Arsenic distribution characteristics and release mechanisms in aquaculture lake sediments.

It is well known that aquaculture can alter the microenvironments of lakes at sediment-water interface (SWI). However, the main mechanisms underlying the effects of aquaculture activities on arsenic (As) transformations are still unclear. In this context, the present study aims to investigate the variations in the sediment As contents in Yangcheng Lake, as well as to assess its chemical transformations, release fluxes, and release mechanisms. The results showed substantial spatial differences in the dissolved As concentrations in the sediment pore water. The As release fluxes at the SWI ranged from 1.32 to 112.09 µg/L, with an average value of 33.68 µg/L. In addition, the highest As fluxes were observed in the aquaculture areas. The transformation of crystalline hydrous Fe oxide-bound As to adsorbed-As in the aquaculture lake sediments increased the ability of As release. The Partial least squares path modeling results demonstrated the great contributions of organic matter (OM) to the As transformations by influencing the sediment microbial communities and Fe/Mn minerals. The changes in the As fractionation and competing adsorption increased the dissolved As concentrations in the 0-10 mm surface sediment. Non-specifically and specifically adsorbed As were the major sources of dissolved As in the sediments. Specifically, microbial reduction of As[V] and dissolution of Fe oxides increased the dissolved As concentrations at the SWI (20 to -20 mm). The results of the current study highlight the positive enhancement effects of aquaculture on As release from sediments.

Non-invasive early detection on esophageal squamous cell carcinoma and precancerous lesions by microbial biomarkers combining epidemiological factors in China.

BACKGROUND: Microbiota may be associated with esophageal squamous cell carcinoma (ESCC) development. However, it is not known the predictive value of microbial biomarkers combining epidemiological factors for the early detection of ESCC and precancerous lesions. METHODS: A total of 449 specimens (esophageal swabs and saliva) were collected from 349 participants with different esophageal statuses in China to explore and validate ESCC-associated microbial biomarkers from genes level to species level by 16S rRNA sequencing, metagenomic sequencing and real-time quantitative polymerase chain reaction. RESULTS: A bacterial biomarker panel including Actinomyces graevenitzii (A.g_1, A.g_2, A.g_3, A.g_4), Fusobacteria nucleatum (F.n_1, F.n_2, F.n_3), Haemophilus haemolyticus (H.h_1), Porphyromonas gingivalis (P.g_1, P.g_2, P.g_3) and Streptococcus australis (S.a_1) was explored by metagenomic sequencing to early detect the participants in Need group (low-grade intraepithelial neoplasia, high-grade intraepithelial neoplasia and ESCC) vs participants without these lesions as the Noneed group. Significant quantitative differences existed for each microbial target in which the detection efficiency rate was higher in saliva than esophageal swab. In saliva, the area under the curve (AUC) based on the microbial biomarkers (A.g_4 ∩ P.g_3 ∩ H.h_1 ∩ S.a_1 ∩ F.n_2) was 0.722 (95% CI 0.621-0.823) in the exploration cohort. Combining epidemiological factors (age, smoking, drinking, intake of high-temperature food and toothache), the AUC improved to 0.869 (95% CI 0.802-0.937) in the exploration cohort, which was validated with AUC of 0.757 (95% CI 0.663-0.852) in the validation cohort. CONCLUSIONS: It is feasible to combine microbial biomarkers in saliva and epidemiological factors to early detect ESCC and precancerous lesions in China.

Spatial pattern of isoniazid-resistant tuberculosis and its associated factors among a population with migrants in China: a retrospective population-based study.

