Discovering new nonlinear optical (NLO) materials that require an optimization between multiple properties is a time-consuming and high-cost process. To speed up material development, a ...first-principles high-throughput screening pipeline for nonlinear optical materials (FHSP-NLO) that combines density functional theory (DFT) codes, linear and nonlinear optical property calculation codes, and data transformation and extraction codes has been developed for searching promising NLO materials from crystals collected in the Inorganic Crystal Scientific Structure Database (ICSD). The tests for a dozen of well-known NLO crystals covering deep-ultraviolet (DUV), UV, vis–NIR, and middle/far-infrared (M-F-IR) wavelength ranges verify the high-accuracy of FHSP-NLO. Subsequently, nearly 300 noncentrosymmetric borates are tested with FHSP-NLO. The screened deep-ultraviolet (DUV) NLO crystals are fully consistent with previously reported results. Besides, five crystals, whose NLO properties have not been reported, i.e., B2S2O9, Al4B6O15, HP-Na2B4O7, KB(SO3CI)4, and H3BO3-3T, are identified as new promising NLO materials. Two hydrated borates Ca2B5O9·H(OH)2 and Ca(B8O11(OH)4), whose second-harmonic generation (SHG) responses are primarily measured, are screened out and suggested to grow large-size crystals for further evaluation. FHSP-NLO provides a powerful and efficient tool to screen and reduce the total number of experiments necessary for searching NLO materials from reported crystals.
To overcome the low efficiency of overall water splitting, highly effective and stable catalysts are in urgent need, especially for the anode oxygen evolution reaction (OER). In this case, nickel ...selenides appear as good candidates to catalyze OER and other substitutable anodic reactions due to their high electronic conductivity and easily tunable electronic structure to meet the optimized adsorption ability. Herein, an interesting phase transition from the hexagonal phase of NiSe (H‐NiSe) to the rhombohedral phase of NiSe (R‐NiSe) induced by the doping of cobalt atoms is reported. The five‐coordinated R‐NiSe is found to grow adjacent to the six‐coordinated H‐NiSe, resulting in the formation of the H‐NiSe/R‐NiSe heterostructure. Further characterizations and calculations prove the reduced splitting energy for R‐NiSe and thus the less occupancy in the t2g orbits, which can facilitate the electron transfer process. As a result, the Co2‐NiSe/NF shows a satisfying catalytic performance toward OER, hydrogen evolution reaction, and (hybrid) overall water splitting. This work proves that trace amounts of Co doping can induce the phase transition from H‐NiSe to R‐NiSe. The formation of less‐coordinated species can reduce the t2g occupancy and thus enhance the catalytic performance, which might guide rational material design.
Trace amounts of cobalt atoms doping can trigger the phase transition from six‐coordinated hexagonal‐NiSe to five‐coordinated rhombohedral‐NiSe. Accordingly, the splitting energy of the 3d orbits is reduced, and additional electron channels can form in the emptier t2g orbits of rhombohedral‐NiSe. As a result, the phase‐transited catalyst shows an enhanced catalytic performance, which is evidenced to originate from the unique electronic structure of five‐coordinated rhombohedral‐NiSe.
Spin engineering is a promising way to modulate the interaction between the metal d‐orbital and the intermediates and thus enhance the catalytic kinetics. Herein, an innovative strategy is reported ...to modulate the spin state of Co by regulating its coordinating environment. o‐c‐CoSe2‐Ni is prepared as pre‐catalyst, then in situ electrochemical impedance spectroscopy (EIS) and in situ Raman spectroscopy are employed to prove phase transition, and CoOOH/Co3O4 is formed on the surface as active sites. In hybrid water electrolysis, the voltage has a negative shift, and in zinc–ethanol–air battery, the charging voltage is lowered and the cycling stability is greatly increased. Coordinated atom substitution and crystalline symmetry change are combined to regulate the absorption ability of reaction intermediates with balanced optimal adsorption. Coordinated atom substitution weakens the adsorption while the crystalline symmetry change strengthens the adsorption. Importantly, the tetrahedral sites are introduced by Ni doping which enables the co‐existence of four‐coordinated sites and six‐coordination sites in o‐c‐CoSe2‐Ni. The dz2 + dx2‐y2 orbital occupancy decreases after the atomic substitution, while increases after replacing the CoSe6‐Oh field with CoSe6‐Oh/CoSe4‐Td. This work explores a new direction for the preparation of efficient catalysts for water electrolysis and innovative zinc–ethanol–air battery.
