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The hexameric assemblies of resorcinarenes and pyrogallolarenes are fascinating structures that can serve as nanoreactors in which new chemistry and catalysis occur. Recently, it was suggested based on SANS or SAXS that

Women with primary ovarian insufficiency exhibit an unfavorable cardiovascular risk profile. A common cause for primary ovarian insufficiency is fragile X premutation (FXPC), and data on the cardiovascular risk factors in women with FXPC are scarce. We aimed to assess the prevalences of abnormal metabolic components among FXPC.Clinical, anthropometric and laboratory data were collected from 71 women with FXPC and compared to 78 women referred for counseling in an in-vitro fertilization clinic (control group). The mean ± SD ages of the FXPC and control groups were 33.5 ± 5.6 and 36.2 ± 5.3 years, respectively (p = 0.003). In a logistic regression analysis, the FXPC group had increased risks for hyperglycemia, hypertriglyceridemia, central obesity and low high-density lipoprotein cholesterol, of 21.8-fold (95% CI 2.7-175, p = 0.004), 6.9-fold (95% CI 2.5-18.7, p 0.0001), 3.1-fold (95% CI 1.4-6.9, p = 0.005) and 2.4-fold (95% CI 1.1-5.2, p = 0.03), compared to the control group. The FXPC group had 2.7-fold higher prevalence of two abnormal metabolic components; 19% met the full criteria of MetS, compared to 3% of the control group. Neither CGG repeats nor ovarian reserve markers were associated with metabolic risk.Carriers of fragile X premutation are at increased metabolic risk from early adulthood; waist circumference, glucose and lipid levels are particularly elevated. We recommend metabolic screening for all women with FMR1 premutation, to enable early interventions for prevention of long-term cardiovascular comorbidities.

An uncharged, water‐soluble per‐ethylene‐glycol pillar[5]arene derivative (1) was synthesized and its aggregation mode, host‐guest chemistry in water and extraction ability was explored. Compound 1 is a liquid at room temperature; in water, limited self‐aggregation occurred at high concentrations as deduced from diffusion NMR and dynamic light scattering. Compound 1 forms pseudo‐rotaxane‐like 1 : 1 host‐guest complexes with 1,ω‐di‐substituted alkanes with association constants on the order of 103–104 m −1. Interestingly, NMR experiments showed that the guest location relative to the host ring system differs among the different complexes. In proof‐of‐concept experiments, compound 1 was shown to extract structurally related organic compounds from benzene into water with significant selectivity. Compound 1, which is a liquid at room temperature and has only limited interactions with its side arms, can, in principle, be regarded as a complement to or as a kind of type I porous liquid., A liquid host based on a per‐ethylene‐glycol pillar[5]arene derivative (1) was prepared and its self‐aggregation, host‐guest chemistry in water and extraction capabilities were studied and evaluated. 1 forms pseudo‐rotaxane‐like complexes with 1,ω‐di‐substituted alkanes, showing Ka values in the range of 103–104 M−1. Host 1 can extract such alkanes with 6–7 fold selectivity and since the interaction with its rim side‐chains is weak, 1 can be regarded as a complement to or as a sort of type 1 porous liquid.

This article provides a complete and comprehensive edition, translation and commentary of KBo 1.51 from Hattuša. It identifies the source as an Akkadian-Hittite list of body parts, some of which are clearly of bovidae, and compares it to two tablets of the same nature: BM 29963 and HS 2944. By doing so, it establishes the existence of a hitherto unknown Akkadian scholarly composition. It discusses the nature of this particular list in relationship with the lexical corpora (Ḫḫ and Uguĝu) and its role as a functional or instructional text in the world of the diviner. The reconstruction of KBo 1.51 also allows us to reconsider some Hittite words and attribute new meanings to them that are otherwise unattested.

