Protein language models-assisted optimization of a uracil-N-glycosylase variant enables programmable T-to-G and T-to-C base editing.

Current base editors (BEs) use DNA deaminases, including cytidine deaminase in cytidine BE (CBE) or adenine deaminase in adenine BE (ABE), to facilitate transition nucleotide substitutions. Combining CBE or ABE with glycosylase enzymes can induce limited transversion mutations. Nonetheless, a critical demand remains for BEs capable of generating alternative mutation types, such as T>G corrections. In this study, we leveraged pre-trained protein language models to optimize a uracil-N-glycosylase (UNG) variant with altered specificity for thymines (eTDG). Notably, after two rounds of testing fewer than 50 top-ranking variants, more than 50% exhibited over 1.5-fold enhancement in enzymatic activities. When eTDG was fused with nCas9, it induced programmable T-to-S (G/C) substitutions and corrected db/db diabetic mutation in mice (up to 55%). Our findings not only establish orthogonal strategies for developing novel BEs but also demonstrate the capacities of protein language models for optimizing enzymes without extensive task-specific training data.

A Novel Fluorescence Probe Based on Azamonardine for Detecting and Imaging Cysteine in Cells and Zebrafish with High Selectivity and Sensitivity.

A novel fluorescent probe based on azamonardine (Aza) fluorophore was designed and synthesized for the highly selective detection of cysteine (Cys) in vivo and in vitro. After reacting with acryloyl chloride, the fluorescence of Aza is effectively quenched, resulting in the formation of the Aza-acryl probe. Upon the addition of Cys, the ester bond of Aza-acryl is cleaved, releasing a new compound (Compound 1) with strong fluorescence, thereby achieving fluorescence turn-on detection of Cys. The structure of Aza-acryl was characterized using X-ray crystallography and NMR spectroscopy. Additionally, density functional theory was employed to elucidate the quenching mechanism of the acyl group on the Aza. Aza-acryl exhibits high selectivity towards Cys and distinguishes it from other biothiols such as homocysteine (Hcy) and glutathione (GSH). The mechanism of Aza-acryl for detecting Cys was investigated through HPLC, NMR spectroscopy, high-resolution mass spectrometry, and reaction kinetics experiments. Aza-acryl demonstrates excellent imaging capabilities for Cys in cells and zebrafish, providing a reliable and selectable tool for the detection and imaging of Cys in biological systems.

Rational design of a novel acryl-modified CQDs fluorescent probe for highly selective detection and imaging of cysteine in vitro and in vivo.

A novel fluorescent nanoprobe CQDs-O-Acryl has been designed and synthesized to directly and accurately identify Cys over other biothiols in PBS (10 mM, pH 7.4) buffer. The carbon quantum dots (CQDs-OH) (λex/em maxima = 495/525 nm) were fabricated by a solvothermal method using resorcinol as the carbon source. The CQDs-O-Acryl was achieved through covalently grafting the acryloyl group on the surface of carbon quantum dots by nuclear reaction based on static quenching. The structure and morphology of CQDs-OH and CQDs-O-Acryl have been characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and UV-vis absorption spectroscopy. Upon the addition of Cys, the ester bond of CQDs-O-Acryl has been broken, and the free CQDs were released by conjugated addition and cyclization reactions successively, emitting strong green fluorescence at 525 nm (λex = 495 nm). Under the optimized conditions, CQDs-O-Acryl exhibited good sensing of Cys within the range 0.095-16 µM (the LOD of 0.095 µM). Due to the high sensitivity, reliability, fast fluorescence response (10 min), and low toxicity of CQDs-O-Acryl, it was successfully applied to fluorescence imaging of Cys in A549 cells and zebrafish.

Primary lacrimal sac lymphoma: a case-based retrospective study in a Chinese population.

