Correlation of DNA load, genotyping, and clinical phenotype of Mycoplasma pneumoniae infection in children.

Introduction: This study aimed to investigate the correlation between Mycoplasma pneumoniae (MP)-DNA load in the bronchoalveolar lavage fluid (BALF) of children with MP pneumonia (MPP) and its subtypes, relevant laboratory data, imaging, extrapulmonary complications in infected children, and its clinical significance in evaluating the disease. Methods: Children hospitalized with MPP at Tianjin Children's Hospital between December 2017 and December 2020 were selected for the study, excluding those with mixed viral, bacterial, and fungal infections. Children were divided into low- and high-load groups according to the MP DNA load in BALF using real-time quantitative fluorescence polymerase chain reaction (PCR). After a successful MP culture, positive specimens were subjected to PCR-Restriction fragment length polymorphism and Multiple-locus variable number tandem repeat analysis typing. Basic data, clinical information, laboratory data, and radiological results were collected from all children included in the study. Results: The PI-I type dominated the different load groups. Children in the low-load group had more wheezing and shortness of breath; however, children in the high-load group had a higher length of hospitalization, maximum fever temperature, higher chills/chilliness, incidence of abdominal pain, and higher C-reactive protein (CRP), procalcitonin (PCT) and aspartate aminotransferase (AST) levels. Children in the high-load group were more likely to have imaging changes such as pleural effusion, and the incidence of respiratory infections and extrapulmonary complications was higher than that of those in the low-load group. We applied Spearman's correlation analysis to clarify the relationship between MP DNA load and the clinical severity of MPP. We found that MP DNA load was positively correlated with length of hospitalization, maximum fever temperature, CRP, PCT, Interleukin-6 (IL-6), and AST levels, and negatively correlated with fever and cough durations, white blood cell count (WBC), and proportion of monocytes (MONO). The degree of correlation was as follows: length of hospitalization > IL-6 > cough duration > AST > fever duration > PCT > WBC > proportion of MONO > maximum fever temperature > CRP levels. Conclusions: MP DNA load was not correlated with MP typing but was significantly correlated with the children's clinical phenotype. Therefore, the MP DNA load helps in the early diagnosis of infection and can better predict disease regression.

Chiral Recognition of D/L-Ribose by Visual and SERS Assessments.

Ribose is the central molecular unit in ribose nucleic acid (RNA). Ribose is a key molecule in the study of many persistent scientific mysteries, such as the origin of life and the chiral homogeneity of biological molecules. Therefore, the chiral recognition of ribose is of great significance. The traditional method of chiral recognition of ribose is HPLC, which is time-consuming, expensive, and can only be operated in the laboratory. There is no report on optical analytical techniques that can quickly detect the chirality of ribose. In this study, a simple and convenient approach for the chiral recognition of ribose has been developed. ß-cyclodextrin(ß-CD)-coated Ag NPs aggregate after adding D-ribose, so that D-/L-ribose can be identified using visual colorimetry and/or surface-enhanced Raman spectroscopy (SERS). The color change visible to the naked eye can readily distinguish the chirality of ribose, while the SERS method can provide the more sensitive analysis of enantiomeric ribose. The advantages of this method are that it is fast, convenient, low cost, and can be operated outside the laboratory. DFT calculations show that D-ribose and cyclodextrin have the same chirality, forming multiple strong hydrogen bonds between them; thus, D/L-ribose will induce different optical effects.

Palladium catalyzed radical relay for the oxidative cross-coupling of quinolines.