Background: Isoniazid-resistant, rifampicin-susceptible tuberculosis (Hr-TB) globally exhibits a high prevalence and serves as a potential precursor to multidrug-resistant tuberculosis (MDR-TB). Recognizing the spatial distribution of Hr-TB and identifying associated factors can provide strategic entry points for interventions aimed at early detection of Hr-TB and prevention of its progression to MDR-TB. This study aims to analyze spatial patterns and identify socioeconomic, demographic, and healthcare factors associated with Hr-TB in Shanghai at the county level. Method: We conducted a retrospective study utilizing data from TB patients with available Drug Susceptible Test (DST) results in Shanghai from 2010 to 2016. Spatial autocorrelation was explored using Global Moran's I and Getis-Ord Gi∗ statistics. A Bayesian hierarchical model with spatial effects was developed using the INLA package in R software to identify potential factors associated with Hr-TB at the county level. Results: A total of 8,865 TB patients with DST were included in this analysis. Among 758 Hr-TB patients, 622 (82.06%) were new cases without any previous treatment history. The drug-resistant rate of Hr-TB among new TB cases in Shanghai stood at 7.20% (622/8014), while for previously treated cases, the rate was 15.98% (136/851). Hotspot areas of Hr-TB were predominantly situated in southwestern Shanghai. Factors positively associated with Hr-TB included the percentage of older adult individuals (RR = 3.93, 95% Crl:1.93-8.03), the percentage of internal migrants (RR = 1.35, 95% Crl:1.15-1.35), and the number of healthcare institutions per 100 population (RR = 1.17, 95% Crl:1.02-1.34). Conclusion: We observed a spatial heterogeneity of Hr-TB in Shanghai, with hotspots in the Songjiang and Minhang districts. Based on the results of the models, the internal migrant population and older adult individuals in Shanghai may be contributing factors to the emergence of areas with high Hr-TB notification rates. Given these insights, we advocate for targeted interventions, especially in identified high-risk hotspots and high-risk areas.

Corrigendum: Assessing heterogeneity of patient and health system delay among TB in a population with internal migrants in China.

[This corrects the article DOI: 10.3389/fpubh.2024.1354515.].

Assessing heterogeneity of patient and health system delay among TB in a population with internal migrants in China.

Backgrounds: The diagnostic delay of tuberculosis (TB) contributes to further transmission and impedes the implementation of the End TB Strategy. Therefore, we aimed to describe the characteristics of patient delay, health system delay, and total delay among TB patients in Shanghai, identify areas at high risk for delay, and explore the potential factors of long delay at individual and spatial levels. Method: The study included TB patients among migrants and residents in Shanghai between January 2010 and December 2018. Patient and health system delays exceeding 14 days and total delays exceeding 28 days were defined as long delays. Time trends of long delays were evaluated by Joinpoint regression. Multivariable logistic regression analysis was employed to analyze influencing factors of long delays. Spatial analysis of delays was conducted using ArcGIS, and the hierarchical Bayesian spatial model was utilized to explore associated spatial factors. Results: Overall, 61,050 TB patients were notified during the study period. Median patient, health system, and total delays were 12 days (IQR: 3-26), 9 days (IQR: 4-18), and 27 days (IQR: 15-43), respectively. Migrants, females, older adults, symptomatic visits to TB-designated facilities, and pathogen-positive were associated with longer patient delays, while pathogen-negative, active case findings and symptomatic visits to non-TB-designated facilities were associated with long health system delays (LHD). Spatial analysis revealed Chongming Island was a hotspot for patient delay, while western areas of Shanghai, with a high proportion of internal migrants and industrial parks, were at high risk for LHD. The application of rapid molecular diagnostic methods was associated with reduced health system delays. Conclusion: Despite a relatively shorter diagnostic delay of TB than in the other regions in China, there was vital social-demographic and spatial heterogeneity in the occurrence of long delays in Shanghai. While the active case finding and rapid molecular diagnosis reduced the delay, novel targeted interventions are still required to address the challenges of TB diagnosis among both migrants and residents in this urban setting.

The combined effects of lanthanum-modified bentonite and Vallisneria spiralis on phosphorus, dissolved organic matter, and heavy metal(loid)s.

