Guest-Stimulated Nonplanar Porphyrins in Flexible Metal-Organic Frameworks.

Nonplanar porphyrins with out-of-plane distortions play crucial roles in many biological functions and chemical applications. The artificial construction of nonplanar porphyrins usually involves organic synthesis and modification, which is a highly comprehensive approach. However, incorporating porphyrins into guest-stimulated flexible systems allows to manipulate the porphyrin distortion through simple ad/desorption of guest molecules. Here, a series of porphyrinic zirconium metal-organic frameworks (MOFs) is reported that exhibit guest-stimulated breathing behavior. X-Ray diffraction analysis and skeleton deviation plots confirm that the material suffers from porphyrin distortion to form a ruffled geometry under the desorption of guest molecules. Further investigation reveals that not only the degree of nonplanarity can be precisely manipulated but also the partial distortion of porphyrin in a single crystal grain can be readily achieved. As Lewis acidic catalyst, the MOF with nonplanar Co-porphyrin exhibits active properties in catalyzing CO2 /propylene oxide coupling reactions. This porphyrin distortion system provides a powerful tool for manipulating nonplanar porphyrins in MOFs with individual distortion profiles for various advanced applications.

Mutations in the RAS and PI3K pathways are associated with metastatic location in colorectal cancers.

BACKGROUND AND OBJECTIVES: Identification of mutations in the downstream epidermal growth factor receptor (EGFR) signaling pathway could provide important insights of EGFR-targeted therapies in colorectal cancers. We analyzed the mutation spectra of the PI3K/PTEN/AKT and RAS/RAF/MAPK pathways in colorectal cancers and the associations of these mutations with sites of metastases or recurrence. METHODS: The study population comprised 1,492 retrospectively collected stages I-IV colorectal cancer specimens. Tissue was obtained between 2000 and 2010 at a single hospital. We analyzed 61 hot spots using MALDI-TOF mass spectrometry for nucleic acid analysis. RESULTS: Mutations were found in the RAS pathway in 47.3% of patients and in the PI3K pathway in 14.3% of patients, with 9.2% of patients carrying mutations in both pathways. Both the RAS and PI3K pathway mutations were significantly associated with proximal tumors, mucinous tumors, and microsatellite instability. Tumors carrying a RAS pathway mutation exhibited a higher frequency of lung and peritoneal metastasis than did tumors with a wild-type gene (P = 0.025 and 0.009, respectively). NRAS gene mutation was significantly associated with lung metastasis (P = 0.001). CONCLUSIONS: Somatic mutations in the RAS pathway of the primary tumor in colorectal cancer can influence patterns of metastasis and recurrence.

Prevalence and predictors of help-seeking behavior among post-partum women with urinary incontinence in China and Indonesia: A cross-sectional survey based on Andersen Help-Seeking Model.

INTRODUCTION: Urinary incontinence (UI) is a prevalent condition among post-partum women, and it can significantly affect their physical and psychosocial well-being. Therefore, it's crucial for post-partum women to discuss any UI symptoms they may be experiencing with their healthcare provider and seek appropriate treatment. PURPOSE: To investigate what leads post-partum women with UI to seek help in China and Indonesia based on the Andersen Help-Seeking Model. METHODS: A cross-sectional digital survey among post-partum women (6 weeks to 1 year) was conducted from May to November 2021 in China and Indonesia. The survey contents included: (1) demographic characteristics, (2) social support, (3) health care needs, (4) capacity and resources. For analysis, descriptive statistics, independent sample t-tests and chi-square tests were used to determine the differences between help-seeking and non-help-seeking women with UI, and logistic regression analysis and the receiver operating characteristic curve (ROC) was used to determine the predictors of heal-seeking behavior in post-partum women with UI. RESULTS: The prevalence of UI was 25 % (215/868) and 31 % (187/605) among post-partum women in China and Indonesia. Among post-partum women with UI, the help-seeking rate was 46 % (98/215) and 52 % (98/187) in China and Indonesia. Incontinence quality of Life, support from women of the family (Yes), knowing the available department for UI (Yes), current knowledge of UI and the current status of UI were independent risk factors for China (P<0.05). Support from husband (Yes), being asked about UI by a doctor (Yes) and the current status of UI were independent risk factors for Indonesia. The obtained area under ROC curve (AUC) for the model were 0.884 and 0.935 in China and Indonesia. CONCLUSIONS: The prevalence of UI and the rate of seeking help for UI in Indonesia were higher than those in China. Social support, needs and the availability of resources and organizational support to assist patients in their help-seeking efforts, were the main predictors affecting help-seeking behavior among post-partum women with UI.

