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The present review article thoroughly analyses natural products and their derived phytoconstituents as a rich source of plausible anticancer drugs. The study thoroughly explores the chemical components derived from various natural sources, thus emphasizing their unique structural characteristics and therapeutic potential as an anticancer agent. The review contains the critical chemical constituents' in‐depth molecular mechanisms, their source's chemical structures and the categories. The review also comprises an exhaustive and comprehensive analysis of different chemical spacing parameters of the anticancer agents derived from natural products. It compares them with USFDA‐approved synthetic anticancer drugs up to 2020, thus providing a meaningful understanding of the relationship between natural and synthetic compounds portraying the anticancer assets. The review also delves more deeply into the chemical analysis of the heterocyclic moieties from the natural product arena, illustrating the anticancer mechanisms. The present article is, therefore, expected to serve as a valuable resource for natural product and medicinal chemists, encouraging and promoting an integrated approach to exploit the potential of natural products in drug discovery development and translational research, which have a prerequisite of bench to bedside approach. The work could guide researchers toward innovative approaches for the ever‐evolving field of anticancer drug discovery. [ABSTRACT FROM AUTHOR]

Low‐dimensional hybrid bismuth halide perovskites have recently emerged as a class of non‐toxic alternative to lead perovskites with promising optoelectronic properties. Here, we report three hybrid bismuth(III)‐iodides: 0‐D (H2DAC)2Bi2I10 ⋅ 6H2O (H2DAC_Bi_I), 0‐D (H2DAF)4Bi2I10 ⋅ 2I3 ⋅ 2I ⋅ 6H2O (H2DAF_Bi_I), and 1‐D (H2DAP)BiI5 (H2DAP_Bi_I) (where H2DAC=trans‐1,4‐diammoniumcyclohexane; H2DAF=2,7‐diammoniumfluorene and H2DAP=1,5‐diammoniumpentane). Their synthesis, single‐crystal X‐ray structures, and photophysical properties are reported. The first two compounds comprise edge‐sharing [Bi2I10]4− dimers, while the last compound has cis‐corner‐sharing 1‐D chains of [BiI6]3− octahedra. Intercalation of triiodide (I3−) and iodide (I−) ions enhance electronic coupling between the [Bi2I10]4− of H2DAF_Bi_I, leading to enhanced optical absorption, compared to H2DAC_Bi_I which lacks such intercalants. Furthermore, calorimetric and variable temperature X‐ray diffraction measurements suggest a centrosymmetric to non‐centrosymmetric phase transition (monoclinic P212121↔orthorhombic Pnma) of H2DAP_Bi_I at 448 K (in heating step) and at 443 K (in cooling step). [ABSTRACT FROM AUTHOR]

Background: The merits of classifying the heterogeneous group of essential tremors into essential tremor (ET) and essential tremor plus (ETP) are debated. Objectives: We studied the electrophysiological and spiral characteristics of tremor in ET and ETP. Methods: We reviewed standardized videos from a tremor database and clinically classified patients into ET, ETP, or dystonic tremor (DT). The following variables were derived from combined tri‐axial accelerometry–surface electromyography (EMG)—peak frequency, total power, peak power, full width half maximum, tremor stability index and EMG‐coherence. We analyzed hand‐drawn spirals to derive mean deviation, tremor variability, inter‐, and intra‐loop widths. We compared these variables among the groups. Results: We recruited 72 participants (81.9% male) with mean age 47.7 ± 16.1 years and Fahn‐Tolosa‐Marin Tremor Rating Scale total score 31.1 ± 14.1. Patients with ET were younger (P = 0.014) and had less severe tremor (P = 0.020) compared to ETP and DT. In ETP group, 48.6% had subtle dystonia. Peak frequency was greater in ETP (7.3 ± 0.3 Hz) compared to DT (6.1 ± 0.4 Hz; P = 0.024). Peak power was greater in ETP and DT for postural tremor. Rest tremor was recordable on accelerometry in 26.7% of ET. Other variables were similar among the groups. Conclusion: Electrophysiological evaluation revealed postural tremor of frequency 6 to 7 Hz in ET, ETP, and DT with subtle differences more severe tremor in ETP and DT, and higher frequency in ETP compared to DT. Our findings suggest a similar tremor oscillator in these conditions, supporting the view that these entities are part of a spectrum of tremor disorders, rather than distinct etiological entities. [ABSTRACT FROM AUTHOR]

