Boosted Second Harmonic Generation of a Chiral Hybrid Lead Halide Resonant to Charge Transfer Exciton from Metal Halide Octahedra to Ligand.

Chiral hybrid organic-inorganic metal halides (HOMHs) offer an ideal platform for the advancement of second-order nonlinear optical (NLO) materials owing to their inherent noncentrosymmetric structures. The enhancement of optical nonlinearity of chiral HOMHs could be achieved by matching the free exciton and/or self-trapped exciton energy levels with desired NLO frequencies. However, the current scarcity of resonance modes and low resonance ratio hamper the further improvements of NLO performance. Herein, we propose a new resonant channel of charge transfer (CT) excited states from metal halide polyhedra to organic ligand to boost the second-order optical nonlinearity of chiral HOMHs. The model lead halide (C7H10N)PbBr3 (C7H10N=1-ethylpyridinium) exhibits a drastically enhanced second harmonic generation in resonance to the deep CT exciton energy, with intensity of up to 111.0 times that of KDP and 10.9 times that of urea. The effective NLO coefficient has been determined to be as high as ~40.2 pm V-1, balanced with a large polarization ratio and high laser damage threshold. This work highlights the contribution of organic ligands in the construction of a resonant channel for enhancing second-order NLO coefficients of metal halides, and thus provides guidelines for designing new chiral HOMHs materials for advanced nonlinear photonic applications.

Induction of Chiral Hybrid Metal Halides from Achiral Building Blocks.

Chiral hybrid organic-inorganic metal halides (HOMHs) with intrinsic noncentrosymmetry have shown great promise for broad applications in chiroptoelectronics, spintronics, and ferroelectronics. However, the construction strategies for chiral HOMHs often involve chiral building blocks in their frameworks, which greatly limit their chemical diversity. Here, we take advantage of a chiral induction approach and have successfully constructed a series of chiral HOMHs, DMA4MX7 (DMA = dimethylammonium, M = Sb or Bi, X = Cl or Br), based on achiral precursors. The resulting chiral products demonstrate a clear enantioenrichment, as confirmed by single-crystal X-ray diffraction analysis and solid-state circular dichroism (CD) spectroscopy. The induction of chiral HOMHs enables superior nonlinear optical performances with very high thermal stability and laser resistance. The successful employment of such a chiral induction approach might facilitate the construction of libraries of chiral HOMH crystals from diverse achiral precursors, in particular those into which it is not easy to introduce intrinsic chiral centers, and would thus pave a new way for rational preparation and application of chiral HOMH materials.

Methylpiperazine based 0D chiral hybrid lead halides for second harmonic generation.

Hybrid organic-inorganic metal halides (HOMHs) have recently attracted broad research interest for their structural tunability and remarkable optoelectronic properties. Among them, chiral HOMHs have demonstrated promising applications in second-order nonlinear optics (NLO) on account of their inherent noncentrosymmetric structures. Herein, we synthesized two new chiral HOMHs, (S-/R-2-C5H14N2)2PbI6, based on S-/R-2-methylpiperazine chiral amines. They feature a band gap close to 2.9 eV with high phase purity as well as environmental and thermal stability. The induction of the chiral optical properties of (S-/R-2-C5H14N2)2PbI6 by chiral organic cations was verified by circular dichroism (CD) spectroscopy. Moreover, the resulted HOMHs materials demonstrate a strong second harmonic generation response with a large laser damage threshold (∼2.97 mJ cm-2), showing promising applications in NLO photonic devices.

Characterizing changes in Maillard reaction indicators in whole milk powder and reconstituted low-temperature pasteurized milk under different preheating conditions.

The chemical properties and quality of milk powder and reconstituted milk can be changed by preheating treatment during milk powder processing. The effect of preheating conditions (low-temperature pasteurization [LT], high-temperature pasteurization [HT], extended shelf-life [ESL], ultra-high-temperature [UHT], and in-container sterilization [CS]), on furosine, furfural compounds, and advanced glycation end products were investigated in milk powders and reconstituted milk. The results revealed that Maillard reaction indicators were affected by preheating intensity; contents of furosine, 5-hydroxymethylfurfural (HMF), 2-furfural, Nε-(carboxymethyl)lysine (CML), and Nε-(carboxyethyl)lysine (CEL) increased, whereas lysine and 5-methyl-furfural (MF) decreased in both milk powder and reconstituted milk with an increase in the intensity of preheating. CML and CEL contents in reconstituted milk increased by 1.7- to 2.4-fold and 1.3- to 1.6-fold, respectibely. The content of CML and CEL in high-preheating powders was 11%-34% and 18%-123% higher than that in LT samples, respectively. Compared with milk powder, furosine was reduced by 22%-55% and MF by 57%-69% in reconstituted milk; HMF increased by 12%-52%, CML and CEL increased 1.7-2.4 times and 1.3-1.6 times, respectively. A superposition effect was observed between preheating intensity and heat process times, which increased the content of Maillard reaction products. PRACTICAL APPLICATION: Our findings revealed the promotion effect of higher preheating conditions on Maillard reaction indicators in milk powder and reconstituted low-temperature pasteurized milk. The results will help reduce some of the harmful Maillard reaction indicators (e.g., advanced glycation end products) formed during heat processing and assist customers in selecting dairy products with low amounts of Maillard reaction products.

