate that market integration significantly enhances corporate enthusiasm for participating in rural revitalization. The mechanism tests show that market integration primarily promotes corporate participation in rural revitalization by facilitating labor mobility and alleviating financing constraints for enterprises. Heterogeneity analysis reveals that the effects are more pronounced among enterprises in the eastern region, state-owned enterprises, and those registered in non-poverty areas. Thus, further advancement of market integration is advocated to promote corporate participation in rural revitalization through enhancing labor mobility and easing financing constraints.

Halide interstitial defects severely hinder the optoelectronic performance of metal halide perovskites, making research on their passivation crucial. We demonstrate, using ab initio nonadiabatic molecular dynamics simulations, that hydrogen vacancies (Hv) at both N and C atoms of the methylammonium (MA) cation in MAPbI3efficiently passivate iodine interstitials (Ii), providing a self-passivation strategy for dealing with the Hvand Iidefects simultaneously. Hvat the N site (Hv-N) introduces a defect state into the valence band, while the state contributed by Hvat the C site (Hv-C) evolves from a shallow level at 0 K to a deep midgap state at ambient temperature, exhibiting a high environmental activity. Both Hv-Nand Hv-Care strong Lewis bases, capable of capturing and passivating Iidefects. Hv-Cis a stronger Lewis base, bonds with Iibetter, and exhibits a more pronounced passivation effect. The charge carrier lifetimes in the passivated systems are significantly longer than in those containing either Hvor Ii, and even in pristine MAPbI3. Our demonstration of the Hvand Iidefect self-passivation in MAPbI3suggests that systematic control of the relative concentrations of Hvand Iican simultaneously eliminate both types of defects, thereby minimizing charge and energy losses. The demonstrated defect self-passivation strategy provides a promising means for defect control in organic–inorganic halide perovskites and related materials and deepens our atomistic understanding of defect chemistry and charge carrier dynamics in solar energy and optoelectronic materials.

It has been established experimentally that aromatic thioketones possess several inherently unique photophysical properties, some of which are highly sensitive even to common hydrocarbon solvents. However, the deeper reasons and the underlying mechanisms remain unclear up to date. In this study, the multistate complete active space second-order perturbation theory (MS-CASPT2) has been utilized to investigate the five lowest-lying electronic states (S0, T1, S1, T2, and S2) of 4H-1-benzopyran-4-thione (BPT) in acetonitrile and hydrocarbons. The results show that the S1, T1, and T2states of BPT are close in energy so that the T2-state-mediated S1→ T2→ T1and T1→ T2→ S1transitions could occur in tens of picoseconds, which exhibits little dependence on the formation of the BPT–solvent complexes and on the bulk-solvent effect. This explains why thermally activated delayed fluorescence from the S1state has been observed for many aromatic thioketones in both inert media and hydrocarbons. Meanwhile, our calculations show that the intracomplex noncovalent interactions could be automatically adjusted by the redistribution of π-electrons in the flexible aromatic rings. This allows the S2→ S1internal conversion to occur efficiently in the vicinity of the two-state conical intersection, which results in the remarkable changes in the S2-state lifetimes and fluorescence quantum yields of many aromatic thioketones from inert media to hydrocarbon solvents. The aforementioned inherent photophysical properties could be qualitatively understood by a simple model of frontier molecular orbitals. This model could be used to understand photophysical properties of other aromatic compounds (such as aldehydes, ketones, amines, and carboxylic acids) in different solvents.

Quantum mechanical tunneling (QMT) has long been recognized as crucial for understanding chemical reaction mechanisms, particularly in reactions involving light atoms like hydrogen. However, recent findings have expanded this understanding to include heavy-atom tunneling reactions. In this report, we present the observation of two heavy-atom tunneling reactions involving the spontaneous conversions from end-on bonded beryllium ozonide complexes, OBeOOO (A) and BeOBeOOO (C), to their corresponding side-on bonded ozonide isomers, OBe(η2-O3) (B) and BeOBe(η2-O3) (D), respectively, in a cryogenic neon matrix. This discovery is supported by the weak temperature dependence of the rate constants and unusually large 16O/18O kinetic isotope effects. Quantum chemistry calculations reveal extremely low barriers (<1 kcal/mol) for both ring-closure reactions. Additionally, instanton theory calculations on both reactions unveil that the tunneling processes involve the concerted motion of all four oxygen atoms.

