Responses of a common tropical epiphyte, Asplenium nidus, to changes in water and nutrient availability.

Epiphytes are highly dependent on atmospheric inputs of water and nutrients. Reductions in water availability associated with warming and climate change and continual atmospheric nitrogen (N) deposition can affect plant growth but few studies have evaluated the effects of changes in both water and nutrient availabilities on epiphytes. We experimentally tested whether epiphyte growth is more water- or nutrient-limited, if nutrient limitation was stronger for nitrogen or phosphorus, and whether nutrient limitation interacts with water availability. We applied watering (high and low) and nutrient addition (control, +N, +P, +N+P) treatments to greenhouse-grown Asplenium nidus, a common epiphytic fern found in many tropical and subtropical wet forests. We measured leaf area production and leaf elemental concentrations to assess how A. nidus growth and physiology respond to changes in water and nutrient availabilities. We found that leaf growth of A. nidus was more affected by water availability than nutrient addition and the effect of adding nutrients was not fully realized under low-water availability. Among the different nutrient treatments, +N+P had the greatest effects on A. nidus growth and physiology in both watering treatments. Watering treatment changed leaf elemental concentrations but not their ratios (i.e. C:N and N:P). Nutrient addition altered C:N and N:P ratios and increased the concentration of the added elements in leaves, with more pronounced increases in the high-watering treatment. We conclude that the growth of A. nidus is more water- than nutrient-limited. When nutrient limitation occurs (i.e. under high-water availability), nutrient co-limitation is stronger than limitation by N or P alone. This result taken together with studies of other epiphytes suggests greater water than nutrient limitation is likely widespread among epiphytic plants. The limited effects of nutrient addition in the low-water treatment suggest that the effect of atmospheric N deposition on epiphyte growth will be limited when water availability is low.

The use of D-dimer in the diagnosis and risk assessment of intracardiac thrombus among patients with dilated cardiomyopathy.

D-dimer is a biomarker of coagulation and fibrinolytic system activation in response to the body's hypercoagulable state. The study aims to investigate the usefulness of D-dimer in diagnosing and assessing the risk of intracardiac thrombus in patients with dilated cardiomyopathy (DCM). Consecutively enrolled in this study were patients with DCM who were admitted to our center for the first time. The diagnostic value was evaluated using the receiver operating characteristic (ROC) curve. Additionally, we used univariate and multivariate logistic regression to investigate the association between D-dimer and intracardiac thrombus. We also performed smooth curve fitting, threshold saturation effect analysis, and subgroup analysis. In total, 534 patients were enrolled in the study, and among them, 65 patients had intracardiac thrombus. Mural thrombus was the predominant type of thrombus, which was mainly located in the left ventricular apex. The optimal cut-off value of D-dimer for the diagnosis of intracardiac thrombus was 484 ng/mL, with a sensitivity and specificity of 0.769 and 0.646, respectively. In both unadjusted and adjusted logistic regression models, a positive association was found between D-dimer and intracardiac thrombus. Curve fitting and threshold effect analysis revealed two inflection points in the relationship between D-dimer and intracardiac thrombus (non-linear test: P = 0.032). When D-dimer was equal to 362 ng/mL, the odds ratio (OR) was 1, and the risk of thrombus gradually increased until it reached 4096 ng/mL, after which the trend no longer increased. Within this range, a twofold increase in D-dimer was associated with a 103.2% increased risk (OR = 2.032; 95% CI 1.293-3.193; P < 0.01). In the subgroup analysis, there was a significant interaction between D-dimer and BMI on intracardiac thrombus (P value for interaction was 0.013), and the risk was higher in patients with a BMI ≥ 25 kg/m2 (OR = 3.44; 95% CI 1.86-6.36; P < 0.01).

Prognostic potential of liver injury in patients with dilated cardiomyopathy: a retrospective study.

