Comparison of N···I and N···O Halogen Bonds in Organoiodine Cocrystals of Heterocyclic Aromatic Diazine Mono--oxides.

A series of cocrystals of halogen bond donors 1,4-diiodotetrafluorobenzene (-FDIB) and tetraiodoethylene (TIE) with five aromatic heterocyclic diazine mono--oxides based on pyrazine, tetramethylpyrazine, quinoxaline, phenazine, and pyrimidine as halogen bonding acceptors were studied. Structural analysis of the mono--oxides allows comparison of the competitive occurrence of N···I vs O···I interactions and the relative strength and directionality of these two types of interactions. Of the aromatic heterocyclic diazine mono--oxide organoiodine cocrystals examined, six exhibited 1:1 stoichiometry, forming chains that utilized both N···I and O···I interactions.

Halogen, chalcogen, and hydrogen bonding in organoiodine cocrystals of heterocyclic thiones: imidazolidine-2-thione, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole.

Through the combination of heterocyclic thiones with variation in the identity of the heterocyclic elements, namely, imidazolidine-2-thione, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole with the common halogen-bond donors 1,2-, 1,3-, and 1,4-diiodotetrafluorobenzene, 1,3,5-trifluorotriiodobenzene, and tetraiodoethylene, a series of 18 new crystalline structures were characterized. In most cases, N-H..

The reaction of thiourea and 1,3-dimethylthiourea towards organoiodines: oxidative bond formation and halogen bonding.

By varying the halogen-bond-donor molecule, 11 new halogen-bonding cocrystals involving thiourea or 1,3-dimethylthiourea were obtained, namely, 1,3-dimethylthiourea-1,2-diiodo-3,4,5,6-tetrafluorobenzene (1/1), CFI·CHNS, 1, thiourea-1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1), CFI·CHNS, 2, 1,3-dimethylthiourea-1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1), CFI·CHNS, 3, 1,3-dimethylthiourea-1,3-diiodo-2,4,5,6-tetrafluorobenzene-methanol (1/1/1), CFI·CHNS·CHO, 4, 1,3-dimethylthiourea-1,3-diiodo-2,4,5,6-tetrafluorobenzene-ethanol (1/1/1), CFI·CHNS·CHO, 5, 1,3-dimethylthiourea-1,4-diiodo-2,3,5,6-tetrafluorobenzene (1/1), CFI·CHNS, 6, 1,3-dimethylthiourea-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), CFI·CHNS, 7, 1,3-dimethylthiourea-1,1,2,2-tetraiodoethene (1/1), CHNS·CI, 8, [(dimethylamino)methylidene](1,2,2-triiodoethenyl)sulfonium iodide-1,1,2,2-tetraiodoethene-acetone (1/1/1), CHINS·I·CHO·CI, 9, 2-amino-4-methyl-1,3-thiazol-3-ium iodide-1,1,2,2-tetraiodoethene (2/3), 2CHNS·2I·3CI, 10, and 4,4-dimethyl-4H-1,3,5-thiadiazine-3,5-diium diiodide-1,1,2,2-tetraiodoethene (2/3), 2CHNS·4I·3CI, 11. When utilizing the common halogen-bond-donor molecules 1,2-, 1,3-, and 1,4-diiodotetrafluorobenzene, as well as 1,3,5-trifluoro-2,4,6-triiodobenzene, bifurcated I..

Polymorphism, Halogen Bonding, and Chalcogen Bonding in the Diiodine Adducts of 1,3- and 1,4-Dithiane.

Through variations in reaction solvent and stoichiometry, a series of S-diiodine adducts of 1,3- and 1,4-dithiane were isolated by direct reaction of the dithianes with molecular diiodine in solution. In the case of 1,3-dithiane, variations in reaction solvent yielded both the equatorial and the axial isomers of S-diiodo-1,3-dithiane, and their solution thermodynamics were further studied via DFT. Additionally, S,S'-bis(diiodo)-1,3-dithiane was also isolated.

Halogen Bonding in Dithiane/Iodofluorobenzene Mixtures: A New Class of Hydrophobic Deep Eutectic Solvents.

While research into deep eutectic solvents (DESs) has expanded over the previous two decades, the focus has remained on the utilization of hydrogen bond donors in these systems. Additionally, the majority of the known DESs rely on at least one ionic component. Through the combination of 1,3-dithiane and 1,2-diiodo-3,4,5,6-tetrafluorobenzene (1,2-F DIB), we report the first known DES based on halogen bonding.

Crystal Engineering Using Polyiodide Halogen and Chalcogen Bonding to Isolate the Phenothiazinium Radical Cation and Its Rare Dimer, 10-(3-Phenothiazinylidene)phenothiazinium.

