Sum rule comparison of narrowband and broadband sum frequency generation spectra and comparison with theory.

Earlier sum frequency generation (SFG) experiments involve one infrared and one visible laser, and a measurement of the intensity of the response, yielding data on the surface sensitive properties of the sample. Recently, both the real and imaginary components of the susceptibility were measured in two different sets of experiments. In one set, a broadband infrared laser was used, permitting observations at very short times, while in another set the infrared laser was narrowband, permitting higher spectral resolution. The differences in the spectrum obtained by the two will be most evident in studying narrow absorption bands, e.g., the band due to dangling OH bonds at a water interface. The direct comparisons in the integrated amplitude (sum rule) of the imaginary part of the dangling OH bond region differ by a factor of 3. Due to variations in experimental setup and data processing, corrections were made for the quartz reference, Fresnel factors, and the incident visible laser wavelength. After the corrections, the agreement differs now by the factors of 1.1 within broadband and narrowband groups and the two groups now differ by a factor of 1.5. The 1.5 factor may arise from the extra heating of the more powerful broadband laser system on the water surface. The convolution from the narrowband SFG spectrum to the broadband SFG spectrum is also investigated and it does not affect the sum rule. Theory and narrowband experiments are compared using the sum rule and agree to a factor of 1.3 with no adjustable parameters.

Phosphorylation of GntR reduces Streptococcus suis oxidative stress resistance and virulence by inhibiting NADH oxidase transcription.

GntR transcription factor of Streptococcus suis serotype 2 (SS2) is a potential substrate protein of STK, but the regulation mechanisms of GntR phosphorylation are still unclear. This study confirmed that STK phosphorylated GntR in vivo, and in vitro phosphorylation experiments showed that STK phosphorylated GntR at Ser-41. The phosphomimetic strain (GntR-S41E) had significantly reduced lethality in mice and reduced bacterial load in the blood, lung, liver, spleen, and brain of infected mice compared to wild-type (WT) SS2. Electrophoretic mobility shift assay (EMSA) and chromatin immunoprecipitation (ChIP) experiments demonstrated that the promoter of nox was bound by GntR. The phosphomimetic protein GntR-S41E cannot bind to the promoter of nox, and the nox transcription levels were significantly reduced in the GntR-S41E mutant compared to WT SS2. The virulence in mice and the ability to resist oxidative stress of the GntR-S41E strain were restored by complementing transcript levels of nox. NOX is an NADH oxidase that catalyzes the oxidation of NADH to NAD+ with the reduction of oxygen to water. We found that NADH is likely accumulated under oxidative stress in the GntR-S41E strain, and higher NADH levels resulted in increased amplified ROS killing. In total, we report GntR phosphorylation could inhibit the transcription of nox, which impaired the ability of SS2 to resist oxidative stress and virulence.

Streptococcal autolysin promotes dysfunction of swine tracheal epithelium by interacting with vimentin.

Streptococcus suis serotype 2 (SS2) is a major zoonotic pathogen resulting in manifestations as pneumonia and septic shock. The upper respiratory tract is typically thought to be the main colonization and entry site of SS2 in pigs, but the mechanism through which it penetrates the respiratory barrier is still unclear. In this study, a mutant with low invasive potential to swine tracheal epithelial cells (STECs) was screened from the TnYLB-1 transposon insertion mutant library of SS2, and the interrupted gene was identified as autolysin (atl). Compared to wild-type (WT) SS2, Δatl mutant exhibited lower ability to penetrate the tracheal epithelial barrier in a mouse model. Purified Atl also enhanced SS2 translocation across STEC monolayers in Transwell inserts. Furthermore, Atl redistributed the tight junctions (TJs) in STECs through myosin light chain kinase (MLCK) signaling, which led to increased barrier permeability. Using mass spectrometry, co-immunoprecipitation (co-IP), pull-down, bacterial two-hybrid and saturation binding experiments, we showed that Atl binds directly to vimentin. CRISPR/Cas9-targeted deletion of vimentin in STECs (VIM KO STECs) abrogated the capacity of SS2 to translocate across the monolayers, SS2-induced phosphorylation of myosin II regulatory light chain (MLC) and MLCK transcription, indicating that vimentin is indispensable for MLCK activation. Consistently, vimentin null mice were protected from SS2 infection and exhibited reduced tracheal and lung injury. Thus, MLCK-mediated epithelial barrier opening caused by the Atl-vimentin interaction is found to be likely the key mechanism by which SS2 penetrates the tracheal epithelium.

