Stereoselective Ring Expansion Metathesis Polymerization with Cationic Molybdenum Alkylidyne N-Heterocyclic Carbene Complexes.

Molybdenum alkylidyne N-heterocyclic carbene (NHC) complexes of the type [Mo(C-p-C6H4Y)(OC(R)(CF3)2)2 (L)(NHC)][B(ArF)4] (Y = OMe, NO2; R = CH3, CF3; L = none, pivalonitrile, tetrahydrofuran; NHC = 1,3-dimesitylimidazol-2-ylidene (IMes), 1,3-dimesityl-3,4-dihydroimidazol-2-ylidene (IMesH2), 1,3-dimesityl-3,4-dichloroimidazol-2-ylidene (IMesCl2), 1,3-diisopropylimidazol-2-ylidene (IiPr); B(ArF)4- = tetrakis(3,5-bis(trifluoromethyl)phen-1-yl)borate) were used in the ring expansion metathesis polymerization (REMP) of cyclic olefins. With cis-cyclooctene (cCOE) cyclic, low molecular weight oligomers were obtained at low monomer concentrations and the cyclic nature of the polymer was confirmed by MALDI-TOF measurements. High-molecular weight cyclic poly(cCOE) became available at high monomer concentrations. Also, post-REMP allowed for converting low-molecular-weight cyclic poly(cCOE) into high-molecular-weight cyclic poly(cCOE). Tailored catalysts together with suitable additives offered access to the stereoselective REMP of functional norbornenes providing functional cis-isotactic (cis-it), cis-syndiotactic (cis-st) and trans-it poly(norbornene)s with up to 99% stereoselectivity. Mechanistic details supported by density functional theory (DFT) calculations are outlined.

A Review of the Role of Robotics in Surgery: To DaVinci and Beyond!

Since its inception in 1985, robotic surgery has evolved into a mainstream surgical approach that has become virtually synonymous with minimally invasive surgery (MIS) and adopted across several specialties offering decreased patient morbidity and improved post-operative outcomes. This article discusses the current role of robotics in MIS and its varied applications, prevalence in the community and the future of the field.

Mechano-tunable chiral metasurfaces via colloidal assembly.

Dynamic control of circular polarization in chiral metasurfaces is being used in many photonic applications. However, simple fabrication routes to create chiral materials with considerable and fully tunable chiroptical responses at visible and near-infrared wavelengths are scarce. Here, we describe a scalable bottom-up approach to construct cross-stacked nanoparticle chain arrays that have a circular dichroism of up to 11°. Due to their layered design, the strong superchiral fields of the inter-layer region are accessible to chiral analytes, resulting in a tenfold enhanced sensitivity in a chiral sensing proof-of-concept experiment. In situ restacking and local mechanical compression enables full control over the entire set of circular dichroism characteristics, namely sign, magnitude and spectral position. Strain-induced reconfiguration opens up an intriguing route towards actively controlled pixel arrays using local deformation, which fosters continuous polarization engineering and multi-channel detection.

Direct Enantioselective Addition of Alkynes to Imines by a Highly Efficient Palladacycle Catalyst.

Enantiopure propargylic amines are highly valuable synthetic building blocks. Much effort has been devoted to develop methods for their preparation. The arguably most important strategy is the 1,2-addition of alkynes to imines. Despite remarkable progress, the known methods using Zn and Cu catalysts suffer from the need for high catalyst loadings, typically ranging from 2-60 mol % for neutral aldimine substrates. Here we report a planar chiral Pd complex acting as very efficient catalyst for direct asymmetric alkyne additions to imines, requiring very low catalyst loadings. Turnover numbers of up to 8700 were accomplished. Our investigation suggests that a Pd-acetylide complex is generated as a catalytically relevant intermediate by the aid of an acac ligand acting as internal catalytic base. It is shown that the catalyst is quite stable under the reaction conditions and that product inhibition is not an issue. A total of 39 examples is shown which all yielded almost enantiopure products.

Regio- and Stereospecific Cyclopolymerization of α,ω-Diynes by Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes.