Controlling amide bond geometries and the secondary structures of β‐peptoids is a challenging task as they contain several rotatable single bonds in their backbone. Herein, we describe the synthesis and conformational properties of novel "β‐azapeptoids" with confined dihedrals. We discuss how the acylhydrazide sidechains in these molecules enforce trans amide geometries (ω ~180°) via steric and stereoelectronic effects. We also show that the Θ(Cα‐Cβ) and Ψ(OC‐Cα) backbone torsions of β‐azapeptoids occupy a narrow range (170–180°) that can be rationalized by the staggered conformational preference of the backbone methylene carbons and a novel backbone nO→σ*Cβ‐N interaction discovered in this study. However, the ϕ (Cβ‐N) torsion remains freely rotatable and, depending on ϕ, the sidechains can be parallel, perpendicular, and anti‐parallel relative to each other. In fact, we observed parallel and perpendicular relative orientations of sidechains in the crystal geometries of β‐azapeptoid dimers. We show that ϕ of β‐azapeptoids can be controlled by incorporating a bulky substituent at the backbone β‐carbon, which could provide complete control over all the backbone dihedrals. Finally, we show that the ϕ and Ψ dihedrals of β‐azapeptoids resemble that of a PPII helix and they retain PPII structure when incorporated in Host–guest proline peptides. [ABSTRACT FROM AUTHOR]

Background: Surgical Site Infection (SSI) of the abdominal incision is a dreaded complication following colorectal surgery. Identifying the intraoperative surgical site microbes may provide clarity in the pathogenesis of SSIs. Genomic sequencing has revolutionized the ability to identify microbes from clinical samples. Utilization of 16S rRNA amplicon sequencing to characterize the intraoperative surgical site may provide the critical information required to predict and prevent infection in colorectal surgery. Methods: This is a pilot, prospective observational study of 50 patients undergoing elective colorectal resection. At completion of surgery, prior to skin closure, swabs were taken from the subcutaneous tissue of the abdominal incision to investigate the microbial profile. Dual swabs were taken to compare standard culture technique and 16S rRNA sequencing to establish if a microbial profile was associated with postoperative SSI. Results: 8/50 patients developed an SSI, which was more likely in those undergoing open surgery (5/15 33.3% versus 3/35, 8.6%; P = 0.029). 16S rRNA amplicon sequencing was more sensitive in microbial detection compared to traditional culture. Both culture and 16S rRNA demonstrated contamination of the surgical site, predominantly with anaerobes. Culture was not statistically predictive of infection. 16S rRNA amplicon sequencing was not statistically predictive of infection, however, it demonstrated patients with an SSI had an increased biodiversity (not significant) and a greater relative abundance (not significant) of pathogens such as Bacteroidacaea and Enterobacteriaceae within the intraoperative site. Conclusions: 16S rRNA amplicon sequencing has demonstrated a potential difference in the intraoperative microbial profile of those that develop an infection. These findings require validation through powered experiments to determine the overall clinical significance. [ABSTRACT FROM AUTHOR]

Background: Neuropathic Tremor (NT) is a postural/kinetic tremor of the upper extremity, often encountered in patients with chronic neuropathies such as paraprotein‐associated and hereditary neuropathies. Objectives: To describe the clinical and electrophysiological features of NT in a previously underrecognized setting‐ during recovery from Guillain‐Barré Syndrome (GBS). Methods: Patients with a documented diagnosis of GBS in the past, presenting with tremor were identified from review of clinical records. Participants underwent structured, videotaped neurological examination, and electrophysiological analysis using tri‐axial accelerometry‐surface electromyography. Tremor severity was assessed using the Fahn‐Tolosa‐Marin Tremor Rating Scale. Results: We describe the clinical and electrophysiological features of 5 patients with GBS associated NT. Our cohort had a fine, fast, and slightly jerky postural tremor of frequency ranging from 8 to 10 Hz. Dystonic posturing and overflow movements were noted in 4/5 patients. Tremor appeared 3 months–5 years after the onset of GBS, when patients had regained near normal muscle strength and deep tendon jerks were well elicitable. Electrophysiological analysis of tremor strongly suggested the presence of a central oscillator in all patients. Conclusion: NT is not limited to chronic inflammatory or hereditary neuropathies and may occur in the recovery phase of GBS. The tremor is characterized by a high frequency, jerky postural tremor with dystonic posturing. Electrophysiological evaluation suggests the presence of a central oscillator, hypothetically the cerebellum driven by impaired sensorimotor feedback. [ABSTRACT FROM AUTHOR]