AIM: To determine the clinical characteristics, pathological types, tumor markers, treatments, and outcomes of Chinese patients with primary lacrimal sac lymphoma. METHODS: This case-based retrospective study analyzed 15 Chinese patients with primary lacrimal sac lymphoma. The clinical data collected included gender, age at diagnosis, symptoms, imaging examination results, pathologic diagnosis, pathogen identification, tumor markers, treatments, follow-up, and prognosis. Descriptive statistics were used to characterize the patients. Progression-free survival (PFS) was defined as the time from surgery to the last follow-up, first record of tumor recurrence, or death. RESULTS: There were 7 males and 8 females with unilateral primary lacrimal sac lymphoma in the left eye (n=6) or right eye (n=9). The initial symptom in 13 patients was epiphora, and 2 patients had redness and swelling in the lacrimal sac area. All patients ultimately developed epiphora, and 12 had masses in the lacrimal sac area. Analysis of preoperative plasma tumor markers indicated 14 patients had elevated homocysteine, 9 had elevated ß2-microglobulin, and 2 had elevated lactate dehydrogenase (LDH); 2 patients had elevations of all three markers, and 1 patient had no elevation of any marker. All patients underwent surgical resection and 12 patients received postoperative chemotherapy. The pathological types were DLBCL (n=8), MALT lymphoma (n=5), and NK/T-cell lymphoma, nasal type (n=2). The mean follow-up time was 25.8mo (range: 4-41) and 2 patients died. Seven patients who underwent mass excision combined with dacryocystorhinostomy (DCR) had no postoperative epiphora. Eight patients who only underwent mass excision had varying degrees of postoperative epiphora. Preoperative LDH elevation and NK/T-cell lymphoma, nasal type were associated with poor prognoses. CONCLUSION: Early diagnosis and treatment can lead to a good prognosis for most patients with primary lacrimal sac lymphoma. Mass resection combined with DCR can reduce the occurrence of post-surgical epiphora. The pathology type and tumor marker status are associated with prognosis.

Identification of a novel mutation in the FGF10 gene in a Chinese family with obvious congenital lacrimal duct dysplasia in lacrimo-auriculo-dento-digital syndrome.

AIM: To identify the pathogenic gene variant in a family with lacrimo-auriculo-dento-digital syndrome [LADD (MIM 149730)] showing congenital lacrimal duct dysplasia as the main clinical manifestation and lay the foundation for future research on the pathogenic gene. METHODS: Ophthalmological examinations, including slit-lamp biomicroscopy and lacrimal duct probing, and computed tomography dacryocystography (CT-DCG) were performed for all participants. The family pedigree was drawn, genetic features were analyzed, and the genomic DNA of the subjects was extracted. Pathogenic genes were screened via whole exome sequencing (WES) and confirmed using Sanger sequencing. RESULTS: Six patients belonged to this three-generation family, and their clinical manifestations included congenital nasolacrimal duct obstruction, congenital absence of lacrimal puncta and canaliculi, lacrimal fistulae, and limb deformities. This pattern indicates autosomal dominant inheritance. Diagnosis was based on the clinical characteristics of LADD syndrome, which presented in all the patients in this family. A novel frameshift mutation in the FGF10 gene (NM_004465.1), c.234dupC (p.Trp79Leus*15), was identified in all patients via WES. The variant was confirmed by Sanger sequencing and classified as a "pathogenic mutation" according to the American College of Medical Genetics and Genomics (ACMG) variant interpretation guidelines. CONCLUSION: A novel frameshift mutation in the FGF10 gene is found in all patients. This finding helps this family with LADD syndrome receiving a more accurate clinical diagnosis and genetic counseling by extending the mutation range of the FGF10 gene.

Baicalin prevents fibrosis of human trabecular meshwork cells via inhibiting the MyD88/NF-κB pathway.

Trabecular meshwork fibrosis contributes to increased aqueous humor outflow resistance, leading to elevated intraocular pressure in primary open-angle glaucoma. Baicalin, an extract from Scutellaria baicalensis Georgi, has shown anti-fibrotic effects in liver, lung, and kidney diseases. However, its anti-fibrotic effect on human trabecular meshwork (HTM) cells has not yet been clarified. In this study, we investigated its effects on TGF-ß2-induced HTM fibrosis as well as the underlying regulatory mechanisms. HTM cells were pretreated with baicalin, TAK-242, and baicalin + TAK-242 for 2 h followed by treatment with or without 5 ng/mL TGF-ß2 for 48 h. Cell viability was assayed using cell counting Kit-8 and fibronectin (FN), laminin (LN), and α-smooth muscle actin (α-SMA) were assessed by western blotting, reverse transcription-polymerase chain reaction (RT-PCR), and immunocytochemistry. Further, the protein and gene expression levels of the TLR4/MyD88/NF-κB pathway (TLR4, MyD88, and NF-κB p65) were also examined by western blotting and RT-PCR, respectively. Thus, we observed that high doses of baicalin (40 µM) decreased (p < 0.1) HTM cell viability and 20 µM baicalin pretreatment was identified as the optimum pretreatment concentration. TGF-ß2 upregulated (p < 0.5) the expression of FN, LN, α-SMA, MyD88, NF-κB p65 proteins and mRNA in HTM cells, and these effects were inhibited by baicalin and TAK-242 (p < 0.5). However, western blot analysis showed that baicalin did not repress TLR4 expression in HTM cells. Therefore, our findings suggested that baicalin could prevent TGF-ß2-induced extracellular matrix (FN, LN) deposition and α-SMA expression in HTM cells by inhibiting the MyD88/NF-κB pathway.