An $(n, k, d; r)_{q}$ -locally repairable code (LRC) is called a Singleton-optimal LRC if it achieves the Singleton-type bound. Analogous to the classical MDS conjecture, the maximal length problem of Singleton-optimal LRCs has attracted a lot of attention in recent years. In this paper, we give an improved upper bound for the length of q-ary Singleton-optimal LRCs with disjoint repair groups such that $(r+1)\mid n$ based on the parity-check matrix approach. In particular, for any Singleton-optimal $(n, k, d; r)_{q}$ -LRCs, we show that: 1) $n\le q+d-4$ , when $r=2$ and $d=3e+8$ with $e\ge 0$ ; 2) $n\leq (r+1)\left \lfloor {{\frac {2(q^{2}+q+1)}{r(r+1)} +e+1}}\right \rfloor $ , when $d\ge 8$ and $\max \left \{{{3,\frac {d-e-6}{e+1}}}\right \}\le r\le \frac {d-e-3}{e+1}$ for any $0\le e\le \left \lfloor {{\frac {d-6}{4} }}\right \rfloor $ . Furthermore, we establish equivalent connections between the existence of Singleton-optimal $(n,k,d;r)_{q}$ -LRCs for $d=6, r=3$ and $d=7, r=2$ with disjoint repair groups and some subsets of lines in finite projective space with certain properties. Consequently, we prove that the length of q-ary Singleton-optimal LRCs with minimum distance $d=6$ and locality $r=3$ is upper bounded by $O(q^{1.5})$ . We construct Singleton-optimal $(8\le n\le q+1,k,d=6,r=3)_{q}$ -LRC with disjoint repair groups such that $4\mid n$ and determine the exact value of the maximum code length for some specific q. We also prove the existence of $(n, k, d=7; r=2)_{q}$ -Singleton-optimal LRCs for $n \approx \sqrt {2}q$ .

Vectorial dual-bent functions have recently attracted some researchers’ interest as they play a significant role in constructing partial difference sets, association schemes, bent partitions, and linear codes. In this paper, we further study vectorial dual-bent functions $F: V_{n}^{(p)}\rightarrow V_{m}^{(p)}$ , where $2\leq m \leq \frac {n}{2}$ , and $V_{n}^{(p)}$ denotes an n-dimensional vector space over the prime field $\mathbb {F}_{p}$ . For certain vectorial dual-bent functions (called vectorial dual-bent functions with Condition A), we present a more concise characterization in terms of partial difference sets than the one given in Wang et al. (2023), and give new characterizations in terms of amorphic association schemes, linear codes, and generalized Hadamard matrices, respectively. When $p=2$ , we characterize vectorial dual-bent functions with Condition A in terms of bent partitions. Through the relationship between vectorial dual-bent functions and bent partitions, new characterizations of certain bent partitions in terms of amorphic association schemes, linear codes, and generalized Hadamard matrices are obtained. For a vectorial dual-bent function $F: V_{n}^{(p)}\rightarrow V_{m}^{(p)}$ with $F(0)=0, F(x)=F(-x)$ , where $2\leq m \leq \frac {n}{2}$ , we give a necessary and sufficient condition under which the preimage set partition of F induces an association scheme. By using two classes of vectorial dual-bent functions, more association schemes are obtained.

The structural, photophysical, and photochemical properties of Ln(depma)(hmpa)2(NO3)3(Ln = La, Ce, Nd, Sm, Eu, Tb, Ho, Er, and Yb) complexes 1-Lnwere investigated with a multidisciplinary approach involving synthesis, photocycloaddition-based crystal engineering, spectroscopic analytical techniques and quantum chemical ab initio calculations. Depending on the Ln3+ion the isostructural 1-Lncomplexes exhibit quite different behavior upon excitation at 350–400 nm. Some 1-Lncomplexes (Ln = La, Ce, Sm, Tb, Yb) emit a broad and strong band near 533 nm arising from paired anthracene moieties, whereas others (Ln = Nd, Eu, Ho, Er) do not. 1-Euis not emissive at all, whereas 1-Nd, 1-Ho, and 1-Erexhibit a Ln3+based luminescence. Upon irradiation with 365 nm ultraviolet (UV) light 1-Ln(Ln = La, Ce, Sm, Tb, Yb) dimerize by means of a photochemically induced [4 + 4] cycloaddition of the anthracene moieties, whereas 1-Ln(Ln = Nd, Eu, Ho, Er) remain monomers. We propose three models, based on the matching of the energy levels between the Ln3+ion and the paired or dimerized anthracene units in the energy-resonance crossing region, as well as on internal conversion-driven and intersystem crossing-driven energy transfer, which explain the Ln3+ion regulated photophysics and photochemistry of the 1-Lncomplexes.