The gypsum and calcite scaling propensities of the thin-film composite polyamide (PA-TFC) reverse osmosis (RO) membrane, modified with a tethered surface layer of polyacrylic acid (PAA) chains, was evaluated and compared to the scaling of selected commercial RO membranes. The tethered PAA layer was synthesized onto a commercial polyamide membrane (i.e., base-PA) via atmospheric pressure plasma-induced graft polymerization (APPIGP). The PAA nano-structured (SNS) base-PA membrane (SNS-PAA-PA) was scaled to a lesser degree, as quantified by a lower permeate flux decline and surface imaging, relative to the tested commercial membranes (Dow SW30, Toray SWRO, and BWRO). The cleaning of gypsum-scaled membranes with D.I. water flushing achieved 100% water permeability recovery for both the SNS-PAA-PA and Dow SW30 membranes, relative to 92–98% permeability restoration for the Toray membranes. The calcium carbonate scaling of SNS-PAA-PA membranes was also lower relative to the commercial membranes, but permeability recovery after D.I. water cleaning was somewhat lower (94%) but consistent with the level of surface scale coverage. In contrast, the calcite and gypsum-scaled membrane areas of the commercial membranes post-cleaning were significantly higher than for the SNS-PAA-PA membrane but with 100% permeability recovery, suggesting the potential for membrane damage when mineral scaling is severe.

PURPOSE To evaluate whether ethnicity affects the risk of full mutation expansion among females heterozygous for FMR1 premutation. METHODS Women who carry the FMR1 premutation alelle of Jewish origin who underwent fragile X prenatal diagnosis between 2011 and 2018 in two medical centers in Israel were included. The heterozygote women and fetuses were analyzed for the number of CGG repeats and AGG interruptions. RESULTS Seven hundred sixty-six subjects were included. Parental ethnicity was fully concordant in 592 cases (Jewish, Ashkenazi, and non-Ashkenazi). Ashkenazi compared with non-Ashkenazi heterozygotes have a significantly higher mean number of CGG repeats (68 ± 8.7, 64 ± 6.4 respectively, P = 0.03) and a lower mean number of AGG interruptions (0.89 ± 0.83, 1.60 ± 1.18 respectively, p = 0.0001). Overall, 56/198 (28.2%) fetuses of Ashkenazi heterozygotes had an expansion to a full mutation compared with 6/98 among the non-Ashkenazi (6.1%) (p = 0.001). Multivariate analysis demonstrated that, in addition to CGG repeats and AGG interruptions (which contributed 68.3% of variance), ethnicity is an independent risk factor for a full mutation expansion (odds ratio [OR] = 2.04, p

NMR has been instrumental in studies of both the structure and dynamics of molecular systems for decades, so it is not surprising that NMR has played a pivotal role in the study of host-guest complexes and supramolecular systems. In this mini-review, selected examples will be used to demonstrate the added value of using (multiparametric) NMR for studying macrocycle-based host-guest and supramolecular systems. We will restrict the discussion to synthetic host systems having a cavity that can engulf their guests thus restricting them into confined spaces. So discussion of selected examples of cavitands, cages, capsules and their complexes, aggregates and polymers as well as organic cages and porous liquids and other porous materials will be used to demonstrate the insights that have been gathered from the extracted NMR parameters when studying such systems emphasizing the information obtained from somewhat less routine NMR methods such as diffusion NMR, diffusion ordered spectroscopy (DOSY) and chemical exchange saturation transfer (CEST) and their variants. These selected examples demonstrate the impact that the results and findings from these NMR studies have had on our understanding of such systems and on the developments in various research fields.

Supramolecular systems in water are of paramount importance and those based on hydrogen bonds are both intriguing and scarce. Here, after studying the peculiar host-guest complexes formed between per-dimethylamino-pillar[5]arene (1) and the bis-sulfonates 2 a-c, we describe the formation of the first hydrogen-bond-based supramolecular pentagonal boxes (SPBs), which are stable in water. These pH-responsive SPBs are constructed from 1 as a body, benzene polycarboxylic acids 3 a,b as lid compounds, and 2 a-c as guests. We demonstrate that encapsulation of 2 a-c in pillar[5]arene 1 and in the highly stable water-soluble SPBs, that is, 1(3 a)2 and 1(3 b)2 , is both temperature and pH dependent and, quite interestingly, depends, on the nature of the lid compounds used for capping the boxes even at high pH. We also highlight the difference in the 1 H NMR characteristics of 2 b and 2 c in the cavity of 1 and the SPBs.

The article analyses the border descriptions of the land of Karkemis according to the treaty between Suppiluliuma and Sattiwaza (CTH 51). We argue that the toponyms that establish the boundaries of...