Preparation, characterization, and electrochemical sensing performance of a novel pristine Cd-MOF and its composite with carbon nanotubes.

A novel Cd(II)-organic framework (Cd-MOF) {[Cd(isba)(bbtz)2(H2O)]·H2O}n (1) and its composite with CNTs (Cd-MOF@CNTs), [H2isba = 2-iodo-4-sulfobenzoicacid; bbtz = 1, 4-bis(1,2,4-triazolyl-1-methyl)benzene], were synthesized successfully under ambient conditions. The Cd-MOF is a 2D (4, 4) topological framework, further extending into a two-fold interpenetrated 3D supramolecular network via hydrogen bonding. The activation energy for proton transfer in the composite Cd-MOF@CNT/Nafion membrane is lower than that in pristine Cd-MOF/Nafion, leading to its more temperature-insensitive proton conductivity. Hence, the proton conduction of the composite Cd-MOF@CNT/Nafion membrane was greatly improved. Cyclic voltammograms indicate that the Cd-MOF/GCE only has an oxidation peak with the peak potential suitable for the oxidation of glucose in 0.1 M NaOH. The i-t current response demonstrates that the Cd-MOF/GCE exhibits sensitive and selective oxidative sensing of glucose in the linear range of 0-5 mM with a limit of detection (LOD) of 9.64 µM. Different from the pristine Cd-MOF, Cd-MOF@CNTs shows a pair of irreversible redox peaks with an anodic peak potential appropriate for the glucose oxidation and a cathodic peak potential suitable for the hydrogen peroxide reduction in 0.1 M NaOH. So, the Cd-MOF@CNTs/GCE can be used not only for the electrocatalytic oxidation of glucose, but also for the electrocatalytic reduction of H2O2. The current-time response curve demonstrates that the Cd-MOF@CNTs/GCE exhibits more sensitive and selective oxidative sensing for glucose exponentially in the 0-18.5 mM range with a lower LOD down to 2.63 µM. The reductive sensing of H2O2 increases linearly in the range of 0-14.0 mM (LOD = 33.70 µM). Moreover, the Cd-MOF@CNTs/GCE can detect glucose and H2O2 efficiently in real-world samples. Cd-MOF@CNTs may act as a dual non-enzymatic electrochemical sensory material for glucose and H2O2.

Poly[[bis-(µ-3-amino-5-carb-oxy-benzoato-κ(2)N:O(1))diaqua-zinc] dihydrate].

The Zn(II) atom in the title polymeric compound, {[Zn(C(8)H(6)NO(4))(2)(H(2)O)(2)]·2H(2)O}(n), lies on a center of inversion and is coordinated by two amine N atoms and two carboxyl-ate O atoms from two 3-amino-5-carb-oxy-benzoate anions along with two water mol-ecules in a distorted octa-hedral geometry. The bridging nature of the anion generates a layer motif parallel to (100). Hydrogen bonds of the N-H⋯O and O-H⋯O types exist in the structure. One H atom of the coordinated water mol-ecule and one H atom of the solvent water mol-ecule are each disordered over two positions in a 1:1 ratio.

1-{[4'-(1H-1,2,4-Triazol-2-ium-1-ylmeth-yl)biphenyl-4-yl]meth-yl}-1H-1,2,4-triazol-2-ium bis-(3-carb-oxy-5-iodo-benzoate)-5-iodo-benzene-3,5-dicarb-oxy-lic acid-water (1/2/2).