In this work, the coordinating environment (coordinated atoms substitution and crystalline symmetry change) of the o‐c‐CoSe2‐Ni is successfully regulated to optimize its dz2 + dx2‐y2 orbital occupancy. Additionally, the transformation of the ligand field caused by the reconstruction further modulates the spin configuration of the catalyst and the moderate dz2 + dx2‐y2 orbital occupancy enhances the ethanol oxidiation.
Background
Nasopharyngeal carcinoma (NPC) is a common type of head and neck cancer in Asia. Adverse effects occur in over 90% of NPC patients treated with radiotherapy or chemoradiation. Angiotensin ...II receptor blockers (ARBs) are commonly used to treat hypertension without serious adverse effects. However, the anticancer activity of ARBs in NPC remains unclear.
Methods
We investigated the survival impacts of ARBs among NPC patients in a retrospective study. The anticancer effects and related signaling pathways of the ARBs valsartan and losartan were also evaluated in vitro and in vivo.
Result
A total of 927 patients with NPC who had hypertension were enrolled in the study, 272 (29.3%) of whom received ARBs. Kaplan‐Meier analysis revealed that patients who used ARBs had higher rates of 5‐year overall survival (OS; 87.8% vs 75.1%; P = .002) and disease‐specific survival (DSS; 95.4% vs 77.7%; P < .001) than those who did not receive this treatment. Additionally, ARBs inhibited cell proliferation and induced apoptosis by increasing levels of cleaved caspase‐3, cleaved caspase‐9, and cytochrome C; the cell population in the sub‐G1 phase; and caspase‐3 activity in NPC‐TW01 cells. ARBs inhibited tumor growth and angiogenesis via apoptosis in an NPC xenografts model. Interestingly, ARBs inhibited phosphorylation of PI3K/AKT signaling in vitro and in vivo, which is markedly attributed to their antitumor effects in NPC.
Conclusion
These data indicate that ARBs not only improve 5‐year OS and DSS among patients with NPC but also exert antiproliferative and antiangiogenesis effects by inducing apoptosis in NPC, supporting that ARBs may be promising agents for treatment of NPC.
Use of angiotensin II receptor blockers (ARBs) is associated with improved survival in patients who have nasopharyngeal carcinoma (NPC). The ARBs valsartan and losartan suppress tumor growth and angiogenesis in NPC xenografts.
Preparing MoS2‐based materials with reasonable structure and catalytic activity to enhance the sluggish kinetics of lithium polysulfides (LiPSs) conversion is of great significance for Li–S batteries ...(LSBs) but still remain a challenge. Hence, hollow nanotubes composed of N‐doped ultrathin MoS2 nanosheets (N‐MoS2 NHTs) are fabricated as efficient S hosts for LSBs by using CdS nanorods as a sacrifice template. Characterization and theoretical results show that the template effectively inhibits the excessive growth of MoS2 sheets, and N doping expands the interlayer spacing and modulates the electronic structure, thus accelerating the mass/electron transfer and enhancing the LiPSs adsorption and transformation. Benefiting from the merits, the N‐MoS2 NHTs@S cathode exhibits an excellent initial capacity of 887.8 mAh g−1 and stable cycling performances with capacity fading of only 0.0436% per cycle at 1.0 C (500 cycles). Moreover, even at high S loading that of 7.5 mg cm−2, the N‐MoS2 NHTs@S cathode also presents initial excellent areal capacity of 7.80 mAh cm−2 at 0.2 C. This study offers feasible guidance for designing advanced MoS2‐based cathode materials in LSBs.