BACKGROUND: Liver injury (LI) has been frequently observed in patients with dilated cardiomyopathy (DCM), whereas its prognostic value remains blurry. We attempted to appraise the prognostic effect of LI in patients with DCM. METHODS: This retrospective study included 523 patients with DCM. LI was defined as a threefold increase in aspartate transaminase (≥ 135 U/L) or alanine transaminase (≥ 180 U/L) or a twofold increase in total bilirubin (≥ 41 umol/L) during hospitalization. The population was segmented into non-liver injury (NLI) group and LI group based on liver function test data. To balance differences in covariates at baseline, 1:1 propensity score matching (PSM) was performed. RESULTS: Patients with LI had lower survival rate, compared with those with NLI (44.6% vs. 73.8%, P < 0.001). Similar results were also found in age (age > 50, 39.6% vs. 70.9%, P < 0.001; age ≤ 50, 51.3% vs. 79.5%, P < 0.001) and gender stratified analysis (male, 46.2% vs. 74.4%, P < 0.001; female 35.7% vs. 72.0%, P = 0.001). After PSM, the survival rate of patients with LI remained lower than those with NLI (44.6% vs. 64.1%, P = 0.019). Multivariable Cox regression analysis manifested that LI (hazard ratio [HR]: 1.692, 95% confidence interval [CI] 1.194-2.398, P = 0.003; HR: 1.675, 95% CI 1.078-2.604, P = 0.022, respectively) showed potent predictive effect on all-cause mortality in patients with DCM, both before and after PSM. CONCLUSIONS: The occurrence of LI herald adverse outcomes in patients with DCM and attention to LI may be conducive to risk stratification and management.

Clinical characteristics and patient outcomes of molecular subtypes of small cell lung cancer (SCLC).

BACKGROUND: Recent studies have shown that according to the expression levels of achaete-scute homolog 1 (ASCL1), neurogenic differentiation factor 1 (NEUROD1), and POU class 2 homeobox 3 (POU2F3), small cell lung cancer (SCLC) can be divided into four subtypes: SCLC-A (ASCL1-dominant), SCLC-N (NEUROD1-dominant), SCLC-P (POU2F3-dominant), and SCLC-I (triple negative or SCLC-inflamed). However, there are limited data on the clinical characteristics and prognosis of molecular subtypes of SCLC. METHODS: Immunohistochemistry (IHC) was used to detect the expression levels of ASCL1, NEUROD1, and POU2F3 in 53 patient samples of resectable SCLC. The subtype was defined by the differential expression of the transcription factors for ASCL1, NEUROD1, and POU2F3 or the low expression of all three factors with an inflamed gene signature (SCLC-A, SCLC-N, SCLC-P, and SCLC-I, respectively). The clinicopathological characteristics, immunological features (programmed death ligand 1 [PD-L1] expression and CD8+ tumor infiltrating lymphocyte [TIL] density), and patient outcomes of the four subtypes of SCLC were analyzed. RESULTS: Positive ASCL1, NEUROD1, and POU2F3 staining was detected in 43 (79.2%), 27 (51.0%), and 17 (32.1%) SCLC specimens by IHC. According to the results of IHC analysis, SCLC was divided into four subtypes: SCLC-A (39.6%), SCLC-N (28.3%), SCLC-P (17.0%), and SCLC-I (15.1%). The 5-year overall survival (OS) rates of these four subtypes were 61.9%, 69.3%, 41.7%, and 85.7%, respectively (P=0.251). There were significant differences in smoking status among different subtypes of SCLC (P= 0.031). However, we did not confirm the correlation between subtypes of SCLC and other clinicopathological factors or immune profiles. Cox multivariate analysis showed that N stage (P=0.025), CD8+ TILs (P=0.024), Ki-67 level (P=0.040), and SCLC-P (P=0.023) were independent prognostic factors for resectable SCLC. CONCLUSIONS: Our IHC-based study validated the proposed classification of SCLC using the expression patterns of key transcriptional regulatory factors. We found that SCLC-P was associated with smokers and was one of the poor prognostic factors of limited-stage SCLC. In addition, no correlation was found between PD-L1 expression or CD8+ TIL density and SCLC subtypes.