Both solvent-free and acetonitrile-containing cationic molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes of the general formula [Mo(NR')(CHCMe2 R)(NHC)(X)+ A- ] (R' = 2,6-Cl2 -C6 H3 , tBu, 2-CF3 -C6 H4 , 2-tBu-C6 H4 , 2,6-iPr2 -C6 H3 , 2,6-Me2 -C6 H3 ; R = Me, Ph; NHC = 1,3-dimesitylimidazol-2-ylidene (IMes), 1,3-di-iPr-imidazol-2-ylidene (IPr), 1,3,5-triphenyl-1,3,4-triazol-2-ylidene); X = CF3 SO3 , C6 F5 O, OCH(CF3 )2 , OC(CF3 )3 , pyrrolide, C6 F5 COO, 2,6-(CF3 )2 -C6 H3 COO; A- = B(ArF )4 - , Al(OC(CF3 )3 )4 - ), have been investigated for their propensity to cyclopolymerize 4,4-disubstituted 1,6-heptadiynes. All metal complexes contain a stereogenic (chiral) metal center, which accounts for the high reactivity and high regioselectivity of insertion (>99%) that are observed for all metal complexes, leading to highly conjugated, α-insertion-derived polyenes that are based on a highly regular polymer backbone and that show absorption maxima close to 600 nm. With the chiral monomer 4-(ethoxycarbonyl)-4-(1S,2R,5S)-(-)-menthoxycarbonyl-1,6-heptadiyne, high syndiospecifity (>99% syndiotactic) is observed. A mechanism explaining the high regio- and stereoselectivity is presented. Thus, α-addition of the monomers proceeds chain-end-controlled trans to the NHC and is preferred over ß-addition through intramolecular Mo-O chelation. Insertion of the monomers entails double inversion at the stereogenic metal center in the course of one complete monomer insertion.

Confinement templates for hierarchical nanoparticle alignment prepared by azobenzene-based surface relief gratings.

Alignment of nanoparticles to hierarchical periodic structures is an emerging field in the development of patterned surfaces. Common alignment methods are based on templates that guide particle self-assembly. These can be formed using lithographic methods offering an almost free choice of the motif, while being expensive and time-consuming for large-scale production. Alternatively, template formation by controlled wrinkling offers a low-cost formation, but often suffers from the formation of defect structures like line-defects and cracks. Here, we show a preparation technique for nanoparticle alignment substrates that is based on the inscription of holographic surface relief gratings with a periodic sinusoidal wave pattern on the surface of azobenzene films. As interference patterns are employed for structure formation, very uniform and defect-free gratings with tunable grating height and grating period can be prepared. These substrates were successfully replicated to poly(dimethyl siloxane) and the replicas used for the alignment of polystyrene latex particles. Accordingly produced substrates exhibiting gratings with a variation in grating height allow for efficient screening of nanoparticle alignment in a geometrical confinement in one single experiment. We anticipate our studies as a promising tool for the development of sensors, tunable gratings and metamaterials.

Improved radiographic outcomes with patient-specific total knee arthroplasty.

Patient-specific guides can improve limb alignment and implant positioning in total knee arthroplasty, although not all studies have supported this benefit. We compared the radiographs of 100 consecutively-performed patient-specific total knees to a similar group that was implanted with conventional instruments instead. The patient-specific group showed more accurate reproduction of the theoretically ideal mechanical axis, with fewer outliers, but implant positioning was comparable between groups. Our odds ratio comparison showed that the patient-specific group was 1.8 times more likely to be within the desired +3° from the neutral mechanical axis when compared to the standard control group. Our data suggest that reliable reproduction of the limb mechanical axis may accrue from patient-specific guides in total knee arthroplasty when compared to standard, intramedullary instrumentation.

Molding Process Retaining Gold Nanoparticle Assembly Structures during Transfer to a Polycarbonate Surface.