Halide double perovskites [A2MIMIIIX6] are an important class of materials that have garnered substantial interest as non‐toxic alternatives to conventional lead iodide perovskites for optoelectronic applications. While numerous studies have examined chloride and bromide double perovskites, reports of iodide double perovskites are rare, and their definitive structural characterization has not been reported. Predictive models have aided us here in the synthesis and characterization of five iodide double perovskites of general formula Cs2NaLnI6 (Ln=Ce, Nd, Gd, Tb, Dy). The complete crystal structures, structural phase transitions, optical, photoluminescent, and magnetic properties of these compounds are reported. [ABSTRACT FROM AUTHOR]

Cis‐trans isomerization of amide bonds impedes de novo design of folded peptoids (poly‐N‐substituted glycines) with precise secondary structures and affects peptoid‐biomolecule binding affinity. Herein, from X‐ray, NMR and DFT studies of azapeptoids, we have discovered a tetrel bonding interaction that stabilizes trans‐peptoids. We show that peptoids having α‐heteroatoms and N‐aryl groups in the sidechain adopt trans‐amide geometries due to the presence of a nX/πAr→σ*Cα−N tetrel bonding interaction between the sidechain α‐heteroatom lone pair (nX) or π‐electrons (πAr) and the σ* orbital of the backbone Cα−N bond. Further, CD spectroscopic studies of oligo‐proline host–guest model peptides showed that azapeptoid residues stabilize polyproline II helical conformation. These data indicate that the sidechain‐backbone tetrel bonding could be leveraged to design peptoids with precise secondary structures for a wide range of biological and material applications. [ABSTRACT FROM AUTHOR]

Background: Social cognition is the study of how people make sense of themselves and others. Impairment in several domains of social cognition is increasingly being recognized in Parkinson's disease (PD). Objectives: We aimed to study multiple domains of social cognition in Indian PD patients using a culturally appropriate, validated instrument. Methods: We recruited 52 individuals with PD and 31 healthy volunteers (HV) and used the Social Cognition Rating Tools in Indian Setting (SOCRATIS) tool to assess theory of mind (ToM), attributional biases and social cue perception. Quality of life (QoL) was assessed using the PDQOL scale. Results: Baseline characteristics were comparable between PD and HV. The mean (SD) FOT index (first order ToM index) was 0.86(0.18) in PD and 0.99(0.07) in HV [P < 0.001]. The PD group showed higher Externalizing Bias [EB, 4.42(3.91)], compared to HV [1.58(3.22), P = 0.001]. The mean (SD) Faux Pas Composite Index (FPCI ALT) was 0.69(0.09) in PD and 0.78(0.13) in HV [P < 0.001]. Social cognition indices were not associated with QoL in PD. Clinical parameters—age, gender, HAM‐D, MOCA, education, levodopa equivalent daily dose of medication, number of PD drugs and trihexyphenidyl use did not predict social cognition. Conclusion: PD patients were less successful than age, gender matched controls in understanding social situations and other's thought processes and had higher tendency to attribute undesirable events to external causes. Deficits in social cognition did not impair the quality of life. [ABSTRACT FROM AUTHOR]

The present study reports the gamma irradiation‐induced surface plasmon resonance (SPR) of Cu nanoparticles (Cu‐NPs) that are embedded in the C60 fullerene matrix. These films were deposited by the thermal co‐evaporation technique. In this study, the fullerene C60 and CuC60 nanocomposite thin films were deposited separately and irradiated using gamma rays at various doses from 250 to 1000 kGy. A broad but well‐defined SPR peak is observed at approximately 618 nm after gamma irradiation at a dose of 1000 kGy as confirmed by UV–visible spectroscopy. An enhancement in the growth of Cu‐NPs with an average diameter of 46.05 nm is obtained at a dose of 1000 kGy. Raman spectroscopy confirms the ordering of fullerene C60 after gamma irradiation. However, the current–voltage measurements show that the resistivity of thin films remains approximately the same even after the highest doses of gamma irradiation. The electronic structures of these nanocomposite thin films were analyzed by X‐ray photoelectron spectroscopy. The incorporation of Cu‐NPs in fullerene C60 changes the nature of the surface from hydrophilic to hydrophobic. These results are understood based on the ionizing nature of the gamma rays. [ABSTRACT FROM AUTHOR]