This work reports on the synthesis of a unique nickel oxide/carboxylated reduced graphene oxide (NiO/c-rGO) nanocomposites electrochemical sensor for the detection of quercetin (QCT). The successful integration of NiO nanoparticles into the c-rGO matrix was confirmed by the characterization and synthesis of both the NiO nanoparticles and c-rGO. After that, the glassy carbon electrode (GCE) was treated with the NiO/c-rGO nanocomposite, which produced a modified GCE with improved electrochemical characteristics. The NiO/c-rGO modified GCE showed a wide linear-range of 0.5 to 750 µM and a low detection limit of 0.016 µM, indicating high sensitivity towards QCT. Additionally, the sensor exhibited excellent selectivity, with very little interference from examined kinds of analytes, both organic and inorganic. Additionally, the sensor’s long-term stability was demonstrated by its steady redox reaction to QCT, with a sensitivity of roughly 96.68% over a 33-day period. The suggested sensor’s use was evaluated by measuring differential pulse voltammetry on real samples, including onions, apple juice, honey, and green tea. These samples’ QCT recovery rates, which varied from 96.00 to 99.40%, showed the precision, dependability, and potency of the suggested sensor. Based on these results, the NiO/c-rGO nanocomposite may be a great material to use in the creation of stable, highly sensitive, and selective electrochemical sensors for QCT detection. The food, pharmaceutical, and clinical diagnostics industries might all benefit greatly from this. This work enhances the field of electrochemical sensor technology and paves the way for the development of further sensors using similar nanocomposites.

The hot-rolled microstructure of medium Mn steel has coarse grains and severe elemental segregation, resulting in low strength and plasticity. Constructing a multiphase structure, refining the microstructure, and regulating elemental segregation enhance the mechanical properties. In this study, liquid nitrogen treatment created a layered distribution of austenite and martensite. Warm rolling was then used to reduce layer thickness and refine grain structure. After liquid nitrogen and warm rolling treatments, the strength and plasticity of medium Mn steel increased to 1270 MPa and 23.3%, respectively, far exceeding the hot-rolled state (724 MPa, 12.8%). Warm rolling also triggers austenite reverted transformation (ART) and introduces high-density dislocations, further improving austenite stability. This strengthening effect is higher than that from intercritical annealing alone. Improved austenite stability delays the transformation induced plasticity (TRIP) effect, preventing brittle fracture and enhancing deformation coordination between layers, significantly increasing the plastic deformation capacity of medium Mn steel.

The activation of halogens (X = Cl, Br, I) by N2O5is linked to NOxsources, ozone concentrations, NO3reactivity, and the chemistry of halide-containing aerosol particles. However, a detailed chemical mechanism is still lacking. Herein, we explored the chemistry of the N2O5···X–systems at the air–water interface. Two different reaction pathways were identified for the reaction of N2O5with X–at the air–water interface: the formation of XNO2or XONO, along with NO3–. In the case of the Cl–system, the ClNO2generation pathway is more favorable, while for the Br–and I–systems, the formation of BrONO and IONO is barrierless, making them the predominant products. Furthermore, the mechanisms of formation of X2from XNO2and XONO were also investigated. The high energy barriers of reactions and the high free energies of the products compared to those of the reactants indicate that ClNO2is stable at the air–water interface. Contrary to the widely held belief regarding X2producing from the reaction of XNO2with X–, our calculations demonstrate that BrONO and IONO initially form stable BrONO···Br–and IONO···I–complexes, which then subsequently react with Br–and I–to form Br3–and I3–, respectively. Finally, Br3–and I3–decompose to form Br2and I2.These findings have significant implications for experimental interpretation and offer new insights into halogen cycling in the atmosphere.

The photochemistry of nitrous acid (HONO), encompassing dissociation into OH and NO as well as the reverse association reaction, plays a pivotal role in atmospheric chemistry. Here, we report the direct observation of nitrosyl-O-hydroxide (HOON) in the photochemistry of HONO, employing matrix-isolation IR and UV–vis spectroscopy. Despite a barrier of approximately 30 kJ/mol, HOON undergoes spontaneous rearrangement to the more stable HONO isomer through quantum mechanical tunneling, with a half-life of 28 min at 4 K. Kinetic isotope effects and instanton theory calculations reveal that the tunneling process involves the concerted motion of the NO moiety (65.2%) and the hydrogen atom (32.3%). Our findings underscore the significance of HOON as a key intermediate in the photolytic dissociation–association cycle of HONO at low temperatures.