Synthesis of Tribenzo[b,d,f]azepines via Palladium-Catalyzed Annulation Reaction of 2-Iodobiphenyls with 2-Halogenoanilines.

A palladium-catalyzed annulation reaction of 2-iodobiphenyls with 2-halogenoanilines has been developed. A variety of 2-iodobiphenyls and 2-halogenoanilines can undergo this transformation. Diversified tribenzo[b,d,f]azepine derivatives can be synthesized in moderate to excellent yields according to this method.

[Nitrogen Removal from Mature Landfill Leachate via Denitrification-Partial Nitritation-ANAMMOX Based on a Zeolite Biological Aerated Filter].

A combined process of denitrification-partial nitritation-ANAMMOX based on a zeolite biological aerated filter (ZBAF) was applied to treat mature landfill leachate. We investigate the partial nitritation characteristics of the ZBAF and the nitrogen removal performance as well as the carbon removal performance of the combined process. Results showed that, based on the selective inhibition of nitrite oxidizing bacteria (NOB) by free ammonia (FA), the ZBAF could successfully achieve stable and efficient partial nitrification of mature landfill leachate, with an average nitrite accumulation rate (NAR) of 93.8% and a maximum nitrite production rate (NPR) of 1.659 kg·(m3·d)-1. After adding 700 mg·L-1 glucose to the influent, due to the synergistic effect of denitrification and anammoxidation, the combined process achieved its best nitrogen removal performance at a reflux ratio of 2.0 and hydraulic retention time (HRT) of 2.2 days. The average ammonia removal efficiency (ARE), total nitrogen removal efficiency (NRE), total nitrogen removal loading rate (NRR), and average chemical oxygen demand (COD) removal efficiency were 97.2%, 90.0%, 0.585 kg·(m3·d)-1, and 45.3%, respectively. Furthermore, the NRR of the anaerobic ammonium oxidation (ANAMMOX) process (NRRANA) reached 1.268 kg·(m3·d)-1. High-throughput sequencing technology was used to analyze the microbial community structure in each device. Results showed that denitrifiers (Paracoccus and Comamonas), ammonia-oxidizing bacteria (AOB) (Nitrosomonas), and ANAMMOX bacteria (Candidatus Kuenenia and Candidatus Anammoxoglobus) were the dominant bacteria in the UASB, ZBAF, and ANAMMOX reactor, respectively, which corresponded to the stable nitrogen removal performance of the combined process.

Enhanced photoelectrocatalytic activity of direct Z-scheme porous amorphous carbon nitride/manganese dioxide nanorod arrays.

Carbon nitride (C3N4) is a promising photocatalyst that can be applied in environmental remediation and energy conversion. However, the absorption range and charge separation efficiency of C3N4 are still severely restricted for its large-scale practical applications. Herein, we demonstrate a simple thermal polymerization and electrodeposition method, followed by partial etching strategy to synthesize direct Z-scheme porous zinc oxide/amorphous carbon nitride/manganese dioxide hybrid core-shell nanorod array (denoted as P-ZnO/ACN/MnO2) by encapsulating amorphous carbon nitride layers (ACN) and manganese dioxide nanosheets (MnO2) on the zinc oxide nanorod arrays (denoted as ZnO). Interestingly, ZnO serves as the collector of charge carriers and MnO2 plays a significant role in protecting ACN from corrosion. The as-prepared Z-scheme P-ZnO/ACN/MnO2 heterojunction exhibits high photocurrent density of 5.2 mA cm-2 at 0.6 V vs. Ag/AgCl, high photoconversion efficiency 0.98%, and universal photoelectrocatalytic degradation activity for degradation of organic dyes under visible light irradiation. The band gap energy and conduction band position of ZnO, ACN and MnO2 are calculated by UV-visible diffuse reflection and Mott-Schottky measurement, which strongly support the direct Z-scheme charge carrier migration mechanism. This finding provides an efficient strategy to construct highly active and stable C3N4-based Z-scheme photocatalytic system.