The present study reports the gamma irradiation‐induced surface plasmon resonance (SPR) of Cu nanoparticles (Cu‐NPs) that are embedded in the C60 fullerene matrix. These films were deposited by the thermal co‐evaporation technique. In this study, the fullerene C60 and CuC60 nanocomposite thin films were deposited separately and irradiated using gamma rays at various doses from 250 to 1000 kGy. A broad but well‐defined SPR peak is observed at approximately 618 nm after gamma irradiation at a dose of 1000 kGy as confirmed by UV–visible spectroscopy. An enhancement in the growth of Cu‐NPs with an average diameter of 46.05 nm is obtained at a dose of 1000 kGy. Raman spectroscopy confirms the ordering of fullerene C60 after gamma irradiation. However, the current–voltage measurements show that the resistivity of thin films remains approximately the same even after the highest doses of gamma irradiation. The electronic structures of these nanocomposite thin films were analyzed by X‐ray photoelectron spectroscopy. The incorporation of Cu‐NPs in fullerene C60 changes the nature of the surface from hydrophilic to hydrophobic. These results are understood based on the ionizing nature of the gamma rays. [ABSTRACT FROM AUTHOR]

Summary: In this paper, a design of reconfigurable frequency mixer is adapted with gallium nitride high‐electron‐mobility transistor (GaN HEMT) architecture under variable gain, different intermediate frequency (IF) bandwidth, and active/passive configuration for multidisciplinary applications supported by wireless local area network (WLAN) framework. The low band (LB) and high band (HB) are reconfigured by shunting the power between the switching and transconductance at the IF stage of the transistor. The transistor switching mode (active and passive) and logic levels are fixed at the input stage, and the input radio frequency (RF) signal is steering between the gate and drain terminals of transistors. The transistor gain is controlled by adjusting transconductance at the input RF stage and the current‐steering in transimpedance stage at the output. The simulation results show that the proposed circuit provides variable gain of 23/25 and 30/32 dB and noise figure of 14.5/12.5 at the LB and HB reconfigurable scenarios. Hence, it is suitable for transceiver optimistic functions with converge large bandwidth through shunting stages of reconfigurable frequency mixer and transconductance. [ABSTRACT FROM AUTHOR]

In the study of normal numbers using the base‐b representation, b⩾2, we know that a number is normal if and only if it is simply normal in all the bases bn, n⩾1. We prove the analogue of this result for continued fraction normality. In particular, we show that two notions of continued fraction normality, one where overlapping occurrences of finite patterns are counted as distinct occurrences, and another where only disjoint occurrences are counted as distinct, are identical. This equivalence involves an analogue of a theorem due to Pillai (Proc. Indian Acad. Sci. Sect. A 11 (1940) 73–80) for base‐b expansions. The proof requires techniques which are fundamentally different, since the continued fraction expansion utilizes a countably infinite alphabet, leading to a non‐compact space. Utilizing the equivalence of these two notions, we provide a new proof of Heersink and Vandehey's recent result that selection of subsequences along arithmetic progressions does not preserve continued fraction normality (Heersink and Vandehey, Arch. Math. 106 (2016) 363–370). [ABSTRACT FROM AUTHOR]

Vacancy‐ordered double perovskites are attracting significant attention due to their chemical diversity and interesting optoelectronic properties. With a view to understanding both the optical and magnetic properties of these compounds, two series of RuIV halides are presented; A2RuCl6 and A2RuBr6, where A is K, NH4, Rb or Cs. We show that the optical properties and spin‐orbit coupling (SOC) behavior can be tuned through changing the A cation and the halide. Within a series, the energy of the ligand‐to‐metal charge transfer increases as the unit cell expands with the larger A cation, and the band gaps are higher for the respective chlorides than for the bromides. The magnetic moments of the systems are temperature dependent due to a non‐magnetic ground state with Jeff=0 caused by SOC. Ru‐X covalency, and consequently, the delocalization of metal d‐electrons, result in systematic trends of the SOC constants due to variations in the A cation and the halide anion. [ABSTRACT FROM AUTHOR]

There has been a great deal of recent interest in extended compounds containing Ru3+ and Ru4+ in light of their range of unusual physical properties. Many of these properties are displayed in compounds with the perovskite and related structures. Here we report an array of structurally diverse hybrid ruthenium halide perovskites and related compounds: MA2RuX6 (X=Cl or Br), MA2MRuX6 (M=Na, K or Ag; X=Cl or Br) and MA3Ru2X9 (X=Br) based upon the use of methylammonium (MA=CH3NH3+) on the perovskite A site. The compounds MA2RuX6 with Ru4+ crystallize in the trigonal space group R3‾m and can be described as vacancy‐ordered double‐perovskites. The ordered compounds MA2MRuX6 with M+ and Ru3+ crystallize in a structure related to BaNiO3 with alternating MX6 and RuX6 face‐shared octahedra forming linear chains in the trigonal P3‾m space group. The compound MA3Ru2Br9 crystallizes in the orthorhombic Cmcm space group and displays pairs of face‐sharing octahedra forming isolated Ru2Br9 moieties with very short Ru–Ru contacts of 2.789 Å. The structural details, including the role of hydrogen bonding and dimensionality, as well as the optical and magnetic properties of these compounds are described. The magnetic behavior of all three classes of compounds is influenced by spin–orbit coupling and their temperature‐dependent behavior has been compared with the predictions of the appropriate Kotani models. [ABSTRACT FROM AUTHOR]

