-cage catalysis and initiation derived from photo-activating host-guest encapsulation.

Coordination cage catalysis has commonly relied on the endogenous binding of substrates, exploiting the cavity microenvironment and spatial constraints to engender increased reactivity or interesting selectivity. Nonetheless, there are issues with this approach, such as the frequent occurrence of product inhibition or the limited applicability to a wide range of substrates and reactions. Here we describe a strategy in which the cage acts as an exogenous catalyst, wherein reactants, intermediates and products remain unbound throughout the course of the catalytic cycle.

Photoinduced electron transfer (PeT) based fluorescent probes for cellular imaging and disease therapy.

Typical PeT-based fluorescent probes are multi-component systems where a fluorophore is connected to a recognition/activating group by an unconjugated linker. PeT-based fluorescent probes are powerful tools for cell imaging and disease diagnosis due to their low fluorescence background and significant fluorescence enhancement towards the target. This review provides research progress towards PeT-based fluorescent probes that target cell polarity, pH and biological species (reactive oxygen species, biothiols, biomacromolecules, ) over the last five years.

Dietary Risk Factors for Incident and Recurrent Symptomatic Kidney Stones.

Objective: To compare dietary factors between incident symptomatic stone formers and controls, and among the incident stone formers, to determine whether dietary factors were predictive of symptomatic recurrence.

Patients And Methods: We prospectively recruited 411 local incident symptomatic kidney stone formers (medical record validated) and 384 controls who were seen at Mayo Clinic in Minnesota or Florida between January 1, 2009, and August 31, 2018. Dietary factors were based on a Viocare, Inc, food frequency questionnaire administered during a baseline in-person study visit.

Utilizing Raman Spectroscopy as a Tool for Solid- and Solution-Phase Analysis of Metalloorganic Cage Host-Guest Complexes.

The host-guest chemistry of coordination cages continues to promote significant interest, not least because confinement effects can be exploited for a range of applications, such as drug delivery, sensing, and catalysis. Often a fundamental analysis of noncovalent encapsulation is required to provide the necessary insight into the design of better functional systems. In this paper, we demonstrate the use of various techniques to probe the host-guest chemistry of a novel PdL cage, which we show is preorganized to selectively bind dicyanoarene guests with high affinity through hydrogen-bonding and other weak interactions.

[CrNi] Heterometallic Coordination Cubes.

Three new heterometallic [CrNi] coordination cubes of formulae [CrNiL(HO)](NO) (), [CrNiL(MeCN)(HO)](ClO) (), and [CrNiLCl] () (where HL = 1-(4-pyridyl)butane-1,3-dione), were synthesised using the paramagnetic metalloligand [CrL] and the corresponding Ni salt. The magnetic skeleton of each capsule describes a face-centred cube in which the eight Cr and six Ni ions occupy the eight vertices and six faces of the structure, respectively. Direct current magnetic susceptibility measurements on () reveal weak ferromagnetic interactions between the Cr and Ni ions, with = + 0.

Kinetic selection of PdL metallocyclic and PdL trigonal prismatic assemblies.

The self-assembly of Pd4L2 metallocylcic and Pd6L3 trigonal prismatic assemblies are described. The selection of one species over the other has been achieved by careful choice of ancilliary ligands, which switch the dynamics of the Pd-pyridine bonds such that a highly unusual and distorted smaller assembly can be kinetically trapped en route to the more energetically favourable larger species. Both assemblies provide promise as easy to access multicavity reaction vessels.

Mono- and ditopic hydroxamate ligands towards discrete and extended network architectures.

A family of mono- and ditopic hydroxamic acids has been employed in the synthesis and structural and physical characterisation of discrete (0D) and (1- and 2-D) extended network coordination complexes. Examples of the latter include the 1-D coordination polymer {[Zn(ii)(LH)]·2MeOH} (5; LH = 2-(methylamino)phenylhydroxamic acid) and the 2-D extended network {[Cu(ii)(LH)(HO)(NO)]·HO} (5; LH = 4-amino-2-(acetoxy)phenylhydroxamic acid). The 12-MC-4 metallacrown [Cu(ii)(LH)(MeOH)(NO)]·3HO·4MeOH (7) represents the first metal complex constructed using the novel ligand N-hydroxy-2-[(2-hydroxy-3-methoxybenzyl)amino]benzamide (LH).

Modular [FeM] (M = Pd, Co, Ni, Cu) Coordination Cages.

The reaction of the simple metalloligand [FeL] [HL = 1-(4-pyridyl)butane-1,3-dione] with a variety of different M salts results in the formation of a family of heterometallic cages of formulae [FePdL]Cl (1), [FeCuL(HO)Br]Br (2), [FeCuL(HO)](NO) (3), [FeNiL(SCN)Cl] (4), and [FeCoL(SCN)(HO)]Cl (5). The metallic skeleton of each cage describes a cube in which the Fe ions occupy the eight vertices and the M ions lie at the center of the six faces. Direct-current magnetic susceptibility and magnetization measurements on 3-5 reveal the presence of weak antiferromagnetic exchange between the metal ions in all three cases.