The use of lanthanum-modified bentonite (LMB) combined with Vallisneria spiralis (V∙s) (LMB + V∙s) is a common method for controlling internal phosphorus (P) release from sediments. However, the behaviors of iron (Fe) and manganese (Mn) under LMB + V∙s treatments, as well as the associated coupling effect on P, dissolved organic matter (DOM), and heavy metal(loid)s (HMs), require further investigations. Therefore, we used in this study a microelectrode system and high-resolution dialysis technology (HR-Peeper) to study the combined effects of LMB and V∙s on P, DOM, and HMs through a 66-day incubation experiment. The LMB + V∙s treatment increased the sediment DO concentration, promoting in-situ formations of Fe (III)/Mn (IV) oxyhydroxides, which, in turn, adsorbed P, soluble tungsten (W), DOM, and HMs. The increase in the concentrations of HCl-P, amorphous and poorly crystalline (oxyhydr) oxides-bound W, and oxidizable HMs forms demonstrated the capacity of the LMB + V∙s treatment to transform mobile P, W, and other HMs forms into more stable forms. The significant positive correlations between SRP, soluble W, UV254, and soluble Fe (II)/Mn, and the increased concentrations of the oxidizable HMs forms suggested the crucial role of the Fe/Mn redox in controlling the release of SRP, DOM, and HMs from sediments. The LMB + V∙s treatment resulted in SRP, W, and DOM removal rates of 74.49, 78.58, and 54.78 %, which were higher than those observed in the control group (without LMB and V∙s applications). On the other hand, the single and combined uses of LMB and V·s influenced the relative abundances of the sediment microbial communities without exhibiting effects on microbial diversity. This study demonstrated the key role of combined LMB and V∙s applications in controlling the release of P, W, DOM, and HMs in eutrophic lakes.

High arsenic pollution of the eutrophic Lake Taihu and its relationship with iron, manganese, and dissolved organic matter: High-resolution synchronous analysis.

Arsenic (As) is a metalloid that can accumulate in eutrophic lakes and cause adverse health effects to people worldwide. However, the seasonal process and dynamic mechanism for As mobilization in eutrophic lake remains effectively unknown. Here we innovatively used the planar optodes (PO), high-resolution dialysis (HR-Peeper) combined with fluorescence excitation-emission matrix coupled with parallel factor (EEM-PARAFAC) analysis technologies. We synchronously investigate monthly O2, As, iron (Fe), manganese (Mn), and naturally occurring dissolved organic matter (DOM) changes in sediments of Lake Taihu at high resolution in field conditions. We find high As contamination from sediments with 61.88-327.07 µg m-2 d-1 release As fluxes during the algal bloom seasons from May to October 2021. Our results show that an increase in DOM, mainly for humic-like components, resulting in high electron transfer capacity (ETC), promoted the reductive dissolution of Fe and Mn oxides to release As. Partial least square-path modeling (PLS-PM) and random forest modeling analysis identified that Mn oxide reductive dissolution directly accelerated sediments As contamination, which is the crucial factor. Understanding crucial factor controlling As release is especially essential in areas of eutrophic lakes developing effective strategies to manage As-rich eutrophic lake sediments worldwide.

Transmission of fluoroquinolones resistance among multidrug-resistant tuberculosis in Shanghai, China: a retrospective population-based genomic epidemiology study.

Fluoroquinolones (FQ) are essential for the treatment of multidrug-resistant tuberculosis (MDR-TB). The FQ resistance (FQ-R) rate in MDR-TB in China and its risk factors remain poorly understood. We conducted a retrospective, population-based genomic epidemiology study of MDR-TB patients in Shanghai, China, from 2009 to 2018. A genomic cluster was defined as strains with genetic distances ≤ 12 single nucleotide polymorphisms. The transmitted FQ-R was defined as the same FQ resistance-conferring mutations shared by ≥ 2 strains in a genomic cluster. We used multivariable logistic regression analysis to identify the risk factors for drug resistance. Among the total 850 MDR-TB patients included in the study, 72.8% (619/850) were male, the median age was 39 (interquartile range 28, 55) years, 52.7% (448/850) were migrants, and 34.5% (293/850) were previously treated patients. Most of the MDR-TB strains belong to the Beijing lineage (91.7%, 779/850). Overall, the genotypic resistance rate of FQ was 34.7% (295/850), and 47.1% (139/295) FQ-R patients were in genomic clusters, of which 98 (33.2%, 98/295) were presumed as transmitted FQ-R. Patients with treatment-naïve (aOR = 1.84; 95% CI: 1.09, 3.16), diagnosed in a district-level hospital (aOR = 2.69; 95% CI: 1.56, 4.75), and streptomycin resistance (aOR = 3.69; 95% CI: 1.65, 9.42) were significantly associated with the transmission of FQ-R. In summary, the prevalence of FQ-R among MDR-TB patients was high in Shanghai, and at least one-third were transmitted. Enforced interventions including surveillance of FQ drug susceptibility testing and screening among MDR-TB before initiation of treatment were urgently needed.