Crystallization-induced emission enhancement of highly electron-deficient dicyanomethylene-bridged triarylboranes.

A highly electron-deficient dicyanomethylene-bridged triarylborane, FMesB-TCN, was reported with a low-lying LUMO and crystallization-induced emission enhancement in its block-shape crystal. DFT calculations revealed lower re-organization energy of the block crystal than that of the weakly emissive acicular crystal. This work explored a novel boron-containing skeleton with interesting optical properties.

MicroRNA-124 inhibits hepatic stellate cells inflammatory cytokines secretion by targeting IQGAP1 through NF-κB pathway.

Liver fibrosis is a health concern that leads to organ failure mediated via production of inflammatory cytokines and fibrotic biomarkers. To date, there was no direct approved antifibrotic therapy, and current treatment was mainly the removal of the causative factor. Recent studies demonstrated that aberrant expression of miR-124 was involved in the progression of various liver diseases including hepatocellular carcinoma (HCC). However, whether miR-124 could function as a transcriptional regulator in the inflammatory cytokines secretion of liver fibrosis remains unclear. In this study, we demonstrated that the expression of miR-124 was downregulated in liver fibrosis tissues and TNF-α-induced LX-2 cells, concomitant with the upregulated expression of IQGAP1, suggesting that miR-124 and IQGAP1 might be associated with the development of inflammation in liver fibrosis. Therefore, we demonstrated that the overexpression of miR-124 and knockdown of IQGAP1 could lead to the downregulation of TNF-α, IL-1ß and IL-6. While knockdown of miR-124 or overexpression of IQGAP1 showed reversed results. Moreover, dual luciferase reporter assays demonstrated that miR-124 specifically targeted the 3'-UTR of IQGAP1, and thus inhibited the expression of IQGAP1. Mechanistically, we found that the expression changes of miR-124 and IQGAP1 could be involved in inhibition or activation of NF-κB signaling pathway in response to TNF-α. In conclusion, these results indicated that miR-124 plays a crucial role in TNF-α-induced LX-2 cells via regulating NF-κB signaling pathway.

Profiles of initial, intermediate, and advanced stages of harmful Maillard reaction products in whole-milk powders pre-treated with different heat loads during 18 months of storage.

This study evaluated the chemical changes in five types of whole-milk powders (WMP) with different heating loads during storage. The WMP was preheated using low-heat [low-temperature long-time (LTLT), high-temperature short-time pasteurization (HTST)] and high-heat process [ultra-pasteurization (ESL), ultra-high-temperature (UHT) treatments, and in-bottle sterilization (BS)]. Furosine increased by 2.5-3.0 times in high-heat WMP and 5.7-8.4 times in low-heat WMP during storage. 5-(hydroxymethyl)furfural (HMF) content in high-heat WMP was on average 1.4- to 2.4-fold higher than in low-heat WMP during storage. The increases in the amount of Nε-(carboxymethyl)lysine (CML) and Nε-(carboxyethyl)lysine (CEL) in high-heat WMP were more than that in low-heat WMP (CML, 3.4-4.9 vs 3.1-3.4 times; CEL, 3.4-4.2 vs 2.7-3.0 times). Pyrraline in high-heat WMP increased by 1.8- to 2.1-fold. 2-Furaldehyde, CML, and CEL increased slowly with 12 months of storage and then accelerated. Storage time significantly contributed to more furosine, HMF, CML, and CEL contents in high-heat WMP.

Quantitation of furosine, furfurals, and advanced glycation end products in milk treated with pasteurization and sterilization methods applicable in China.