Multiple Hydrogen-Bonding Bifunctional Thiourea-Catalyzed Asymmetric Dearomative [4 + 2] Annulation of 3-Nitroindoles: Highly Enantioselective Access to Hydrocarbazole Skeletons.

A method for the enantioselective construction of hydrocarbazole skeletons through dearomative [4 + 2] annulation of 3-nitroindoles with Nazarov reagents is reported. The reactions use multiple hydrogen-bonding bifunctional thiourea as catalyst and are highly diastereo- and enantioselective (up to >20:1 dr and >99% ee). The protocol was demonstrated by preparative-scale experiment and the versatile conversion of the products. The multiple hydrogen-bonding in the catalyst plays a pivotal role in the reactivity and stereoselectivity.

Cytotoxic triterpenoid saponins from Clematis tangutica.

Eight previously undescribed oleanane-type triterpenoid saponins, clematangoticosides A-H, together with eight known saponins, were isolated from the whole plants of Clematis tangutica (Maxim.) Korsh. Their structures were elucidated by extensive spectroscopic analysis, in combination with chemical methods (acid hydrolysis and mild alkaline hydrolysis). Clematangoticosides D-G were found to be unusual 23, 28-bidesmosidic glycosides. The cytotoxic activities of all of the isolated saponins were evaluated against the four human cancer cell lines SGC-7901, HepG2, HL-60 and U251MG. Clematoside S, sapindoside B, kalopanax saponin A, and koelreuteria saponin A exhibited cytotoxicity against all of the test cancer cell lines with IC50 values in the range of 1.88-27.20 µM, while clematangoticoside D and F showed selective cytotoxicity against SGC-7901 with IC50 values of 24.22 and 21.35 µM, respectively.

Serum bisphenol A concentration and premature thelarche in female infants aged 4-month to 2-year.

OBJECTIVES: To estimate the association between serum bisphenol A and premature thelarche in female infants aged 4-mo to 2-y. METHODS: A total of 251 female infants (aged 4 mo to 2 y) with premature thelarche and 33 healthy age-matched control subjects were analyzed. All participants underwent physical examination and serum bisphenol A was measured by ultra-performance liquid chromatography tandem mass spectrometry. RESULTS: Serum bisphenol A concentration in the premature thelarche group (3.48 ng/ml, 95%CI: 0.09-140.26) was significantly higher than that in the control group (1.70 ng/ml, 95%CI: 0.06-51.78) (p = 0.039). There was no correlation between age and serum bisphenol A (BPA) level. Univariate logistic regression analysis showed that serum BPA concentration positively associated with premature thelarche, and the effect of BPA fell down as the age grew. CONCLUSIONS: This hospital-based study implied that there is an association between serum BPA concentrations and premature thelarche. Additionally, serum BPA levels were markedly higher in infants aged 4-mo to 2-y-old, raising a concern for public health authorities.

A new alternariol glucoside from fungus Alternaria alternate cib-137.

A new secondary metabolite, 2-O-methylalternariol 4-O-ß-[4-methoxyl-glucopyranoside] (1), together with four known compounds alternariol methyl ether (2), altenuene (3), isoaltenuene (4) and 2-(2'S-hydroxypropyl)-5-methyl-7-hydroxychromone (5), was isolated from the fungus Alternaria alternate cib-137. Its structure was elucidated on the basis of spectroscopic data. Compounds 3 and 4 demonstrated moderate activity against Staphylococcus aureus.

Evaluation of relative isotopic abundance measurements in a quadrupole time-of-flight mass spectrometer for elemental composition determination of natural products in traditional Chinese medicine.