Contrasting effects of a traditional material of polyaluminum chloride and an emerging material of lanthanum carbonate capping on sediment internal phosphorus immobilization.

Polyaluminum chloride (PAC) is a traditional material used for immobilizing sediment internal phosphorus (P) in field-scale experiment. Lanthanum carbonate (LC) is an emerging material which have been used in immobilizing sediment internal P in laboratory. To promote LC in practice, the premise is that it does have advantages over traditional material when used. Herein, a 90-day incubation experiment was conducted comparing the effectiveness and mechanism of LC and PAC capping in controlling sediment internal P. The results of isotherm experiment and XPS analysis indicated that the adsorption mechanism of P onto LC and PAC involved ligand exchange and formation of inner-sphere La/Al-O-P complexes. The incubation experiment revealed that PAC capping was more effective in reducing pore water soluble reactive phosphorus (SRP), exhibiting a reduction of up to 81.32 % but showed a decrease trend. However, LC capping resulted in a reduction of pore water SRP up to 52.84 % and maintained stability. On average, LC and PAC capping reduced SRP flux by 0.27 and 0.32 µg·m-2d-1, respectively relative to the control sediment. Moreover, LC capping facilitated the formation of Fe(III)/Mn(IV) oxyhydroxides, leading to an increased P adsorption, whereas PAC capping facilitated the reduction of Fe(III)/Mn(IV) minerals with P release. Additionally, LC capping resulted in the reduction of a higher ratio of mobile P/TP to stable P forms than PAC capping, as compared to the control. In contrast to PAC capping which converted mobile P to stable NaOH-rP, LC capping transformed mobile P and NaOH-rP into more stable HCl-P and ResP. Both LC and PAC capping caused variations in sediment bacterial communities. Nevertheless, PAC capping heightened the risk of Co, Ni, Cu, and Pb releases in sediment compared to LC capping. In summary, this study suggested that LC capping surpassed PAC capping in immobilizing sediment internal P.

Combining lanthanum-modified bentonite and calcium peroxide to enhance phosphorus removal from lake sediments.

Lanthanum-modified bentonite (LMB) and calcium peroxide (CP) are known for their effective removal phosphorus (P) capacities. The present study aims to investigate the effects of the combined use of LMB and CP（LMB + CP）on the sediment P, dissolved organic matter (DOM) and iron (Fe) concentrations through a 90-day incubation experiment. The combined treatment showed strong removal effects on sediment P and DOM. Indeed, the SRP and DOM concentrations in the 0-10 cm sediment layer decreased following the combined application of LMB and CP by 40.67 and 28.95%, respectively, compared to those of the control group (CK). In contrast, the HCl-P in the 0-5 cm sediment layer increased following the combined treatment by 13.28%. In addition, compared with the single application of LMB, the LMB + CP treatment significantly reduced the soluble Fe (Ⅱ) in the sediment pore water and promoted the oxidation of Fe. Therefore, LMB + CP can enhance the removal of internal P from sediments. The DOM removal and Fe oxidation in sediment pore waters are beneficial for enhancing the adsorption of P by LMB. On the other hand, the single and combined applications of LMB and CP increased the richness of the sediment microbial communities while exhibiting slight effects on their diversity. According to the results of this study, the combined use of LMB and oxidizing materials represents a novel method for treating lakes with high internal phosphorus and DOM loads in sediments.

Simultaneous immobilization of sediment internal phosphorus, arsenic and tungsten by lanthanum carbonate capping.