Deep Learning Based Prediction of Myopia Control Effect in Children Treated With Overnight Orthokeratology.

OBJECTIVES: To develop and validate a deep learning-based model for predicting 12-month axial length (AL) elongation using baseline factors and early corneal topographic changes in children treated with orthokeratology (Ortho-K) and to investigate the association between these factors and myopia control impact. METHODS: A total of 115 patients with Ortho-K were enrolled. Influential baseline factors that have a statistically significant correlation with 12-month AL from medical records were selected using Pearson correlation coefficients. Simultaneously, the height, area, and volume of the defocus region were directly calculated from the corneal topography. Then, the prediction model was developed by combining multiple linear regression and deep neural network and evaluated in an independent group (83 patients for developing the algorithm and 32 patients for evaluation). RESULTS: Age ( r= -0.30, P <0.001), spherical equivalent refractive (SE; r =0.20, P =0.032), and sex ( r =0.19, P =0.032) were significantly correlated with the AL elongation while pupil diameter, flat k, steep k, horizontal corneal diameter (white to white), anterior chamber depth, and cell density were not ( P >0.1). The prediction model was developed using age, SE, and corneal topographic variation, and the validation of the model demonstrated its effectiveness in predicting AL elongation. CONCLUSIONS: The AL elongation was accurately predicted by the deep learning model, which effectively incorporated both baseline factors and corneal topographic variation.

Rate-Distortion-Perception Optimized Neural Speech Transmission System for High-Fidelity Semantic Communications.

We consider the problem of learned speech transmission. Existing methods have exploited joint source-channel coding (JSCC) to encode speech directly to transmitted symbols to improve the robustness over noisy channels. However, the fundamental limit of these methods is the failure of identification of content diversity across speech frames, leading to inefficient transmission. In this paper, we propose a novel neural speech transmission framework named NST. It can be optimized for superior rate-distortion-perception (RDP) performance toward the goal of high-fidelity semantic communication. Particularly, a learned entropy model assesses latent speech features to quantify the semantic content complexity, which facilitates the adaptive transmission rate allocation. NST enables a seamless integration of the source content with channel state information through variable-length joint source-channel coding, which maximizes the coding gain. Furthermore, we present a streaming variant of NST, which adopts causal coding based on sliding windows. Experimental results verify that NST outperforms existing speech transmission methods including separation-based and JSCC solutions in terms of RDP performance. Streaming NST achieves low-latency transmission with a slight quality degradation, which is tailored for real-time speech communication.

Controllable self-rotating array beam with an arc-shaped accelerating trajectory.

In this study, a modified interfering vortex phase mask (MIVPM) is proposed to generate a new type of self-rotating beam. The MIVPM is based on a conventional and stretched vortex phase for generating a self-rotating beam that rotates continuously with increasing propagation distances. A combined phase mask can produce multi-rotating array beams with controllable sub-region number. The combination method of this phase was analyzed in detail. This study proves that this self-rotating array beam has an effectively enhanced central lobe and reduced side lobe owing to adding a vortex phase mask compared with a conventional self-rotating beam. Furthermore, the propagation dynamics of this beam can be modulated by varying the topological charge and constant a. With an increase in the topological charge, the area crossed by the peak beam intensity along the propagation axis increases. Meanwhile, the novel self-rotating beam is used for optical manipulation under phase gradient force. The proposed self-rotating array beam has potential applications in optical manipulation and spatial localization.

Vimentin affects inflammation and neutrophil recruitment in airway epithelium during Streptococcus suis serotype 2 infection.