One-step microwave synthesis of red-emissive carbon dots for cell imaging in extreme acidity and light emitting diodes.

Red emissive carbon dots (R-CDs) have received great attention in biological fields due to their deep tissue penetrability, great bioimaging capability, low interference from auto-fluorescence, and potential for optoelectronic applications. Herein, excitation-independent, highly acid-sensitive R-CDs were successfully obtained via one-step microwave treatment of o-phenylenediamine (o-PD) and phosphoric acid and carefully purified by column chromatography. The relationship between the fluorescence emission and surface groups of the R-CDs was studied in detail using XPS, NMR, and fluorescence spectroscopy, and the different mechanisms of action of the R-CDs and acid in H2O and ethanol were determined. The excellent anti-interference ability and biocompatibility of the R-CDs were confirmed, and the probes were successfully used for imaging A549 and Escherichia coli (E. coli) cells in extreme acidity. Finally, based on their relatively high quantum yield and long wavelength emission, the application potential of the R-CDs in the fabrication of red light-emitting diodes (LEDs) was investigated.

A red-emitting Europium(III) complex as a luminescent probe with large Stokes shift for the sequential determination of Cu2+ and biothiols in real samples.

In this work, a novel Eu3+-DTPA-bis(AMC) complex with red luminescence was designed and synthesized for sequential detection of Cu2+ and biothiols (Cys/Hcy/GSH) based on the displacement strategy with the good selectivity, high sensitivity, and large Stokes shift (288 nm). The possible detection mechanism was verified by UV-vis, the high-resolution mass spectrometry, and the fluorescence decay curve. The experimental parameters, including the solution pH, the incubation time, the concentration ratio of Eu3+-DTPA-bis(AMC) to Cu2+ and biothiols concentration, were optimized. Under the optimal conditions, it shows a good linear relationship between the concentration (0-10 µM) of Cu2+ and the fluorescence intensity of Eu3+-DTPA-bis(AMC), with a low detection limit of 0.065 µM. The linear range and the limit of detection of the Eu3+-DTPA-bis(AMC)/Cu2+ system for Cys/Hcy/GSH were 2.5-22.5/5-45/5-50 µM and 0.11/0.07/0.05 µM, respectively. Surprisingly, the high or low concentration of Eu3+-DTPA-bis(AMC)/Cu2+ can significantly affect the selectivity of the sensing system to biothiols (Cys/GSH/Hcy). When the concentration of the Eu3+-DTPA-bis(AMC)/Cu2+ system is 10.0 µΜ, it could recognize biothiols (Cys/GSH/Hcy) from other substances, but when the concentration is as low as 3.3 µM, it could further specifically distinguished Cys from Hcy/GSH. Owing to the high anti-interference characteristics, accuracy and specificity, the sensing system was well applied to the cascade detection of Cu2+ in actual environmental samples and Cys in biological and food samples, including FBS, urine, milk, beverage, fresh juice with the satisfactory recoveries from 96.20 to 106.80 %.

Chinese Herbal Medicine Adjusting Brain Microenvironment via Mediating Central Nervous System Lymphatic Drainage in Alzheimer's Disease.

Due to its complex pathogenesis and lack of effective therapeutic methods, Alzheimer's disease (AD) has become a severe public health problem worldwide. Recent studies have discovered the function of central nervous system lymphatic drainage, which provides a new strategy for the treatment of AD. Chinese herbal medicine (CHM) has been considered as a cure for AD for hundreds of years in China, and its effect on scavenging ß-amyloid protein in the brain of AD patients has been confirmed. In this review, the mechanism of central nervous system lymphatic drainage and the regulatory functions of CHM on correlation factors were briefly summarized. The advances in our understanding regarding the treatment of AD via regulating the central lymphatic system with CHM will promote the clinical application of CHM in AD patients and the discovery of new therapeutic drugs.

