Digital Light Processing of Thermoresponsive Hydrogels from Polyproline-Based Star Polypeptides.

The first report of star poly(L-proline) crosslinkers is disclosed for digital light processing 3D printing of thermoresponsive hydrogels. Through chain end functionalization of star poly(L-proline)s with methacryloyl groups, access to high-resolution defined 3D hydrogel structures via digital light processing is achieved through photoinitiated free radical polymerization. Changing the poly(L-proline) molecular weight has a direct influence on both thermoresponsiveness and printability, while shape-morphing behavior can be induced thermally.

Synthesis and Solvent Free DLP 3D Printing of Degradable Poly(Allyl Glycidyl Ether Succinate).

Digital light processing (DLP) printing forms solid constructs from fluidic resins by photochemically crosslinking polymeric resins with reactive functional groups. DLP is used widely due to its efficient, high-resolution printing, but its use and translational potential has been limited in some applications as state-of-the-art resins experience unpredictable and anisotropic part shrinkage due to the use of solvent needed to reduce resin viscosity and layer dependent crosslinking. Herein, poly(allyl glycidyl ether succinate) (PAGES), a low viscosity, degradable polyester, was synthesized by ring opening copolymerization and used in combination with degradable thiol crosslinkers to afford a solvent free resin that can be utilized in DLP printing.

Type I interferon governs immunometabolic checkpoints that coordinate inflammation during Staphylococcal infection.

Macrophage metabolic plasticity is central to inflammatory programming, yet mechanisms of coordinating metabolic and inflammatory programs during infection are poorly defined. Here, we show that type I interferon (IFN) temporally guides metabolic control of inflammation during methicillin-resistant Staphylococcus aureus (MRSA) infection. We find that staggered Toll-like receptor and type I IFN signaling in macrophages permit a transient energetic state of combined oxidative phosphorylation (OXPHOS) and aerobic glycolysis followed by inducible nitric oxide synthase (iNOS)-mediated OXPHOS disruption.

Poly(l-proline)-Stabilized Polypeptide Nanostructures via Ring-Opening Polymerization-Induced Self-Assembly (ROPISA).

Poly(proline) II helical motifs located at the protein-water interface stabilize the three-dimensional structures of natural proteins. Reported here is the first example of synthetic biomimetic poly(proline)-stabilized polypeptide nanostructures obtained by a straightforward ring-opening polymerization-induced self-assembly (ROPISA) process through consecutive -carboxyanhydride (NCA) polymerization. It was found that the use of multifunctional 8-arm initiators is critical for the formation of nanoparticles.

Are adverse events during surgery for benign prostatic hyperplasia device related? A review of the MAUDE database.

Purpose: The Manufacturer and User Facility Device Experience database contains anonymous, voluntary medical device reports. A review of device-related adverse events associated with Benign Prostatic Hyperplasia surgeries was completed. The objective was to evaluate the occurrence and contributing factors to clinically significant complications in a cohort of patients electing to undergo surgical intervention for Benign Prostatic Hyperplasia.

Investigation of the Effectiveness of Photo Deprotection of Polypeptides in Solution and within the Core of Miniemulsion-Derived Nanoparticles.

Homopolymerization of ortho-nitrobenzyl (NB)-protected l-cysteine and l-glutamic acid was systematically studied in different solvents and at different monomer to initiator ratios, revealing the best reaction control in dimethylformamide (DMF) across a range of degrees of polymerization. In the subsequent ultraviolet (UV)-cleavage studies, it was found that quantitative deprotection upon UV exposure at 365 nm was not achievable for either of the homopolypeptides as confirmed by H NMR and UV/visible (UV/vis) analyses. While the poly(NB-l-cysteine) deprotected more readily with no effect of the polypeptide molecular weight, lower molecular weight poly(NB-l-glutamate) reached maximum deprotection faster than high molecular weight samples.

Modelling energy-harvesting processes in primitive cells: Proton transport across bilayers driven by the oxidation of sulfite.

A frequently debated topic related to the origin of life centers around the question of how complex forms of life on today's Earth may have evolved over time from simpler predecessors. For example, the question of how proton concentration gradients across cellular membranes developed in ancestral protocells remains unanswered. This process, which is indispensable for the generation of chemical energy in modern organisms, is driven by energy derived from redox processes in the respiratory chain.