The relative isotopic abundance (RIA) measurement errors of a quadrupole time-of-flight (Q-ToF) instrument incorporating analog-to-digital converter detectors were systemically evaluated by stochastically collecting about 200 data in positive ion mass spectrometry (MS) mode. Errors varied with peak intensities at definite spectral acquisition rates but were very close, even if peak intensities changed sharply at different spectral acquisition rates with the same concentration. Intensity thresholds were systematically defined at 1 Hz of spectral acquisition rates. RIA measurement errors were also evaluated using peak area. It seemed that peak area was better adapted for the high-intensity ions while peak intensity was suited for very low-intensity ions. Several known compounds were selected for RIA measurements for product ions in tandem mass spectropmetry (MS/MS) mode. An extract of a representative traditional Chinese medicinal, Paederia scandens was analyzed with high-performance liquid chromatography-electrospray ionization-QToF-MS/MS. The unique elemental compositions of some compounds could not be identified even with exact masses and MS/MS spectra of measured and reference compounds. RIA errors, especially of (M+2)M(-1), provided vital information for determining the elemental composition.

Analysis of cipadesin limonoids from Cipadessa cinerascens using electrospray ionization quadrupole time-of-flight tandem mass spectrometry and quantum chemical calculations.

RATIONALE: Limonoids, a class of tetranortriterpenoids, exhibit various biological effects, such as insect antifeedant and growth regulating activities, antimicrobial activity, potent cell adhesion inhibitory effects, antimalarial activity, anticancer activities, and antioxidant activity. The potential application brings the need for reliable, fast and low-cost analysis of this class of compounds. METHODS: Six cipadesin limonoids (1-6), including a pairs of isomers, from leaves and barks of Cipadessa cinerascens were investigated by electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS) in positive-ion mode. Characteristic processes were further studied by theoretical calculations. RESULTS: 1,3-Hydrogen rearrangement might play a significant role in the cleavage of -O- bridge bond in ring B and further produces some characteristic ions. For [M + Na](+) precursor ions, the product ion at m/z 133 might indicate the structure of ring A and the losses of CO(2) and AcOH occur readily. Interestingly, the radical product ion at m/z 460 from [M + Na](+) ions seems to be the characteristic ion for compound 1. A deuterium-labeling experiment supported the processes forming the radical ion. For [M + NH(4)](+) ions, high-abundance product ions resulting from sequential loss of AcOH can be observed. In addition, a pairs of isomers was unambiguously differentiated based on MS or MS/MS spectra. CONCLUSIONS: In summary, sufficient information obtained from fragmentation experiments of [M + Na](+), [M + NH(4)](+) or [M + H](+) precursor ions is especially valuable for rapid identification of these limonoids or their metabolites in complex mixtures. The high-abundance radical product ion is of scientific interest.

Analysis of sesterterpenoids from Aspergillus terreus using ESI-QTOF and ESI-IT.

INTRODUCTION: Biosynthesis of terretonin was studied due to the interesting skeleton of this series of sesterterpenoids. Very recently, López-Gresa reported two new sesterterpenoids (terretonins E and F) which are inhibitors of the mammalian mitochondrial respiratory chain. Mass spectrometry (MS), especially tandem mass spectrometry, has been one of the most important physicochemical methods for the identification of trace natural products due to it rapidity, sensitivity and low levels of sample consumption. The potential application prospect and unique skeleton prompted us to study structural characterisation using MS. OBJECTIVE: To obtain sufficient information for rapid structural elucidation of this class of compounds using MS. METHODOLOGY: The elemental composition of the product ions was confirmed by low-energy ESI-CID-QTOF-MS/MS analyses. The fragmentation pathways were postulated on the basis of ESI-QTOF-MS/MS/MS and ESI-IT-MS(n) spectra. Common features and major differences between ESI-QTOF-MS/MS and IT-MS(n) spectra were compared. For ESI-QTOF-MS/MS/MS experiments, capillary exit voltage was raised to induce in-source dissociation. Ammonium acetate or acetic acid were added into solutions to improve the intensity of [M + H]+. The collision energy was optimised to achieve sufficient fragmentation. Some fragmentation pathways were unambiguously proposed by the variety of abundance of fragment ions at different collision energies even without MS(n) spectra. RESULTS: Fragmentation pathways of five representative sesterterpenoids were elucidated using ESI-QTOF-MS/MS/MS and ESI-IT-MS(n) in both positive- and negative-ion mode. The key group of characterising fragmentation profiles was ring B, and these fragmentation patterns are helpful to identify different types of sestertepenoids. CONCLUSION: Complementary information obtained from fragmentation experiments of [M + H]+ (or [M + NH4]+ and [M-H](-) precursor ions is especially valuable for rapid identification of this kind of sesterterpenoid.