Physicochemical n‐Grams Tool (PnGT) is an open‐source standalone software for calculating physicochemical descriptors of protein. PnGT was developed using the Python scripting language and developed the user interface using Tkinter. The software currently calculates 33 physicochemical descriptors along with the sequence length for the given protein primary sequence. The descriptor generated by this tool can be directly utilized as the feature vector for the development of proteomics statistical or machine learning predictive model. [ABSTRACT FROM AUTHOR]

Triple‐negative breast cancer (TNBC) liver metastasis is associated with poor prognosis and low patient survival. It occurs when tumor cells disseminate from primary tumors, circulate in blood/lymph [circulating tumor cells (CTCs)], and acquire distinct characteristics during disease progression toward the metastatic phenotype. The purpose of this study was to decipher the genomic/transcriptomic properties of TNBC liver metastasis and its recurrence for potential therapeutic targeting. We employed a negative depletion strategy to isolate and interrogate CTCs from the blood of patients with TNBC, and to establish sequential generations of CTC‐derived xenografts (CDXs) through injection of patient CTCs in immunodeficient mice. The isolation and validation of CDX‐derived cell populations [analyses of CTCs were paired with bone marrow‐resident cells (BMRTCs) and liver tissue cells obtained from the same animal] were performed by multiparametric flow cytometry, immune phenotyping, and genomic sequencing of putative CTCs. Comprehensive characterization of gene expression arrays from sequentially generated CDX‐derived cell populations, online gene expression arrays, and TCGA databases were employed to discover a CTC‐driven, liver metastasis‐associated TNBC signature. We discovered a distinct transcriptomic signature of TNBC patient‐isolated CTCs from primary TNBCs, which was consistent throughout sequential CDX modeling. We established a novel TNBC liver metastasis‐specific CDX model that selectively recapitulates CTC biology for four sequential generations of mice. The evaluation of online databases and CDX‐derived populations revealed 597 genes specific to the TNBC liver metastasis signatures. Further investigation of the TNBC liver metastasis signature predicted 16 hub genes, 6 biomarkers with clinically available drugs, and 22 survival genes. The sequential interrogation of CDX‐CTCs is an innovative liquid biopsy‐based approach for the discovery of organ metastasis‐specific signatures of CTCs. This represents the first step for mechanistic and analytical validation in their application as prognostic indicators and therapeutic targets. Targeting CTC drug candidate biomarkers along with combination therapy can improve the clinical outcome of TNBC patients in general and recurrence of liver metastasis in particular. [ABSTRACT FROM AUTHOR]

Graphene is a well‐known 2D material with potential applications. In recent years, 2D materials of other elements have come to the fore. These are borophene in group III, silicene, germanene and stanene in group IV and phosphorene, arsenene, antimonene and bismuthene in group V. In this article, we discuss the synthesis, structure and properties of the elemental 2D materials beyond graphene. Of the various elemental 2D materials, borophene, silicene and phosphorene are interesting in terms of stability and properties leading to possible applications. We have described potential applications of other 2D materials as well. [ABSTRACT FROM AUTHOR]

GLO:HWR/01jul21:ans16530-fig-0001.jpg PHOTO (COLOR): 1 (a) Axial contrast-enhanced computed tomography (CT) view with a corresponding representative diagram showing the ileocolocolic intussusception and left paraduodenal herniation. (b) Coronal CT view with a corresponding representative diagram showing the ileocolocolic intussusception, middle mesocolic and left paraduodenal herniation. gl Emergency exploratory laparotomy revealed small bowel proximal to the site of intussusception dilated and congested. [Extracted from the article]

Covalent functionalization of the semiconducting chalcogenide nanoparticles ZnS, ZnSe and CdS by reaction with organic halides, specifically iodobenzenes, has been demonstrated. DFT calculations have thrown light on the electronic structure of the functionalized chalcogenides. Chalcogenides with bonded phenyl groups exhibit a long wavelength charge-transfer band as predicted by theory. Functionalization has been carried out with fluorophores as well. Functionalization of semiconducting chalcogenide particles offers many possibilities for study of their properties and application. [ABSTRACT FROM AUTHOR]