A room temperature spin crossover ionic liquid.

Two new paramagnetic ionic liquids (ILs) comprising a mononuclear iron(III) or manganese(III) complex cation, charge balanced by a dicyanamide anion are reported which show a range of spin states. Both are liquids at room temperature and the Fe(III) based IL exhibits a spin crossover close to 300 K. The spin crossover profile is independent of the solvation, and is both air and moisture stable.

Relationship Between Microbiota of the Colonic Mucosa vs Feces and Symptoms, Colonic Transit, and Methane Production in Female Patients With Chronic Constipation.

Background & Aims: In fecal samples from patients with chronic constipation, the microbiota differs from that of healthy subjects. However, the profiles of fecal microbiota only partially replicate those of the mucosal microbiota. It is not clear whether these differences are caused by variations in diet or colonic transit, or are associated with methane production (measured by breath tests).

[Cr(III)8M(II)6](12+) Coordination Cubes (M(II)=Cu, Co).

[Cr(III)8M(II)6](12+) (M(II) =Cu, Co) coordination cubes were constructed from a simple [Cr(III) L3 ] metalloligand and a "naked" M(II) salt. The flexibility in the design proffers the potential to tune the physical properties, as all the constituent parts of the cage can be changed without structural alteration. Computational techniques (known in theoretical nuclear physics as statistical spectroscopy) in tandem with EPR spectroscopy are used to interpret the magnetic behavior.

Trans fatty acid intake is associated with increased risk and n3 fatty acid intake with reduced risk of non-hodgkin lymphoma.

We evaluated the association of dietary fat and protein intake with risk of non-Hodgkin lymphoma (NHL) in a clinic-based study in 603 cases (including 218 chronic lymphocytic leukemia/small lymphocytic lymphoma, 146 follicular lymphoma, and 105 diffuse large B-cell lymphoma) and 1007 frequency-matched controls. Usual diet was assessed with a 128-item food-frequency questionnaire. Unconditional logistic regression was used to estimate ORs and 95% CIs, and polytomous logistic regression was used to assess subtype-specific risks.

Relative intake of macronutrients impacts risk of mild cognitive impairment or dementia.

High caloric intake has been associated with an increased risk of cognitive impairment. Total caloric intake is determined by the calories derived from macronutrients. The objective of the study was to investigate the association between percent of daily energy (calories) from macronutrients and incident mild cognitive impairment (MCI) or dementia.

Controlled metabolic diet reduces calcium oxalate supersaturation but not oxalate excretion after bariatric surgery.

Objective: To identify the effect of a controlled metabolic diet on reducing urinary calcium oxalate (CaOx) supersaturation in subjects with hyperoxaluric nephrolithiasis after potentially malabsorptive forms of bariatric surgery.

Methods: Subjects with a history of CaOx kidney stones and mild hyperoxaluria after bariatric surgery (n = 9) collected baseline 24-hour urine samples while consuming a free choice diet. They were then instructed to consume a controlled diet low in oxalate (70-80 mg/d), normal in calcium (1000 mg/d), and moderate in protein before 2 final 24-hour urine collections.

Food-frequency questionnaire-based estimates of total antioxidant capacity and risk of non-Hodgkin lymphoma.

Antioxidants, primarily from fruits and vegetables, have been hypothesized to protect against non-Hodgkin lymphoma (NHL). The oxygen radical absorbance capacity (ORAC) assay, which measures total antioxidant capacity of individual foods and accounts for synergism, can be estimated using a food-frequency questionnaire (FFQ). We tested the hypothesis that higher intake of antioxidant nutrients from foods, supplements and FFQ-based ORAC values are associated with a lower risk of NHL in a clinic-based study of 603 incident cases and 1,007 frequency-matched controls.

Diet, but not oral probiotics, effectively reduces urinary oxalate excretion and calcium oxalate supersaturation.

We examined the effect of a controlled diet and two probiotic preparations on urinary oxalate excretion, a risk factor for calcium oxalate kidney stone formation, in patients with mild hyperoxaluria. Patients were randomized to a placebo, a probiotic, or a synbiotic preparation. This tested whether these probiotic preparations can increase oxalate metabolism in the intestine and/or decrease oxalate absorption from the gut.

Polyunsaturated fatty acids and reduced odds of MCI: the Mayo Clinic Study of Aging.

Mono- and polyunsaturated fatty acids (MUFA, PUFA) have been associated with a reduced risk of dementia. The association of these fatty acids with mild cognitive impairment (MCI) is not fully established. The objective of the study was to investigate the cross-sectional association of dietary fatty acids with MCI in a population-based sample.

Vegetables, unsaturated fats, moderate alcohol intake, and mild cognitive impairment.

Background/aims: To investigate associations of the Mediterranean diet (MeDi) components and the MeDi score with mild cognitive impairment (MCI).

Methods: Participants (aged 70-89 years) were clinically evaluated to assess MCI and dementia, and completed a 128-item food frequency questionnaire.

Results: 163 of 1,233 nondemented persons had MCI.