Outcomes and predictors of survival for tracheal cancer.

Introduction: Primary tracheal cancer is uncommon, with poor survival. While surgical resection is the mainstay of therapy, the role of chemotherapy and radiation is poorly defined. We aimed to study the impact of treatment modalities on survival.

High Molecular Weight Polyproline as a Potential Biosourced Ice Growth Inhibitor: Synthesis, Ice Recrystallization Inhibition, and Specific Ice Face Binding.

Ice-binding proteins (IBPs) from extremophile organisms can modulate ice formation and growth. There are many (bio)technological applications of IBPs, from cryopreservation to mitigating freeze-thaw damage in concrete to frozen food texture modifiers. Extraction or expression of IBPs can be challenging to scale up, and hence polymeric biomimetics have emerged.

Alkali-Metal-Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis-Amide Zn(TMP).

Reminiscent of Lochmann-Schlosser superbase recipes, the addition of two molar equivalents of KOtBu to Zn(TMP) (TMP=2,2,6,6-tetramethylpiperidide) transforms this mild zinc bis-amide base to a powerful metalating agent able to perform facile regioselective zincation of a wide range of sensitive fluoroarenes. Structural authentication of the intermediates post Zn-H exchange demonstrates activation of both TMP groups to form a range of higher order bis-aryl potassium zincates, isolable as solids and further functionalized in electrophilic interception reactions. Studies assessing the role of KOtBu reveal that the first equivalent undergoes co-complexation with Zn(TMP) , enabling kinetic activation of the amide groups; whereas the second equivalent stabilizes the metalated intermediate preventing ligand redistribution.

Block Co-PolyMOC Micelles and Structural Synergy as Composite Nanocarriers.

Conventional micelles of amphiphilic block copolymers (BCPs) disassemble into individual polymer chains upon dilution to a critical concentration, which causes the premature release of the encapsulated drugs and reduces the drug's bioavailability. Here, by integrating the emerging metal-organic cage (MOC) materials with BCPs, we introduce a new type of composite micellar nanoparticles, block co-polyMOC micelles (or BCPMMs), that are self-assembled in essence yet remarkably stable against dilution. BCPMMs are fabricated a stepwise assembly strategy that combines MOCs and BCPs in a well-defined, unimolecular core-shell structure.

Assessing Alkali-Metal Effects in the Structures and Reactivity of Mixed-Ligand Alkyl/Alkoxide Alkali-Metal Magnesiates.

Advancing the understanding of using alkali-metal alkoxides as additives to organomagnesium reagents in Mg-Br exchange reactions, a homologous series of mixed-ligand alkyl/alkoxide alkali-metal magnesiates [MMg(CH SiMe ) (dmem)] [dmem=2-{[2-(dimethylamino)ethyl]methylamino} ethoxide; M=Li, 1; Na, 2; (THF)K, 3] has been prepared. Structural and spectroscopic studies have established the constitutions of these heteroleptic/heterometallic species, which are retained in arene solution. Evaluation of their reactivity towards 2-bromoanisole has uncovered a marked alkali-metal effect with potassium magnesiate 3 being the most efficient of the three ate reagents.

Relationship between operative duration and perioperative outcomes after radical cystectomy.

Unlabelled: INTRODUCTION Prolonged operative times have been associated with an increased risk in complications in other major abdominal surgeries. This study tests the hypothesis that longer operative times will be associated with an increased risk in perioperative complications after radical cystectomy (RC).

Materials And Methods: Adult patients who underwent RC from January 1, 2012, through December 31, 2016, were identified from the National Surgical Quality Improvement Program (NSQIP) database.

Variation in Lymph Node Yield After Radical Cystectomy.

Objectives: To test the hypothesis that lymph node yield will vary by pathology assistant (PA) in patients undergoing radical cystectomy (RC) with pelvic lymph node dissection (PLND).

Methods: This is a single-institution retrospective review that included patients who underwent an RC with PLND for bladder cancer from January 1, 2007, to January 1, 2018. Predicted mean lymph node counts were generated using multivariable regression analysis.