Traditional approaches for transition-metal catalyzed oxidative cross-coupling reactions rely on sp2-hybridized starting materials, such as aryl halides, and more specifically, homogeneous catalysts. We report a heterogeneous Pd-catalyzed radical relay method for the conversion of a heteroarene C(sp3)-H bond into ethers. Pd nanoparticles are supported on an ordered mesoporous composite which, when compared with microporous activated carbons, greatly increases the Pd d charge because of their strong interaction with N-doped anatase nanocrystals. Mechanistic studies provide evidence that electron-deficient Pd with Pd-O/N coordinations efficiently catalyzes the radical relay reaction to release diffusible methoxyl radicals, and highlight the difference between this surface reaction and C-H oxidation mediated by homogeneous catalysts that operate with cyclopalladated intermediates. The reactions proceed efficiently with a turn-over frequency of 84 h-1 and high selectivity toward ethers of >99%. Negligible Pd leaching and activity loss are observed after 7 catalytic runs.

DFT-based Raman spectral study of astaxanthin geometrical isomers.

Astaxanthin is a carotenoid widely used in food additives, nutritional product and medicines, which shows many physiological functions such as antioxidant, anti-inflammatory, anti-hypertensive and anti-diabetic activities. It has been recognized that astaxanthin has all-trans and nine cis isomers, and these geometrical isomers have very different biological activities. The process of selective enrichment, metabolism and isomerization of astaxanthin in animals remains to be studied. Therefore, identifying isomers and obtaining their structural parameters are important for understanding the active mechanism of different molecular isomers. Although the traditional methods such as high-performance liquid chromatography (HPLC) and nuclear magnetic resonance (NMR) spectroscopy can be used to distinguish these isomers, these methods generally require considerable testing time, cost, sample volume, and hardly be applied in vivo. In this work, Raman spectroscopy combined with density functional theory (DFT) calculation was introduced to study different geometrical isomers of astaxanthin. The theoretical and experimental Raman spectra are in agreement, and we have demonstrated that all the known ten geometrical isomers of astaxanthin can be readily distinguished using this spectroscopic approach. The astaxanthin molecular vibrational modes, geometric structures, energies of ten geometric isomers are systematically scrutinized. Moreover, a lot of structural and Raman problems unsolved previously have been solved by the DFT-based spectral analysis. Therefore, this work provides an effective way for identification of different astaxanthin geometrical isomers, and may have important significance for promoting the research of astaxanthin isomers on biological property mechanisms and related applications in food molecular science.

Breaking scaling relationships in alkynol semi-hydrogenation by manipulating interstitial atoms in Pd with d-electron gain.

Pd catalysts are widely used in alkynol semi-hydrogenation. However, due to the existence of scaling relationships of adsorption energies between the key adsorbed species, the increase in conversion is frequently accompanied by side reactions, thereby reducing the selectivity to alkenols. We report that the simultaneous increase in alkenol selectivity and alkynol conversion is achieved by manipulating interstitial atoms including B, P, C, S and N in Pd catalysts. A negative linear relationship is observed between the activation entropies of 2-methyl-3-butyn-2-ol and 2-methyl-3-buten-2-ol which is highly related to the filling of d-orbital of Pd catalysts by the modification of p-block elements. A catalyst co-modified by B and C atoms has the maximum d charge of Pd that achieves a 17-fold increase in the turn-over frequency values compared to the Lindlar catalysts in the semi-hydrogenation of 2-methyl-3-butyn-2-ol. When the conversion is close to 100%, the selectivity can be as high as 95%.

Theoretical and experimental study of the infrared and Raman spectra of L-lysine acetylation.

Acetylation is a common and extremely important protein modification in biology, referring to the covalent attachment of an acetyl group to the amino group. There are two forms of protein acetylation, which are lysine Nε-acetylation and N-terminal Nα-acetylation, respectively. Protein lysine Nε-acetylation is a globally important post-translational modification which plays a critical regulatory role in almost all aspects of cell metabolism. In addition, whether lysine on the N-terminal of protein can undergo Nα-acetylation is still a controversial viewpoint. Carrying out further molecular study of the role of acetylation is also the one of challenges. In order to investigate the protein acetylation more effectively, it is thus necessary to have a thorough and comprehensive understanding of lysine acetylation. In this work, both Raman and infrared (IR) spectra of L-lysine Nε-Ace-Lys, Nα-Ace-Lys, and NαNε-Ace-Lys were explored through both experimental experiment and theoretical computation based on density function theory (DFT). Vibration assignments and geometry structures of three acetylated lysines were therefore obtained for the first time in this work. The IR or Raman spectra of four molecules are very different from each other, which can be easily distinguished from the characteristic bands at 1500-1700 cm-1 and 3200-3400 cm-1 regions. Therefore, this work may provide the guide for probing the protein acetylation by Raman and IR spectroscopy.