The neutral carb-oxy-lic acid mol-ecule and the carboxyl-ate anion in the title compound, C(18)H(18)N(6) (2+)·2C(8)H(4)IO(4) (-)·2C(8)H(5)IO(4)·2H(2)O, are both nearly planar (r.m.s. deviations = 0.034 and 0.045 Å, respectively). In the cation, the mid-point of the C-C bond linking the two benzene rings lies on a center of inversion, and the triazole ring is approximately perpendicular to the adjacent benzene ring [dihedral angle = 83.2 (3)°]. In the crystal, the cations, anions, carb-oxy-lic acid and lattice water mol-ecules are linked by N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds, generating a ribbon running along [1-10]. The crystal studied was a non-merohedral twin with the components in a 51.2 (1):48.8 (1) ratio.

Poly[[diaqua-(1,10-phenanthroline-κN,N')(µ(3)-4-sulfonato-benzene-1,2-di-car-boxyl-ato-κO:O,O:O)erbium(III)] dihydrate].

The 4-sulfophthalate trianion in the polymeric complex, {[Er(C(8)H(3)O(7)S)(C(12)H(8)N(2))(H(2)O)(2)]·2H(2)O}(n), bridges three water/phenanthroline-coordinated Er(III) ions to form a three-dimensional network architecture. The metal atom is further chelated by a carboxyl-ate group and is covalently bonded to a monodentate carboxyl-ate group as well as to a monodentate sulfonate group in a distorted square anti-prismatic geometry. The coordinating water molecules and the lattice water molecules, one of which is disordered over two positions [major component 65 (3)%], are hydrogen bonded to the network.

Poly[[diaqua-(1,10-phenanthroline-κN,N')(µ(3)-4-sulfonato-benzene-1,2-dicarboxyl-ato-κO:O,O:O)dysprosium(III)] dihydrate].

The 4-sulfophthalate trianion in the polymeric title complex, {[Dy(C(8)H(3)O(7)S)(C(12)H(8)N(2))(H(2)O)(2)]·2H(2)O}(n), bridges three water/phenanthroline-coordinated Dy(III) atoms to form a three-dimensional network architecture. The metal atom is further chelated by a carboxyl-ate group and is covalently bonded to a monodentate carboxyl-ate group and to a monodentate sulfonate group in a distorted square-anti-prismatic geometry. The coordinating and the solvent water mol-ecules are hydrogen bonded to the network. In the crystal, one solvent water mol-ecule is disordered over two positions [major component = 59 (3)%].

A bibliometric analysis of the recent advances in diazepam from 2012 to 2021.

Background: Diazepam is a classic benzodiazepine drug that has been widely used for disorders such as anxiety, sleep disorders, and epilepsy, over the past 59 years. The study of diazepam has always been an important research topic. However, there are few bibliometric analyses or systematic studies in this field. This study undertook bibliometric and visual analysis to ascertain the current status of diazepam research, and to identify research hotspots and trends in the past 10 years, to better understand future developments in basic and clinical research. Methods: Articles and reviews of diazepam were retrieved from the Web of Science core collection. Using CiteSpace, VOSviewer, and Scimago Graphica software, countries, institutions, authors, journals, references, and keywords in the field were visually analyzed. Results: A total of 3,870 publications were included. Diazepam-related literature had high volumes of publications and citations. The majority of publications were from the USA and China. The highest number of publications and co-citations, among the authors, was by James M Cook. Epilepsia and the Latin American Journal of Pharmacy were the journals with the most publications on diazepam and Epilepsia was the most frequently cited journal. Through a comprehensive analysis of keywords and references, we found that current research on diazepam has focused on its mechanism of action, application in disease, pharmacokinetics, risk, assessment, and management of use, status epilepticus, gamma-aminobutyric acid receptors (GABAR), intranasal formulation, gephyrin, and that ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) is the current research hotspot. Conclusion: Research on diazepam is flourishing. We identified research hotspots and trends in diazepam research using bibliometric and visual analytic methods. The clinical applications, mechanisms of action, pharmacokinetics, and assessment and management of the use of diazepam are the focus of current research and the development trend of future research.

(5-Amino-isophthalato-κN)triaqua-(1,10-phenanthroline-κN,N')nickel(II) trihydrate.