16-O-Methyl-cafestol.

THE TITLE COMPOUND [SYSTEMATIC NAME: (3bS,5aS,7R,8R,10aR,10bS)-7-meth-oxy-10b-methyl-3b,4,5,6,7,8,9,10,10a,10b,11,12-dodeca-hydro-5a,8-methano-5aH-cyclo-hepta-l[5,6]naph-tho[2,1-b]furan-7-methanol], C(21)H(30)O(3), was isolated from the beans of Coffea robusta. The mol-ecule contains five fused rings including a furan ring. The two six-membered rings are in chair conformations, but the third six-membered ring and the five-membered aliphatic ring adopt envelope conformations. Inter-molecular O-H⋯O hydrogen bonding is present in the crystal structure.

(3S,NR)-3-Hydroxy-methyl-2-methyl-2-(3-methyl-but-2-en-1-yl)-1,2,3,4-tetra-hydro-isoquinolinium bromide-1,1'-bi-2-naphthol (1/1).

In the title compound, C(16)H(24)NO(+)·Br(-)·C(20)H(14)O(2), the N-hetero-cyclic six-membered ring assumes a half-chair conformation. The two naphthalene ring systems are nearly perpendicular to one another, making a dihedral angle of 89.5 (2)°. Inter-molecular O-H⋯Br hydrogen bonding helps to stabilize the crystal structure.

Vulnerability to unidirectional conduction block and reentry in rabbit left ventricular wedge preparation: effects of stimulation sequence and location.

Many factors influence the initiation of unidirectional conduction block and reentry. To explore the influential factors on the temporal vulnerable window of the unidirectional conduction block, we investigated the effect of stimulation sequence and location on the temporal vulnerability in epicardial and endocardial sites in an arterially perfused rabbit left ventricular wedge preparation at three basic cycle lengths (BCL) of 2,000, 1,000 and 500 ms. An extrastimulus (S2) was introduced at coupling intervals incremented by 1 ms to scan the entire diastolic interval. The results showed that the vulnerable window increased with the lengthening of BCL, which ranged from 48.55 +/- 18.04 ms at BCL of 500 ms to 92.50 +/- 25.59 ms at BCL of 2,000 ms for endocardial, and is a similar style for epicardial from 21.00 +/- 14.02 ms at BCL of 500 ms to 75.71 +/- 16.34 ms at BCL of 2,000 ms (P < 0.05). The vulnerable window of endocardial was wider than that of epicardial (P < 0.05). Furthermore, the window size for reentry was about 39% smaller than that for unidirectional conduction block. Meanwhile, we found that increasing the number of premature beats enlarged the vulnerable window markedly due to enhanced transmural dispersion of repolarization (TDR) of ventricle. The vulnerable window is an effective index to evaluate the increased risk for unidirectional conduction block. Therefore, the factors that increase the vulnerable window are associated with the higher incidence of ventricular arrhythmias.

Brevianamide J, a new indole alkaloid dimer from fungus Aspergillus versicolor.

Brevianamide J (1), a new indole alkaloid dimer, was isolated together with four new diketopiperazine alkaloids (brevianamide K-N, 2-5) from the solid-state fermented culture of Aspergillus versicolor. Their structures were elucidated on the basis of spectral data. X-ray crystallographic analysis confirmed the structures of 1 and 4.