Improved C_(3-4) transfer for treatment of root avulsion of the brachial plexus upper trunk Animal experiments and clinical application

Experimental rats with root avulsion of the brachial plexus upper trunk were treated with the improved C34 transfer for neurotization of 05-6. Results showed that Terzis grooming test scores were significantly increased at 6 months after treatment, the latency of C5-6 motor evoked potential was gradually shortened, and the amplitude was gradually increased. The rate of C3 instead of C5 and the C4 ＋ phrenic nerve instead of C6 myelinated nerve fibers crossing through the anastomotic stoma was approximately 80%. Myelinated nerve fibers were arranged loosely but the thickness of the myelin sheath was similar to that of the healthy side. In clinical applications, 39 patients with root avulsion of the brachial plexus upper trunk were followed for 6 months to 4.5 years after treatment using the improved C3 instead of C5 nerve root transfer and C4 nerve root and phrenic nerve instead of C6 nerve root transfer. Results showed that the strength of the brachial biceps and deltoid muscles recovered to level IIHV, scapular muscle to level Ill-W, latissimus dorsi and pectoralis major muscles to above level Ⅲ, and the brachial triceps muscle to level 0 Ill. Results showed that the improved 03-4 transfer for root avulsion of the brachial plexus upper trunk in animal models is similar to clinical findings and that C3-4 and the phrenic nerve transfer for neurotization of C5-6 can innervate the avulsed brachial plexus upper trunk and promote the recovery of nerve function in the upper extremity.

Terpyridine-based metallo-cuboctahedron nanomaterials for efficient photocatalytic degradation of persistent organic pollutants

Metal–organic cage photocatalysts with nanoscale dimensions have received wide attention in the field of photocatalytic environmental pollutant treatment due to their large cavities,easy modification,high tunability,and enriched active sites.Herein,we prepared a series of dihydroanthracene-cored terpyridine-based metallo-cuboctahedron nanomaterials through a selfassembly method,which exhibited satisfactory degradation performance for persistent organic pollutants under visible light irradiation.In particular,under light conditions,S1-Zn,one of the prepared nanomaterials,produced photogenerated holes oxidizing water molecules to∙OH,which attacked ibuprofen(IBU)for up to 95% degradation.Simultaneously,the corresponding photogenerated electrons reduced the dissolved oxygen in water,producing 66.2μmol/L hydrogen peroxide.The obtained supramolecular photocatalytic materials have a stable structure with non-precious metals and do not require a sacrificial agent.The metal sites of metallo-cuboctahedrons adsorb pollutants and transfer captured holes to them,accelerating degradation and promoting simultaneous H_(2)O_(2) production.This work not only proposes a simple and efficient synthesis method for supramolecular photocatalysts but also opens up opportunities for efficient,low-cost,and multifunctional materials for environmental persistent organic pollutants treatment.

Sandwich-like Heterochromophore Metallo-Supramolecules Based on Dense Chromophore Arrangements with Energy and Chirality Transfer Properties

Multichromophoric architectures with wellorganized chromophoric arrangements are of vital importance to gain insights into interchromophoric interactions.Herein,we report a novel heteroleptic self-assembly strategy and construct three achiral and one chiral sandwich-like heterochromophore complexes(Zn_(4)L^(G)L^(A-C)_(2)and Zn_(4)L_(G)L^(D)_(2)).Possible dynamic products,including homoleptic oligomers and isomers,are eliminated,producing achiral complexes with exceptional purity.Isomers are observed in chiral complexes due to the flexible geometry of LD.Perfectly aligned chromophore arrangements with precise spacing and orientations are evidenced by single-crystal X-ray diffraction.The distinct segments in the ligands lead to different interchromophoric interactions.Impressively,energy transfer and tunable emission,including white-light emission,are achieved for Zn_(4)L^(G)L^(A)_(2)and Zn_(4)L^(G)L^(B)_(2).In addition,chirality transfer is observed for Zn_(4)L_(G)L^(D)_(2),due to conformational restriction from chiral LD,leading to chiral rotational conformations of tetraphenylethylene moiety in LG.