Pasteurization and sterilization, normally carried out in milk, can induce the Maillard reaction, which can produce substances that are harmful to health. Quantitation of initial, intermediate, and advanced Maillard reaction products in milk was conducted for pasteurization (low-temperature long-time [LTLT], high-temperature short-time [HTST]) and sterilization (ultra-high temperature [UHT], in-bottle sterilization [BS]) methods. Total lysine and lactose decreased by 32.8% and 6.7% in BS milk, respectively. The generation of furosine in sterilized milk and pasteurized milk ranged from 2.5- to 5.0-fold and 1.4- to 2.8-fold higher, respectively, than those in raw milk. 5-(Hydroxymethyl)furfural increased by 4.7- and 8.4-fold in UHT and BS milk, and 2-furaldehyde (F) was not quantified in raw and LTLT milk. The concentrations of Nε-(carboxymethyl)lysine (CML) was nearly 4.4- to 6.7-fold higher than that of Nε-(carboxyethyl)lysine in the heated milk samples. CML in UHT and BS milk were around 1.4-fold and 1.6-fold higher than that in raw milk, respectively. The concentration of these Maillard reaction products in sterilized milk was significantly higher than those in raw, LTLT, and HTST milk. The results of this study could improve safety control in the dairy industry with respect to pasteurization and sterilization procedures.

Hint1 gene deficiency enhances the supraspinal nociceptive sensitivity in mice.

INTRODUCTION: Previous studies have indicated a possible role of histidine triad nucleotide-binding protein 1 (HINT1) on sustaining the regulatory crosstalk of N-methyl-D-aspartate acid glutamate receptors (NMDARs) and G-protein-coupled receptors (GPCRs) such as the µ-opioid receptor (MOR). Both receptors are present in the midbrain periaqueductal gray neurons, an area that plays a central role in the supraspinal antinociceptive process. METHODS: In the present study, a battery of pain-related behavioral experiments was applied to Hint1 knockout, heterozygous and wild-type mice. Both the male and female mice were investigated to assess the differences between genders. RESULTS: Hint1-/- mice presented significant shorter latency at 50°C in both male and female in hot plate test while no significant difference was found in tail filck test. In Von Frey hairs test Hint1-/- mice were more sensitive than Hint1+/+ mice, presenting a lower withdrawal threshold and enhanced relative frequency of paw withdrawal. The average flinches and licking time of Hint1-/- mice were more than that of Hint1+/+ mice in formalin test. CONCLUSION: The absence of Hint1 gene-enhanced supraspinal nociceptive sensitivity in mice, including thermal, mechanical and inflammatory hyperalgesia. Meanwhile, there was no certain evidence indicating the haploinsufficiency and gender differences of Hint1 gene in pain-related behaviors.

Two-stage additional evidence support association of common variants in the HDAC3 with the increasing risk of schizophrenia susceptibility.

Schizophrenia (SCZ) is a complex neuropsychiatric disorder with high heritability. Abnormal gene methylation was found to play a key role in the development of SCZ, suggesting that histone deacetylases (HDACs) may increase the expression of several key genes in the brain. However, recent studies evaluating the association between SCZ and genetic polymorphisms in histone deacetylase 3 (encoded by HDAC3) have shown conflicting results. In this study, we designed a two-stage case-control study to investigate the association of the HDAC3 with SCZ. Fourteen tag single nucleotide polymorphisms (SNPs) entirely covering the region of HDAC3 were analyzed in the testing group of 1,421 patients and 2,823 healthy controls, and the SNP rs14251 was found to be significant (and rs2530223 to be nominally significant). The significant result of rs14251 was successfully replicated in the validation group consisting of 896 cases and 1,815 healthy controls (P = 0.009276, OR = 1.219), and also confirmed by haplotype based analyses (rs976552-rs14251, global P < 0.001). To sum up, our results provide additional evidence that HDAC3 confers the increasing risk of SCZ susceptibility in Han Chinese individuals, suggesting this gene as a potential genetic modifier for SCZ development. © 2016 Wiley Periodicals, Inc.

Polymorphic distribution and forensic effectiveness study of eight miniSTR in Chinese Uyghur ethnic group.

We obtained the allelic frequencies and forensic efficiency data for eight mini short tandem repeat loci including Penta E, D12S391, D6S1043, D2S1338, D19S433, CSF1PO, Penta D and D19S253 loci from a sample of 128 unrelated Uyghur individuals from China. The amplification products of the eight STR loci are <240 bp in size. A total of 94 alleles were observed and the corresponding allelic frequencies ranged from 0.0039 to 0.3438 in the present study. Observed genotype distributions for each locus do not show deviations from Hardy-Weinberg equilibrium expectations. The combined power of discrimination, combined power of exclusion and combined matching probability of the eight STR loci equaled to 0.999999999963373, 0.9997770 and 3.6627 × 10(-11), respectively. Because of the small fragment length of PCR products and the high degree of polymorphisms, the eight STR loci are highly beneficial for the forensic analysis of degraded DNA samples which are commonly observed in forensic cases. The STR data of the Uyghur group were compared with the previously published population STR data of other groups from different ethnic or areas, and significant differences were observed among these groups at some loci.