In this study, lanthanum carbonate (LC) was selected as a capping agent to examine its effectiveness in immobilizing sediment internal phosphorus (P), arsenic (As) and tungsten (W). With a 180-day incubation experiment, it was determined that LC capping efficiently reduced the concentrations of soluble reactive P (SRP), soluble As and soluble W in pore water, with the highest reduction rate of 83.39%, 56.21% and 68.52%, respectively. The primary mechanisms involved in the adsorption of P, As and W by LC were precipitation reactions and ligand exchange. Additionally, P, As and W were immobilized by LC capping through the transformation of fractions from mobile and less stable forms to more stable forms. Furthermore, LC capping led to an increase in the Eh value, which promoted the oxidation of soluble Fe (Ⅱ) and soluble Mn. The significantly positive correlation and synchronized variations observed between SRP, soluble As, soluble W, and soluble Fe (II) indicated that the effects of LC on Fe redox played a crucial role in immobilizing sediment internal P, As and W. However, the oxidation of Mn, promoted by LC, played a more significant role in immobilizing sediment internal As than P and W. These effects resulted in LC capping achieving the highest reduction of SRP, soluble As and soluble W flux at 145.22, 22.19, and 0.58 µg m-2d-1. It is of note that LC capping did not lead to an elevated release hazard of Co, Ni, Cu, and Pb, barring Cd. Besides, LC capping did not modify the entire microbial communities in the sediment, but altered the proportional representation of specific microorganisms. Generally, LC has potential as a capping agent capable of simultaneously immobilizing sediment internal P, As and W.

Designing a Hybrid Perovskite with Enlarged Birefringence and Bandgap for Modulation of Light Polarization.

Birefringent crystals have important applications in optoelectronics areas due to their ability to modulate and polarize light. Despite increasing discovery of the birefringence potential of new crystals, it remains a great challenge to optimize both birefringence and bandgap simultaneously. Herein, a 1D chain-like hybrid perovskite birefringent crystal designed by 3D-to-1D dimensional tailoring, (GAM)2 PbI7 ·H2 O (GAM = C5 N10 H10 ), is presented, showing enlarged birefringence of 0.49@550 nm and enlarged optical bandgap (2.48 eV). Consequently, the birefringent quality factor of (GAM)2 PbI7 ·H2 O is up to 2.8 times that of the template MAPbI3 . In particular, the birefringence is much larger than those of commercial birefringent crystals and surpasses that of the vast majority of hybrid perovskite known to date. Theoretical calculations reveal that the strongly anisotropic arrangement of (GAM)2.5+ π-conjugated cations and ordered PbI6 octahedra contributes to the large birefringence and wide bandgap of (GAM)2 PbI7 ·H2 O. It is believed that this work will provide a new pathway toward the rational design and synthesis of hybrid perovskite birefringent crystals for compact wide-bandgap polarization dependent devices.

Degradation of algae promotes the release of arsenic from sediments under high-sulfate conditions.

Sulfate concentrations in eutrophic waters continue to increase; however, the transformations of arsenic (As) in sediments under these conditions are unclear. In this study, we constructed a series of microcosms to investigate the effect of algal degradation on As transformations in sediments with high sulfate concentrations. The results showed that both the elevated sulfate levels and algal degradation enhanced the release of As from sediments to the overlying water, and degradation of algal in the presence of elevated sulfate levels could further contribute to As release. Sulfate competed with arsenate for adsorption in the sediments, leading to As desorption, while algal degradation created a strongly anaerobic environment, leading to the loss of the redox layer in the surface sediments. With high sulfate, algal degradation enhanced sulfate reduction, and sulfur caused the formation of thioarsenates, which may cause re-dissolution of the arsenides, enhancing As mobility by changing the As speciation. The results of sedimentary As speciation analysis indicated that elevated sulfur levels and algal degradation led to a shift of As from Fe2O3/oxyhydroxide-bound state to specifically adsorbed state at the sediment water interface. This study indicated that algal degradation increases the risk of As pollution in sulfate-enriched eutrophic waters.