Streptococcus suis serotype 2 (SS2) frequently colonizes the swine upper respiratory tract and can cause Streptococcal disease in swine with clinical manifestations of pneumonia, meningitis, and septicemia. Previously, we have shown that vimentin, a kind of intermediate filament protein, is involved in the penetration of SS2 through the tracheal epithelial barrier. The initiation of invasive disease is closely related to SS2-induced excessive local inflammation; however, the role of vimentin in airway epithelial inflammation remains unclear. Here, we show that vimentin deficient mice exhibit attenuated lung injury, diminished production of proinflammatory cytokines interleukin-6 (IL-6), tumor necrosis factor-alpha (TNF-α), and the IL-8 homolog, keratinocyte-derived chemokine (KC), and substantially reduced neutrophils in the lungs following intranasal infection with SS2. We also found that swine tracheal epithelial cells (STEC) without vimentin show decreased transcription of IL-6, TNF-α, and IL-8. SS2 infection caused reassembly of vimentin in STEC, and pharmacological disruption of vimentin filaments prevented the transcription of those proinflammatory cytokines. Furthermore, deficiency of vimentin failed to increase the transcription of nucleotide oligomerization domain protein 2 (NOD2), which is known to interact with vimentin, and the phosphorylation of NF-κB protein p65. This study provides insights into how vimentin promotes excessive airway inflammation, thereby exacerbating airway injury and SS2-induced systemic infection.

Sum frequency generation, calculation of absolute intensities, comparison with experiments, and two-field relaxation-based derivation.

The experimental sum frequency generation (SFG) spectrum is the response to an infrared pulse and a visible pulse and is a highly surface-sensitive technique. We treat the surface dangling OH bonds at the air/water interface and focus on the absolute SFG intensities for the resonant terms, a focus that permits insight into the consequences of some approximations. For the polarization combinations, the calculated linewidths for the water interface dangling OH SFG band at 3,700 [Formula: see text] are, as usual, too large, because of the customary neglect of motional narrowing. The integrated spectrum is used to circumvent this problem and justified here using a Kubo-like formalism and theoretical integrated band intensities rather than peak intensities. Only relative SFG intensities are usually reported. The absolute integrated SFG intensities for three polarization combinations for sum frequency, visible, and infrared beams are computed. We use molecular dynamics and the dipole and the polarizability matrix elements obtained from infrared and Raman studies of [Formula: see text]O vapor. The theoretical expressions for two of the absolute susceptibilities contain only a single term and agree with experiment to about a factor of 1.3, with no adjustable parameters. The Fresnel factors are included in that comparison. One of the susceptibilities contains instead four positive and negative terms and agrees less well. The expression for the SFG correlation function is normally derived from a statistical mechanical formulation using a time-evolving density matrix. We show how a derivation based on a two-field relaxation leads to the same final result.

Intelligent Path-Selection-Aided Decoding of Polar Codes.

CRC-aided successive cancellation list (CA-SCL) decoding is a powerful algorithm that dramatically improves the error performance of polar codes. Path selection is a major issue that affects the decoding latency of SCL decoders. Generally, path selection is implemented using a metric sorter, which causes its latency to increase as the list grows. In this paper, intelligent path selection (IPS) is proposed as an alternative to the traditional metric sorter. First, we found that in the path selection, only the most reliable paths need to be selected, and it is not necessary to completely sort all paths. Second, based on a neural network model, an intelligent path selection scheme is proposed, including a fully connected network construction, a threshold and a post-processing unit. Simulation results show that the proposed path-selection method can achieve comparable performance gain to the existing methods under SCL/CA-SCL decoding. Compared with the conventional methods, IPS has lower latency for medium and large list sizes. For the proposed hardware structure, IPS's time complexity is O(klog2(L)) where k is the number of hidden layers of the network and L is the list size.

Pre-Configured Error Pattern Ordered Statistics Decoding for CRC-Polar Codes.

In this paper, we propose a pre-configured error pattern ordered statistics decoding (PEPOSD) algorithm and discuss its application to short cyclic redundancy check (CRC)-polar codes. Unlike the traditional OSD that changes the most reliable independent symbols, we regard the decoding process as testing the error patterns, like guessing random additive noise decoding (GRAND). Also, the pre-configurator referred from ordered reliability bits (ORB) GRAND can better control the range and testing order of EPs. An offline-online structure can accelerate the decoding process. Additionally, we also introduce two orders to optimize the search order for testing EPs. Compared with CRC-aided OSD and list decoding, PEPOSD can achieve a better trade-off between accuracy and complexity.

Dense Conductive Metal-Organic Frameworks as Robust Electrocatalysts for Biosensing.