PURPOSE: While FMR1 premutation carriers (CGG 55–200) were shown to have reduced success with IVF treatment (lower oocyte yield), studies reporting on the association between the number of CGG repeats and patients’ response to controlled ovarian hyperstimulation (COH) are inconsistent. In the present study, we aim to explore whether the number of CGG repeats in women with premutation in FMR1 gene, undergoing COH for IVF, correlates with COH variables and whether the number of AGG interruptions may function as a “protective factor” by improving the ovarian response to COH. METHODS: Retrospective study, in an academic IVF-PGD unit. Fifty-seven consecutive FMR1 premutation carriers who underwent 285 IVF treatment cycles were included. The numbers of CGG repeats and AGG interruptions were retrieved and correlated to the demographics and COH variables. RESULTS: There were no significant association between the numbers of CGG or the AGG interruptions and the number of oocyte retrieved or the peak estradiol levels. The lack of association was also observed when including all the IVF treatment cycles or only the first or last IVF treatment cycle. Moreover, no associations were found between the number of CGG repeats or AGG interruptions and other COH variables, i.e., duration of stimulation, the total dose of gonadotropin used, or the number of top-quality embryos. CONCLUSIONS: No associations were observed between the number of CGG repeats or AGG interruptions and any of the COH variables. Further studies are required to identify early biomarkers of POI to empower FMR1 premutation carriers with risk assessment tools to consider procedures such as fertility preservation.

Pretreatment of reverse osmosis (RO) feed water of high mineral scaling propensity was evaluated with respect to downstream RO membrane scaling, for two different feed pretreatment configurations. The pretreatment schemes included (i) media sand filtration, followed by a hydrocyclone (HC) and (ii) a hydrocyclone, microfilter, and a UF module, where both configurations included mesh screens for added protection. The first pretreatment configuration reduced the source water turbidity to ~0.5 NTU, while treatment that included UF feed yielded turbidity of

The confined space inside the hexameric pyrogallol[4]arene capsule (CP6) has been exploited for the catalysis of the 1,3-dipolar cycloaddition (1,3-DC) between the proline-based iminium derivative I and nitrone 3, in the presence of the non-competitive benzene solvent.

Water use patterns were explored for three small communities that are located in proximity to agricultural fields and rely on their local wells for potable water supply. High-resolution water use data, collected over a four-year period, revealed significant temporal variability. Monthly, daily, and hourly water use patterns were well described by autoregressive moving average (ARMA) models. Model development was supported by unsupervised clustering analysis via self-organizing maps (SOMs) that revealed similarities of water use patterns and confirmed the time-series water use model attributes. The inclusion of ambient temperature and rainfall as model attributes improved ARMA model performance for daily and hourly water use from R2 ~0.86–0.87 to 0.94–0.97 and from R2 ~0.85–0.89 to 0.92–0.98, respectively. Water use predictions for an entire year forward in time was feasible demonstrating ARMA models’ performance of (i) R2 ~0.90–0.94 and average absolute relative error (AARE) of ~2.9–4.9% for daily water use, and (ii) R2 ~0.81–0.95 and AARE ~1.9–3.8% for hourly water use. The study suggests that ARMA modeling should be useful for analysis of temporally variable water use in support of water source management, as well as assessing capacity building for small water systems including water treatment needs and wastewater handling.

The observed induction time for seeded gypsum crystallization was investigated with respect to gypsum particle seed size and mass loading. The induction time was significantly shortened in the pres...

Cannabis is one of the most widely used plant drugs in the world today. In spite of the large number of scientific reports on medical marijuana, there still exists much controversy surroun...

Tethered poly(acrylic acid) (PAA) chains, synthesized onto polysulfone (PSf) surfaces, were characterized with respect to surface topography and chain characteristics via AFM force spectroscopy. The tethered PAA chains were synthesized by surface activation with an impinging atmospheric pressure plasma stream (He, He/O2 and He/H2), followed by free-radical acrylic acid graft polymerization. The number average molecular weight of the tethered PAA chains was estimated to be of in the range of ∼13,000–35,000 with chain-chain separation of 1.5–2.4 nm. Deionized and high salinity water contact angles for the PAA-PSf surfaces were in the range of ∼ 29–38°, indicating hydrophilic surfaces, relative to 80° contact angle for the native hydrophobic PSf surface. In DI water the tethered PAA chains had significantly greater chain extension than in a high salinity aqueous environment. Ultrafiltration fouling stress tests with alginic acid in a high salinity water and post cleaning with non-saline water demonstrated permeability restoration of up to 90–100% for a PAA-PSf membrane relative to 50–70% for the native PSf membrane. The present study suggests the merit of exploring and optimizing surface modification of membranes for saline water filtration to reduce irreversible fouling and improve cleaning effectiveness using non-saline water.