CdS quantum dots-decorated InOOH: Facile synthesis and excellent photocatalytic activity under visible light.

For the first time, CdS quantum dots (QDs)-decorated InOOH (CdS-In for short) was synthesized by a facile photodeposition method. The experiment results showed that CdS-In samples exhibited excellent activity and stability towards photocatalytic reduction of nitro aromatics. The conversion ratio of 4-nitroaniline (4-NA) over CdS-In sample that was prepared with photodeposition time of 120 min (CdS-In-120) reached up to 99.4% under visible light irradiation for 40 min, which was even higher than that achieved over commercial CdS (86.2%). Besides the significant enhancement of visible light absorption, quantum sized CdS were decorated evenly on the surface of InOOH, which was very beneficial for the high activity. Furthermore, the heterogeneous junction formed at the interface of CdS QDs and InOOH can significantly increase the separation efficiency of photogenerated charge carriers. Active species control experiment and electron spin resonance (ESR) technique have proved that photogenerated electrons are the main active species towards photocatalytic reduction of nitro aromatics. It is anticipated that our study would offer meaningful insights for exploring novel InOOH-based visible light photocatalysts towards efficient reduction of nitro aromatics.

Poria cocos polysaccharide attenuates damage of nervus in Alzheimer's disease rat model induced by D-galactose and aluminum trichloride.

Poria cocos polysaccharide (PCP) is a compound from Poria cocos, and which is used as a classical tonic agent. This article aims to investigate the effects of PCP on neuronal damage of hippocampus and cognitive function in a rat model of Alzheimer's disease induced by D-galactose and aluminum trichloride. Oxiracetam (ORC) was used as a positive drug in this experiment. The rats were treated with PCP at doses of 100, 200 and 300 mg/kg/day for 30 days and ORC at dose of 346 mg/kg/day after modeling. The results of behavioral test showed that PCP could prevent cognitive decline in Alzheimer's disease rats as assessed by Y-maze test and Morris water maze test. Results of hippocampus slices showed that neurons were integrated and regularly arranged in the groups, which were administered along with PCP. Moreover, PCP could reduce neuronal apoptosis in hippocampus of Alzheimer's disease rats. Furthermore, the activities of superoxide dismutase in the hippocampus were elevated by PCP administration, while acetyl cholinesterase, reactive oxygen, malondialdehyde and inflammatory factors levels were reduced. In addition, we found PCP could attenuate MAPK/NF-κB signal pathway in the hippocampus. All results illustrated that PCP could exert neuroprotective effects at least partly through alleviating oxidative stress, apoptosis, inflammation and inhibiting the MAPK/NF-κB pathway in Alzheimer's disease rats induced by D-galactose and aluminum trichloride.

Photothermometric analysis of bismuth ions using aggregation-induced nanozyme system with a target-triggered surface cleaning effect.

The development of nanozyme-based photothermometric sensing for point-of-care testing (POCT) heavy metal ions is of great significance for disease diagnosis and health management. Considering the low catalytic activity of most nanozymes at physiological pH, we found bismuth ions (Bi3+) could effectively enhance the peroxidase (POX)-like activity of cetyltrimethylammonium bromide and citrate-capped octahedral gold nanoparticle (CTAB/Cit-AuNP) nanozymes. It is mainly based on Bi3+ ions being able to trigger the surface cleaning effect of CTAB/Cit-AuNPs. Because the more active Bi3+ ions could effectively bind with citrate on the gold surface and competitively destroy the electrostatic interaction between citrate and CTAB, resulting in the removal of CTAB ligands from the gold surface. Without the ligand protection, CTAB/Cit-AuNPs aggregated immediately, and further resulted in a significant activation of the POX-like activity of AuNP nanozymes. Based on this principle, we introduced the enzyme substrate 3,3',5,5'-tetramethylbenzidine (TMB) into this aggregation-induced nanozyme system, and rationally designed a photothermometric platform to quickly and sensitively detect Bi3+ ions by using the good photothermal effect of the oxidation product of TMB (oxTMB). The developed photothermometric method only using a common thermometer has a limit of detection (LOD) as low as 45.7 nM for POCT analysis of Bi3+ ions. This study not only provides a more accurate understanding of the aggregation-induced nanozymes based on the surface cleaning principle, but also shows the potential applications of aggregation-induced nanozymes in the POCT field.