Preparing MoS2‐based materials with reasonable structure and catalytic activity to enhance the lithium polysulfides conversion is significant for Li–S batteries (LSBs) but still faces challenges. Hence, hollow nanotubes composing N‐doped MoS2 nanosheets (N‐MoS2 NHTs) are fabricated as cathode for LSBs by using CdS nanorods as a sacrifice template, and the batteries with the N‐MoS2 NHTs cathode show excellent performance.
The efficacy and safety of maternal tenofovir disoproxil fumarate (TDF) in reducing mother‐to‐infant hepatitis B virus (HBV) transmissions is not clearly understood. We conducted a prospective, ...multicenter trial and enrolled 118 hepatitis B surface antigen (HBsAg)– and hepatitis B e antigen–positive pregnant women with HBV DNA ≥7.5 log10 IU/mL. The mothers received no medication (control group, n = 56, HBV DNA 8.22 ± 0.39 log10 IU/mL) or TDF 300 mg daily (TDF group, n = 62, HBV DNA 8.18 ± 0.47 log10 IU/mL) from 30‐32 weeks of gestation until 1 month postpartum. Primary outcome was infant HBsAg at 6 months old. At delivery, the TDF group had lower maternal HBV DNA levels (4.29 ± 0.93 versus 8.10 ± 0.56 log10 IU/mL, P < 0.0001). Of the 121/123 newborns, the TDF group had lower rates of HBV DNA positivity at birth (6.15% versus 31.48%, P = 0.0003) and HBsAg positivity at 6 months old (1.54% versus 10.71%, P = 0.0481). Multivariate analysis revealed that the TDF group had lower risk (odds ratio = 0.10, P = 0.0434) and amniocentesis was associated with higher risk (odds ratio 6.82, P = 0.0220) of infant HBsAg positivity. The TDF group had less incidence of maternal alanine aminotransferase (ALT) levels above two times the upper limit of normal for ≥3 months (3.23% versus 14.29%, P = 0.0455), a lesser extent of postpartum elevations of ALT (P = 0.007), and a lower rate of ALT over five times the upper limit of normal (1.64% versus 14.29%, P = 0.0135) at 2 months postpartum. Maternal creatinine and creatinine kinase levels, rates of congenital anomaly, premature birth, and growth parameters in infants were comparable in both groups. At 12 months, one TDF‐group child newly developed HBsAg positivity, presumably due to postnatal infection and inefficient humoral responses to vaccines. Conclusions: Treatment with TDF for highly viremic mothers decreased infant HBV DNA at birth and infant HBsAg positivity at 6 months and ameliorated maternal ALT elevations. (Hepatology 2015;62:375–386
SnO2@CMK‐8 composite, a highly promising anode for Na‐ion batteries (NIBs), was incorporated with polyvinylidene difluoride (PVDF), sodium carboxymethylcellulose (NaCMC), sodium polyacrylate (NaPAA), ...and NaCMC/NaPAA mixed binders to optimize the electrode sodiation/desodiation properties. Synergistic effects between NaCMC and NaPAA led to the formation of an effective protective film on the electrode. This coating layer not only increased the charge–discharge Coulombic efficiency, suppressing the accumulation of solid–electrolyte interphases, but also kept the SnO2 nanoparticles in the CMK‐8 matrix, preventing the agglomeration and removal of oxide upon cycling. The adhesion strength and stability towards the electrolyte of the binders were evaluated. In addition, the charge–transfer resistance and apparent Na+ diffusion of the SnO2@CMK‐8 electrodes with various binders were examined and post‐mortem analyses were conducted. With NaCMC/NaPAA binder, exceptional electrode capacities of 850 and 425 mAh g−1 were obtained at charge–discharge rates of 20 and 2000 mA g−1, respectively. After 300 cycles, 90 % capacity retention was achieved. The thermal reactivity of the sodiated electrodes was studied by using differential scanning calorimetry. The binder effects on NIB safety, in terms of thermal runaway, are discussed.