Interleukin-6 serum levels are independently associated with severe adenovirus pneumonia in children: a cross-sectional study.

Background: This study aimed to explore the potential association between interleukin-6 (IL-6) serum levels and severe adenovirus pneumonia (SAP) in children. Methods: A retrospective hospital-based cross-sectional study was conducted on children with SAP who presented to the Tianjin Children's Hospital between January 2019 and December 2020. Serum IL-6 levels were categorized into quintiles (Q1-5). The primary outcome variable was the occurrence of SAP. The patients' clinical features, laboratory findings, and radiographic characteristics were also assessed, and a descriptive bivariate analysis was carried out. Multivariable logistic regression analysis was applied to evaluate the relationship of IL-6 with SAP after adjustment for confounders. The nonlinear relationship between IL-6 and SAP was also analyzed. P value <0.05 was considered statistically significant. Results: In total, 542 patients met our inclusion criteria (223 males and 319 females). The mean IL-6 serum level was 38.51 pg/mL (range, 1.50-659.2 pg/mL). After adjustment for confounders, the odds ratio (OR) per SD (standard deviation) increase in IL-6 was 1.66 [95% confidence interval (CI): 1.14, 2.41]. The multivariable-adjusted OR (95% CI) of SAP across the Q1-Q5 categories of IL-6 were as follows: 1.00 (reference), 1.17 (0.59, 2.35), 1.79 (0.88, 3.63), 2.31 (1.12, 4.76), and 2.85 (1.32, 6.14) (P for trend =0.002). The risk of SAP increased with the IL-6 serum level up to 40.78 pg/mL (adjusted OR 1.029, 95% CI: 1.008-1.051; P=0.007); however, when the IL-6 level exceeded 40.78 pg/mL, it had no association with the risk of SAP (OR 1.003, 95% CI: 0.996-1.010; P=0.384). Conclusions: Our findings suggest that the serum level of IL-6 is associated with the risk of SAP in children. The levels of IL-6 in children should therefore be of concern to clinicians.

DFT and Raman study of all-trans astaxanthin optical isomers.

Astaxanthin (AST) is a xanthophyll carotenoid widely distributed in aquatic animals, which has many physiological functions such as antioxidant, anti-inflammatory, anti-hypertensive and anti-diabetic activities. AST has three optical isomers, including a pair of enantiomers (3S,3'S and 3R,3'R) and a meso form (3R,3'S). Different optical isomers have differences in a variety of physiological functions. Traditionally, High Performance Liquid Chromatography (HPLC) has been used to distinguish these isomers. In this work, it was found that Raman spectroscopy can be employed to distinguish the three optical isomers. The intensities of two Raman bands at 1190 and 1215 cm-1 of three isomers are different. Density Functional Theory (DFT) calculations are performed to analyze the spectral differences. The mainly occupied conformers of these three optical isomers are speculated and identified.

Remodeling Chromatin Induces Z-DNA Conformation Detected through Fourier Transform Infrared Spectroscopy.