Due to the fascinating properties such as high porosity, large surface areas, and tunable chemical components, metal-organic frameworks (MOFs) have emerged in many fields including catalysis, energy storage, and gas separation. However, the intrinsic electrical insulation of MOFs severely restricts their application in electrochemistry. Here, we synthesize a series of 2D conductive MOFs (cMOFs) through tuning the structure with atomic precision using simple hydrothermal methods. Various electroactive probes are used to reveal the structure-property relationships in 2D cMOFs. Then, we demonstrate the first exploration and implementation of 2D cMOFs toward the construction of electrochemical biosensors. In particular, the biosensor based on Cu3(tetrahydroxy-1,4-quinone)2 [Cu3(THQ)2] displays a remarkably improved electrocatalytic performance at a much lower potential. The mechanism study reveals the essential role of charge-transfer interactions between the dense catalytic sites of Cu3(THQ)2 and analytes. Furthermore, the Cu3(THQ)2-based biosensor demonstrates robust anti-interference capability, good stability, fast response speed, and an ultralow detection limit for paraoxon. These promising results indicate the great potential of cMOFs in biomedical, food safety, and environmental sensing applications.

Renoprotective effects of oleanolic acid and its possible mechanisms in rats with diabetic kidney disease.

Dyslipidemia and inflammation have great roles in the development of diabetic nephropathy (DN). Oleanolic acid (OA) is a natural triterpenoid that possesses multiple pharmacological properties including anti-oxidation, anti-inflammatory and hypoglycemia. In the present study, the effects of OA on diabetic kidney disease (DKD) and its underlying mechanisms were investigated in DKD rats. Twenty-five of a total thirty-five male Sprague-Dawley (SD) rats were used to establish for Type 2 diabetes mellitus (T2DM) model by high-fat diet combined with streptozotocin (STZ). Then rats were randomly assigned into four group: control group (n = 10), T2DM group (n = 9), OA (50 mg/kg) group (n = 7), OA (100 mg/kg) group (n = 8). Rats were sacrificed at the end of 18 weeks after feeding by intraperitoneal injection of pentobarbital sodium. Body weight (BW), fasting blood glucose (FBG), kidney weight (KW), serum lipid, 24-h urinary microalbumin (UMA), serum creatinine (Scr) and uric acid (UA) were measured. Histopathological changes were observed by PAS staining and electron microscope. The expressions of nephrin, CD68, Collagen-IV, AMPK, p-AMPK, PGC-1α, TLR4, NF-κB and TGF-ß1 in kidney were also detected by immunohistochemistry or western blot. OA significantly decreased the levels of FBG, kidney index (KI), serum lipid levels, 24 h UMA, Scr, UA in diabetic rats. Additionally, OA obviously attenuated renal lipid accumulation and renal structure abnormalities in diabetic rats. Furthermore, the expression levels of nephrin, p-AMPK/AMPK, PGC-1α were elevated, while CD68, Collagen-IV, TLR4, NF-κB and TGF-ß1 expressions were decreased in renal tissues of OA treated diabetic rats. OA showed dose-independent. OA can alleviate renal injury in diabetic rats through improving lipid metabolism and inflammation via AMPK/PGC-1α and TLR4/NF-κB signaling pathway.

Self-healing property of the self-rotating beam.

In this study, we demonstrate the self-healing of self-rotating beams with asymmetric intensity profiles. The proposed self-rotating beam exhibits an asymmetric intensity profile and self-healing properties in free-space propagation. In addition, the rotation direction and beam intensity profile of the self-rotating beam can be adjusted using the parameters a and b in the phase function. The effects of the position and size of the obstruction on the self-healing property of a self-rotating beam were studied both experimentally and numerically. The simulation and experimental results demonstrate that a self-rotating beam can overcome a block of obstacles and regenerate itself after a characteristic distance. Transverse energy flows were used to explain the self-healing properties. Moreover, the beam rotates during propagation, which can be used to capture and manipulate microscopic particles in a three-dimensional space. It is expected that these rotating beams with self-healing properties will be useful in penetrating obstacles for optical trapping, transportation, and optical therapy.

Self-rotating beam in the free space propagation.

We introduce a class of self-rotating beams whose intensity profile tends to self-rotate and self-bend in the free space propagation. The feature of the self-rotating beams is acceleration in the three-dimensional (3D) space. The acceleration dynamics of the self-rotating beams is controllable. Furthermore, multiple self-rotating beams can be generated by a combined diffractive optical element (DOE) simultaneously. Such a beam can be viewed as evolution of a vortex beam by changing the exponential constant of phase. We have generated this beam successfully in the experiment and observed the expected phenomenon, which is basically consistent with the result of the numerical simulation. Our results may provide new insight into the self-rotating beam and extend potential applications in optical imaging.