We simulated hot-electron relaxation in black phosphorus using the nonadiabatic molecular dynamics (NA-MD) approach with a non-Condon effect in momentum space beyond the harmonic approximation. By comparing simulations at the Γ point in a large supercell with those using a few k-points in a smaller supercell─while maintaining the same number of electronic states within the same energy range, we demonstrate that both setups yield remarkably consistent energy relaxation times, regardless of the initial state energy. This consistency arises from the complementary effects of supercell size in real space and the number of k-points in the reciprocal space. This finding confirms that simulations at a single k-point in large size supercells are an effective approximation for NA-MD with a non-Condon effect. This approach offers significant advantages for complex photophysics, such as intervalley scattering and indirect bandgap charge recombination, and is particularly suitable for large systems without the need for a harmonic approximation.

Different from the previous neutral reaction solvent system, this work explores the synthesis of Al-oxo rings in ionic environments. Deep eutectic solvents (DESs) formed by quaternary ammonium salts hydrogen bond acceptor (HBA) and phenols hydrogen bond donor (HBD) further reduce the melting point of the reaction system and provide an ionic environment. Further, the quaternary ammonium salt was chosen as the HBA because it contains a halogen anion that matches the size of the central cavity of the molecular ring. Based on this thought, five Al8ion pair cocrystals were synthesized via “DES thermal”. The general formula is Q+⊂ {Cl@[Al8(BD)8(μ2-OH)4L12]} (AlOC-180–AlOC-185, Q+= tetrabutylammonium, tetrapropylammonium, 1-butyl-3-methylimidazole; HBD = phenol, p-chlorophenol, p-fluorophenol; HL = benzoic acid, 1-naphthoic acid, 1-pyrenecarboxylic acid, anthracene-9-carboxylic acid). Structural studies reveal that the phenol-coordinated Al molecular ring and the quaternary ammonium ion pair form the cocrystal compounds. The halogen anions in the DES component are confined in the center of the molecular ring, and the quaternary ammonium cations are located in the organic shell. Such an adaptive cocrystal binding pattern is particularly evident in the structures coordinated with low-symmetry ligands such as naphthoic acid and pyrene acid. Finally, the optical behavior of these cocrystal compounds is understood from the analysis of crystal structure and theoretical calculation.

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.

Herein, we have used the “on-the-fly” ring-polymer surface-hopping simulation method with the centroid approximation (RPSH-CA), in combination with the multireference OM2/MRCI electronic structure calculations to study the photoinduced dynamics of a green fluorescent protein (GFP) chromophore analogue in the gas phase, i.e., o-HBI, at 50, 100, and 300 K with 1, 5, 10, and 15 beads (3600 1 ps trajectories). The electronic structure calculations identified five new minimum-energy conical intersection (MECI) structures, which, together with the previous one, play crucial roles in the excited-state decay dynamics of o-HBI. It is also found that the excited-state intramolecular proton transfer (ESIPT) occurs in an ultrafast manner and is completed within 20 fs in all the simulation conditions because there is no barrier associated with this ESIPT process in the S1state. However, the other excited-state dynamical results are strongly related to the number of beads. At 50 and 100 K, the nuclear quantum effects (NQEs) are very important; therefore, the excited-state dynamical results change significantly with the bead number. For example, the S1decay time deduced from time-dependent state populations becomes longer as the bead number increases. Nevertheless, an essentially convergent trend is observed when the bead number is close to 10. In contrast, at 300 K, the NQEs become weaker and the above dynamical results converge very quickly even with 1 bead. Most importantly, the NQEs seriously affect the excited-state decay mechanism of o-HBI. At 50 and 100 K, most trajectories decay to the S0state via perpendicular keto MECIs, whereas, at 300 K, only twisted keto MECIs are responsible for the excited-state decay. The present work not only comprehensively explores the temperature-dependent photoinduced dynamics of o-HBI, but also demonstrates the importance and necessity of NQEs in nonadiabatic dynamics simulations, especially at relatively low temperatures.

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.