A flexible RO (FLERO) membrane desalination configuration employing a pressure intensifier and partial concentrate recycle was investigated with respect to operational flexibility and specific energy consumption (SEC). Decomposition of FLERO configuration and its operation into a membrane processing and concentrate recycle units allows fluid flow regulation at low pressure and adjustable product water recovery. Operational analysis, along with experimental evaluation using a small-scale spiral wound system, demonstrated a desalting capability over a wide range of both permeate recovery and source water salinity. Moreover, in the FLERO configuration a relatively low-pressure pump can be used, even for seawater desalination. However, the SEC for the FLERO configuration is higher, at the same recovery and permeate productivity, relative to conventional single-pass with energy recovery. Nonetheless, given its operational flexibility, in terms of handling both a wide range of source water salinity and recovery and source water salinity and need for low-pressure RO water feed pump. Given the above, FLERO should be ideal for small-scale applications, particularly in remote locations, and field evaluation is warranted to establish its long-term benefits. Large-scale FLERO applications would depend on the availability of suitable energy recovery devices of sufficient efficiency for large desalination capacity.

The influence of surface modification of zirconia (ZrO2) membrane with tethered poly(vinyl pyrrolidone) (PVP) chains was evaluated with respect to the impact of pH and ionic strength on hydraulic resistance and fouling resistance in the filtration of bovine serum albumin (BSA) and lysozyme (Lys) as model protein foulants. The tethered PVP surface layer led to membrane permeability and fouling propensity that were responsive to both pH and ionic strength. The PVP-modified membrane (PVP-ZrO2) hydraulic resistance increased by up to ~48% over a pH range of 6–11, but with no discernible impact at lower pH. Membrane hydraulic resistance was virtually unaffected by ionic strength over the 0.001–1 M range. However, reversible foulant cake resistance in BSA and Lys solution filtration increased with elevated ionic strength, owing in part to the weakening of protein–protein repulsion. Irreversible BSA and Lys fouling was affected by the operational pH relative to the protein isoelectric point (IEP) and reduced under conditions of chain swelling. Irreversible membrane fouling resistance for both proteins was significantly lower, by ~11–49% and 18–74%, respectively, for the PVP-ZrO2 membrane relative to the unmodified ZrO2 membrane. The present results suggest the merit of further exploration of fouling reduction and improvement of membrane cleaning effectiveness via tuning pH and ionic strength triggered conformational responsiveness of the tethered target polymer layer.

This chapter provides an overview of Mesopotamian Wisdom Literature. The introduction discusses the origins and distribution of Mesopotamian Wisdom Literature. It moves on to demonstrate how Mesopotamian Wisdom Literature can be approached. The chapter treats four subcategories of Wisdom Literature: proverbs and instructions, Vanity Theme works, existential works, and satire and parody. The conclusion offers an assessment of the nature of Mesopotamian Wisdom Literature and refers to its transmission and diffusion to other literatures of the East Mediterranean basin, the ancient Near East, the biblical Wisdom books, and beyond.

FMR1 premutation (55–200 CGG repeats) results in fragile X-associated primary ovarian insufficiency (FXPOI). We evaluated expression levels of folliculogenesis-related mediators, follicle-stimulating hormone (FSH) receptor and anti-Mullerian hormone (AMH), to gain insights into the mechanisms underlying the reduced ovarian function. Mural granulosa cells (MGCs) were collected from FMR1 premutation carriers and noncarriers undergoing IVF treatments. At baseline, MGCs of carriers demonstrated significantly higher mRNA expression levels of AMH (3.5 ± 2.2, n = 12 and 0.97 ± 0.5, n = 17, respectively; p = 0.0003) and FSH receptor (5.6 ± 2.8 and 2.7 ± 2.8, respectively; p = 0.02) and higher AMH protein expression on immunostaining. Accordingly, FMR1 premutation-transfected COV434 cells exhibited higher AMH protein expression than COV434 cells transfected with 20 CGG repeats. We conclude that FMR1 premutation may lead to dysregulation of AMH expression levels, probably due to a compensatory mechanism. Elucidating the pathophysiology of FXPOI may help in early detection of ovarian dysfunction and tailoring IVF treatments to FMR1 premutation carriers.