[Industrial Emission Characteristics and Control Countermeasures of VOCs in Chinese Rapid Economic Development Areas].

With the rapid development of China's economy, volatile organic compounds (VOCs) as the precursor of smog and ozone are of increasing concern, especially in rapidly developing areas. This paper is a systematic analysis of VOCs emissions and distribution trends in 12 typical industrial sectors, garbage and wastewater treatment plants, comprehensive industrial parks, and residential districts in Beijing-Tianjin-Hebei, Yangtze River Delta, and Pearl River Delta Regions. The results show that pharmacy, rubber producing, as well as paint spraying are the top three industries among the 12 typical industries with the highest average VOCs emission concentrations at 541, 499, and 450 mg·m-3, respectively. By comparison, the average emission concentration of VOCs from the pharmaceutical industry in Yangtze River Delta and Beijing-Tianjin-Hebei Region was, respectively, about 112 and 1.00×103 mg·m-3. The paint spraying industry in the Pearl River Delta region has the highest emission rate with an average concentration of 1.04×103 mg·m-3. The investigation pertaining to the distribution of different VOCs categories indicates that highly toxic aromatics and halogenated hydrocarbons account for the highest emissions in paint spraying and pharmaceutical industries, reaching ratios of 55.99% and 26.57%, respectively. Additionally, among the three major economic zones, the VOCs concentration is the lowest in residential areas and comprehensive industrial parks in the Yangtze River Delta but the highest in the Beijing-Tianjin-Hebei Region, which is consistent with the distribution of industrial emissions in each region. Moreover, the research reveals that VOCs concentration in residential districts experienced a fluctuating reduction from 2002 to 2018. The significant reduction since 2016 suggests that formulated policies, laws and standards, along with the performed techniques have made significant contributions to the control of VOCs.

Berberine hydrochloride inhibits inflammation and fibrosis after canalicular laceration repair in rabbits.

AIMS: This study was designed to investigate the molecular mechanisms underlying the anti-inflammatory and anti-fibrosis effects of Berberine hydrochloride (BBR) following canalicular laceration (CL) surgical repair. MAIN METHODS: We used a rabbit CL model in this study. BBR and the control medicine were administered during and after the surgical operation. The degree of fibrosis in the canaliculi was evaluated using hematoxylin and eosin and Masson's trichrome staining 7 days after the operation. Inflammation inside the canaliculi was observed using a transcanalicular endoscope. Expression levels of inflammatory cell cytokines [tumor growth factor-ß1 (TGF-ß1), connective tissue growth factor (CTGF), intracellular adhesion molecule-I (ICAM-1), and interleukin-ß1 (IL-1ß)] were detected using immunohistochemistry. P38 and ERK1 phosphorylation and activation were determined using western blot analysis. KEY FINDINGS: The degree of inflammation and fibrosis were less in the BBR groups compared to Surgery group. The anti-inflammatory and anti-fibrosis effects of BBR were concentration-dependent. The levels of TGF-ß1, CTGF, ICAM-1, and IL-1ß were significantly lower in the BBR groups compared to Surgery group. BBR reduced the phosphorylation of P38 compared to Surgery group. SIGNIFICANCE: In conclusion, this study shows that BBR can reduce local fibrosis after CL surgical repair via its anti-inflammatory and anti-fibrosis effects.

Preliminary report on screening IGSF3 gene mutation in families with congenital absence of lacrimal puncta and canaliculi.

AIM: To investigate the variation of IGSF3 gene in three families with congenital absence of lacrimal puncta and canaliculi, and to lay a foundation for further research on the pathogenic gene of congenital lacrimal duct agenesis. METHODS: The members of the three families were recruited. The ophthalmologic examinations in details, including slit-lamp biomicroscope, intraocular pressure and fundus examination, etc. were carried out. All patients were checked with paracentesis of puncta membrane and lacrimal duct probing, as well as the computed tomography-dacryocystography (CT-DCG). Peripheral blood of 14 participants (3 normal) from three families were collected, 4 mL each, for genomic DNA extraction, and 11 exon fragments of IGSF3 gene were amplified and sequenced by polymerase chain reaction (PCR) to determine whether there were IGSF3 genetic variation. RESULTS: A total of 14 members from three families were screened for 4 synonymous variants: c.930C>T (p.Pro366=), c.1359T>C (p.Ser709=), c.1797G>A (p.Ser855=), c.1539G>A (p.Ser769=), and 6 missense variants: c.1507G>A (p.Gly759Ser), c.1783T>C (p.Trp851Arg), c.1952G>T (p.Ser 907Ile), c.3120C>G (p.Asp1040Glu), c.3123C>G (p.Asp1041Glu), c.3139_3140insGAC (p.Asp1046_Pro1047insAsp), and the latter three were only found in two patients with absence of lacrimal puncta and canaliculi combined with congenital osseous nasolacrimal canal obstruction from the first family. CONCLUSION: The same IGSF3 gene mutation c.3139_3140insGAC is found in the patients with congenital absence of lacrimal puncta and canaliculi combine with osseous nasolacrimal canal obstruction.