The Ni(II) atom in the title compound, [Ni(C(8)H(5)NO(4))(C(12)H(8)N(2))(H(2)O)(3)]·3H(2)O, is six-coordinated in an NiN(3)O(3) octa-hedral geometry. The triply water-coordinated Ni(II) atom is chelated by the phenantroline ligand and is additionally coordinated by the amino group of the 5-amino-isophtalate anion. The anion, the coordinated and the uncoordinated water mol-ecules inter-act through an extensive O-H⋯O and N-H⋯O hydrogen-bonding network, generating a three-dimensional cage-like network.

5-Amino-2,4,6-triiodo-isophthalic acid-4,4'-bipyridine N,N'-dioxide-water (1/1/1).

The aromatic rings of the N,N'-dioxide molecule in the title compound, C(8)H(4)NI(3)O(4)·C(10)H(8)N(2)O(2)·H(2)O, are twisted by 14.0 (2)°. The -CO(2)H substituents of the 5-amino-2,4,6-triiodo-isophthalic acid are twisted by 83.0 (2) and 86.5 (2)° out of the plane of the aromatic ring. In the crystal, the three components are linked by O-H⋯O hydrogen bonds into a three-dimensional network. An N-H⋯O inter-action also occurs. One of the amino H atom is not involved in hydrogen bonding.

Conditional survival for high-risk early-stage cervical cancer patients with lymph node metastasis after hysterectomy.

BACKGROUND: To estimate conditional survival (CS) for high-risk early-stage cervical cancer patients with lymph node metastasis after hysterectomy. METHODS: 1964 T1-2N1M0 cervical cancer patients who underwent primary hysterectomy from 2004 to 2015 were extracted from the Surveillance, Epidemiology, and End Result (SEER) Program. Univariate and multivariate cox regression analysis were used to identify independent risk factors. 5-year conditional disease-specific survival (CDS5) and 5-year conditional relative survival (CRS5) were estimated. CDS5 and CRS5 stratified by risk factors were further calculated. RESULTS: CDS5 and CRS5 increased from 71.0% and 73.7% at 0-year to 89.2% and 91.7% at 5-year, respectively. Inversely, the actuarial disease-specific survival and RS dropped from 71.0% and 73.7% at 5-year to 63.3% and 67.6% at 10-year, respectively. Patients with unfavorable factors had a bigger gap between actuarial survival and CS. Both CDS5 and CRS5 curves across stratas of each prognostic factor had a tendency to level off with time elapsing. Notably, CRS5 couldn't exceed 95% even after 5-year follow-up except for patients with grade I disease (CRS5 at 5-year: 100%) or tumor size less than 2 cm (CRS5 at 5-year: 96%). CONCLUSION: CS increased over time while actuarial survival decreased as time passed. Patients with unfavorable factors had bigger improvement in CS than those with favorable factors. Excess mortality still existed in these patients after 5-year follow-up compared to the general population except for patients with grade I disease or tumor size <2 cm, who might gradually decrease follow-up times after 5-year.

2,2'-Biimidazolium 5-amino-2,4,6-tri-bromo-isophthalate.

In the cation of the title salt, C(6)H(8)N(4) (2+)·C(8)H(2)Br(3)NO(4) (2-), the dihedral angle between the two five-membered rings is 2.1 (3)°. In the anion, the mean planes of the carboxyl units are twisted from the benzene ring by 84.3 (4) and 86.2 (3)°. In the crystal, the components are linked by imidazolium-carboxyl-ate N-H⋯O hydrogen bonds, generating a chain running along [10].

(5-Amino-isophthalato-κN)triaqua-(1,10-phenanthroline-κN,N')cobalt(II) trihydrate.

The Co(II) atom in the title compound, [Co(C(8)H(5)NO(4))(C(12)H(8)N(2))(H(2)O)(3)]·3H(2)O, is six-coordinated in a CoN(3)O(3) octa-hedral geometry; the water-coordinated Co(II) atom is chelated by the N-heterocycle. An inter-molecular N-H⋯O hydrogen bond occurs. The carboxyl-ate entity coordinates through the amino group. The carboxyl-ate donor unit, coordinated and uncoordinated water mol-ecules inter-act through O-H⋯O and N-H⋯O hydrogen bonds, generating a tightly-held three-dimensional cage-like network.