Efficacy and safety of recombinant human endostatin during peri-radiotherapy period in advanced non-small-cell lung cancer.

Background: This study aimed to retrospectively investigate the efficacy and safety of recombinant human endostatin (Rh-endostatin) combined with radiotherapy in advanced non-small-cell lung cancer (NSCLC). Methods: Patients with unresectable stage III and IV NSCLC who treated with radiotherapy were enrolled. Patients who received Rh-endostatin infusion throughout the whole peri-radiotherapy period formed the Endostar group, and those who received no Rh-endostatin infusion were the control group. Results: The median progression-free survival was 8.0 and 4.4 months (hazard ratio: 0.53; 95% CI: 0.32-0.90; p = 0.019) and median overall survival was 40.0 and 13.1 months (hazard ratio: 0.53; 95% CI: 0.28-0.98; p = 0.045) for the Endostar and control groups, respectively. The Endostar group exhibited a numerically lower rate of radiation pneumonitis relapse, radiation pneumonitis death and pulmonary fibrosis. Conclusion: Rh-endostatin infusion throughout the peri-radiotherapy period enhanced radiosensitivity and showed better survival outcomes and a tendency toward fewer radiation-related pulmonary events in patients with NSCLC.

Recombinant human endostatin (Rh-endostatin/Endostar) combined with chemotherapy has been approved as first-line standard treatment in patients with advanced non-small-cell lung cancer (NSCLC) in China. This study aimed to retrospectively investigate the efficacy and safety of Rh-endostatin combined with radiotherapy in advanced NSCLC. Patients with unresectable stage III and IV NSCLC who treated with radiotherapy were enrolled. Patients who received Rh-endostatin infusion throughout the whole peri-radiotherapy period were the Endostar group, and those receiving no Rh-endostatin infusion were the control group. Results showed that the median progression-free survival was 8.0 and 4.4 months, and median overall survival was 40.0 and 13.1 months, for the Endostar and control groups, respectively. The Endostar group had a lower rate of radiation pneumonitis relapse, radiation pneumonitis death and pulmonary fibrosis. In conclusion, Rh-endostatin infusion throughout the peri-radiotherapy period enhanced radiosensitivity and showed better survival outcomes and a tendency toward fewer radiation-related pulmonary events in patients with NSCLC.

rSEM: System-Entropy-Measure-Guided Routing Algorithm for Industrial Wireless Sensor Networks.

In this paper, a new system entropy measure is used to optimize the routing algorithm in power consumption. We introduce the system entropy measure into the problem of industrial wireless sensor networks (iWSNs) routing and propose a high-performance routing algorithm guided by the system entropy measure (rSEM). Based on the cluster iWSNs architecture, the rSEM selects the cluster heads and cluster member nodes successively, according to the system entropy measure, and constructs the iWSNs with the minimum system entropy. The method of the cluster head selection is traversal, while the method of the cluster member selection is a greedy algorithm to reduce the complexity. The experiments show that the power consumption of the iWSNs generated by the rSEM is in the same order of magnitude as that of Dijkstra in both 2D and 3D scenarios. In addition, the delay of the rSEM is slightly higher than that of LEACH. Therefore, the rSEM is suitable for networks that are sensitive to both the delay and power consumption. The rSEM puts forward a new idea for the design of routing for the next-generation iWSNs, which improves the overall network performance according to the network topology, instead of relying on the power consumption or delay performance only.

Joint Intra/Inter-Slot Code Design for Unsourced Multiple Access in 6G Internet of Things.

Unsourced multiple access (UMA) is the technology for massive, low-power, and uncoordinated Internet-of-Things in the 6G wireless system, improving connectivity and energy efficiency on guaranteed reliability. The multi-user coding scheme design is a critical problem for UMA. This paper proposes a UMA coding scheme based on the T-Fold IRSA (irregular repetition slotted Aloha) paradigm by using joint Intra/inter-slot code design and optimization. Our scheme adopts interleave-division multiple access (IDMA) to enhance the intra-slot coding gain and the low-complexity joint intra/inter-slot SIC (successive interference cancellation) decoder structure to recover multi-user payloads. Based on the error event decomposition and density evolution analysis, we build a joint intra/inter-slot coding parameter optimization algorithm to minimize the SNR (signal-to-noise ratio) requirement at an expected system packet loss rate. Numerical results indicate that the proposed scheme achieves energy efficiency gain by balancing the intra/inter-slot coding gain while maintaining relatively low implementation complexity.