Binders, keepers: Binder selection is crucial for the sodiation/desodiation kinetics, cycling stability, SEI growth, and thermochemical stability of composite anodes in Na‐ion batteries. A sodium carboxymethylcellulose/sodium polyacrylate mixed binder was used to obtain exceptional electrode capacities of 850 and 425 mAh g−1 at charge–discharge rates of 20 and 2000 mA g−1, respectively, and 90 % capacity retention was achieved after 300 cycles.
Oxonitridosilicates, in which O atoms in SiO
4
are partially substituted by N atoms, are proposed to improve optical anisotropies of silicates as UV NLO materials. The optical properties calculation ...showed that the heteroleptic SiO
x
N
4−
x
(
x
= 1-3) tetrahedra have strong polarizability anisotropy and large hyperpolarizability. Accordingly, nine noncentrosymmetric (NCS) oxonitridosilicate crystals collected in the inorganic crystal structural database (ICSD) are evaluated by using the first principles method. Finally, Si
2
N
2
O and LiSiON are screened out owing to wide band gaps (6.49 and 6.95 eV), large birefringences (0.102 and 0.060 at 1064 nm), and large SHG coefficients (3.3 and 2.2 times that of
d
36
(KDP)). More importantly, the cation selection and structural characteristics that are beneficial for enhancing the band gap and birefringence are identified. This study provides a novel strategy to design and find UV NLO crystals.
Oxonitridosilicates are proposed to improve optical anisotropies of silicates as ultraviolet nonlinear optical materials by using the first principles method.
Owing to wide infrared (IR) transparency ranges, high laser damage thresholds, and being easy to grow in open air, germanates are emerging as promising mid-infrared (mid-IR) nonlinear optical (NLO) ...materials. However, the germanates as NLO materials have not been investigated comprehensively and the crystals with large second harmonic generation (SHG) response have not been identified. Herein, we used the first-principles high-throughput screening pipeline for NLO materials to search for excellent NLO crystals from germanates collected in the inorganic crystal structure database. After two steps of screening, three crystals are picked out from 128 structures based on their predicted energy gaps, birefringences, and SHG coefficients. Subsequently, the three germanates are synthesized and measured. The results show that Pb3Ga2Ge4O14 and Ba2TiGe2O8 exhibit a wide energy gap (>3.1 eV) and a strong phase-matchable SHG intensity that are comparable to the benchmark AgGaS2 (0.8 and 1.2 × AgGaS2, respectively). In addition, the statistical analyses of different categories classified according to their cations show that the d0-transition metal and lone pair cations are more conducive to achieving a larger SHG response and birefringence compared to other cations in germanates. It gives a guideline for exploring new mid-IR NLO materials.
Multiple triggered‐release strategies are widely utilized to control the release of caged target molecules. Among them, photocages with conditional triggers provide extra layers of control in ...photorelease. In this work, a series of pH‐responsive photocages was designed that could be triggered under irradiation and specific intracellular pH values. pH‐sensitive phenolic groups were conjugated with o‐nitrobenzyl (oNB) to form azo‐phenolic NPX photocages with tunable pKa. These azo‐phenol‐based oNB photocages showed differentiable photoreleasing profiles at pH 5.0, 7.2 and 9.0. By attaching fluorogenic cargos, it was shown that one of the photocages, NPdiCl, could be used to differentiate between acidic pH 5.0 and neutral pH 7.2 in cells under artificial pH conditions. Finally, NPdiCl was identified as a promising pH‐responsive photocage for photoreleasing cargo inside acidic tumor cells.
pH‐sensitive phenolic groups can be attached to the o‐nitrobenzyl (oNB) group to form azo‐phenolic NPX photocages with tunable pKa. One of the photocages in this study, NPdiCl, is identified as a promising pH‐responsive photocage for photoreleasing cargo inside acidic tumor cells.