Tetra-kis(1H-imidazole-κN)(2-phenyl-propanedioato-κO,O)nickel(II).

In the title complex, [Ni(C(9)H(6)O(4))(C(3)H(4)N(2))(4)], the Ni(II) ion is O,O'-chelated by the phenyl-malonato ligand and coordinated by four imidazole ligands in a slightly distorted octa-hedral geometry. In the crystal structure, symmetry-related mol-ecules are linked by N-H⋯O hydrogen bonds, generating a three-dimensional network.

catena-Poly[[tetra-aqua-[µ(2)-1,4-bis-(1,2,4-triazol-1-yl)butane-κN:N]cadmium(II)] sulfate].

In the polymeric title compound, {[Cd(C(8)H(12)N(6))(H(2)O)(4)]SO(4)}(n), the Cd(II) atom is located on an inversion center and coordinated by four water mol-ecules and two 1,4-bis-(1,2,4-triazol-yl)butane ligands in a distorted CdO(4)N(2) octa-hedral geometry. The 1,4-bis-(1,2,4-triazol-yl)butane ligand is centrosymmetric, the mid-point of the central C-C bond being located on an inversion center. It links adjacent water-coordinated metal atoms into polymeric chains running along the c axis. Adjacent chains are linked by O-H⋯N hydrogen bonds. The S atom of the sulfate anion is located on a twofold rotation axis, thus the sulfate anion is equally disordered over two sites. The sulfate anion links with the polymeric chains via O-H⋯O hydrogen bonds, generating a three-dimensional supra-molecular network.

4-(4-Pyrid-yl)pyridinium 3-amino-5-carb-oxy-2,4,6-triiodo-benzoate-5-amino-2,4,6-triiodo-isophthalic acid (1/1).

In the title ammonium carboxyl-ate-carb-oxy-lic acid co-cystal, C(10)H(9)N(2) (+)·C(8)H(3)I(3)NO(4) (-.)C(8)H(4)I(3)NO(4), the carboxyl-ate anion and carb-oxy-lic acid mol-ecule are linked by O-H⋯O and N-H⋯O hydrogen bonds to form a chain running along the c axis of the monoclinic unit cell. The chains are linked by pyridinum and pyridine N-H⋯O hydrogen bonds, generating a layer motif. O-H⋯N and O-H⋯O hydrogen bonds are also observed.

Diaqua-bis(1,10-phenanthroline-κN,N')zinc(II) 2-hydr-oxy-5-sulfonatobenzoate tetra-hydrate.

The water-coordinated metal centre in the title salt, [Zn(C(12)H(8)N(2))(2)(H(2)O)(2)]C(7)H(4)O(6)S·4H(2)O, is chelated by the two bidentate N-heterocycles, leading to an overall distorted octa-hedral environment. The cation, dianion and solvent water mol-ecules inter-act by O-H⋯O hydrogen bonds to form a layer motif. The SO(3) group is disordered over two positions with respect to the O atoms in a 0.76 (1):0.24 (1) ratio. One of the solvent water molecules is also disordered over two positions in a 0.56 (4):0.44 (4) ratio.

trans,trans,trans-Diaqua-bis(nicotin-amide-κN)bis-(2-nitro-benzoato-κO)copper(II).

The water-coordinated metal atom in the title compound, [Cu(C(7)H(4)NO(4))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], lies on a center of inversion in an all-trans octa-hedral environment with slight distortions. The mol-ecule inter-acts with adjacent mol-ecules through O-H⋯O and N-H⋯O hydrogen bonds, forming a layered network parallel to (010).

catena-Poly[[(2,2'-bipyridine-κN,N')cobalt(II)]-µ-oxalato-κO,O:O,O].

In the title compound, [Co(C(2)O(4))(C(10)H(8)N(2))](n), the oxalate group chelates two adjacent metal atoms, resulting in a zigzag chain running along the a axis. The Co(II) centre exists in an all cis-octa-hedral coordination geometry.