The SWI/SNF complex is a highly conserved chromatin remodeling complex and can hydrolyze ATP by its catalytic subunit BRG1 or BRM to reconstruct the chromatin. To investigate whether this ATP-dependent chromatin remodeling could affect the DNA conformation, we therefore regulated (knocked down or overexpressed) BRG1/BRM in the cells and applied Fourier transform infrared (FTIR) spectroscopy to probe DNA conformational changes. As a result, we found that BRG1/BRM was indeed associated with the DNA conformational changes, in which knockdown of BRG1/BRM reduced Z-DNA conformation, while overexpression of BRG1/BRM enhanced Z-DNA conformation. This Z-DNA conformational transformation was also verified using the Z-DNA-binding proteins. Therefore, this work has provided a direct analytical tool to probe Z-DNA transformation upon ATP-dependent chromatin remodeling.

[Efficacy and safety of vitamin D as adjuvant therapy for childhood pneumonia: a Meta analysis].

OBJECTIVE: To study the efficacy and safety of vitamin D as an adjuvant therapy for childhood pneumonia through a systematic review. METHODS: Cochrane Library, PubMed, EMbase, CNKI, Wanfang Data, and Weipu Data were searched for randomized controlled trials (RCTs) of vitamin D as the adjuvant therapy for childhood pneumonia published up to August 2019. Literature screening, quality assessment, and data extraction were performed based on inclusion and exclusion criteria. Revman 5.3 was used to perform the Meta analysis of outcome indicators. RESULTS: A total of 7 RCTs with 1 527 children were included, with 762 children in the vitamin D adjuvant therapy group and 765 children in the control group. The results of the Meta analysis showed that vitamin D adjuvant therapy had no effect on recovery time (P=0.67), length of hospital stay (P=0.73), and time to relief of fever (P=0.43). Furthermore, it did not reduce the recurrence rate (P=0.14), rate of adverse events (P=0.20), and mortality rate (P=0.98) of childhood pneumonia. CONCLUSIONS: Current evidence shows that vitamin D adjuvant therapy has no marked efficacy in the treatment of childhood pneumonia.

A facile and label-free SERS approach for inspection of fipronil in chicken eggs using SiO2@Au core/shell nanoparticles.

Fipronil is a phenylpyrazole insecticide commonly used in agriculture and residential applications. In this paper, we reported a novel label-free surface-enhanced Raman spectroscopy (SERS) method for detection of fipronil residues in chicken eggs (mostly accumulated on the egg membrane). We fabricated the SERS substrates composed of the SiO2@Au core/shell nanoparticles and probed the contamination of fipronil residue on the egg membrane. The identification of the characteristic Raman bands of fipronil was achieved with the aid of density functional theory (DFT) calculation, with which we could analyzed the trace amount of fipronil in a quantitative way. As such, this work may provide a practical solution to quick inspection of fipronil contamination in chicken eggs or other foods.

Assessment of norfloxacin degradation induced by plasma-produced ozone using surface-enhanced Raman spectroscopy.

In this work, we employed surface-enhanced Raman spectroscopy (SERS) combined with density functional theory (DFT) calculation to investigate the pathways/mechanisms of the norfloxacin degradation by oxygen plasma produced ozone. The main degradation products were analyzed by the spectroscopic method, which revealed the breakage of the C-F bond and fracture of piperazinyl and quinolone moieties. In particular, we showed that the main degradation pathway was defluorination of norfloxacin, and this process could be quantitatively assessed by our proposed SERS approach.

Understanding the infrared and Raman spectra of ganoderic acid A: An experimental and DFT study.

Ganoderic Acids (GAs) are the major medicinal compounds in Ganoderma lucidum used as traditional Chinese medicine since ancient times. Ganoderic acid A (GAA) is the first discovered ganoderic acids reported in the literature, which is also one of most abundant triterpenoids of Ganoderma lucidum. Especially, GAA has been extensively investigated in recent decades for its positive medicinal activities. However, the vibrational properties of GAs have rarely been studied or reported. In this work, we focused on the typical GAA and studied the infrared (IR) and Raman spectra based on both experiments and DFT calculations. As such, we could not only achieve the assignments of the vibrational modes, but also from the IR and Raman spectra, we found that the spectral region from 1500 cm-1 to 1800 cm-1 is particularly useful for distinguishing different types of GAs. In addition, its dehydrogenated derivative ganoderenic acid A (GOA) was also studied, which could be identified due to its spectral feature of strong IR and Raman bands around 1620 cm-1. This work therefore may facilitate the application of IR and Raman spectroscopies in the inspection and quality control of Ganoderma lucidum.