Abstract: Two new supramolecular assemblies formed by [Cu2(Hdiphba)4] (H2diphba=4‐hydroxy‐3,5‐di‐iso‐propylbenzoic acid) in protic and aprotic solvents have been investigated. Methanol gives rise a 3D hydrogen‐bonded network comprised of [Cu2(Hdiphba)4] and extremely rare twisted‐boat methanol cyclohexamer synthons. While, dimethyl sulfoxide (DMSO), an aprotic solvent, gives a 2D assembly in which DMSO bridges [Cu2(Hdiphba)4] units to form 1D rectangular channels, entrapping guest DMSO arranged in a zig‐zag chain. The solvent molecules could be replaced with neutral N,N’‐donor linkers to form 1D coordination polymers. [ABSTRACT FROM AUTHOR]

Aim In multiple myeloma ( MM), the growth and survival of myeloma cells is controlled by interleukin-6 ( IL-6), the plasma levels of which is controlled by a guanine/cytosine substitution occurring in position -174 of IL-6 gene promoter region. We studied the occurrence of IL-6-174 G/ C polymorphism in patients of MM and correlated the presence of genotypes with serum IL-6 levels and tumor staging. Methods One hundred three patients with MM and 117 age- and sex-matched healthy controls were staged by International Staging System. IL-6 genotypes were evaluated by polymerase chain reaction and restriction enzyme analysis. Serum levels of IL-6 were assessed by enzyme-linked immunosorbent assay. Results Frequency of GG, GC and CC genotypes did not differ significantly between cases ( GG 52%, GC 40%, CC 9%) and controls. The median serum level of IL-6 was significantly higher among the GC genotype versus other genotypes (24 ng/mL, P = 0.007) as compared with the GG versus other genotypes (12 ng/mL, P = 0.001). GC was associated more with stage 3 disease (27%) than was GG (11%) or CC (22% P = 0.001). Conclusions At position 174 of the IL-6 promoter, patients with GC genotype had higher serum levels of IL-6 and presented with more severe disease compared with patients with GG or CC genotype. [ABSTRACT FROM AUTHOR]

Aliovalent anion substitution in metal oxides and other inorganic materials has a remarkable effect on the electronic structures of these materials as recently demonstrated in N- and F-cosubstituted ZnO. We have examined ZnO where O is partially substituted with N and Cl and found significant changes in the bond lengths by single-crystal X-ray crystallography in the case of ZnO0.6N0.2Cl0.2. Moderate substitution of N and Cl brings the band gap of ZnO down to 1.93 eV and ren-ders ZnO coloured. These materials are photocatalytically active for hydrogen production. Complete substitution of O by N and Cl results in Zn2NCl, a colourless insulator. First-principles calculations have shown how the presence of a band originating from N-2p states occupying the top of the valence band is responsible for the reduction in the band gap in ZnO. The calculations have also thrown light on the stability and electronic structures of the N- and Cl-cosubstituted ZnO compounds. [ABSTRACT FROM AUTHOR]

Mixed organohalidopalladium complexes of the type trans-(NHC)2Pd(R)Br were conveniently obtained from trans-(NHC)2PdBr2 type complexes by a ligand-substitution reaction. In particular, the trans-[1-(1S)-menthyl-4-(R1)-1,2,4-triazol-5-ylidene]2Pd(R2)Br [R1 = Et, R2 = CH2Ph (3a1); R1 = Et, R2 = o-OMeC6H4 (3a2); R1 = R2 = CH2Ph (3b1); R1 = CH2Ph, R2 = o-OMeC6H4 (3b2)] complexes were obtained from the corresponding palladium(II) precursor complexes, 2a,b, by reaction with the respective Grignard reagents, in good to excellent yields (74–93 %). Three of the four mixed organohalidopalladium complexes, 3a1,a2,b1, have been structurally characterized by single-crystal X-ray diffraction, which revealed the trans disposition of the NHC ligands around the palladium center. The use of these mixed organohalidopalladium complexes in the Suzuki–Miyaura cross-coupling reaction was established for all of the complexes, 3a1–b2, which yielded the desired cross-coupled products upon treatment with various ArB(OH)2 [Ar = 1-naphthyl, 4-(1,1′-biphenyl), 9-phenanthrenyl, 4-FC6H4, and 2,6-Me2C6H3] compounds, in the presence of NaOH as a base, in CH3CN, in three hours, under reflux conditions. [ABSTRACT FROM AUTHOR]