A systematic review and meta-analysis on the relative and attributable risk of Helicobacter pylori infection and cardia and non-cardia gastric cancer.

INTRODUCTION: This study aimed to update the association between Helicobacter pylori (H. pylori) infection and gastric cancer (GC). METHODS: We searched PubMed, Embase, and Cochrane Library from 1990 to December 2021 to identify prospective studies. Pooled odds ratios (ORs) and 95% confidence intervals (CIs) were summarized to validate the relationship between H. pylori infection and GC. RESULTS: Including 27 studies, findings indicated a strong link between H. pylori and non-cardia gastric cancer (NCGC) in both Europe/North America (OR=5.37, 95%CI:4.39-6.57) and Asia (OR = 2.50, 95%CI:1.89-3.32), and a positive association with cardia gastric cancer (CGC) in Asia (OR = 1.74, 95%CI:1.38-2.19), but an inverse association in European/American populations (OR = 0.64, 95%CI: 0.51 to 0.79). Furthermore, the strength of association was greater in studies that detected H. pylori by immunoblotting versus ELISA, and also in studies testing for H. pylori detection further back in time prior to cancer diagnosis (Ptrend<0.05). Approximately 79% of NCGC in Asia and 87% in Europe/North America, along with 62% of CGC in Asia, could be attributable to H. pylori infection. CONCLUSIONS: The meta-analysis supports the significant attributable risk of H. pylori infection for GC and underscores the potential impact of targeting H. pylori in GC prevention programs. PROSPERO REGISTRATION: CRD42021274120.

A Two-Dimensional Hybrid Perovskite With Heat Switching Birefringence.

Birefringent crystals that can switch light polarization have important applications in optoelectronics. In the last decades, birefringence is mostly optimized by chemical strategies. Recently, switching birefringence by physical means has attracted much attention. Here, this work reports the observation of heat switching birefringence in a 2D layered hybrid halide perovskite (C2 N3 H4 )2 PbCl4 ((C2 N3 H4 )+ =1,2,4-triazolium). This heat switching birefringence leads to a significant change in the interference color for the crystal plate under the illumination of orthogonal polarized light. Structure analyses reveal a heat dependent structure transition in (C2 N3 H4 )2 PbCl4 , whose birefringence is switched by the change in the distortion degree of PbCl6 octahedron. This discovery may be beneficial to the further development of stimuli-responsive polarization optical devices.

Assessing the spatial heterogeneity of tuberculosis in a population with internal migration in China: a retrospective population-based study.

Background: Internal migrants pose a critical threat to eliminating Tuberculosis (TB) in many high-burden countries. Understanding the influential pattern of the internal migrant population in the incidence of tuberculosis is crucial for controlling and preventing the disease. We used epidemiological and spatial data to analyze the spatial distribution of tuberculosis and identify potential risk factors for spatial heterogeneity. Methods: We conducted a population-based, retrospective study and identified all incident bacterially-positive TB cases between January 1st, 2009, and December 31st, 2016, in Shanghai, China. We used Getis-Ord Gi* statistics and spatial relative risk methods to explore spatial heterogeneity and identify regions with spatial clusters of TB cases, and then used logistic regression method to estimate individual-level risk factors for notified migrant TB and spatial clusters. A hierarchical Bayesian spatial model was used to identify the attributable location-specific factors. Results: Overall, 27,383 bacterially-positive tuberculosis patients were notified for analysis, with 42.54% (11,649) of them being migrants. The age-adjusted notification rate of TB among migrants was much higher than among residents. Migrants (aOR, 1.85; 95%CI, 1.65-2.08) and active screening (aOR, 3.13; 95%CI, 2.60-3.77) contributed significantly to the formation of TB high-spatial clusters. With the hierarchical Bayesian modeling, the presence of industrial parks (RR, 1.420; 95%CI, 1.023-1.974) and migrants (RR, 1.121; 95%CI, 1.007-1.247) were the risk factors for increased TB disease at the county level. Conclusion: We identified a significant spatial heterogeneity of tuberculosis in Shanghai, one of the typical megacities with massive migration. Internal migrants play an essential role in the disease burden and the spatial heterogeneity of TB in urban settings. Optimized disease control and prevention strategies, including targeted interventions based on the current epidemiological heterogeneity, warrant further evaluation to fuel the TB eradication process in urban China.