Extramedullary hematopoiesis: A report of two cases.

Extramedullary hematopoiesis (EMH) is defined as hematopoiesis occurring in organs outside of the bone marrow. The present report describes two cases of thalassemic patients with paraspinal medullary hematopoiesis and analyzes the clinical manifestations, imaging, pathology, diagnosis and treatment of EMH. In addition, a supplementary review of previously published cases is provided along with a review of the related literature. Computed tomography (CT) of the first case revealed multiple paraspinal masses, and the largest was 6.2×8.0 cm in diameter. Likewise, CT of the second patient revealed multiple paraspinal masses in the bottom of the left thoracic cavity, and the largest was measured 10.1×10.5 cm. The two cases underwent surgical biopsy and the findings were compatible with a diagnosis of EMH. In conclusion, EMH is a compatible and rare disease, and should be distinguished from other neoplasms. EMH must considered when masses with characteristic radiologic appearance are detected in patients with thalassemia intermedia.

Conformational and vibrational analyses of meta-tyrosine: An experimental and theoretical study.

M-tyrosine is one kind of positional isomer of tyrosine which is widely applied in agrichemical, medicinal chemistry, and food science. However, the structural and vibrational features of m-tyrosine have not been reported or systematically investigated. In this work, potential energy surface (PES) calculations were used for searching and determining the stable zwitterionic conformers of m-tyrosine, and the Raman spectra of m-tyrosine and deuterated m-tyrosine were measured and interpreted based on theoretical computation. For the spectral simulation, several DFT-based quantum chemistry (QC) methods were employed, and the M06-2X functional with SMD solvent model was found to be best in reproducing the Raman spectra and geometrical property. As such, this study has not only presented a detailed study of m-tyrosine's vibrational property which is lack in the literature, but also may shed some light on the optimal choice of QC methods for calculation of conformations and vibrational properties of zwitterionic amino acids.

Nuclear-Spin-Induced Circular Dichroism in the Infrared Region for Liquids.

Recently, the nuclear-spin-induced optical rotation (NSOR) and circular dichroism (NSCD) for liquids were discovered and extensively studied and developed. However, so far, nuclear-spin-induced magnetic circular dichroism in the IR region (IR-NSCD) has not been explored, even though all polyatomic molecules exhibit extensive IR spectra. Herein, IR-NSCD is proposed and discussed theoretically. The results indicate that in favorable conditions the IR-NSCD angle may be much larger than the NSOR angle in the UV/Vis region due to a vibrational resonance effect and can be measurable by using the NSOR experiment scheme. IR-NSCD can automatically combine and give NMR spectra and IRCD spectra of the nuclear spin prepolarized samples in liquids, which, in principle, could be developed to become a unique, novel analytical tool.

ß-Cyclodextrin coated SiO2@Au@Ag core-shell nanoparticles for SERS detection of PCBs.

A new type of surface-enhanced Raman scattering (SERS) substrate consisting of ß-cyclodextrin (ß-CD) coated SiO2@Au@Ag nanoparticles (SiO2@Au@Ag@CD NPs) has been achieved. Our protocol was a simplified approach as the fabrication and modification of the silver shell were realized in a single-step reaction by taking advantage of ß-CD as both the reducing and stabilizing agents. The as-synthesized SiO2@Au@Ag@CD NPs were uniform in size and demonstrated high SERS activity and reproducibility. The substrates consisting of the SiO2@Au@Ag@CD NPs were employed for SERS detection of polychlorinated biphenyls (PCBs) including PCB-3, PCB-29 and PCB-77. The SERS detection sensitivity was significantly improved due to enrichment of more PCB molecules captured by ß-CD on the substrate surface, as confirmed by the appearance of the new Raman bands which are attributed to the complexes between ß-CD and PCBs according to the theoretical simulation. Therefore, this work presents a novel approach to the fabrication of effective SERS substrates that can be employed for rapid determination of trace amounts of PCBs in the environment with high detection sensitivity and recognition selectivity.