Prior studies established constitutively active AP-1, NF- κB, and STAT3 signaling in oral cancer. Differential expression/activation of specific members of these transcription factors has been documented in HPV-positive oral lesions that respond better to therapy. We performed a comprehensive analysis of differentially expressed, transcriptionally active members of these pivotal signaling mediators to develop specific signatures of HPV-positive and HPV-negative oral lesions by immunohistochemical method that is applicable in low-resource settings. We examined a total of 31 prospective and 30 formalin-fixed, paraffin-embedded tissues from treatment-naïve, histopathologically and clinically confirmed cases diagnosed as oral or oropharyngeal squamous cell carcinoma ( OSCC/ OPSCC). Following determination of their HPV status by GP5 + / GP6 + PCR, the sequential sections of the tissues were evaluated for expression of JunB, JunD, c-Fos, p50, p65, STAT3, and pSTAT3(Y705), along with two key regulatory proteins pEGFR and p16 by IHC. Independent analysis of JunB and p65 showed direct correlation with HPV positivity, whereas STAT3 and pSTAT3 were inversely correlated. A combined analysis of transcription factors revealed a more restrictive combination, characterized by the presence of AP-1 and NF- κB lacking involvement of STAT3 that strongly correlated with HPV-positive tumors. Presence of STAT3/ pSTAT3 with NF- κB irrespective of the presence or absence of AP-1 members was present in HPV-negative lesions. Expression of pSTAT3 strongly correlated with all the AP-1/ NF- κB members (except JunD), its upstream activator pEGFRY1092, and HPV infection-related negative regulator p16. Overall, we show a simple combination of AP-1, NF- κB, and STAT3 members' expression that may serve as molecular signature of HPV-positive lesions or more broadly the tumors that show better prognosis. [ABSTRACT FROM AUTHOR]

Covalent functionalization has been effectively employed to attach benzene functionalities to MoS2 and MoSe2 nanosheets by the reaction with para-substituted iodobenzenes bearing −OCH3, −H, and −NO2 as the substituents, where the electron-donating and electron-withdrawing power of the para substituent varies significantly. The functionalization is based on the formation of a C−S or C−Se linkage at the expense of the C−I bond on reaction of the iodobenzene with electron-rich 1T-MoS2 or 1T-MoSe2. The degree of functionalization is in the range 4-24 % range, the value increases with the electron-withdrawing power of the para substituent. Semiconducting 2H-MoS2 and 2H-MoSe2 nanosheets can also be functionalized with iodobenzene by carrying out the reaction in the presence of a Pd0 catalyst. We have also carried out functionalization of 1T-MoS2 with pyrene, coumarin, and porphyrin derivatives. By using first-principles density functional calculations, we show that the bonding of the functional groups with the 1T phase is stronger than with the 2H phase. This is reflected in notable changes in the electronic structure of the former upon functionalization; a gap opens up in the electronic spectrum of the 1T phase. Functionalization with para-substituted benzenes leads to a change in the work function. [ABSTRACT FROM AUTHOR]

Computed tomography (CT) of the abdomen and pelvis showed loops of small bowel clustered within a sac-like structure in the umbilical region extending into the right side of the abdomen (Fig. SEP is a rare chronic inflammatory condition of the peritoneum characterized by encasement of loops of small bowel within the abdomen by a membranous sac. Diagnosis is usually made on the basis of radiographic and intraoperative findings of small bowel encasement, with histopathology usually revealing a fibrinous membrane with a mononuclear infiltrate. [Extracted from the article]

Starting from a flexible tri-carboxylic acid ligand H3L {H3L = 2,4,6-tris[(4′-carboxyphenoxy)methyl]-1,3,5-trimethylbenzene}, a 3D metal-organic framework [Zn(HL)(H2O)] n ( 1) and a 2D polymeric layered solid {[(CH3)2NH2)]2[Cd2L2(DMA)2]} n ( 2) were hydrothermally synthesized. The complexes were characterized by elemental analyses, FT-IR spectroscopy, TGA, and single-crystal X-ray diffraction. The X-ray structural analyses reveal that the complex 1 is an example of a doubly interpenetrated 3D helical MOF with mutually entwined right- and left-handed helices to form an overall racemic framework. Complex 2 is made up of fourfold interwoven 2D nets in the solid state. [ABSTRACT FROM AUTHOR]