Impacts of calcium peroxide on phosphorus and tungsten releases from sediments.

In this study, CaO2 was used as a capping material to control the release of Phosphate (P) and tungsten (W) from the sediment due to its oxygen-releasing and oxidative properties. The results revealed significant decreases in SRP and soluble W concentrations after the addition of CaO2. The mechanisms of P and W adsorption by CaO2 were mainly chemisorption and ligand exchange mechanisms. In addition, the results showed significant increases in HCl-P and amorphous and poorly crystalline(oxyhydr)oxides bound W after the addition of CaO2. The highest reduction rates of sediment SRP and soluble W release were 37 and 43%, respectively. Furthermore, CaO2 can promote the redox of iron (Fe) and manganese (Mn). On the other hand, a significant positive correlation was observed between SRP/soluble W and soluble Fe (II) and between SRP/soluble W and soluble Mn, indicating that the effects of CaO2 on Fe and Mn redox play a crucial role in controlling P and W releases from sediments. However, the redox of Fe plays a key role in controlling sediment P and W release. Therefore, CaO2 addition can simultaneously inhibit sediment internal P and W release.

A Second-Order Nonlinear Optical Material Consisting of Two π-Conjugated Groups.

This work reports a new second-order nonlinear optical (NLO) material [C(NH2 )3 ]3 C3 N3 S3 (GU3 TMT), consisting of π-conjugated planar (C3 N3 S3 )3- and triangular [C(NH2 )3 ]+ groups. Interestingly, GU3 TMT exhibits a large NLO response (2.0×KH2 PO4 ) and moderate birefringence 0.067 at wavelength 550 nm, even though (C3 N3 S3 )3- and [C(NH2 )3 ]+ do not exhibit the most favorable arrangement in the structure of GU3 TMT. First-principles calculations suggest that NLO properties mainly originate from the highly π-conjugated (C3 N3 S3 )3- rings, and the π-conjugated [C(NH2 )3 ]+ triangles contribute much less to the overall NLO response. This work will inspire new thoughts with in-depth on the role of π-conjugated groups in NLO crystals.

Ba1.09Pb0.91Be2(BO3)2F2: The First Pb-Containing Beryllium Borate Fluoride with Trigonal Prismatic PbO6 and 2D [Be3B3O6F3]∞ Layers.

Ba1.09Pb0.91Be2(BO3)2F2 (BPBBF), a previously unreported lead-containing beryllium borate fluoride, has been successfully grown through a high-temperature flux method. Its structure is solved by single-crystal X-ray diffraction (SC-XRD), and it is optically characterized via infrared, Raman, UV-vis-IR transmission, and polarizing spectra as well. SC-XRD data suggests that it can be indexed by a trigonal unit cell (space group P3m1) with lattice parameters a = 4.7478(6) Å, c = 8.3856(12) Å, Z = 1, and V = 163.70(5) Å. This material could be considered as a derivative of the Sr2Be2B2O7 (SBBO) structural motif. It consists of 2D [Be3B3O6F3]∞ layers in the crystallographic ab plane, with divalent Ba2+ or Pb2+ cations serving as spacers among the adjacent layers. Ba and Pb were found to adopt a disordered arrangement in the trigonal prismatic coordination within the BPBBF structural lattice, which is evidenced by both structural refinements against SC-XRD data and energy dispersive spectroscopy. The UV absorption edge (279.1 nm) and birefringence (Δn = 0.054@ 546.1 nm) of BPBBF are confirmed by UV-vis-IR transmission and polarizing spectra, respectively. The discovery of this previous unreported SBBO-type material, BPBBF, along with other reported analogues such as BaMBe2(BO3)2F2 (M = Ca, Mg, and Cd), provide a prodigious example for tuning the bandgap, birefringence, and short UV absorption edge via simple chemical substitution.