Untangling the Complexity of Mixed Lithium/Magnesium Alkyl/Alkoxy Combinations Utilised in Bromine/Magnesium Exchange Reactions.

While it is known that the addition of Group 1 alkoxides to s-block organometallics can have an activating effect on reactivity, the exact nature of this effect is not that well understood. Here we describe the activation of sBu Mg towards substituted bromoarenes by adding one equivalent of LiOR (R=2-ethylhexyl), where unusually both sBu groups can undergo efficient Br/Mg exchange. Depending on the substitution pattern on the bromoarene two different types of organometallic intermediates have been isolated, either a mixed aryl/alkoxide [{LiMg(2-FG-C H ) (OR)} ] (FG=OMe; NMe ) or a homoaryl [(THF) Li Mg(4-FG-C H ) ] (FG=OMe, F).

Arrhythmias in Pregnancy.

The prevalence of arrhythmias in pregnant women are rising, particularly among women with a history of structural heart disease or prior arrhythmia. The physiological changes of pregnancy increase the risk of both benign and pathologic arrhythmias, with atrial fibrillation representing the most common pathologic arrhythmia. While bradyarrhythmias rarely require treatment during pregnancy, pharmacotherapy is frequently required for tachyarrhythmias.

Regioselective Bromine/Magnesium Exchange for the Selective Functionalization of Polyhalogenated Arenes and Heterocycles.

Using the bimetallic combination sBu Mg⋅2 LiOR (R=2-ethylhexyl) in toluene enables efficient and regioselective Br/Mg exchanges with various dibromo-arenes and -heteroarenes under mild reaction conditions and provides bromo-substituted magnesium reagents. Assessing the role of Lewis donor additives in these reactions revealed that N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDTA) finely tunes the regioselectivity of the Br/Mg exchange on dibromo-pyridines and quinolines. Combining spectroscopic with X-ray crystallographic studies, light has been shed on the mixed Li/Mg constitution of the organometallic intermediates accomplishing these transformations.

Outcome prediction following radical nephroureterectomy for upper tract urothelial carcinoma.

Objective: To predict overall survival, cancer, and metastasis specific survival in upper tract urothelial carcinoma (UTUC) following radical nephroureterectomy (RNU).

Materials And Methods: All nonmetastatic UTUC patients who underwent RNU with a curative intent at 1 institution between December 1998 and January 2017 were included.  Detailed data were collected.

How the Beneficial Effects of Alvimopan Differ With Surgical Approach for Radical Cystectomy.

Objective: To assess whether the beneficial perioperative effects of alvimopan differ with surgical approach for patients who undergo open radical cystectomy (ORC) vs robot-assisted radical cystectomy (RARC).

Methods: This retrospective study reviewed all patients who underwent cystectomy with urinary diversion at our institution between January 1, 2007, and January 1, 2018. Data were collected on demographic characteristics, comorbidities, surgical approach, alvimopan therapy, hospital length of stay (LOS), days until return of bowel function (ROBF), and complications.

Donor-influenced Structure-Activity Correlations in Stoichiometric and Catalytic Reactions of Lithium Monoamido-Monohydrido-Dialkylaluminates.

A series of heteroleptic monoamido-monohydrido-dialkylaluminate complexes of general formula [iBu AlTMPHLi⋅donor] were synthesized and characterised in solution and in the solid state. Applying these complexes in catalytic hydroboration reactions with representative aldehydes and ketones reveals that all are competent, however a definite donor substituent effect is discernible. The bifunctional nature of the complexes is also probed by assessing their performance in metallation of a triazole and phenylacetylene and addition across pyrazine.

Elephantiasis Nostras Verrucosa. Excision with full-thickness skin grafting of the penis, scrotum, and perineal area.

Background: Elephantiasis nostras verrucosa is a rare cutaneous complication of chronic lymphatic obstruction. It is most commonly caused by bacterial infection, trauma, neoplasia, obesity, and venous stasis.

Main Observations: In this report, we describe a case of elephantiasis nostras verrucosa involving the scrotum and perineal area in a 32-year-old.