Silencing Prx1 and/or Prx5 sensitizes human esophageal cancer cells to ionizing radiation and increases apoptosis via intracellular ROS accumulation.

AIM: To investigate whether down-regulation of peroxiredoxin 1 (Prx1) and/or peroxiredoxin 5 (Prx5) sensitizes human esophageal cancer cells to ionizing radiation (IR). METHODS: Human esophageal carcinoma cell lines Eca-109 and TE-1 were used. Prx mRNA expression profiles in Eca-109 and TE-1 cells were determined using RT-PCR. Two highly expressed isoforms of Prxs, Prx1 and Prx5, were silenced by RNA interference (RNAi). Following IR, intracellular reactive oxygen species (ROS) and apoptosis were measured using flow cytometry, the activities of catalase, superoxide dismutase and glutathione peroxidase were measured, and the radiosensitizing effect of RNAi was observed. Tumor xenograft model was also used to examine the radiosensitizing effect of RNAi in vivo. RESULTS: Down-regulation of Prx1 and/or Prx5 by RNAi does not alter the activities of catalase, superoxide dismutase and glutathione peroxidase, but made human tumor cells more sensitive to IR-induced apoptosis both in vitro and in vivo. When the two isoforms were decreased simultaneously, intracellular ROS and apoptosis significantly increased after IR. CONCLUSION: Silencing Prx1 and/or Prx5 by RNAi sensitizes human Eca-109 and TE-1 cells to IR, and the intracellular ROS accumulation may contribute to the radiosensitizing effect of the RNAi.

[The reproductive system impairment of adult male rats induced by cocaine].

OBJECTIVE: To investigate the reproductive system impairment induced by cocaine in adult male rats and the possible underlying mechanism. METHODS: Thirty adult male rats were randomly divided into experimental and control groups, with 15 rats in each group. Rats of the experimental group were injected cocaine hydrochloride (15 mg/kg body weight) subcutaneously daily for four weeks. The weight of body and testis, as well as the level of serum hormone of the rats were examined. In addition, the apoptosis rate of testicular tissue by TUNEL and the expression of Fas gene in testicular tissue were examined by immunohistochemistry. RESULTS: Compared with the control, the weight of testis in the cocaine exposed group decreased significantly (P<0.05), and the serum testosterone level decreased significantly (P<0.05). Moreover, both the apoptosis rate and the expression of Fas gene increased in the testicular tissue of rats in the cocaine exposed group in comparison to the control group (P<0.05). The apoptosis rate was significantly correlated with the expression of Fas gene (r=0.9012, P<0.05). CONCLUSION: Cocaine may cause reproductive system injury in adult male rats, and Fas-mediated apoptosis may be one of the functional mechanisms involved in the reproductive system injuried by cocaine.

[Adverse drug events and its forensic medical identification].

OBJECTIVE: To investigate the basic principles and important rules of forensic identification of adverse drug events and to accumulate basic data and to provide references for forensic identification of similar cases. METHODS: Thirty-three cases of adverse drug events in our forensic identification files were retrospectively reviewed, analyzed, and summarized. RESULTS: There were 27 live and 6 dead victims included in this study. Our study showed a gradually increasing numbers of adverse drug cases in forensic identification year by year with a slight female predominance (20/33 cases, 60.6%). Of the 33 victims, nearly two-thirds (21/33, 63.6%) were due to hospital errors including only one case of drug overdose (1/21, 4.8%), whereas the rest were not related to the hospital errors. Eight cases (8/33, 24.2%) were caused by illegal medical practitioners due to improper use of medication. CONCLUSION: Investigators need to pay more attention to the characteristics and complexities of adverse drug events on a case by case basis encountered in increasing numbers of more and more such forensic identification.

[A debate about mental disability expertise of the disability evaluation criteria of traffic accident injurious].

In recent years, mental disability estimation are more than ever in the practice of forensic psychiatric expertise. The standards about mental disability estimation in the Disability Evaluation Criteria of Traffic Accident Injury are ambiguous and difficult to operate, it cause to different understanding in one case. This article discuss some common questions through 3 aspects in mental disability expertise according to some typical cases, there are the first, we should compare the IQ score before and after injurious in intelligence estimate. The second, the mental disability estimation should be done at least one year after the end of medicine treatment. The third, mental estimate scale should be used in mental disability estimation.