Utilizing facile one-electron oxidation of 10H-phenothiazine by molecular diiodine, the solid-state structure of the 10H-phenothiazinium radical cation was obtained in three cation:iodide ratios, as well as its THF and acetone solvates. Oxidation of 10H-phenothiazine with molecular diiodine in DMSO or DMF provided the structure of the radical coupling product 10-(3-phenothiazinyldene)phenothiazinium, which has not been crystallographically characterized to date. The radical cations were balanced by a mixture (I ) , (I ) , (I ) , and I anions, where a variety of chalcogen, halogen, and hydrogen bonding interactions stabilize the structures to reveal these interesting cationic species.

Halogen Bonding of Organoiodines and Triiodide Anions in (NMe Ph) Salts.

To study the role of the triiodide (I ) anion in establishing various halogen bonding patterns, the trimethylphenylammonium iodide (NMe PhI) salt was reacted with diiodine (I ) in the presence of a series of organoiodines, tetraiodoethylene (TIE), 1,2-diiodo-3,4,5,6-tetrafluorobenzene (o-F DIB), 1,4-diiodo-2,3,5,6-tetrafluorobenzene (p-F DIB), and 1,3,5-trifluoro-2,4,6-triiodobenzene (1,3,5-F I B) to form cocrystals of the organoiodines with the trimethylphenylammonium triiodide (NMe PhI ) salt. Single-crystal X-ray crystallography revealed the (I ) anion served as a halogen bond acceptor for the organoiodine donors, forming a variety of 1-D, 2-D, and 3-D packing arrangements through I⋅⋅⋅I halogen bonding. Significant asymmetry was observed within the (I ) anion.

Halogen and Chalcogen Bonding Between the Triphenylphosphine Chalcogenides (Ph P=E; E=O, S, Se) and Iodofluorobenzenes.

A series of cocrystals of Ph P=E (E=O, S, Se) with organoiodines were studied to understand the roles of noncovalent interactions including chalcogen (ChB) and halogen (XB) bonding in their formation. The structure of the cocrystal of Ph P=S and 1,2-diiodotetrafluorobezene was determined, which demonstrates a similar chalcogen⋅⋅⋅iodine XB pattern to the previously reported isomorphic Ph P=Se structure. The cocrystalline structures resulting from the combination of 1,3-diiodotetrafluorobenzene (1,3-F DIB), as well as iodopentafluorobenzene, with all three triphenylphosphine chalcogenides, were also determined.

Detecting and correlating bacterial populations to visual color change of polydiacetylene-coated filters.

Membrane filters were coated with 10,12-pentacosadiynoic acid (PCDA) then polymerized on the filter for rapid bacterial detection and quantification. The polymerized PCDA (pPDCA)-coated filter changed color in response to Salmonella Typhimurium and Escherichia coli but not to Listeria innocua. The time required for color change of pPCDA-coated filters was determined by a visual panel.

Single-crystal X-ray diffraction dataset for 3,5-difluoro-2,6-bis(4-iodophenoxy)-4-phenoxypyridine.

The data in this article are related to the research article "Utilizing the Regioselectivity of Perfluoropyridine towards the Preparation of Phenyoxyacetylene Precursors for Partially Fluorinated Polymers of Diverse Architecture." The X-ray structure analysis of 3,5-difluoro-2,6-bis(4-iodophenoxy)-4-phenoxypyridine has revealed an asymmetric unit containing two molecules, linked via both Type I and Type II C-I∙∙∙I-C halogen bonding interactions. The packing is further consolidated via Ar-H∙∙∙π interactions.

Superior Capsular Reconstruction With Arthroscopic Rotator Cuff Repair in a "Functional Biologic Augmentation" Technique to Treat Massive Atrophic Rotator Cuff Tears.

Surgical treatment of patients with massive rotator cuff tears is unpredictable because of a low healing rate and high incidence of clinical failure. Arthroscopic superior capsular reconstruction has emerged as a promising technique in treating younger, active patients with massive irreparable rotator cuff tears. Superior capsular insufficiency has been theorized to be a factor in the higher failure rate for repairs of massive tears, and there have been proposals of superior capsular repair in addition to rotator cuff repair to facilitate better healing of massive rotator cuff tears.

Arthroscopic Superior Capsular Reconstruction With Acellular Dermal Allograft Using Push-In Anchors for Glenoid Fixation.