Diagnosis of lacrimal punctum lesions using optical coherence tomography: a preliminary study.

AIM: To study the imaging characteristics of lacrimal punctum lesion with optical coherence tomography (OCT), and provide imaging basis for the diagnosis and treatment of lacrimal punctum diseases. METHODS: A total of 25 patients (28 eyes) with epiphora and lacrimal puncta lesions were enrolled. Lacrimal puncta lesions included: punctum membrane obstruction in 7 cases (9 eyes), punctum agenesis in 1 case (1 eye), a mass protruded from the punctum in 1 case (1 eye), slit puncta in 1 case (1 eye), peri-puncta mass in 2 cases (2 eyes), chronic dacryocystitis in 4 cases (4 eyes), and primary puncta stenosis in 9 cases (10 eyes; 3 eyes mild, 4 eyes moderate and 3 eyes severe). All patients were examined by slit lamp microscopy and OCT to observe the morphological characteristics of abnormal punctum. RESULTS: Two types of complete membrane obstruction and incomplete membrane obstruction of puncta were observed in OCT images of 7 patients. No lacrimal punctum and lacrimal canalicular cavity were found in 1 case with punctum agenesis. OCT images showed that a narrow lumen remained in the lacrimal puncta in 1 patient with a mass protruded from the punctum. OCT of punctum in a patient with slit punctum after stent placement showed stent and abnormal lacrimal structure. No abnormal intraluminal structure was found in 2 cases of peri-puncta mass after OCT scan, and the lacunar space was narrower than that of the contralateral eye. OCT of puncta in 4 patients with chronic dacryocystitis showed that pus floated in tear with lump-like medium-low reflex. In 9 patients with primary lacrimal puncta stenosis, OCT image could clearly show the changes of puncta lumen in different degrees and shapes. CONCLUSION: OCT is feasible for the examination of pathological punctum, and can provide imaging basis for the diagnosis and treatment of punctum disease.

Synthesis of three-dimensional Au-graphene quantum dots@Pt core-shell dendritic nanoparticles for enhanced methanol electro-oxidation.

Au-graphene quantum dots (GQDs)@Pt core-shell nanodendrites are synthesized through a two-step reduction approach, in which Au forms the core, GQDs form an intermediate layer and dendritic Pt forms the shell. Among the above synthesized catalysts, the GQDs can manipulate the binding of reaction intermediates on the Pt surface as well as assemble π-π * conjugate bonds, thus forming a dendritic Pt shell instead of a compact Pt shell. The obtained core-shell structure was characterized by transmission electron microscopy, energy-dispersive x-ray and x-ray photoelectron spectroscopy. The methanol electro-oxidation was investigated in alkaline media on the Au-GQDs@Pt modified electrode via cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy analysis. In particular, we discovered that Au-Pt assembled with GQDs could dramatically improve the activity and stability of the catalysts, owing to the synergistic effect raised by the GQDs, which exhibit prominent electron conductivity and great chemical/physical stability. It was also found that the Pt/Au mole ratios could control the Pt shell thickness, which significantly affected the catalytic methanol oxidation activity of the Au-GQDs@Pt nanodendrites. The Au-GQDs@Pt nanodendrites with optimum Pt/Au mole ratios of 1.0 exhibited a 2.5 times increase in electrocatalytic activity toward methanol oxidation compared with the commercial catalyst (Pt/C), and its CO tolerance was also greatly improved. The above results show that the Au-GQDs@Pt nanocatalysts have potential application prospects in direct methanol fuel cells.