Sporulation initiation in Bacillus subtilis is controlled by the phosphorylated form of the master regulator Spo0 A which controls transcription of a multitude of sporulation genes. In this study, we investigated the importance of temporal dynamics of phosphorylated Spo0 A ( Spo0 A∼ P) accumulation by rewiring the network controlling its phosphorylation. We showed that simultaneous induction of KinC, a kinase that can directly phosphorylate Spo0 A, and Spo0 A itself from separately controlled inducible promoters can efficiently trigger sporulation even under nutrient rich conditions. However, the sporulation efficiency in this artificial two-component system was significantly impaired when KinC and/or Spo0 A induction was too high. Using mathematical modelling, we showed that gradual accumulation of Spo0 A∼ P is essential for the proper temporal order of the Spo0 A regulon expression, and that reduction in sporulation efficiency results from the reversal of that order. These insights led us to identify premature repression of DivIVA as one possible explanation for the adverse effects of accelerated accumulation of Spo0 A∼ P on sporulation. Moreover, we found that positive feedback resulting from autoregulation of the native spo0A promoter leads to robust control of Spo0 A∼ P accumulation kinetics. Thus we propose that a major function of the conserved architecture of the sporulation network is controlling Spo0 A activation dynamics. [ABSTRACT FROM AUTHOR]

Delivery of growth factors or bioactive molecules plays an important role in tissue engineering, as the duration to which these are supplied can modulate the cell fate. Thus, the delivery method plays an important role, and the same is presented in this work wherein the exogenous supply of alpha-ketoglutarate (a-KG) gave better results for fast proliferating cells as compared to delivery by microspheres or microspheres incorporated scaffolds which can be used while culturing slow growing cells. All these studies were performed in two dimensional (2D) and three dimensional (3D) setups in which chitosan-gelatin-polypyrrole has been used as 3-D scaffolds. Chitosan and gelatin microspheres alone as well as incorporated in the cryogels were characterized. MTT assay done using neuro-2a cell line showed approximately 42% and 70% increment in cellular proliferation when gelatin and chitosan microspheres were added in a 3-D setup, respectively, as compared to the control. Biochemical analysis of ammonia showed 6-fold reductions in ammonia level in a 3-D setup compared to the control. We also studied the synthesis of a neurotransmitter-like glutamate and found that its concentration increased up to 0.25 mg/ml when the microspheres were added exogenously in a 3-D system. [ABSTRACT FROM AUTHOR]

A tissue-engineered polymeric scaffold should provide suitable macroporous structure similar to that of extracellular matrix which can induce cellular activities and guide tissue regeneration. Cryogelation is a technique in which appropriate monomers or polymeric precursors frozen at sub-zero temperature leads to the formation of supermacroporous cryogel matrices. In this study carrageenan-gelatin (natural polymers) cryogels were synthesized by using glutaraldehyde and 1-ethyl-3-[3-dimethylaminopropyl] carbodiimide hydrochloride and N-hydroxysuccinimide (EDC-NHS) as crosslinking agent at optimum concentrations. Matrices showed large and interconnected pores which were in the range of 60-100 m diameter. Unconfined compression analysis showed elasticity and physical integrity of all cryogels, as these matrices regained their original length after 90% compressing from the original size. Moreover Young's modulus was found to be in the range of 4-11 kPa for the dry cryogel sections. These cryogels also exhibited good in vitro degradation capacity at 37 °C within 4 weeks of incubation. Supermacroporous carrageenan-gelatin cryogels showed efficient cell adherence and proliferation of Cos-7 cells which was examined by SEM. PI nuclear stain was used to observe cell-matrix interaction. Cytotoxicity of the scaffolds was checked by MTT assay which showed that cryogels are biocompatible and act as a potential material for tissue engineering and regenerative medicine. [ABSTRACT FROM AUTHOR]

Circadian clocks gate cellular proliferation and, thereby, therapeutically target availability within proliferative pathways. This temporal coordination occurs within both cancerous and noncancerous proliferating tissues. The timing within the circadian cycle of the administration of drugs targeting proliferative pathways necessarily impacts the amount of damage done to proliferating tissues and cancers. Concurrently measuring target levels and associated key pathway components in normal and malignant tissues around the circadian clock provides a path toward a fuller understanding of the temporal relationships among the physiologic processes governing the therapeutic index of antiproliferative anticancer therapies. The temporal ordering among these relationships, paramount to determining causation, is less well understood using two- or three-dimensional representations. We have created multidimensional multimedia depictions of the temporal unfolding of putatively causative and the resultant therapeutic effects of a drug that specifically targets these ordered processes at specific times of the day. The systems and methods used to create these depictions are provided, as well as three example supplementary movies. [ABSTRACT FROM AUTHOR]