Massive irreparable rotator cuff tears in the younger, active patient can be one of the most challenging pathologies to treat in shoulder surgery. Over the last few years, the superior capsular reconstruction (SCR) technique, which has shown favorable initial clinical results, has emerged as a promising new technique that aims to restore glenohumeral mechanics and improve patient function. SCR can be technically challenging, and improvements have been made consistently to the technique.

Arthroscopic Superior Capsular Reconstruction With Acellular Dermal Allograft for the Treatment of Massive Irreparable Rotator Cuff Tears: Short-Term Clinical Outcomes and the Radiographic Parameter of Superior Capsular Distance.

Purpose: This outcome analysis presents 88 consecutive shoulders presenting with irreparable rotator cuff tears that we treated with arthroscopic superior capsular reconstruction (SCR) using an acellular dermal allograft. We also present the concept of superior capsular distance to quantitatively measure the decreased distance present upon restoration of superior capsular integrity.

Methods: A retrospective review was conducted of patients treated with arthroscopic SCR with a minimum 12-month follow-up.

Trifluoromethylation of perfluorinated diacylfluorides: synthesis of the diketone CF3C(O)CF2C(O)CF3 and of new perfluorinated diol (CF3)2C(OH)CF2C(OH)(CF3)2.

Perfluoromalonyl difluoride reacts with TMS-CF3 (1:1) in the presence of KF to give the new diketone CF2(C(O)CF3)2. A large excess (5:1) of TMS-CF3 results in the presumed potassium dialkoxide [(CF3)2COK]2CF2 which yields the 1,3-ditertiarydiol [(CF3)2C(OH)]2CF2 on reaction with H2SO4.

Comparative analysis of single-row versus double-row repair of rotator cuff tears.

Purpose: Our goal in this analysis was to compare clinical outcomes and radiographic healing rates of double-row (DR) transosseous-equivalent versus single-row (SR) Mason-Allen configuration (MAC) arthroscopic repair techniques.

Methods: A prospective, nonrandomized assessment of 132 arthroscopic rotator cuff repair patients included 78 SR repair patients and 54 with DR repair. Tears measured between 1.

Arthroscopic posterior labral repair in athletes: Outcome analysis at 2-year follow-up.

Purpose: The purpose of this outcome analysis was to evaluate the clinical presentation of isolated posterior labral tears resulting from athletic injury and to use multiple outcome measurements to evaluate postoperative results after arthroscopic repair with respect to satisfaction, function, and return to sport.

Methods: Seventy-five consecutive patients injured during athletic activity were treated surgically during the 2-year period from 2005 to 2006 for labral pathologies. Twenty-eight patients were treated for isolated posterior labral tears.

Preparation, characterization, and sensing behavior of polydiacetylene liposomes embedded in alginate fibers.

Polydiacetylene (PDA)-doped calcium alginate fibers were created by the solution blending of polymerized 10,12-pentacosadiynoic acid liposomes with sodium alginate in water prior to extrusion. The liposomes maintained their blue color during wet spinning and drying of the fibers but changed to red with exposure to specific external stimuli (heat, solvent, and chemical). In the latter case, the color change only occurred when the fibers were sufficiently permeable for the reacting species to reach the interior.

Complementary halogen and hydrogen bonding: sulfur...iodine interactions and thioamide ribbons.

Complementary halogen bonding and hydrogen bonding coexist in co-crystals of organoiodines with molecules containing the thioamide functionality. Thiourea.organoiodine co-crystals are shown to exhibit a remarkably reliable synthon with complementary N-H.

A reassignment of the EPR spectra previously attributed to Cu@C60.

EPR spectra attributed to the endohedral metallofullerene Cu@C60 are better explained by the previously characterized Cu(II) dithiocarbamate family of compounds.

Arthroscopic coracoclavicular ligament reconstruction using biologic and suture fixation.

Presented in this report is a modified arthroscopic approach to acromioclavicular joint reconstruction via suture and allograft fixation. An arthroscopic approach is used to expose the base of the coracoid by use of electrocautery. After an open distal clavicle excision is performed, clavicular and coracoid tunnels are created under arthroscopic visualization as previously described by Wolf and Pennington.

The glenoid center point: a magnetic resonance imaging study of normal scapular anatomy.

Using 10 normal cadaveric glenoids, Matsen and colleagues described the anatomic concept and clinical use of the glenoid centering point during shoulder arthroplasty. In the study reported here, we used magnetic resonance imaging scans of 50 patients with nonarthritic conditions of the glenohumeral joint to evaluate the relationship between the glenoid center line and the scapular neck. Results from this larger group of patients confirmed that a reproducible anatomic relationship of the glenoid centering line and the centering point on the anterior glenoid neck exists and can be used to restore normal anatomy in cases of posterior glenoid wear.