A Multiple-Stimuli-Responsive Amphiphilic Copolymer for Antifouling and Antibacterial Functionality via a "Resistance-Kill-Release" Mechanism.

In recent years, polymers with stimuli-responsive properties have been increasingly reported on due to their diverse applications. However, most of the studies have only focused on the performance of polymers under specific scenarios. The laws of changes in the properties in response to various external stimuli have been less systematically and quantitatively studied. In this paper, we prepared an amphiphilic polymer (PadaMX and PAdaM3QA-X) with temperature-, pH-, ion-, and ß-cyclodextrin (ß-CD)-responsive properties. According to the cloud point tested by the UV-Vis method, the lower critical soluble temperature (LCST) of PAdaM3QA-10% was more sensitive to a change in pH and less sensitive to a change in ions compared with PadaM3 due to quaternized side chains with a stronger intramolecular mutual repulsion. We then fabricated the coatings with responsive properties by immobilizing the adamantyl groups on ß-CD-modified surfaces. The hydrophilicity of the coatings was improved after quaternization, as proven by the water contact angle (WCA) measurement. The antifouling and antibacterial performance was further evaluated via the fluorescence intensity of bovine serum albumin (BSA) adsorbed on the surfaces and the spread plate method. A 78.4% BSA desorption rate and a 96.8% sterilization rate were achieved by the PAdaM3QA-10% coating. In summary, this work prepared a multiple-stimuli-responsive amphiphilic copolymer for antifouling and antibacterial functionality via a "resistance-kill-release" mechanism.

Nitrogen-Doped Graphdiyne as a Robust Electrochemical Biosensing Platform for Ultrasensitive Detection of Environmental Pollutants.

Owing to its unique chemical structure, natural pores, high structure defects, good surface hydrophilicity and biocompatibility, and favorable electrical conductivity, nitrogen-doped graphdiyne (NGDY) has been attracting attention in the application of electrochemical sensing. Taking advantage of these fascinating electrochemical properties, for the first time, two types of electrochemical enzymatic biosensors were fabricated for the respective detection of organophosphorus pesticides (OPs) and phenols based on the immobilization of acetylcholinesterase or tyrosinase with NGDY. Results revealed that the sensitivities of the NGDY-based enzymatic biosensors were almost twice higher than that of the matching biosensor in the absence of NGDY, proving that NGDY plays a vital role in immobilizing the enzymes and improving the performance of the fabricated biosensors. The effects of nitrogen doping on improving the biosensing performance were studied in depth. Graphitic N atoms can enhance the electrical conductivity, while imine N and pyridinic N can help to adsorb and accumulate the substance molecules to the electrode surface, all of which contribute to the significantly improved performance. Furthermore, these two types of biosensors also demonstrated excellent reproducibility, high stability, and good recovery rate in real environmental samples, which showed a valuable way for the rapid detection of OPs and phenols in the environment. With these excellent performances, it is strongly anticipated that NGDY has tremendous potential to be applied to many other biomedical and environmental fields.

Small Amount Makes a Big Difference: Critical (n - 1)d Valence Orbitals of Heavy Alkaline Earth Metals inside Cage Clusters.

Heavy alkaline earth metals (Aes) are usually considered to engage in chemical bonding by donating the two electrons on ns atomic orbitals (AOs). In this work, a series of typical endohedrally doped cage clusters Ae@cage (Ae = Ca, Sr, Ba; cage = C32, C74, C94, B40, Si20, Sn12, Au16) were thoroughly investigated by means of density functional theory calculations. We found that their occupied molecular orbitals have ∼1 to 14% contributions from Ae-(n - 1)d AOs due to electron back-donation from the cage. Though the amount is small, it is hard to ignore: with the d orbitals, all these endohedral clusters exhibit obviously shortened Ae-cage distances, greatly enhanced encapsulation stabilities, changed highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps, and much lowered Ae valences far from ideal +2. Evidently, the valence orbitals of Ca/Sr/Ba in these systems should include both ns and (n - 1)d. By disclosing the critical role of unnoticed metal orbitals, our work provides completely new insights into the cluster field.