Highly emissive tribenzotriquinacene-based double-rimed nanocube

The study of discrete nanosized cages has gone a long way to seek aesthetically appealing structures and to carry out functional applications.Although the construction of supramolecular cages via a bottom-up self-assembly process has been well developed,the sophisticated synthesis still remains a challenge.Here we report the design and assembly of a giant double-rimed nanocube Zn_(24)LH_(8),built with 8 tribenzotriquinacene as six-connected vertices and 24<tpy-Zn^(2+)-tpy>(tpy=terpyridine)connectivities serving as the edges.From the single-crystal structure of tribenzotriquinacene-based ligand LH,the bowl-shaped ligand defines a suitable rigid platform for the spatially well-defined attachment of three sets of parallel vertices,which promotes the quantitative formation of the desired three-dimensional(3D)double-rimed cubic architectures.The formed nanocube Zn_(24)LH_(8)possesses molecular weight up to 25.6 kDa and side length 5.3 nm.Remarkably,the Zn_(24)LH_(8)exhibits strong cyan light emission with high luminescence quantum yields in solution and in the solid state based on the inherent cage-confinement induced emission enhancement.By adding orange-emissive Rhodamine B,emission tuning experiments were achieved including white light emission.This work presents a new system for the imitation of complex assemblies and provides a promising candidate for emissive materials.

Trefoil-shaped metallacycle and metallacage via heteroleptic self-assembly

Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional(2D)and three-dimensional(3D)supramolecules,but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge.Here we report two discrete trefoil-shaped metallacycle S1 and metallacage s2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands.The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic'Mitsubishi motif.The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2.The formed metallacage S2 possesses a molecular weight up to 36 kDa,diameter 6.6 nm and height 3.0 nm.All supramolecular coordination complexes were fully characterized by NMR spectroscopy(^(1)H NMR,2D COSY,2D NOESY,2D DOSY),high-resolution electrospray ionization mass sectrometry ESI-MS.ESI-TWIM-MS,TEM and AFM.

Tetraphenylethylene-Based Emissive Supramolecular Metallacages Assembled by Terpyridine Ligands

We report the preparation and emission properties of tetraphenylethylene(TPE)-based metallacages with aggregation-induced emission(AIE)activities through coordination-driven self-assembly.Two supramolecular cages,[Zn6LA3]and[Zn6LB3],were assembled via TPE-decorated terpyridine(tpy)ligands,LA and LB,respectively,with Zn(II)ions.We performed a subtle change by introducing extra alkyne connectivity into LB to increase the degree of conjugation and geometric constraint,compared with LA.As a result,we obtained a highly emissive cage,[Zn6LB3],even in a dilute solution.

From Mechanically Interlocked Structures to Host-Guest Chemistry Based on Twisted Dimeric Architectures by Adjusting Space Constraints

Mechanically interlocked molecules(MIMs)and host–guest chemistry have received great attention in the past few decades.However,it remains challenging to design architectures with mechanically interlocked features and construct cavities for guest molecule recognition using similar building blocks.In this study,we designed and constructed a series of novel twisted supramolecular structures by assembling various multitopic terpyridine(tpy)ligands with the same diameter and Zn(II)ions.The obtained complexes exhibited evolutional architectures and showed distinctively different space-constraint effects.Specifically,the assembled dimer SA,SB,and SBH displayed mechanically interlocked phenomena,including[2]catenane and[3]catenane,with an increase in concentration.However,no interlocked structures were observed in complexes SC and SCH constructed by hexatopic tpy ligands due to the significant space constraints.The single-crystal data of complex SCH further proved significant space constraints and illustrated the formation of a relatively closed cavity,which showed excellent host–guest properties for different calixarenes,especially high affinity for calix[6]arene.

Molecular hexagram and octagram:Position determined 3D metallo-supermolecules and concentration-induced transformation

The reaction of a metallo-organic ligand(LA)in which two"V"-shaped bisterpyridines attaching to metaposition of"X"-shaped tetraterpyridine via connectivity and Zn^(2+)ions gave rise to 3D supramolecular architectures:octagram(Zn_(8)LA_(4)).However,a position varied ligand(LB)in which two"V"-shaped bisterpyridines locating at the ortho-position of"X"-shaped tetraterpyridine afforded a different 3D hexagram(Zn_(6)LB_(3)).Full characterizations included NMR(^(1)H,^(13)C,^(2)D COSY,NOESY and DOSY),ESI-MS,TWIM-MS,TEM and AFM.The resulted structures were directly determined by the position of two"V"-shaped bisterpyridines attaching to"X"-shaped tetraterpyridine.