To evaluate whether ethnicity affects the risk of full mutation expansion among females heterozygous for FMR1 premutation.Women who carry the FMR1 premutation alelle of Jewish origin who underwent fragile X prenatal diagnosis between 2011 and 2018 in two medical centers in Israel were included. The heterozygote women and fetuses were analyzed for the number of CGG repeats and AGG interruptions.Seven hundred sixty-six subjects were included. Parental ethnicity was fully concordant in 592 cases (Jewish, Ashkenazi, and non-Ashkenazi). Ashkenazi compared with non-Ashkenazi heterozygotes have a significantly higher mean number of CGG repeats (68 ± 8.7, 64 ± 6.4 respectively, P = 0.03) and a lower mean number of AGG interruptions (0.89 ± 0.83, 1.60 ± 1.18 respectively, p = 0.0001). Overall, 56/198 (28.2%) fetuses of Ashkenazi heterozygotes had an expansion to a full mutation compared with 6/98 among the non-Ashkenazi (6.1%) (p = 0.001). Multivariate analysis demonstrated that, in addition to CGG repeats and AGG interruptions (which contributed 68.3% of variance), ethnicity is an independent risk factor for a full mutation expansion (odds ratio [OR] = 2.04, p 0.001) and accounted for 9% of the variation of a full mutation expansion.Apart from significant differences regarding the number of CGG repeats and AGG interruptions between Ashkenazi and non-Ashkenazi heterozygotes, ethnicity independently affects the risk of a full mutation.

Diffusion NMR is a useful analytical tool for the characterization of supramolecular systems in solution. In this mini-review, after a short introduction and some methodological tips, we discuss, from a personal point of view, the use of diffusion NMR in the study of calixarene- and other arene-based supramolecular systems. We will demonstrate, through selected examples, how diffusion has been used to study, in solution, the structures and other characteristics of supramolecular systems based on calixarene and related systems ranging from different complexes and aggregates to molecular capsules and to supramolecular oligomers and polymers.

Two-component supramolecular organogels based on per-carboxylato- and per-amino pillar[6]arenes (2 and 4a–c) were prepared for the first time, and found to display very different characteristics as compared to those displayed by the corresponding pillar[5]arene derivatives (1 and 3a–c). Pillar[6]arenes derivatives, in contrast to pillar[5]arene derivatives, do not form organogels in alcoholic solutions and the formed gels in chlorinated solvents are, generally, more fragile. We analyzed the gelation ability of all the pairs between 1, 2, 3a–c and 4a–c, several three-component mixtures in 1 : 1 : 1 and 2 : 1 : 1 ratios, as well as four-component mixtures in ∼10 : 1 CDCl3 : DMSOd6 solutions. The obtained results clearly show that shape complementarity is an important determinant of gel formation in these supramolecular pillar[n]arene-based organogels. We also found that shape directed molecular sorting occurs in the gelation process of these two-component supramolecular organogels.

Labeling of smart PEG-dendron hybrids with fluorinated groups transformed their assemblies into enzyme-responsive micellar probes for

A deep cavitand binds long-chain trans,trans- and trans,cis-bis-formamide isomers in water solution giving a pair of caviplexes in a ca. 60:40 ratio. Both caviplexes display in/out guest exchange dynamics that are slow on the 1 H NMR chemical shift timescale, but fast on the EXSY timescale. We apply diffusion-ordered NMR spectroscopy (DOSY) to characterize the caviplexes. On the diffusion timescale, the guest in/out exchange processes feature intermediate dynamics allowing the assessment of their kinetic stabilities. We found that the trans,cis-bis-formamide isomers form kinetically more stable caviplexes than the trans,trans-counterparts. We also show that the kinetic stabilities of the bis-formamide caviplexes relate well with their relative thermodynamic stabilities. Fortunately, the tuning of the DOSY parameters allowed the observation of the exchange dynamics as slow processes on the experiment timescale.