New nuclear-spin-induced Cotton-Mouton effect in fluids at high DC magnetic field.

Based on Buckingham and Pople's theory of magnetic double refraction, a theoretical expression is derived for a new Cotton-Mouton effect φ(C-M)((IB)) in liquid induced by the crossed effect between the high dc magnetic field B(0) and the nuclear magnetic moment m(z)((l)). It contains temperature-independent and -dependent parts. The latter is proportional to the product between anisotropy of polarizability and the nuclear magnetic shielding tensor. For this new effect φ(C-M)((IB)), its order in magnitude for a molecule with large polarizability anisotropy is estimated to be comparable to the nuclear-spin-induced optical Faraday rotation (NSOFR). In the multipass approach, φ(C-M)((IB)) can be eliminated by time-reversal symmetry arguments, but NSOFR is enhanced.

[The possible mechanism of lung injury induced by severe acute respiratory syndrome coronavirus spike glycoprotein].

OBJECTIVE: To investigate the role of severe acute respiratory syndrome coronavirus (SARS-CoV) in the induction of acute lung injury by promoting the synthesis of chemokine/cytokines in human endothelial cells. METHODS: Twenty-three SARS patients were enrolled in this study, comprising 15 male and 8 female, aged 27 - 55 years, mean (36 +/- 6) years. They were treated at Guangzhou Institute of Respiratory Disease from February to May in 2003. Chemokines/cytokines in the blood of patients with SARS were dynamically screened by liquid chip system. The lung was studied histopathologically using immunohistochemical technique. Spike glycoprotein of SARS-CoV was recombined by using insect-baculovirus expression system and Nickel affinity Magnet Beads, and then used to stimulate cultured human umbilical vein endothelial cells (HUVEC). Morphological changes of HUVEC were observed by microscope. Levels of chemokines/cytokines involved in immunoreaction in response to virus infection were detected in the supernatants of those cells cultured with the Spike glycoprotein by liquid chip system. RESULTS: Interferon-gamma inducible protein 10 (IP-10) was markedly elevated in the blood during the early stage of SARS [(7,600 +/- 2,400) ng/L, P < 0.01], and remained at a high level in the progressive stage [(8,100 +/- 2,300) ng/L, P < 0.01] and the end stage [(8,000 +/- 2,800) ng/L, P < 0.01] until convalescence [(1,250 +/- 450) ng/L, P > 0.05]. Moreover, IP-10 was highly expressed in the lung. Vacuoles appeared in part of HUVEC after Spike glycoprotein stimulation. As time going on, the HUVEC turned to be round in shape and even disrupted. Under normal condition, no detectable IP-10 was found in HUVEC. A high level of IP-10 [(179 +/- 34), (889 +/- 212), (1,676 +/- 199) ng/L, all P < 0.05] was detected in the HUVEC 12 h after Spike glycoprotein (5, 20, 40 mg/L) stimulation respectively, and presented with a significant dose-dependent response. CONCLUSIONS: (1) A significant increase of IP-10 activity in the blood was found in patients with SARS-CoV infection, and remained at a high level until the stage of convalescence. A strong IP-10 protein expression was also found in SARS-CoV infected lung in autopsy. (2) The Spike glycoprotein of SARS-CoV induced a high level of IP-10 in endothelial cells, which in turn damaged endothelial cells. (3) The Spike glycoprotein of SARS-CoV induced IP-10 production by a way independent of IFN-gamma.