The immobilization of gold nanoparticle (AuNP) linear surface assemblies on polycarbonate (PC) melt surface via molding is investigated. The order of the particle assemblies is preserved during the molding process. The assemblies on PC exhibit plasmonic coupling features and dichroic properties. The structure of the assemblies is quantified based on Scanning Electron Microscopy (SEM) and image analysis data using an orientational order parameter. The transfer process from mold to melt shows high structural fidelity. The order parameter of around 0.98 reflects the orientation of the lines and remains unaffected, independent of the injection direction of the melt relative to the particle lines. This is discussed in the frame of fountain flow during injection molding. The particles were permanently fixed and withstood the injection molding process, detachment of the substrate, and extraction in boiling ethanol. The plasmonic particles coupled strongly within the dense nanoparticle lines to produce anisotropic optical properties, as quantified by dichroic ratios of 0.28 and 0.52 using ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy. AuNP line assemblies on a polymer surface may be a basis for plasmonic devices like surface-enhanced Raman scattering (SERS) sensors or a precursor for nanowires. Their embedding via injection molding constitutes an important link between particle-self-assembly approaches for optically functional surfaces and polymer processing techniques.

Technical surgical skill assessment of neurovascular bundle dissection and urinary continence recovery after robotic-assisted radical prostatectomy.

Purpose: To examine the association between the quality of neurovascular bundle dissection and urinary continence recovery after robotic-assisted radical prostatectomy. Materials and Methods: Patients who underwent RARPs from 2016 to 2018 in two institutions with ≥1-year postoperative follow-up were included. The primary outcomes were time to urinary continence recovery. Surgical videos were independently assessed by 3 blinded raters using the validated Dissection Assessment for Robotic Technique (DART) tool after standardized training. Cox regression was used to test the association between DART scores and urinary continence recovery while adjusting for relevant patient features. Results: 121 RARP performed by 23 surgeons with various experience levels were included. The median follow-up was 24 months (95% CI 20 - 28 months). The median time to continence recovery was 7.3 months (95% CI 4.7 - 9.8 months). After adjusting for patient age, higher scores of certain DART domains, specifically tissue retraction and efficiency, were significantly associated with increased odds of continence recovery (p<0.05). Conclusions: Technical skill scores of neurovascular bundle dissection vary among surgeons and correlate with urinary continence recovery. Unveiling the specific robotic dissection skillsets which impact patient outcomes has the potential to focus surgical training.

Expectations Facing Reality: Complication Management after Aquablation Treatment for Lower Urinary Tract Symptoms.

Aquablation is a modality recently introduced for surgical treatment of men with symptomatic benign prostatic hyperplasia. Large multi-institutional studies have shown a relatively low rate of high-grade (Clavien-Dindo grade ≥3) complications. Postoperative bleeding primarily depends on prostate volume and approached 8.3% in the initial cumulative experience, for which catheter traction was the predominant hemostatic technique. A systematic and reproducible technique for cautery loop hemostasis has reduced the hemorrhage rate to 1.4%. PATIENT SUMMARY: Aquablation is a surgical treatment option for enlarged prostate glands that are causing urinary problems. This technique uses a water jet to remove prostate tissue and has a relatively low rate of serious complications.

Botryoid Wilms Tumor: A Rare Diagnosis With an Atypical Presentation.

Wilms tumor commonly presents as an asymptomatic abdominal mass. In some cases, it can be accompanied with hypertension, constitutional symptoms, and hematuria when involving the collecting system. Below, we review the case of a child diagnosed with botryoid Wilms tumor involving the upper calyces and renal pelvis in which the presenting symptom was a concern for a foreign body in her left ear, and the only abnormality during initial history and physical examination was stage II hypertension.

Hybridized Guided-Mode Resonances via Colloidal Plasmonic Self-Assembled Grating.

For many photonic applications, it is important to confine light of a specific wavelength at a certain volume of interest at low losses. So far, it is only possible to use the polarized light perpendicular to the solid grid lines to excite waveguide-plasmon polaritons in a waveguide-supported hybrid structure. In our work, we use a plasmonic grating fabricated by colloidal self-assembly and an ultrathin injection layer to guide the resonant modes selectively. We use gold nanoparticles self-assembled in a linear template on a titanium dioxide (TiO2) layer to study the dispersion relation with conventional ultraviolet-visible-near-infrared spectroscopic methods. Supported with finite-difference in time-domain simulations, we identify the optical band gaps as hybridized modes: plasmonic and photonic resonances. Compared to metallic grids, the observation range of hybridized guided modes can now be extended to modes along the nanoparticle chain lines. With future applications in energy conversion and optical filters employing these cost-efficient and upscalable directed self-assembly methods, we discuss also the application in refractive index sensing of the particle-based hybridized guided modes.