Molecular characterization of aldehydes and ketones in particle phase of mainstream and sidestream cigarette smoke.

Aldehydes and ketones (AKs) in cigarette smoke are risk to humans and environment. Due to the complexity of itself and the interference of the smoke tar matrix, the aldehydes and ketones in particle phase (AKPs) of mainstream smoke (MSS) and sidestream smoke (SSS) have not been well investigated. In this study, the AKPs of MSS and SSS were derivatized into polar products by reaction with Girard T reagent. The derivatives were isolated rapidly by column chromatography and analysed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Fifteen species of aldehydes and ketones were detected by positive ion electrospray ionization (ESI) FT-ICR MS: O1-6, N1O1-4, N2O1-3 and N3O2-3. The total number of AKPs obtained by ESI FT-ICR MS in MSS and SSS is about 1100 and 970, respectively. After hydrolysis, the original AKPs were obtained and 63 carbonyls were identified and quantified by gas chromatography-mass spectrometry (GCMS). The nitrogen-containing and high-oxygen AKPs were further characterized by Orbitrap mass spectrometry. Structures of compounds with high relative abundance in the mass spectrum were speculated (e.g. a series of degradants of cembrenediol) by comparison with the results of GCMS.

Au-Pt bimetallic nanoparticles decorated on sulfonated nitrogen sulfur co-doped graphene for simultaneous determination of dopamine and uric acid.

In this work, a novel nanohybrid (AuPtNPs/S-NS-GR) of well-defined Au-Pt bimetallic nanoparticles (Au-PtNPs) decorated on sulfonated nitrogen sulfur co-doped graphene (S-NS-GR) was developed. Firstly, nitrogen sulfur co-doped graphene (NS-GR) was synthesized by one-step thermal annealing method. Secondly, phenyl SO3H- group was introduced onto the surface of NS-GR via diazotization reaction, which could provide more binding sites for the formation of metal nanoparticles. Finally, Au-Pt bimetallic nanoparticles were anchored on the surface of S-NS-GR by using electrochemical deposition. The prepared material was characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), Raman spectroscopy and electrochemical impedance spectra (EIS). In addition, the electrocatalytic activity towards dopamine (DA) and uric acid (UA) was systematically studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. Under optimum conditions, the linear ranges for the detection of DA and UA were 1.0×10-8 - 4.0×10-4 M and 1.0×10-6 - 1.0×10-3 M with the limits of detection (LOD, S/N = 3) of 0.006µM and 0.038µM, respectively. Furthermore, the modified electrode was applied to real sample analysis.

Enforced Tubular Assembly of Electronically Different Hexakis(m-Phenylene Ethynylene) Macrocycles: Persistent Columnar Stacking Driven by Multiple Hydrogen-Bonding Interactions.

Hexakis(m-phenylene ethynylene) (m-PE) macrocycles 1-4, sharing the same hydrogen-bonding side chains but having backbones of different electronic properties, are designed to probe the effectiveness of multiple H-bonding interactions in enforcing columnar assemblies. 1H NMR, absorption, fluorescence, and circular dichroism (CD) spectroscopy indicate that, compared with analogous macrocycles that self-associate based on aromatic stacking which is highly sensitive to the electronic nature of the macrocyclic backbones, macrocycles 1-4 all exhibit strong aggregation down to the micromolar (µM) concentrations in nonpolar solvents. Increasing solvent polarity quickly weakens aggregation. In THF and DMF, the macrocycles exist as free molecules. The observed solvent effects, along with the behavior of 5-F6 that cannot self-associate via H-bonding, confirm that H-bonding plays the dominating role in driving the self-association of 1-4. The backbone electronic nature does not change the self-assembling pattern common to 1-4. Fluorescence and CD spectra confirm that macrocycles 1-4 assemble anisotropically, forming helical stacks in which adjacent molecules undergo relative rotation to place individual benzene residues in the favorable offset fashion. Columnar alignment of 1-4 is confirmed by atomic force microscopy (AFM), which resolves single tubes consisting of stacked macrocycles. In addition, macrocycles with backbones of different electronic properties are found to undergo heteroassociation, forming hybrid nanotubes. This study has demonstrated the generality of enforcing the alignment of shape-persistent macrocycles, which represents an invaluable addition to the small number of known tubular stacks capable of accommodating structurally varied molecular components and provides self-assembling nanotubes with inner pores allowing ready structural and functional modification.