Recent years have witnessed the development of cluster materials as they are atomically precise molecules with uniform size and solution-processability, which are unattainable with traditional nanoparticles or framework materials. The motivation for studying Al(III) chemistry is not only to understand the aggregation process of aluminum in the environment but also to develop novel low-cost materials given its natural abundance. However, the Al-related clusters are underdeveloped compared to the coinage metals, lanthanides, and transition metals. The challenge in isolating crystalline compounds is the lack of an effective method to realize the controllable hydrolysis of Al(III) ions. Compared with the traditional hydrolysis of inorganic Al(III) salts in highly alkaline solutions and hydrolysis of aluminum trialkyl compounds conducted carefully in an inert operating environment, we herein developed an effective way to control the hydrolysis of aluminum isopropanol through an alcoxalation reaction. By solvothermal/low melting point solid melting synthesis and using “ligand aggregation, solvent regulation, and supracluster assembly” strategies, our laboratory has established an organic-inorganic hybrid system of aluminum oxo clusters (AlOCs). The employment of organic ligands promotes the aggregation and slows the hydrolysis of Al(III) ions, which in turn improves the crystallization process. The regulation of the structure types can be achieved through the selection of ligands and the supporting solvents. Compared with the traditional condensed polyoxoaluminates, we successfully isolated a broad range of porous AlOCs, including aluminum molecular rings and Archimedes aluminum oxo cages. By studying ring expansion, structural transformation, and intermolecular supramolecular assembly, we demonstrate unique and unprecedented structural controllability and assembly behavior in cluster science. The advancement of this universal synthetic method is to realize materials customization through modularly oriented supracluster assembly. In this Account, we will provide a clear-cut definition and terminology of “ligand aggregation, solvent regulation, and supracluster assembly”. Then we will discuss the discovery in this area by using a strategy, such as aluminum molecular ring, ring size expansion, ring supracluster assembly, etc. Furthermore, given the internal and external pore structures, as well as the solubility and modifiability of the AlOCs, we will demonstrate their potential applications in both the solid and liquid phases, such as iodine capture, the optical limiting responses, and dopant in polymer dielectrics. The strategy herein can be applied to extensive cluster science and promote the research of main group element chemistry. The new synthetic method, fascinating clusters, and unprecedented assembly behaviors we have discovered will advance Al(III) chemistry and will also lay the foundation for functional applications.

Herein, we employed linear-response time-dependent functional theory nonadiabatic dynamic simulations to explore the photoinduced exciton dynamics of a chiral single-walled carbon nanotube CNT(6,5) covalently doped with a 4-nitrobenzyl group (CNT65-NO2). The results indicate that the introduction of a sp3defect leads to the splitting of the degenerate VBM/VBM-1 and CBM/CBM+1 states. Both the VBM upshift and the CBM downshift are responsible for the experimentally observed redshifted E11* trapping state. The simulations reveal that the photoinduced exciton relaxation dynamics completes within 500 fs, which is consistent with the experimental work. On the other hand, we also conducted the nonadiabatic carrier (electron and hole) dynamic simulations, which completely ignore the excitonic effects. The comparison demonstrates that excitonic effects are indispensable. Deep analyses show that such effects induce several dark states, which play an important role in regulating the photoinduced dynamics of CNT65-NO2. The present work demonstrates the importance of including excitonic effects in simulating photoinduced processes of carbon nanotubes. In addition, it not only rationalizes previous experiments but also provides valuable insights that will help in the future rational design of novel covalently doped carbon nanotubes with superior photoluminescent properties.

A significant decline in both incidence and prevalence of cervical cancers after widespread-introducing cervical screening strategy by Papanicolau test (Pap test) has been found in the world, but cervical cancer is still one of the most common female cancers, reporting the fourth prevalence and also one of the leading causes to result in main women-associated morbidity and mortality, particularly for those women living in low- and middle-income countries. Cervical cancer is one of the most important health concerns directly destroying the global health-care system, partly because of not only increasing the disability either secondary to diseases themselves of victims or mediated by treatment-related adverse events to the survivors but also acting as a leading cause of death of diseased patients worldwide, alarming the urgent need to do something to minimize the catastrophic diseases-related heavy socioeconomic burden. It is fortunate that cervical cancer is a preventable disease, based on its strong association with human papillomavirus (HPV) infection (more than 95%), particularly for those high-risk HPV (HR-HPV) and its high possibility by detecting HPV infection before the development of cervical cancer as well as an effective prevention by HPV vaccination. That is why WHO (World Health Organization) considers cervical cancer as a public problem and attempts to accelerate the elimination of cervical cancer program by three-pillar approach (90:70:90% targets), including (1) 90% of girls are fully vaccinated with HPV vaccine by 15 years of age; (2) 70% of women are screened with a high-performance test by 35 and 45 years of age and precancerous lesions are treated early; and (3) 90% of women identified with cervical diseases receive appropriate and adequate treatment. Herein, this review focuses on the HPV vaccination as Part I, including global recommendations and Taiwan government's policy for HPV vaccination.