Mechanotunable Surface Lattice Resonances in the Visible Optical Range by Soft Lithography Templates and Directed Self-Assembly.

We demonstrate a novel colloidal self-assembly approach toward obtaining mechanically tunable, cost-efficient, and low-loss plasmonic nanostructures that show pronounced optical anisotropy upon mechanical deformation. Soft lithography and template-assisted colloidal self-assembly are used to fabricate a stretchable periodic square lattice of gold nanoparticles on macroscopic areas. We stress the impact of particle size distribution on the resulting optical properties. To this end, lattices of narrowly distributed particles (∼2% standard deviation in diameter) are compared with those composed of polydisperse ones (∼14% standard deviation). The enhanced particle quality sharpens the collective surface lattice resonances by 40% to achieve a full width at half-maximum as low as 16 nm. This high optical quality approaches the theoretical limit for this system, as revealed by electromagnetic simulations. One hundred stretching cycles demonstrate a reversible transformation from a square to a rectangular lattice, accompanied by polarization-dependent optical properties. On the basis of these findings we envisage the potential applications as strain sensors and mechanically tunable filters.

Highly Oriented Nanowire Thin Films with Anisotropic Optical Properties Driven by the Simultaneous Influence of Surface Templating and Shear Forces.

The functional properties of nanoparticle thin films depend strongly on the arrangement of the nanoparticles within the material. In particular, anisotropic optoelectronic properties can be achieved through the aligned assembly of 1D nanomaterials such as silver nanowires (AgNWs). However, the control of the hierarchical organization of these nanoscale building blocks across multiple length scales and over large areas is still a challenge. Here, we show that the oriented deposition of AgNWs using grazing incidence spraying of the nano-object suspensions on a substrate comprising parallel surface wrinkles readily produces highly oriented monolayer thin films on macroscopic areas (>5 × 5 mm2). The use of textured substrates enhances the degree of ordering as compared to flat ones and increases the area over which AgNWs are oriented. The resulting microscopic linear arrangement of AgNWs evaluated by scanning electron microscopy (SEM) reflects in a pronounced macroscopic optical anisotropy measured by conventional polarized UV-vis-NIR spectroscopy. The enhanced ordering obtained when spraying is done in the same direction as the wrinkles makes this approach more robust against small rotational offsets during preparation. On the contrary, the templating effect of the wrinkle topography can even dominate the shear-driven alignment when spraying is performed perpendicular to the wrinkles: the concomitant but opposing influence of topographic confinement (alignment along the wrinkles) and of spray-induced shear forces (orientation along the spraying direction) lead to films in which the predominant orientation of AgNWs gradually changes from one direction to its perpendicular one over the same substrate in a single processing step. This demonstrates that exploiting the subtle balance between shear forces and substrate-nanowire interactions mediated by wrinkles offers a new way to control the self-assembly of nanoparticles into more complex patterns.

Optically anisotropic substrates via wrinkle-assisted convective assembly of gold nanorods on macroscopic areas.

We demonstrate the large-scale organisation of anisotropic nanoparticles into linear assemblies displaying optical anisotropy on macroscopic areas. Monodisperse gold nanorods with a hydrophilic protein shell are arranged by dip-coating on wrinkled surfaces and subsequently transferred to indium tin oxide (ITO) substrates by capillary transfer printing. We elucidate how tuning the wrinkle amplitude enables us to precisely adjust the assembly morphology and fabricate single, double and triple nanorod lines. For the single lines, we quantify the order parameter of the assemblies as well as interparticle distances from scanning electron microscopy (SEM) images. We find an order parameter of 0.97 and a mean interparticle gap size of 7 nm. This combination of close to perfect uni-axial alignment and close-packing gives rise to pronounced macroscopic anisotropic optical properties due to strong plasmonic coupling. We characterise the optical response of the assemblies on ITO-coated glass via UV/vis/NIR spectroscopy and determine an optical order parameter of 0.91. The assemblies are thus plasmonic metamaterials, as their periodicity and building block sizes are well below the optical wavelength. The presented approach does not rely on lithographic patterning and provides access to functional materials, which could have applications in subwavelength waveguiding, photovoltaics, and for large-area metamaterial fabrication.